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Silicon-Containing Polymeric Materials

A topical collection in Polymers (ISSN 2073-4360). This collection belongs to the section "Polymer Chemistry".

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Editor

Prof. Dr. Ignazio Blanco

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Collection Editor
Department of Civil Engineering and Architecture, University of Catania, Viale A. Doria 6, 95125 Catania, Italy
Interests: materials; polymers; thermal properties; nanocomposites; composites
Special Issues, Collections and Topics in MDPI journals

Topical Collection Information

Dear Colleagues,

When thinking about a chemical element that has contributed to the technological progress over the last two centuries, carbon and all carbon-based materials immediately come to mind. By the way, especially during the last century, Silicon and its related materials follow very closely. The versatility of silicon-based materials and silicon’s abundance in the earth's crust make us sure that it will continue to play, in the years to come, a vital role in everyday life. In addition to silicones, or polysiloxanes, which have been known and manufactured for many years, silica-reinforced polymers, silsesquioxaness, and POSS-based polymers also offer a multitude of very useful consumer products. The combination of silicon and oxygen atoms with organic groups has lead to the generation of new and modified silicon-containing polymeric materials, thus providing an exciting mixture of properties and offering a wide spectrum of practical applications. We are interested in articles that explore silicon-containing polymeric materials and their applications.

Prof. Dr. Ignazio Blanco
Collection Editor

Related Special Issues

Published Papers (130 papers)

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2023

Jump to: 2022, 2021, 2020, 2019, 2018, 2017, 2016, 2015

10 pages, 3464 KiB  
Article
Electrochemical Deposition of Polypyrrole in the Presence of Silanes as Adhesion Promoters
by Andres Castro-Beltran, Clemente G. Alvarado-Beltran, Jesus F. Lara-Sanchez, Wencel de la Cruz, Felipe F. Castillon-Barraza and Rodolfo Cruz-Silva
Polymers 2023, 15(10), 2354; https://doi.org/10.3390/polym15102354 - 18 May 2023
Cited by 1 | Viewed by 2123
Abstract
Polypyrrole adhesion to indium–tin oxide electrodes was improved by adding pre-hydrolyzed alkoxysilanes to the electrodeposition media. The pyrrole oxidation and film growth rates were studied by potentiostatic polymerization in acidic media. The morphology and thickness of the films were studied by contact profilometry [...] Read more.
Polypyrrole adhesion to indium–tin oxide electrodes was improved by adding pre-hydrolyzed alkoxysilanes to the electrodeposition media. The pyrrole oxidation and film growth rates were studied by potentiostatic polymerization in acidic media. The morphology and thickness of the films were studied by contact profilometry and surface-scanning electron microscopy. The bulk and surface semiquantitative chemical composition was studied by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. Finally, the adhesion was studied by scotch-tape adhesion test, where both alkoxysilanes showed a significant improvement in adhesion. We proposed a hypothesis for the improvement in adhesion, that involves the formation of siloxane material as well as in situ surface modification of the transparent metal oxide electrode. Full article
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13 pages, 3466 KiB  
Article
Off-Stoichiometry Thiol–Ene Polymers: Inclusion of Anchor Groups Using Allylsilanes
by Kirill Puchnin, Dmitriy Ryazantsev, Egor Latipov, Vitaliy Grudtsov and Alexander Kuznetsov
Polymers 2023, 15(6), 1329; https://doi.org/10.3390/polym15061329 - 7 Mar 2023
Cited by 1 | Viewed by 1654
Abstract
The use of polymers in silicon chips is of great importance for the development of microelectronic and biomedical industries. In this study, new silane-containing polymers, called OSTE-AS polymers, were developed based on off-stoichiometry thiol–ene polymers. These polymers can bond to silicon wafers without [...] Read more.
The use of polymers in silicon chips is of great importance for the development of microelectronic and biomedical industries. In this study, new silane-containing polymers, called OSTE-AS polymers, were developed based on off-stoichiometry thiol–ene polymers. These polymers can bond to silicon wafers without pretreatment of the surface by an adhesive. Silane groups were included in the polymer using allylsilanes, with the thiol monomer as the target of modification. The polymer composition was optimized to provide the maximum hardness, the maximum tensile strength, and good bonding with the silicon wafers. The Young’s modulus, wettability, dielectric constant, optical transparency, TGA and DSC curves, and the chemical resistance of the optimized OSTE-AS polymer were studied. Thin OSTE-AS polymer layers were obtained on silicon wafers via centrifugation. The possibility of creating microfluidic systems based on OSTE-AS polymers and silicon wafers was demonstrated. Full article
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16 pages, 3903 KiB  
Article
Improvement of Heat Resistance of Fluorosilicone Rubber Employing Vinyl-Functionalized POSS as a Chemical Crosslinking Agent
by Jae Il So, Chung Soo Lee, Byeong Seok Kim, Hyeon Woo Jeong, Jin Sung Seo, Sung Hyeon Baeck, Sang Eun Shim and Yingjie Qian
Polymers 2023, 15(5), 1300; https://doi.org/10.3390/polym15051300 - 4 Mar 2023
Cited by 4 | Viewed by 2550
Abstract
Fluorosilicone rubber (F-LSR) is a promising material that can be applied in various cutting-edge industries. However, the slightly lower thermal resistance of F-LSR compared with that of conventional PDMS is difficult to overcome by applying nonreactive conventional fillers that readily agglomerate owing to [...] Read more.
Fluorosilicone rubber (F-LSR) is a promising material that can be applied in various cutting-edge industries. However, the slightly lower thermal resistance of F-LSR compared with that of conventional PDMS is difficult to overcome by applying nonreactive conventional fillers that readily agglomerate owing to their incompatible structure. Polyhedral oligomeric silsesquioxane with vinyl groups (POSS-V) is a suitable material that may satisfy this requirement. Herein, F-LSR-POSS was prepared using POSS-V as a chemical crosslinking agent chemically bonded with F-LSR through hydrosilylation. All F-LSR-POSSs were successfully prepared and most of the POSS-Vs were uniformly dispersed in the F-LSR-POSSs, as confirmed by Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (1H-NMR), scanning electron microscopy (SEM), and X-ray diffraction (XRD) measurements. The mechanical strength and crosslinking density of the F-LSR-POSSs were determined using a universal testing machine (UTM) and dynamic mechanical analysis (DMA), respectively. Finally, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) measurements confirmed that the low-temperature thermal properties were maintained, and the heat resistance was significantly improved compared with conventional F-LSR. Eventually, the poor heat resistance of the F-LSR was overcome with three-dimensional high-density crosslinking by introducing POSS-V as a chemical crosslinking agent, thereby expanding the potential fluorosilicone applications. Full article
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2022

Jump to: 2023, 2021, 2020, 2019, 2018, 2017, 2016, 2015

21 pages, 4692 KiB  
Article
Optical Penetration and “Fingerprinting” Analysis of Automotive Optical Liquid Silicone Components Based on Wavelet Analysis and Multiple Recognizable Performance Evaluation
by Hanjui Chang, Shuzhou Lu, Yue Sun, Guangyi Zhang and Longshi Rao
Polymers 2023, 15(1), 86; https://doi.org/10.3390/polym15010086 - 25 Dec 2022
Cited by 3 | Viewed by 1737
Abstract
The residual stress phenomenon in the injection process of an optical lens affects the quality of optical components, and the refractive error caused by geometric errors is the most serious, followed by the degradation of the accuracy and function of optical components. It [...] Read more.
The residual stress phenomenon in the injection process of an optical lens affects the quality of optical components, and the refractive error caused by geometric errors is the most serious, followed by the degradation of the accuracy and function of optical components. It is very important to ensure that the lens geometry remains intact and the refractive index is low. Therefore, a parameter design method for an optical liquid silicon injection molding was proposed in this study. Wavelet analysis was applied to the noise reduction and feature extraction of the cavity pressure/pressure retaining curve of the injection molding machine, and multiple identifiable performance evaluation methods were used to identify and optimize the parameters of the molding process. Taking an automotive LED lens as an example, Moldex3D simulation software was used to simulate the molding of an LED lens made of LSR material, and two key injection molding factors, melt temperature and V/P switching point, were analyzed and optimized. In this paper, the transmittance and volume shrinkage of LED lenses are taken as quality indexes, and parameters are optimized by setting different V/P switching points and melt temperature schemes. The experimental results show that the residual stress is negatively correlated with transmittance, and the higher the residual stress, the lower the transmittance. Under the optimum process parameters generated by this method, the residual stress of plastic parts is significantly optimized, and the optimization rate is above 15%. In addition, when the V/P switching point is 98 and the melt temperature is 30 °C, the product quality is the best, the volume shrinkage rate is the smallest, and the size is 2.895%, which also means that the carbon emissions are the lowest. Full article
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22 pages, 7889 KiB  
Article
New Light-Green Thermally Activated Delayed Fluorescence Polymer Based on Dimethylacridine-Triphenyltriazine Light-Emitting Unit and Tetraphenylsilane Moiety as Non-Conjugated Backbone
by René A. Hauyon, Denis Fuentealba, Nancy Pizarro, María C. Ortega-Alfaro, Víctor M. Ugalde-Saldívar, Patricio A. Sobarzo, Jean Medina, Luis García, Ignacio A. Jessop, Carmen M. González-Henríquez, Alain Tundidor-Camba and Claudio A. Terraza
Polymers 2023, 15(1), 67; https://doi.org/10.3390/polym15010067 - 24 Dec 2022
Cited by 4 | Viewed by 3400
Abstract
In the search for solution-processable TADF materials as a light emitting layer for OLED devices, polymers have attracted considerable attention due to their better thermal and morphological properties in the film state with respect to small molecules. In this work, a new polymer [...] Read more.
In the search for solution-processable TADF materials as a light emitting layer for OLED devices, polymers have attracted considerable attention due to their better thermal and morphological properties in the film state with respect to small molecules. In this work, a new polymer (p-TPS-DMAC-TRZ) with thermally activated delayed fluorescence (TADF) light-emitting characteristics was prepared from a conjugation-break unit (TPS) and a well-known TADF core (DAMC-TRZ). This material was designed to preserve the photophysical properties of DAMC-TRZ, while improving other properties, such as thermal stability, promoted by its polymerization with a TPS core. Along with excellent solubility in common organic solvents such as toluene, chloroform and THF, the polymer (Mn = 9500; Mw = 15200) showed high thermal stability (TDT5% = 481 °C), and a Tg value of 265 °C, parameters higher than the reference small molecule DMAC-TRZ (TDT5% = 305 °C; Tg = 91 °C). The photoluminescence maximum of the polymer was centered at 508 nm in the solid state, showing a low redshift compared to DMAC-TRZ (500 nm), while also showing a redshift in solution with solvents of increasing polarity. Time-resolved photoluminescence of p-TPS-DMAC-TRZ at 298 K, showed considerable delayed emission in solid state, with two relatively long lifetimes, 0.290 s (0.14) and 2.06 s (0.50), and a short lifetime of 23.6 ns, while at 77 K, the delayed emission was considerably quenched, and two lifetimes in total were observed, 24.6 ns (0.80) and 180 ns (0.20), which was expected from the slower RISC process at lower temperatures, decreasing the efficiency of the delayed emission and demonstrating that p-TPS-DMAC-TRZ has a TADF emission. This is in agreement with room temperature TRPL measurements in solution, where a decrease in both lifetime and delayed contribution to total photoluminescence was observed when oxygen was present. The PLQY of the mCP blend films with 1% p-TPS-DMAC-DMAC-TRZ as a dopant was determined to be equal to 0.62, while in the pure film, it was equal to 0.29, which is lower than that observed for DMAC-TRZ (0.81). Cyclic voltammetry experiments showed similarities between p-TPS-DMAC-TRZ and DAMC-TRZ with HOMO and LUMO energies of −5.14 eV and −2.76 eV, respectively, establishing an electrochemical bandgap value of 2.38 eV. The thin film morphology of p-TPS-DMAC-TRZ and DMAC-TRZ was compared by AFM and FE-SEM, and the results showed that p-TPS-DMAC-TRZ has a smoother surface with fewer defects, such as aggregations. These results show that the design strategy succeeded in improving the thermal and morphological properties in the polymeric material compared to the reference small molecule, while the photophysical properties were mostly maintained, except for the PLQY determined in the pure films. Still, these results show that p-TPS-DMAC-TRZ is a good candidate for use as a light-emitting layer in OLED devices, especially when used as a host-guest mixture in suitable materials such as mCP. Full article
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38 pages, 1817 KiB  
Review
Modifications of Textile Materials with Functional Silanes, Liquid Silicone Softeners, and Silicone Rubbers—A Review
by Jerzy J. Chruściel
Polymers 2022, 14(20), 4382; https://doi.org/10.3390/polym14204382 - 17 Oct 2022
Cited by 32 | Viewed by 9137
Abstract
General information concerning different kinds of chemical additives used in the textile industry has been described in this paper. The properties and applications of organofunctional silanes and polysiloxanes (silicones) for chemical and physical modifications of textile materials have been reviewed, with a focus [...] Read more.
General information concerning different kinds of chemical additives used in the textile industry has been described in this paper. The properties and applications of organofunctional silanes and polysiloxanes (silicones) for chemical and physical modifications of textile materials have been reviewed, with a focus on silicone softeners, silane, and silicones-based superhydrophobic finishes and coatings on textiles composed of silicone elastomers and rubbers. The properties of textile materials modified with silanes and silicones and their practical and potential applications, mainly in the textile industry, have been discussed. Full article
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15 pages, 6194 KiB  
Article
Preparation and Properties of PED-TDI Polyurethane-Modified Silicone Coatings
by Xiaojun Xi, Zhanping Zhang and Yuhong Qi
Polymers 2022, 14(15), 3212; https://doi.org/10.3390/polym14153212 - 6 Aug 2022
Cited by 2 | Viewed by 2827
Abstract
To explore the influence mechanisms of polyurethane soft segments on modified silicone coatings, a series of modified coatings was prepared by introducing different contents of hydroxypropyl-terminated polydimethylsiloxane (PDMS2200) into the soft segment of polyurethane. ATR-FTIR, NMR, CLSM, AFM, contact angle measurement, the tensile [...] Read more.
To explore the influence mechanisms of polyurethane soft segments on modified silicone coatings, a series of modified coatings was prepared by introducing different contents of hydroxypropyl-terminated polydimethylsiloxane (PDMS2200) into the soft segment of polyurethane. ATR-FTIR, NMR, CLSM, AFM, contact angle measurement, the tensile test, bacterial adhesion, and the benthic diatom adhesion test were used to investigate the structure, morphology, roughness, degree of microphase separation, surface energy, tensile properties, and antifouling properties of the modified coatings. The results show that PDMS2200 could aggravate the microphase separation of the modified coatings, increase the surface-free energy, and reduce its elastic modulus; when the microphase separation exceeded a certain degree, increasing PDMS2200 would decrease the tensile properties. The PED-TDI polyurethane-modified silicone coating prepared with the formula of PU-Si17 had the best tensile properties and antifouling properties among all modified coatings. Full article
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2021

Jump to: 2023, 2022, 2020, 2019, 2018, 2017, 2016, 2015

10 pages, 1991 KiB  
Article
Features of Functionalization of the Surface of Alumina Nanofibers by Hydrolysis of Organosilanes on Surface Hydroxyl Groups
by Mikhail M. Simunin, Anton S. Voronin, Yurii V. Fadeev, Yurii L. Mikhlin, Denis A. Lizunov, Alexandr S. Samoilo, Dmitrii Yu. Chirkov, Svetlana Yu. Voronina and Stas V. Khartov
Polymers 2021, 13(24), 4374; https://doi.org/10.3390/polym13244374 - 14 Dec 2021
Cited by 9 | Viewed by 3436
Abstract
Small additions of nanofiber materials make it possible to change the properties of polymers. However, the uniformity of the additive distribution and the strength of its bond with the polymer matrix are determined by the surface of the nanofibers. Silanes, in particular, allow [...] Read more.
Small additions of nanofiber materials make it possible to change the properties of polymers. However, the uniformity of the additive distribution and the strength of its bond with the polymer matrix are determined by the surface of the nanofibers. Silanes, in particular, allow you to customize the surface for better interaction with the matrix. The aim of our work is to study an approach to silanization of nanofibers of aluminum oxide to obtain a perfect interface between the additive and the matrix. The presence of target silanes on the surface of nanofibers was shown by XPS methods. The presence of functional groups on the surface of nanofibers was also shown by the methods of simultaneous thermal analysis, and the stoichiometry of functional groups with respect to the initial hydroxyl groups was studied. The number of functional groups precipitated from silanes is close to the number of the initial hydroxyl groups, which indicates a high uniformity of the coating in the proposed method of silanization. The presented technology for silanizing alumina nanofibers is an important approach to the subsequent use of this additive in various polymer matrices. Full article
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11 pages, 52771 KiB  
Article
Crosslinked Fluorinated Poly(arylene ether)s with POSS: Synthesis and Conversion to High-Performance Polymers
by Yashu He, Jingting Wang, Igor S. Sirotin, Vyacheslav V. Kireev and Jianxin Mu
Polymers 2021, 13(20), 3489; https://doi.org/10.3390/polym13203489 - 11 Oct 2021
Cited by 2 | Viewed by 1952
Abstract
This study reports on a series of crosslinked poly(arylene ether)s with POSS in the main chain. The fluorinated and terminated poly(arylene ether)s were first synthesized by the nucleophilic reaction of diphenol POSS and decafluorodiphenyl monomers, including decafluorobiphenyl, decaflurobenzophenone, and decafluorodiphenyl sulfone. They were [...] Read more.
This study reports on a series of crosslinked poly(arylene ether)s with POSS in the main chain. The fluorinated and terminated poly(arylene ether)s were first synthesized by the nucleophilic reaction of diphenol POSS and decafluorodiphenyl monomers, including decafluorobiphenyl, decaflurobenzophenone, and decafluorodiphenyl sulfone. They were then reacted with 3-hydroxyphenyl acetylene to produce phenylacetylene-terminated poly(arylene ether)s. The polymers were of excellent processability. When heated to a high temperature, the polymers converted into a crosslinked network, exhibiting a low range of dielectric constant from 2.17 to 2.58 at 1 HMz, strong resistance against chemical solutions, low dielectric losses, and good thermal and hydrophobic properties. Full article
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18 pages, 8357 KiB  
Article
Surface Recovery Investigation of Silicone Rubber Composites for Outdoor Electrical Insulation under Accelerated Temperature and Humidity
by M. Hassan Raza, Abraiz Khattak, Asghar Ali, Safi Ullah Butt, Bilal Iqbal, Abasin Ulasyar, Ahmad Aziz Alahmadi, Nasim Ullah and Adam Khan
Polymers 2021, 13(18), 3024; https://doi.org/10.3390/polym13183024 - 7 Sep 2021
Cited by 8 | Viewed by 3180
Abstract
Degradation of silicon rubber due to heat and humidity affect its performance in outdoor applications. To analyze the effects of high temperature and humidity on room temperature vulcanized (RTV) silicone rubber (SiR) and its composites, this study was performed. Five different sample compositions [...] Read more.
Degradation of silicon rubber due to heat and humidity affect its performance in outdoor applications. To analyze the effects of high temperature and humidity on room temperature vulcanized (RTV) silicone rubber (SiR) and its composites, this study was performed. Five different sample compositions including neat silicone rubber (nSiR), microcomposites (15 wt% silica(SMC 15% SiO2) and 15 wt% ATH(SMC 15% ATH), nanocomposite (2.5 wt% silica(SNC 2.5% SiO2) and hybrid composite (10 wt% micro alumina trihydrate with 2 wt% nano silica(SMNC 10% ATH 2% SiO2) were prepared and subjected to 70 ˚C temperature and 80% relative humidity in an environmental chamber for 120 h. Contact angle, optical microscopy and Fourier transform infrared (FTIR) spectroscopy were employed to analyze the recovery properties before and after applying stresses. Different trends of degradation and recovery were observed for different concentrations of composites. Addition of fillers improved the overall performance of composites and SMC 15% ATH composite performed better than other composites. For high temperature and humidity, the ATH-based microcomposite was recommended over silica due to its superior thermal retardation properties of ATH. It has been proved that ATH filler is able to withstand high temperature and humidity. Full article
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13 pages, 2317 KiB  
Article
Cobalt-Mediated Radical Copolymerization of Vinylidene Fluoride and 2,3,3,3-Trifluoroprop-1-ene
by Panagiotis G. Falireas and Bruno Ameduri
Polymers 2021, 13(16), 2676; https://doi.org/10.3390/polym13162676 - 11 Aug 2021
Cited by 2 | Viewed by 2321
Abstract
New copolymers based on vinylidene fluoride (VDF) and 2,3,3,3-tetrafluoroprop-1-ene (1234yf) were synthesized by organometallic-mediated radical copolymerization (OMRcP) using the combination of bis(tert-butylcyclohexyl) peroxydicarbonate initiator and bis(acetylacetonato)cobalt(II), (Co(acac)2) as a controlling agent. Kinetics studies of the copolymerization of the fluoroalkenes [...] Read more.
New copolymers based on vinylidene fluoride (VDF) and 2,3,3,3-tetrafluoroprop-1-ene (1234yf) were synthesized by organometallic-mediated radical copolymerization (OMRcP) using the combination of bis(tert-butylcyclohexyl) peroxydicarbonate initiator and bis(acetylacetonato)cobalt(II), (Co(acac)2) as a controlling agent. Kinetics studies of the copolymerization of the fluoroalkenes copolymers were monitored by GPC and 19F NMR with molar masses up to 12,200 g/mol and dispersities (Đ) ranging from 1.33 to 1.47. Such an OMRcP behaves as a controlled copolymerization, evidenced by the molar mass of the resulting copolymer-monomer conversion linear relationship. The reactivity ratios, ri, of both comonomers were determined by using the Fineman-Ross and Kelen-Tüdos fitting model leading to rVDF = 0.384 ± 0.013 and r1234yf = 2.147 ± 0.129 at 60 °C, showing that a lower reactivity of VDF integrated in the copolymer to a greater extent leads to the production of gradient or pseudo-diblock copolymers. In addition, the Q (0.03) and e (0.06 and 0.94) parameters were assessed, as well as the dyad statistic distributions and mean square sequence lengths of PVDF and P1234yf. Full article
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17 pages, 28004 KiB  
Article
Hard Coating Materials Based on Photo-Reactive Silsesquioxane for Flexible Application: Improvement of Flexible and Hardness Properties by High Molecular Weight
by Jong Tae Leem, Woong Cheol Seok, Ji Beom Yoo, Sangkug Lee and Ho Jun Song
Polymers 2021, 13(10), 1564; https://doi.org/10.3390/polym13101564 - 13 May 2021
Cited by 11 | Viewed by 5292
Abstract
EPOSS of polyhedral oligomeric silsesquioxanes (POSS) mixture structure and LPSQ of ladder-like polysilsesquioxane (LPSQ) structure were synthesized via sol–gel reaction. EPSQ had a high molecular weight due to polycondensation by potassium carbonate. The EPSQ film showed uniform surface morphology due to regular double-stranded [...] Read more.
EPOSS of polyhedral oligomeric silsesquioxanes (POSS) mixture structure and LPSQ of ladder-like polysilsesquioxane (LPSQ) structure were synthesized via sol–gel reaction. EPSQ had a high molecular weight due to polycondensation by potassium carbonate. The EPSQ film showed uniform surface morphology due to regular double-stranded structure. In contrast, the EPOSS-coated film showed nonuniform surface morphology due to strong aggregation. Due to the aggregation, the EPOSS film had shorter d-spacing (d1) than the EPSQ film in XRD analysis. In pencil hardness and nanoindentation analysis, EPSQ film showed higher hardness than the EPOSS film due to regular double-stranded structure. In addition, in the in-folding (r = 0.5 mm) and out-folding (r = 5 mm) tests, the EPSQ film did not crack unlike the EPOSS coated film. Full article
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17 pages, 4511 KiB  
Article
Properties of Silicone Rubber-Based Composites Reinforced with Few-Layer Graphene and Iron Oxide or Titanium Dioxide
by Vineet Kumar, Anuj Kumar, Minseok Song, Dong-Joo Lee, Sung-Soo Han and Sang-Shin Park
Polymers 2021, 13(10), 1550; https://doi.org/10.3390/polym13101550 - 12 May 2021
Cited by 29 | Viewed by 4763
Abstract
The increasing demand for polymer composites with novel or improved properties requires novel fillers. To meet the challenges posed, nanofillers such as graphene, carbon nanotubes, and titanium dioxide (TiO2) have been used. In the present work, few-layer graphene (FLG) and iron [...] Read more.
The increasing demand for polymer composites with novel or improved properties requires novel fillers. To meet the challenges posed, nanofillers such as graphene, carbon nanotubes, and titanium dioxide (TiO2) have been used. In the present work, few-layer graphene (FLG) and iron oxide (Fe3O4) or TiO2 were used as fillers in a room-temperature-vulcanized (RTV) silicone rubber (SR) matrix. Composites were prepared by mixing RTV-SR with nanofillers and then kept for vulcanization at room temperature for 24 h. The RTV-SR composites obtained were characterized with respect to their mechanical, actuation, and magnetic properties. Fourier-transform infrared spectroscopy (FTIR) analysis was performed to investigate the composite raw materials and finished composites, and X-ray photoelectron spectroscopy (XPS) analysis was used to study composite surface elemental compositions. Results showed that mechanical properties were improved by adding fillers, and actuation displacements were dependent on the type of nanofiller used and the applied voltage. Magnetic stress-relaxation also increased with filler amount and stress-relaxation rates decreased when a magnetic field was applied parallel to the deformation axes. Thus, this study showed that the inclusion of iron oxide (Fe3O4) or TiO2 fillers in RTV-SR improves mechanical, actuation, and magnetic properties. Full article
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15 pages, 4375 KiB  
Article
Novel Organochlorinated Xerogels: From Microporous Materials to Ordered Domains
by Guillermo Cruz-Quesada, Maialen Espinal-Viguri, María Victoria López-Ramón and Julián J. Garrido
Polymers 2021, 13(9), 1415; https://doi.org/10.3390/polym13091415 - 27 Apr 2021
Cited by 4 | Viewed by 2327
Abstract
Hybrid silica xerogels combine the properties of organic and inorganic components in the same material, making them highly promising and versatile candidates for multiple applications. They can be tailored for specific purposes through chemical modifications, and the consequent changes in their structures warrant [...] Read more.
Hybrid silica xerogels combine the properties of organic and inorganic components in the same material, making them highly promising and versatile candidates for multiple applications. They can be tailored for specific purposes through chemical modifications, and the consequent changes in their structures warrant in-depth investigation. We describe the synthesis of three new series of organochlorinated xerogels prepared by co-condensation of tetraethyl orthosilicate (TEOS) and chloroalkyltriethoxysilane (ClRTEOS; R = methyl [M], ethyl [E], or propyl [P]) at different molar ratios. The influence of the precursors on the morphological and textural properties of the xerogels was studied using 29Si NMR (Nuclear Magnetic Resonance), FTIR (Fourier-Transform Infrared Spectroscopy), N2, and CO2 adsorption, XRD (X-ray Diffraction), and FE-SEM (Field-Emission Scanning Electron Microscopy). The structure and morphology of these materials are closely related to the nature and amount of the precursor, and their microporosity increases proportionally to the molar percentage of ClRTEOS. In addition, the influence of the chlorine atom was investigated through comparison with their non-chlorinated analogues (RTEOS, R = M, E, or P) prepared in previous studies. The results showed that a smaller amount of precursor was needed to detect ordered domains (ladders and T8 cages) in the local structure. The possibility of coupling self-organization with tailored porosity opens the way to novel applications for this type of organically modified silicates. Full article
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10 pages, 1864 KiB  
Article
Synthesis and Thermal Degradation Study of Polyhedral Oligomeric Silsesquioxane (POSS) Modified Phenolic Resin
by Degang Wang, Jie Ding, Bing Wang, Yingluo Zhuang and Zhixiong Huang
Polymers 2021, 13(8), 1182; https://doi.org/10.3390/polym13081182 - 7 Apr 2021
Cited by 24 | Viewed by 4391
Abstract
In this paper, a new polyhedral oligomeric silsesquioxane containing a phenol group (POSS-Phenol) is prepared through the Michael addition reaction, which is added to the synthesis of phenolic resin as a functional monomer. Infrared spectroscopy (IR) is used to demonstrate the chemistry structure [...] Read more.
In this paper, a new polyhedral oligomeric silsesquioxane containing a phenol group (POSS-Phenol) is prepared through the Michael addition reaction, which is added to the synthesis of phenolic resin as a functional monomer. Infrared spectroscopy (IR) is used to demonstrate the chemistry structure of the synthesized POSS modified phenolic resin. After introducing POSS into the resole, a comprehensive study is conducted to reveal the effects of POSS on the thermal degradation of phenolic resin. First, thermal degradation behaviors of neat phenolic resin and modified phenolic resin are carried out by thermogravimetric analysis (TGA). Then, the gas volatiles from thermal degradation are investigated by thermogravimetric mass spectrometry (TG-MS). Finally, the residues after thermal degradation are characterized by X-ray diffraction (XRD). The research indicates that POSS modified phenolic resin shows a better thermal stability than neat phenolic resin, especially at high temperatures under air atmosphere. On the one hand, the introduction of the POSS group can effectively improve the release temperature of oxygen containing volatiles. On the other hand, the POSS group forms silica at high temperatures under air, which can effectively inhibit the thermal oxidation of phenolic resin and make phenolic resin show a better high-temperature oxidation resistance. Full article
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14 pages, 2976 KiB  
Article
The Influence of Zinc Waste Filler on the Tribological and Mechanical Properties of Silicone-Based Composites
by Maciej Mrówka, Anna Woźniak, Seweryn Prężyna and Sebastian Sławski
Polymers 2021, 13(4), 585; https://doi.org/10.3390/polym13040585 - 15 Feb 2021
Cited by 18 | Viewed by 2922
Abstract
Silicones are often used for various types of coatings, but due to their poor mechanical properties, they often require modification to meet specific requirements. At the same time, various production processes throughout the world generate different types of waste, the disposal of which [...] Read more.
Silicones are often used for various types of coatings, but due to their poor mechanical properties, they often require modification to meet specific requirements. At the same time, various production processes throughout the world generate different types of waste, the disposal of which is harmful to the environment. One possible solution is to use production waste as a filler. In this paper, the authors investigated how the use of metallurgical production waste products as fillers changed the mechanical properties of silicone composites prepared by casting. Composite samples were characterized using tensile tests, resilience, pin-on-disc, Schopper–Schlobach abrasion, hardness, and density measurements. Based on the obtained results, the authors assessed the effect of each of the fillers used in different weight proportions. The results showed that the silicone composite filled with 5 wt% zinc dust showed the lowest decrease in tensile strength and Young’s modulus, with a simultaneous significant reduction in abrasion compared with the reference sample. This research shows that zinc waste can be successfully introduced into a silicone matrix in cases where it is important to reduce abrasive wear. Full article
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12 pages, 3285 KiB  
Article
New Functionalized Ionic Liquids Based on POSS for the Detection of Fe3+ Ion
by Wensi Li and Shengyu Feng
Polymers 2021, 13(2), 196; https://doi.org/10.3390/polym13020196 - 7 Jan 2021
Cited by 8 | Viewed by 2662
Abstract
This study reports a novel series of imidazolium ionic liquids (ILs) based on polyhedral oligomeric silsesquioxanes (POSS) towards effective detection of metal ions, especially Fe3+ ion. 1H, 13C, 29Si NMR, high resolution mass spectra (HRMS) and Fourier transform infrared spectra [...] Read more.
This study reports a novel series of imidazolium ionic liquids (ILs) based on polyhedral oligomeric silsesquioxanes (POSS) towards effective detection of metal ions, especially Fe3+ ion. 1H, 13C, 29Si NMR, high resolution mass spectra (HRMS) and Fourier transform infrared spectra (FTIR) were applied to confirm the structures of the ILs based on POSS (ILs-POSS). The three ILs-POSS were synthesized via a green chemistry approach—a thiol-ene “click” reaction without metal ions as catalysts. Furthermore, the spherical vesicle structures of the ILs-POSS were observed and caused by self-assembly behaviors. Through comprehensive characterizations, these ILs-POSS have performed excellent thermal stabilities and low glass transition temperatures. In addition, we found it very meaningful that the limits of detection (LODs) of the three ILs-POSS for the detection of the Fe3+ ion were 7.91 × 10−8 M, 1.2 × 10−7 M, and 1.2 × 10−7 M, respectively. These data illustrate that these ILs-POSS have great potential for the detection of the Fe3+ ion. In conclusion, this study not only prepared novel ILs-POSS, but also provided new materials as fluorescent sensors in the detection of Fe3+. Full article
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6 pages, 213 KiB  
Editorial
Silicon-Containing Polymeric Materials
by Ignazio Blanco
Polymers 2021, 13(2), 188; https://doi.org/10.3390/polym13020188 - 7 Jan 2021
Cited by 5 | Viewed by 2337
Abstract
When thinking about a chemical element that has contributed to the technological progress over the last two centuries, carbon and all carbon-based materials immediately come to mind [...] Full article

2020

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8 pages, 1937 KiB  
Communication
Dielectric Elastomers UV-Cured from Poly(dimethylsiloxane) Solution in Vinyl Acetate
by Seung Koo Park, Meejeong Choi, Dong Wook Kim, Bong Je Park, Eun Jin Shin, Suntak Park and Sungryul Yun
Polymers 2020, 12(11), 2660; https://doi.org/10.3390/polym12112660 - 11 Nov 2020
Cited by 4 | Viewed by 2796
Abstract
Poly(dimethylsiloxane) (PDMS) has been extensively used as an electroactive polymer material because it exhibits not only excellent moldability but also mechanical properties sufficient enough for electroactive performance despite low dielectric permittivity. Its low dielectric property is due to its molecular non-polarity. Here, we [...] Read more.
Poly(dimethylsiloxane) (PDMS) has been extensively used as an electroactive polymer material because it exhibits not only excellent moldability but also mechanical properties sufficient enough for electroactive performance despite low dielectric permittivity. Its low dielectric property is due to its molecular non-polarity. Here, we introduce a polar group into a PDMS elastomer by using vinyl acetate (VAc) as a crosslinker to improve the dielectric permittivity. We synthesized a high-molecular weight PDMS copolymer containing vinyl groups, namely poly(dimethylsiloxane-co-methylvinylsiloxane) (VPDMS), and prepared several of the VPDMS solutions in VAc. We obtained transparent PDMS films by UV curing of the solution layers. Electromechanical actuation-related physical properties of one of the UV-cured films were almost equivalent to or superior to those of platinum-catalyzed hydrosilylation-cured PDMS films. In addition, saponification of the UV-cured film significantly improved the electrical and mechanical properties (ɛ′ ~ 44.1 pF/m at 10 kHz, E ~ 350 kPa, ɛ ~ 320%). The chemical introduction of VAc into PDMS main chains followed by saponification would offer an efficacious method of enhancing the electroactive properties of PDMS elastomers. Full article
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9 pages, 5661 KiB  
Article
High Refractive-Index Hybrids Consisting of Water-Soluble Matrices with Bipyridine-Modified Polyhedral Oligomeric Silsesquioxane and Lanthanoid Cations
by Kazunari Ueda, Takahiro Kakuta, Kazuo Tanaka and Yoshiki Chujo
Polymers 2020, 12(7), 1560; https://doi.org/10.3390/polym12071560 - 14 Jul 2020
Cited by 4 | Viewed by 2918
Abstract
We report high refractive-index (RI) films composed of polyhedral oligomeric silsesquioxane (SSQ) matrices and various lanthanoid cations. The SSQ matrices were constructed from octaammonium SSQ by connecting with bipyridine dicarboxylic acid, which is expected to capture cations. By modulating the feed ratio between [...] Read more.
We report high refractive-index (RI) films composed of polyhedral oligomeric silsesquioxane (SSQ) matrices and various lanthanoid cations. The SSQ matrices were constructed from octaammonium SSQ by connecting with bipyridine dicarboxylic acid, which is expected to capture cations. By modulating the feed ratio between SSQ and dicarboxylic acid, the series of the SSQ matrices were obtained with variable cross-linking ratios among the SSQ units. Thin transparent films were able to be prepared through the drop-casting method with the aqueous mixtures containing SSQ matrices and various kinds of lanthanoid salts up to 40 wt %. From RI measurements, it was revealed that the increase of the amount of the metal ion can significantly lift up the RI values. In particular, critical losses of Abbe numbers, which theoretically have the trade-off relationship toward increases in RI values, were hardly detected. This effect could be obtained by cation assembly in local spots that are assisted by SSQ. Full article
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15 pages, 3999 KiB  
Article
Preparation of Tri(alkenyl)functional Open-Cage Silsesquioxanes as Specific Polymer Modifiers
by Katarzyna Mituła, Michał Dutkiewicz, Julia Duszczak, Monika Rzonsowska and Beata Dudziec
Polymers 2020, 12(5), 1063; https://doi.org/10.3390/polym12051063 - 6 May 2020
Cited by 7 | Viewed by 3222
Abstract
The scientific reports on polyhedral oligomeric silsesquioxanes are mostly focused on the formation of completely condensed T8 cubic type structures and recently so-called double-decker derivatives. Herein, we report on efficient synthetic routes leading to trifunctionalized, open-cage silsesquioxanes with alkenyl groups of varying [...] Read more.
The scientific reports on polyhedral oligomeric silsesquioxanes are mostly focused on the formation of completely condensed T8 cubic type structures and recently so-called double-decker derivatives. Herein, we report on efficient synthetic routes leading to trifunctionalized, open-cage silsesquioxanes with alkenyl groups of varying chain lengths from -vinyl to -dec-9-enyl and two types of inert groups (iBu, Ph) at the silsesquioxane core. The presented methodology was focused on hydrolytic condensation reaction and it enabled obtaining titled compounds with high yields and purity. A parallel synthetic methodology that was based on the hydrosilylation reaction was also studied. Additionally, a thorough characterization of the obtained compounds was performed, also in terms of their thermal stability, melting and crystallization temperatures (TGA and DSC) in order to show the changes in the abovementioned parameters dependent on the type of reactive as well as inert groups at Si-O-Si core. The presence of unsaturated alkenyl groups has a profound impact on the application potential of these systems, i.e., as modifiers or comonomers for copolymerization reaction. Full article
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13 pages, 6593 KiB  
Article
A Novel Acetylene-Functional/Silicon-Containing Benzoxazine Resin: Preparation, Curing Kinetics and Thermal Properties
by Qilin Mei, Honghua Wang, Danliao Tong, Jiuqiang Song and Zhixiong Huang
Polymers 2020, 12(5), 999; https://doi.org/10.3390/polym12050999 - 26 Apr 2020
Cited by 10 | Viewed by 3363
Abstract
Benzoxazine resin has been paid more attention in the fields of aviation, electronics, automobiles and new energy industries because of its excellent comprehensive performance. Further application is limited, however, by shortcomings such as high brittleness and high curing temperature. Furthermore, higher thermal stability [...] Read more.
Benzoxazine resin has been paid more attention in the fields of aviation, electronics, automobiles and new energy industries because of its excellent comprehensive performance. Further application is limited, however, by shortcomings such as high brittleness and high curing temperature. Furthermore, higher thermal stability is imperiously demanded in special areas. Incorporating both an acetylene group and silicon into the benzoxazine monomer is a promising possible solution to improve the curing processability, thermal properties and toughness of benzoxazine. In this paper, an acetylene-functional/silicon-containing benzoxazine monomer was prepared by two-step synthesis, and acetylene-functional benzoxazine was also prepared as a comparison. FTIR and 1H NMR confirmed the molecular structure of acetylene-functional/silicon-containing benzoxazine. Differential scanning calorimetry (DSC) analysis showed that the initial and peak degradation temperatures of acetylene-functional/silicon-containing benzoxazine were decreased by 21 °C and 18 °C compared with acetylene-functional benzoxazine, respectively. The apparent activation energy of the curing reaction of acetylene-functional/silicon-containing benzoxazine was 83.1 kJ/mol, which was slightly lower than acetylene-functional benzoxazine (84.7 kJ/mol). TGA results showed that the acetylene-functional/silicon-containing benzoxazine had a higher thermal stability than acetylene-functional benzoxazine. The temperatures of 5% weight loss of acetylene-functional/silicon-containing benzoxazine were 380 °C in nitrogen and 485 °C in air, and the char yield at 1000 °C was 80% in nitrogen and 21% in air, respectively. The results of mechanical properties showed that the impact strength of acetylene-functional/silicon-containing benzoxazine was higher than acetylene-functional benzoxazine by 35.4%. The tensile and flexural strengths of acetylene-functional/silicon-containing benzoxazine were slightly higher than that of acetylene-functional benzoxazine. Full article
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19 pages, 2561 KiB  
Article
Hyperbranched Poly(ether-siloxane)s Containing Ammonium Groups: Synthesis, Characterization and Catalytic Activity
by Paweł G. Parzuchowski, Aleksandra Świderska, Marlena Roguszewska, Karolina Rolińska, Dominik Wołosz and Mariusz Mamiński
Polymers 2020, 12(4), 856; https://doi.org/10.3390/polym12040856 - 7 Apr 2020
Cited by 2 | Viewed by 4212
Abstract
In this article we report an easy synthetic route towards hyperbranched polyglycerols (Amm-HBPGs) containing trimethylammonium groups and siloxane or hydroxyl end-groups. Siloxane derivatives of Amm-HBPGs were synthesized in an efficient five-step procedure including an anionic ring opening copolymerization of the phthalimide-epoxy monomer with [...] Read more.
In this article we report an easy synthetic route towards hyperbranched polyglycerols (Amm-HBPGs) containing trimethylammonium groups and siloxane or hydroxyl end-groups. Siloxane derivatives of Amm-HBPGs were synthesized in an efficient five-step procedure including an anionic ring opening copolymerization of the phthalimide-epoxy monomer with glycidol, followed by reactions with allyl bromide, hydrosililation with hydrogenheptamethyltrisiloxane, hydrazinolysis of phthalimide groups and quaternization of resulting amine groups with methyl iodide. Hydroxyl derivatives were obtained by quaternization of previously reported aminated HBPG’s with methyl iodide. Polymeric products were characterized using various NMR techniques, FTIR, and elemental analysis. Both Amm-HBPGs were shown to be effective in catalysis of addition of CO2 to oxirane. The hydrophilic catalysts showed higher efficiency but synthesis of ethylene carbonate was accompanied by formation of small amounts of ethylene glycol. The siloxane-containing catalyst was easily separable from reaction mixture showing high potential in the process of converting carbon dioxide into valuable chemical raw materials. Full article
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10 pages, 2823 KiB  
Article
Study of POSS on the Properties of Novel Inorganic Dental Composite Resin
by Jiahui Wang, Yizhi Liu, Jianxin Yu, Yi Sun and Weili Xie
Polymers 2020, 12(2), 478; https://doi.org/10.3390/polym12020478 - 20 Feb 2020
Cited by 19 | Viewed by 3713
Abstract
Various amounts of methacryl polyhedral oligomeric silsesquioxane (POSS) were explored to be incorporated into novel nano SiO2 dental resin composites using light curing method. The scanning electron microscopy (SEM), optical microscopy, fourier transform infrared spectroscopy (FTIR), nanoindentation, nanoscratch and three-point flexure tests [...] Read more.
Various amounts of methacryl polyhedral oligomeric silsesquioxane (POSS) were explored to be incorporated into novel nano SiO2 dental resin composites using light curing method. The scanning electron microscopy (SEM), optical microscopy, fourier transform infrared spectroscopy (FTIR), nanoindentation, nanoscratch and three-point flexure tests were performed. The volumetric shrinkage and mechanical properties such as hardness, elastic modulus, resistance, flexural strength and fracture energy were analyzed. With the additions of POSS, the volume shrinkage decreased and the mechanical properties initially increased. The effects of POSS on these properties were studied to provide a reference for clinically selecting a composite resin with excellent properties. Full article
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15 pages, 4587 KiB  
Article
Main Chain–Type Block Copolymers through Atom Transfer Radical Polymerization from Double-Decker–Shaped Polyhedral Oligomeric Silsesquioxane Hybrids
by Wei-Cheng Chen, Yu-Hsuan Tsao, Chih-Feng Wang, Chih-Feng Huang, Lizong Dai, Tao Chen and Shiao-Wei Kuo
Polymers 2020, 12(2), 465; https://doi.org/10.3390/polym12020465 - 17 Feb 2020
Cited by 13 | Viewed by 4037
Abstract
In this study, we synthesized two main chain–type block copolymers featuring hydrogen bond donor and acceptor segments through atom transfer radical polymerization (ATRP) using a bifunctionalized polyhedral oligomeric silsesquioxane (POSS) nanoparticle as the initiator. Hydrosilylation of vinylbenzyl chloride at the two corners of [...] Read more.
In this study, we synthesized two main chain–type block copolymers featuring hydrogen bond donor and acceptor segments through atom transfer radical polymerization (ATRP) using a bifunctionalized polyhedral oligomeric silsesquioxane (POSS) nanoparticle as the initiator. Hydrosilylation of vinylbenzyl chloride at the two corners of a double-decker silsesquioxane (DDSQ) provided the bifunctionalized benzyl chloride initiator VBC-DDSQ-VBC, which we applied as a platform to prepare a main chain–type polystyrene homopolymer (PS-DDSQ-PS), the diblock copolymer poly(styrene–b–4-vinylpyridine) (P4VP-b-PS-DDSQ-PS-b-P4VP), and the diblock copolymer poly(styrene–b–tert-butoxystyrene) (PtBuOS-b-PS-DDSQ-PS-b-PtBuOS) through sequential ATRP. Selective hydrolysis of the tert-butoxyl units of PtBuOS-b-PS-DDSQ-PS-b-PtBuOS yielded the strongly hydrogen bonding diblock copolymer poly (styrene-b-vinylphenol) (PVPh-b-PS-DDSQ-PS-b-PVPh). We used Fourier transfer infrared spectroscopy, nuclear magnetic resonance spectroscopy, size exclusion chromatography, differential scanning calorimetry, mass-analyzed laser desorption ionization mass spectrometry, and transmission electron microscopy to investigate the chemical structures, thermal behavior, and self-assembled nanostructures formed by these main chain–type block copolymers based on DDSQ. Full article
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2019

Jump to: 2023, 2022, 2021, 2020, 2018, 2017, 2016, 2015

11 pages, 2415 KiB  
Article
Novel Siloxane-Modified Epoxy Resins as Promising Encapsulant for LEDs
by Chih-Hao Lin, Wha-Tzong Whang, Chun-Hua Chen, Shu-Chen Huang and Kai-Chi Chen
Polymers 2020, 12(1), 21; https://doi.org/10.3390/polym12010021 - 20 Dec 2019
Cited by 14 | Viewed by 5275
Abstract
This study investigated a new category of transparent encapsulant materials for light-emitting diodes (LEDs). It comprised a phenyl group that contained siloxane-modified epoxy (SEP-Ph) hybridized with a cyclic tetrafunctional siloxane-modified epoxy (SEP-D4) with methylhexahydrophthalic anhydride (MHHPA) as a curing agent. The SEP-Ph/SEP-D4 = [...] Read more.
This study investigated a new category of transparent encapsulant materials for light-emitting diodes (LEDs). It comprised a phenyl group that contained siloxane-modified epoxy (SEP-Ph) hybridized with a cyclic tetrafunctional siloxane-modified epoxy (SEP-D4) with methylhexahydrophthalic anhydride (MHHPA) as a curing agent. The SEP-Ph/SEP-D4 = 0.5/0.5 (sample 3) and SEP-D4 (sample 4) could provide notably high optical transmittance (over 90% in the visible region), high-temperature discoloration resistance, low stress, and more crucially, noteworthy sulfurization resistance. The lumen flux retention of the SEP encapsulated surface mounted device LEDs remained between approximately 97% and 99% after a sulfurization test for 240 h. The obtained comprehensive optical, mechanical, and sulfurization resistance proved the validity and uniqueness of the present design concept with complementary physical and chemical characteristics. Full article
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20 pages, 4262 KiB  
Review
Progress in the Synthesis of Bifunctionalized Polyhedral Oligomeric Silsesquioxane
by Mingyue Wang, Hong Chi, Joshy K.S. and Fuke Wang
Polymers 2019, 11(12), 2098; https://doi.org/10.3390/polym11122098 - 14 Dec 2019
Cited by 51 | Viewed by 6997
Abstract
Polyhedral oligomeric silsesquioxane (POSS) has been considered as one of the most promising nanofillers in academic and industrial research due to its unique multifunctional nanostructure, easy functionalization, hybrid nature, and high processability. The progress of POSS has been extensive, particularly applications based on [...] Read more.
Polyhedral oligomeric silsesquioxane (POSS) has been considered as one of the most promising nanofillers in academic and industrial research due to its unique multifunctional nanostructure, easy functionalization, hybrid nature, and high processability. The progress of POSS has been extensive, particularly applications based on single- or multiple-armed POSS. In polymer hybrids, in order to enhance the properties, bifunctional POSS has been incorporated into the backbone chain of the polymer. This review summarizes recent developments in the synthesis, modification, and application of bifunctional POSS-containing composite materials. This includes amino-POSS, hydroxyl-POSS, aromatic ring-POSS, ether-POSS, and vinyl groups-POSS and their applications, exemplified by polyurethanes (PUs) and polyimides (PIs). In addition, the review highlights the enhancement of thermal, mechanical, and optical properties of the composites. Full article
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14 pages, 1963 KiB  
Article
Synthesis of Monoacryloxypropyl-POSS-based Hybrid Epoxyacrylate Copolymers and Their Application in Thermally Curable Structural Self-Adhesive Tapes
by Agnieszka Kowalczyk, Krzysztof Kowalczyk and Konrad Gziut
Polymers 2019, 11(12), 2058; https://doi.org/10.3390/polym11122058 - 11 Dec 2019
Cited by 12 | Viewed by 3843
Abstract
New organic-inorganic hybrid copolymers (EA-POSSs) based on butyl acrylate, glycidyl methacylate, hydroxybutyl acrylate, acryloiloxybenzophenone and acryloxypropyl-heptaisobutyl-POSS (A-POSS) were prepared via free-radical solution polymerization (FRP) and applied as a component of thermally curable structural self-adhesive tapes (SATs). The EA-POSS with 0.25, 0.5 or 1 [...] Read more.
New organic-inorganic hybrid copolymers (EA-POSSs) based on butyl acrylate, glycidyl methacylate, hydroxybutyl acrylate, acryloiloxybenzophenone and acryloxypropyl-heptaisobutyl-POSS (A-POSS) were prepared via free-radical solution polymerization (FRP) and applied as a component of thermally curable structural self-adhesive tapes (SATs). The EA-POSS with 0.25, 0.5 or 1 mol % of A-POSS exhibited significantly higher dynamic viscosity (ca. +104%), Mw (+61%) and polydispersity (+109%; measured using gel permeation chromatography) as well as lower Tg value (−16 °C) in relation to the A-POSS-free copolymer (EA-0). Differential scanning calorimetry (DSC) measurements (one glass transition process) confirmed statistic chain structure of the EA-POSS materials. Replacement of EA-0 by the EA-POSS copolymers in a SATs recipe caused simultaneous improvement of their self-adhesive features, i.e., adhesion (+70%), tack (+21%) and cohesion (+1590%). Moreover, the POSS-based copolymers improved the shear strength of thermally cured Al/SAT/Al overlap joints; the best mechanical resistance (before and after accelerated ageing tests) was observed for the sample containing 0.5 mol % of A-POSS (an increment range of 50–294% in relation to the A-POSS-free joints). Thermogravimetric analysis (TGA) revealed markedly improved thermal stability of the A-POSS-based SATs as well. Full article
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14 pages, 3023 KiB  
Article
Synthesis and Characterization of Aminosilane Grafted Cellulose Nanocrystal Modified Formaldehyde-Free Decorative Paper and its CO2 Adsorption Capacity
by Wenkai Zhu, Meixiu Ji, Yang Zhang, Zhe Wang, Wei Chen and Yuanyuan Xue
Polymers 2019, 11(12), 2021; https://doi.org/10.3390/polym11122021 - 6 Dec 2019
Cited by 18 | Viewed by 3649
Abstract
As one of the main consumables of interior decoration and furniture, decorative paper can be seen everywhere in the indoor space. However, because of its high content of formaldehyde, it has a certain threat to people’s health. Therefore, it is necessary to develop [...] Read more.
As one of the main consumables of interior decoration and furniture, decorative paper can be seen everywhere in the indoor space. However, because of its high content of formaldehyde, it has a certain threat to people’s health. Therefore, it is necessary to develop and study new formaldehyde-free decorative paper to meet the market demand. In this work, we have obtained formaldehyde-free decorative paper with high CO2 adsorption capacity. Here, cellulose nanocrystals (CNC) were prepared by hydrolyzing microcrystalline cellulose with sulfuric acid. The N-(2-aminoethyl) (3-amino-propyl) methyldimethoxysilane (AEAPMDS) was grafted onto the CNCs by liquid phase hydrothermal treatment, and the aqueous solution was substituted by tert-butanol to obtain aminated CNCs (AEAPMDS-CNCs). The as-prepared AEAPMDS-CNCs were applied to formaldehyde-free decorative paper by the spin-coating method. The effects of various parameters on the properties of synthetic materials were systematically studied, and the optimum reaction conditions were revealed. Moreover, the surface bond strength and abrasion resistance of modified formaldehyde-free decorative paper were investigated. The experimental results showed that AEAPMDS grafted successfully without destroying the basic morphology of the CNCs. The formaldehyde-free decorative paper coated with AEAPMDS-CNCs had high CO2 adsorption capacity and exhibited excellent performance of veneer to plywood. Therefore, laminating the prepared formaldehyde-free decorative paper onto indoor furniture can achieve the purpose of capturing indoor CO2 and have a highly potential use for the indoor decoration. Full article
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16 pages, 7217 KiB  
Article
Molecular Insights into Sequence Distributions and Conformation-Dependent Properties of High-Phenyl Polysiloxanes
by Lin Zhu, Xiao Cheng, Wenlu Su, Jiaxin Zhao and Chuanjian Zhou
Polymers 2019, 11(12), 1989; https://doi.org/10.3390/polym11121989 - 2 Dec 2019
Cited by 17 | Viewed by 4163
Abstract
The excellent performance and wide applications of phenyl polysiloxanes are largely due to their phenyl units and monomer sequences. However, the relationship between molecular structure and material properties has not been explicitly elucidated. In this work, the sequence distribution and microstructure of random [...] Read more.
The excellent performance and wide applications of phenyl polysiloxanes are largely due to their phenyl units and monomer sequences. However, the relationship between molecular structure and material properties has not been explicitly elucidated. In this work, the sequence distribution and microstructure of random copolymers were quantitatively investigated by means of a molecular dynamics (MD) simulation combined with experimental verification. The results of 29Si NMR showed that the large number of phenyl units not only shortened the length of the dimethyl units, but also significantly increased the proportion of consecutive phenyl units. The simulation results indicated the attraction between adjacent phenyl groups that were effectively strengthened intra- and inter- molecular interactions, which determined the equilibrium population of conformations and the dynamics of conformational transitions. Furthermore, the evolution of bond angle distribution, torsion distribution, and mean-squared displacements (MSD) shed light on the conformational characteristics that induce the unique thermodynamics properties and photophysical behavior of high-phenyl polysiloxanes. Differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA), spectrofluorimetry, and laser scanning confocal microscopy (LSCM) were performed to verify the conclusions drawn from the simulation. Overall, the complementary use of MD simulations and experiments provided a deep molecular insight into structure–property relationships, which will provide theoretical guidance for the rational design and preparation of high-performance siloxanes. Full article
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21 pages, 9576 KiB  
Article
Surface Modification of Fumed Silica by Plasma Polymerization of Acetylene for PP/POE Blends Dielectric Nanocomposites
by Xiaozhen He, Ilkka Rytöluoto, Rafal Anyszka, Amirhossein Mahtabani, Eetta Saarimäki, Kari Lahti, Mika Paajanen, Wilma Dierkes and Anke Blume
Polymers 2019, 11(12), 1957; https://doi.org/10.3390/polym11121957 - 28 Nov 2019
Cited by 26 | Viewed by 5861
Abstract
Novel nanocomposites for dielectric applications-based polypropylene/poly(ethylene-co-octene) (PP/POE) blends filled with nano silica are developed in the framework of the European ‘GRIDABLE’ project. A tailor-made low-pressure-plasma reactor was applied in this study for an organic surface modification of silica. Acetylene gas was used as [...] Read more.
Novel nanocomposites for dielectric applications-based polypropylene/poly(ethylene-co-octene) (PP/POE) blends filled with nano silica are developed in the framework of the European ‘GRIDABLE’ project. A tailor-made low-pressure-plasma reactor was applied in this study for an organic surface modification of silica. Acetylene gas was used as the monomer for plasma polymerization in order to deposit a hydrocarbon layer onto the silica surface. The aim of this modification is to increase the compatibility between silica and the PP/POE blends matrix in order to improve the dispersion of the filler in the polymer matrix and to suppress the space charge accumulation by altering the charge trapping properties of these silica/PP/POE blends composites. The conditions for the deposition of the acetylene plasma-polymer onto the silica surface were optimized by analyzing the modification in terms of weight loss by thermogravimetry (TGA). X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray fluorescence spectroscopy (EDX) measurements confirmed the presence of hydrocarbon compounds on the silica surface after plasma modification. The acetylene plasma modified silica with the highest deposition level was selected to be incorporated into the PP/POE blends matrix. X-ray diffraction (XRD) showed that there is no new crystal phase formation in the PP/POE blends nanocomposites after addition of the acetylene plasma modified silica. Differential scanning calorimetry results (DSC) show two melting peaks and two crystallization peaks of the PP/POE blends nanocomposites corresponding to the PP and POE domains. The improved dispersion of the silica after acetylene plasma modification in the PP/POE blends matrix was shown by means of SEM–EDX mapping. Thermally stimulated depolarization current (TSDC) measurements confirm that addition of the acetylene plasma modified silica affects the charge trapping density and decreases the amount of injected charges into PP/POE blends nanocomposites. This work shows that acetylene plasma modification of the silica surface is a promising route to tune charge trapping properties of PP/POE blend-based nanocomposites. Full article
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19 pages, 8301 KiB  
Article
Facile Fabrication of Superhydrophobic Surface from Fluorinated POSS Acrylate Copolymer via One-Step Breath Figure Method and Its Anti-Corrosion Property
by Meng Liu, Xiaochen Zhang, Dong Wang, Jiaji Cheng, Xiujiang Pang, Wenjuan Qu, Chunxu Li and Shaoxiang Li
Polymers 2019, 11(12), 1953; https://doi.org/10.3390/polym11121953 - 28 Nov 2019
Cited by 16 | Viewed by 4473
Abstract
Novel fluorinated polyhedral oligomeric silsesquioxane (POSS) acrylic copolymers were synthesized by the radical solution polymerization. The superhydrophobic coating was prepared using a one-step breath figure method. Chemical constitution, morphology, hydrophobicity, and anticorrosion ability of as-prepared coatings were investigated by the corresponding equipment. The [...] Read more.
Novel fluorinated polyhedral oligomeric silsesquioxane (POSS) acrylic copolymers were synthesized by the radical solution polymerization. The superhydrophobic coating was prepared using a one-step breath figure method. Chemical constitution, morphology, hydrophobicity, and anticorrosion ability of as-prepared coatings were investigated by the corresponding equipment. The addition of proper fluorinated POSS can synchronously promote the formation of the micro-nano convex structure and the enrichment of fluorinated groups on the surface. Compared to commercial acrylic coating, the fluorinated POSS coating presented enhanced anticorrosion performance. The impedance was the highest and the corrosion current density was the lowest for superhydrophobic coating with 25 wt % fluorinated POSS. Full article
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13 pages, 8679 KiB  
Article
Improvement of Rice Husk/HDPE Bio-Composites Interfacial Properties by Silane Coupling Agent and Compatibilizer Complementary Modification
by Jingmeng Sun, Yao Pang, Yingni Yang, Junqi Zhao, Rongqi Xia, Yanchen Li, Yi Liu and Hongwu Guo
Polymers 2019, 11(12), 1928; https://doi.org/10.3390/polym11121928 - 22 Nov 2019
Cited by 30 | Viewed by 5356
Abstract
Composites using agricultural and forestry residues as raw materials with potentially high-performance, multifunctional and biodegradable ecological advantages, are viewed as very promising for new-generation lightweight and low-cost bio-based sustainable building materials. At present, the research on wood-plastic composite materials is relatively mature. However, [...] Read more.
Composites using agricultural and forestry residues as raw materials with potentially high-performance, multifunctional and biodegradable ecological advantages, are viewed as very promising for new-generation lightweight and low-cost bio-based sustainable building materials. At present, the research on wood-plastic composite materials is relatively mature. However, it is still a challenge to effectively use other biomass and improve the interface of the high-polymer compound system. Herein, we proposed a simple and effective method to enhance the interfacial adhesion properties of rice husk fibre and High Density Polyethylene (HDPE) composites by the silane coupling agent KH-550 and compatibilizer Maleic anhydride grafted polyethylene (MAPE) with complementary modification. It was found that the coupling agent KH-550 cross-linked with the hydroxyl group on the husk fibre surface and solidified with the high polymer by –NH–, –C=O– functional group generation. Compatibilizer MAPE strengthened the two phases by covalently bonding with an ester linkage and lowered the roughness of the cross-section of the composites. Meanwhile the modification enhanced the dispersibility, and mechanical properties of the husk-high polymer compound system, the bending and flexural strength were improved by 11.5% and 28.9% with KH-550, and MAPE added, respectively. The flexural strength of the composites increased by 40.7% after complementary modification. Furthermore, the complementary modification treatment reduced the hydrophilic hydroxyl groups and increased the molecular chain to improve the water-resistance, elastic modulus and toughness of the composite. This study prepared a bio-composite, which is expected to expand the use of agricultural and forestry residues as an extension of wood-plastic composites. Full article
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7 pages, 3059 KiB  
Article
Dispersed-Monolayer Graphene-Doped Polymer/Silica Hybrid Mach-Zehnder interferometer (MZI) Thermal Optical Switch with Low-Power Consumption and Fast Response
by Yue Cao, Daming Zhang, Yue Yang, Baizhu Lin, Jiawen Lv, Xianwang Yang, Haowen Zhao, Fei Wang, Baohua Li and Yunji Yi
Polymers 2019, 11(11), 1898; https://doi.org/10.3390/polym11111898 - 18 Nov 2019
Cited by 7 | Viewed by 2981
Abstract
This article demonstrates a dispersed-monolayer graphene-doped polymer/silica hybrid Mach–Zehnder interferometer (MZI) thermal optical switch with low-power consumption and fast response. The polymer/silica hybrid MZI structure reduces the power consumption of the device as a result of the large thermal optical coefficient of the [...] Read more.
This article demonstrates a dispersed-monolayer graphene-doped polymer/silica hybrid Mach–Zehnder interferometer (MZI) thermal optical switch with low-power consumption and fast response. The polymer/silica hybrid MZI structure reduces the power consumption of the device as a result of the large thermal optical coefficient of the polymer material. To further decrease the response time of the thermal optical switch device, a polymethyl methacrylate, doped with monolayer graphene as a cladding material, has been synthesized. Our study theoretically analyzed the thermal conductivity of composites using the Lewis–Nielsen model. The predicted thermal conductivity of the composites increased by 133.16% at a graphene volume fraction of 0.263 vol %, due to the large thermal conductivity of graphene. Measurements taken of the fabricated thermal optical switch exhibited a power consumption of 7.68 mW, a rise time of 40 μs, and a fall time of 80 μs at a wavelength of 1550 nm. Full article
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11 pages, 1142 KiB  
Communication
Facile Functionalization of Poly(Dimethylsiloxane) Elastomer by Varying Content of Hydridosilyl Groups in a Crosslinker
by Seung Koo Park, Bong Je Park, Mee Jeong Choi, Dong Wook Kim, Jae Woong Yoon, Eun Jin Shin, Sungryul Yun and Suntak Park
Polymers 2019, 11(11), 1842; https://doi.org/10.3390/polym11111842 - 8 Nov 2019
Cited by 6 | Viewed by 3664
Abstract
Crosslinked poly(dimethylsiloxane) (PDMS) has been widely used as a dielectric elastomer for electrically driven actuators because it exhibits high elasticity, low initial modulus, and excellent moldability in spite of low dielectric constant. However, further improvement in the characteristics of the PDMS elastomer is [...] Read more.
Crosslinked poly(dimethylsiloxane) (PDMS) has been widely used as a dielectric elastomer for electrically driven actuators because it exhibits high elasticity, low initial modulus, and excellent moldability in spite of low dielectric constant. However, further improvement in the characteristics of the PDMS elastomer is not easy due to its chemical non-reactivity. Here, we report a simple method for functionalizing the elastomer by varying content of hydridosilyl groups in PDMS acted as a crosslinker. We synthesized poly(dimethylsiloxane-co-methylvinylsiloxane) (VPDMS) and poly(dimethylsiloxane-co-methylsiloxane) (HPDMS). Tri(ethylene glycol) divinyl ether (TEGDE) as a polar molecule was added to the mixture of VPDMS and HPDMS. TEGDE was reacted to the hydridosilyl group in HPDMS during crosslinking between VPDMS and HPDMS in the presence of platinum as a catalyst. Permittivity of the crosslinked film increased from ca. 25 to 36 pF/m at 10 kHz without a decline in other physical properties such as transparency and elasticity (T > 85%, E ~150 kPa, ɛ ~270%). It depends on the hydridosilyl group content of HPDMS. The chemical introduction of a new molecule into the hydridosilyl group in HPDMS during crosslinking would provide a facile, effective method of modifying the PDMS elastomers. Full article
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15 pages, 3488 KiB  
Article
Preparation and Characterization of Soy Protein Isolate-Based Nanocomposite Films with Cellulose Nanofibers and Nano-Silica via Silane Grafting
by Zhiyong Qin, Liuting Mo, Murong Liao, Hua He and Jianping Sun
Polymers 2019, 11(11), 1835; https://doi.org/10.3390/polym11111835 - 7 Nov 2019
Cited by 38 | Viewed by 5263
Abstract
Soy protein isolate (SPI) has attracted considerable attention in the field of packaging technology due to its easy processability, biodegradability, and good film-forming characteristics. However, SPI-based films often suffer from inferior mechanical properties and high moisture sensitivity, thus restricting their practical application. In [...] Read more.
Soy protein isolate (SPI) has attracted considerable attention in the field of packaging technology due to its easy processability, biodegradability, and good film-forming characteristics. However, SPI-based films often suffer from inferior mechanical properties and high moisture sensitivity, thus restricting their practical application. In the present study, herein, a biobased nanocomposite film was developed by cross-linking SPI matrix from the synergistic reinforcement of cellulose nanofibers (CNF) and nano-silica (NS) particles. First, we functionalized the CNF with NS using a silane agent (KH560) as an efficient platform to enhance the interfacial interaction between SPI and CNF/NS, resulting from the epoxy-dominated cross-linking reaction. The chemical structure, thermal stability, and morphology of the resultant nanocomposite films were comprehensively investigated via Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). These results supported successful surface modification and indicated that the surface-tailored CNF/NS nanohybrid possesses excellent adhesion with SPI matrix through covalent and hydrogen-bonding interactions. The integration of CNF/NS into SPI resulted in nanocomposite films with an improved tensile strength (6.65 MPa), representing a 90.54% increase compared with the pristine SPI film. Moreover, the resulting composites had a significantly decreased water vapor permeation and a higher water contact angle (91.75°) than that of the unmodified film. The proposed strategy of synergistic reinforcements in the biobased composites may be a promising and green approach to address the critical limitations of plant protein-based materials in practical applications. Full article
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15 pages, 3202 KiB  
Article
Core-Shell Structure Design of Hollow Mesoporous Silica Nanospheres Based on Thermo-Sensitive PNIPAM and pH-Responsive Catechol-Fe3+ Complex
by Weili Peng, Zeping Zhang, Minzhi Rong and Mingqiu Zhang
Polymers 2019, 11(11), 1832; https://doi.org/10.3390/polym11111832 - 7 Nov 2019
Cited by 20 | Viewed by 5928
Abstract
A kind of core-shell hybrid nanoparticle comprised of a hollow mesoporous silica nanoparticles (HMS) core and a copolymer shell bearing N-(3,4-dihydroxyphenethyl) methacrylamide (DMA) and N-isopropylacrylamide (NIPAM) as responsive moieties was prepared. Moreover, the factors that could impact the surface morphology and hierarchical porous [...] Read more.
A kind of core-shell hybrid nanoparticle comprised of a hollow mesoporous silica nanoparticles (HMS) core and a copolymer shell bearing N-(3,4-dihydroxyphenethyl) methacrylamide (DMA) and N-isopropylacrylamide (NIPAM) as responsive moieties was prepared. Moreover, the factors that could impact the surface morphology and hierarchical porous structure were discussed. In the presence of Fe3+, catechol-Fe3+ complexes were formed to achieve pH-responsive polymer shell, combining with thermal-sensitiveness of poly(N-isopropylacrylamide). Doxorubicin (DOX) was applied as a model drug and the behaviors of its loading/release behaviors were investigated to prove the idea. The results exhibited a significant drug loading capacity of 8.6% and embed efficiency of 94.6% under 1 mg ml–1 DOX/PBS solution. In fact, the loading capacity of drug can be easily improved to as high as 28.0% by increasing the DOX concentration. The vitro cytotoxicity assay also indicated that the as-prepared nanoparticles have no significant cytotoxicity on RAW 264.7 cells. The in vitro experiment showed that the cumulative release of DOX was obviously dependent on the temperature and pH values. This pH/temperature-sensitive hollow mesoporous silica nanosphere is expected to have potential applications in controlled drug release. Full article
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19 pages, 5479 KiB  
Article
Preparation and Performance of Silica/ESBR Nanocomposites Modified by Bio-Based Dibutyl Itaconate
by Haijun Ji, Hui Yang, Liwei Li, Xinxin Zhou, Lan Yin, Liqun Zhang and Runguo Wang
Polymers 2019, 11(11), 1820; https://doi.org/10.3390/polym11111820 - 6 Nov 2019
Cited by 10 | Viewed by 3531
Abstract
Ester-functionalized styrene-butadiene rubber (dibutyl itaconate-styrene-butadiene rubber) (D-ESBR) was synthesized by low-temperature emulsion polymerization using dibutyl itaconate (DBI) as a modified monomer containing ester groups. Nonpetroleum-based silica with hydroxy groups was used as a filler to enhance the D-ESBR, which can provide excellent mechanical [...] Read more.
Ester-functionalized styrene-butadiene rubber (dibutyl itaconate-styrene-butadiene rubber) (D-ESBR) was synthesized by low-temperature emulsion polymerization using dibutyl itaconate (DBI) as a modified monomer containing ester groups. Nonpetroleum-based silica with hydroxy groups was used as a filler to enhance the D-ESBR, which can provide excellent mechanical properties, low rolling resistance, and high wet skid resistance. During the preparation of the silica/D-ESBR nanocomposites, a hydrogen-bonding interface was formed between the hydroxy groups on the surface of silica and the ester groups in the D-ESBR macromolecules. As the content of ester groups in the D-ESBR increases, the dispersion of silica in the nanocomposites is gradually improved, which was verified by rubber process analyzer (RPA) and scanning electron microscopy (SEM). Overall mechanical properties of the silica/D-ESBR modified with 5 wt % DBI were improved and became superior to that of the non-modified nanocomposite. Compared with the non-modified silica/D-ESBR, the DBI modified silica/D-ESBR exhibited a lower tan δ value at 60 °C and comparable tan δ value at 0 °C, indicating that the DBI modified silica/D-ESBR had lower rolling resistance without sacrificing wet skid resistance. Full article
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13 pages, 5660 KiB  
Article
Silicone Resin Polymer Used in Preventive Maintenance of Asphalt Mixture Based on Fog Seal
by Peide Cui, Shaopeng Wu, Haiqin Xu and Yang Lv
Polymers 2019, 11(11), 1814; https://doi.org/10.3390/polym11111814 - 5 Nov 2019
Cited by 27 | Viewed by 3159
Abstract
The commonly used materials in fog seal are emulsified asphalt and modified emulsified asphalt. Nevertheless, there are some intractable problems including aging under ultraviolet, poor permeability, and moisture susceptibility. Therefore, silicone resin polymer was used as a kind of innovative fog seal material [...] Read more.
The commonly used materials in fog seal are emulsified asphalt and modified emulsified asphalt. Nevertheless, there are some intractable problems including aging under ultraviolet, poor permeability, and moisture susceptibility. Therefore, silicone resin polymer was used as a kind of innovative fog seal material in this study. Physicochemical properties of solidified silicone resin were characterized. X-ray computed tomography and 3D reconstruction technology were used to evaluate permeability and distribution of silicone resin polymer in an asphalt mixture. Moisture sensitivity and high-temperature performance of the asphalt mixture maintained by silicone resin polymer were also detected. The results show that surface characteristic of silicone resin can effectively isolate moisture, thereby improving moisture resistance of the asphalt mixture. Silicone resin was found to be evenly distributed throughout the pores of a sample when the dosage was 400 or 600 mL/m2. The pore filling rate increased by 16.3% when the dosage was changed from 200 to 400 mL/m2, whereas it only increased by 3.7% when dosage increased from 400 to 600 mL/m2. Moisture damage resistance of asphalt mixtures generally increased as the dosage of silicone was increased. However, as the dosage increased from 400 to 600 mL/m2, the growth rate in residual Marshall stability (RMS) and tensile strength ratio (TSR) slowed significantly since the pore filling effect of silicone has reached the upper limit. Dosage of silicone resin has little effect on the results of the rutting test while it has significant influence on Hamburg wheel tracking test (HWT). Furthermore, it was found that 400 mL/m2 is the optimum silicone dosage for open-graded friction course (OGFC)-13 mixture in consideration of permeability, distribution, performance of mixture, and economic cost. Full article
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5 pages, 198 KiB  
Editorial
POSS-Based Polymers
by Joseph D. Lichtenhan, Krzysztof Pielichowski and Ignazio Blanco
Polymers 2019, 11(10), 1727; https://doi.org/10.3390/polym11101727 - 22 Oct 2019
Cited by 43 | Viewed by 3853
Abstract
The combination of functional polymers with inorganic nanostructured compounds has become a major area of research and technological development owing to the remarkable properties and multifunctionalities deriving from their nano and hybrid structures [...] Full article
22 pages, 13356 KiB  
Article
Hybrid Silica-Phytic Acid Coatings: Effect on the Thermal Stability and Flame Retardancy of Cotton
by Marco Barbalini, Luca Bertolla, Jaromír Toušek and Giulio Malucelli
Polymers 2019, 11(10), 1664; https://doi.org/10.3390/polym11101664 - 12 Oct 2019
Cited by 32 | Viewed by 3820
Abstract
New hybrid sol–gel coatings based on tetraethoxysilane (TEOS) and phytic acid (PA) were designed and applied to cotton; the flame-retardant properties of the treated fabrics were thoroughly investigated by means of flame-spread and forced-combustion tests. The first goal was to identify the TEOS:PA [...] Read more.
New hybrid sol–gel coatings based on tetraethoxysilane (TEOS) and phytic acid (PA) were designed and applied to cotton; the flame-retardant properties of the treated fabrics were thoroughly investigated by means of flame-spread and forced-combustion tests. The first goal was to identify the TEOS:PA weight ratio that allowed the achievement of the best flame-retardant properties, with the lowest final dry add-on on the fabrics. Therefore, different TEOS:PA sols were prepared and applied to cotton, and the resulting coated fabrics were thoroughly investigated. In particular, solid-state NMR spectroscopy was exploited for assessing the condensation degree during the sol–gel process, even for evaluating the occurrence of possible reactions between phytic acid and the cellulosic substrate or the alkoxy precursor. It was found that a total dry add-on of 16 wt % together with 70:30 TEOS:PA weight ratio provided cotton with self-extinction, as clearly indicated by flame-spread tests. This formulation was further investigated in forced-combustion tests: a significant reduction of heat release rate (HRR), of the peak of HRR, and of total heat release (THR) was found, together with a remarkable increase of the residues after the test. Unfortunately, the treated fabrics were not resistant to washing cycles, as they significantly lost their flame-retardant properties, consequently to the partial removal of the deposited hybrid coatings. Full article
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11 pages, 2508 KiB  
Article
Facile Strategy of Improving Interfacial Strength of Silicone Resin Composites Through Self-Polymerized Polydopamine Followed via the Sol-Gel Growing of Silica Nanoparticles onto Carbon Fiber
by Yawen Zheng, Xiaoyun Wang and Guangshun Wu
Polymers 2019, 11(10), 1639; https://doi.org/10.3390/polym11101639 - 10 Oct 2019
Cited by 25 | Viewed by 3813
Abstract
In the present research, to enhance interfacial wettability and adhesion between carbon fibers (CFs) and matrix resin, hydrophilic silica nanoparticles (SiO2) were utilized to graft the surface of CFs. Polydopamine (PDA) as a “bio-glue” was architecturally built between SiO2 and [...] Read more.
In the present research, to enhance interfacial wettability and adhesion between carbon fibers (CFs) and matrix resin, hydrophilic silica nanoparticles (SiO2) were utilized to graft the surface of CFs. Polydopamine (PDA) as a “bio-glue” was architecturally built between SiO2 and CFs to obtain a strong adhesion strength and homogenous SiO2 distribution onto the surface of CFs. The facile modification strategy was designed by self-polymerization of dopamine followed by the hydrolysis of tetraethoxysilane (TEOS) onto carbon fibers. Surface microstructures and interfacial properties of CFs, before and after modification, were systematically investigated. The tight and homogeneous coverage of SiO2 layers onto the CF surface, with the assistance of a PDA layer by self-polymerization of dopamine, significantly enhanced fiber surface roughness and wettability, resulting in an obvious improvement of mechanical interlocking and interfacial interactions between CFs and matrix resin. The interlaminar shear strength (ILSS) and the interfacial shear strength (IFSS) of CF/PDA/SiO2 reinforced composites exhibited 57.28% and 41.84% enhancements compared with those of untreated composites. In addition, impact strength and the hydrothermal aging resistance of the resulting composites showed great improvements after modification. The possible reinforcing mechanisms during the modification process have been discussed. This novel strategy of developed SiO2-modified CFs has interesting potential for interfacial improvements for advanced polymer composites. Full article
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22 pages, 16339 KiB  
Article
In situ Fabrication of Multi-Walled Carbon Nanotubes/Silica Hybrid Colloidosomes by Pickering Emulsion Templating Using Trialkoxysilanes of Opposite Polarity
by Franziska Grzegorzewski, Avital Benhaim, Yafit Itzhaik Alkotzer, Einat Zelinger, Noga Yaakov and Guy Mechrez
Polymers 2019, 11(9), 1480; https://doi.org/10.3390/polym11091480 - 10 Sep 2019
Cited by 12 | Viewed by 4635
Abstract
A simple and effective way to prepare multi-walled carbon nanotubes (MWNT)//silica hybrid microcapsules (colloidosomes) is presented. These microcapsules have been generated by emulsion templating in a biphasic oil-in-water (o/w) system. Two trialkoxysilanes of complementary polarity, (3-aminopropyl)triethoxysilane (APTES) and dodecyltriethoxysilane (DTES), were used to [...] Read more.
A simple and effective way to prepare multi-walled carbon nanotubes (MWNT)//silica hybrid microcapsules (colloidosomes) is presented. These microcapsules have been generated by emulsion templating in a biphasic oil-in-water (o/w) system. Two trialkoxysilanes of complementary polarity, (3-aminopropyl)triethoxysilane (APTES) and dodecyltriethoxysilane (DTES), were used to chemically immobilize the silica nanoparticles at the o/w interface and stabilize the as-generated Pickering emulsions. The effects of varying the o/w ratio and the concentration of the added solids on the type of emulsion formed, the oil droplet size, as well as the emulsion stability have been investigated. The emulsion phase fraction was dependent on the silica content while the droplet size increased with increasing oil volume percentage. A solid shell emerged around the oil droplets from copolymerization between silane monomers. The thickness of the resulting shells was several hundreds of nm. Although MWNTs and silica nanoparticles both were co-assembled at the o/w interface, silica has shown to be the sole stabilizer, with APTES being crucial for the formation of the shell structure. Drop-casting of the emulsion and air-drying led to hierarchical open porous MWNT-silica nanocomposites. These new structures are promising as electrically conductive thin films for variety of applications, such as electro-optics, encapsulation, or chemical sensing. Full article
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11 pages, 3247 KiB  
Article
A Simple Preparation Route for Bio-Phenol MQ Silicone Resin via the Hydrosilylation Method and its Autonomic Antibacterial Property
by Jianye Ji, Xin Ge, Weijie Liang, Ruiyuan Liang, Xiaoyan Pang, Ruoling Liu, Shuyi Wen, Jiaqi Sun, Xunjun Chen and Jianfang Ge
Polymers 2019, 11(9), 1389; https://doi.org/10.3390/polym11091389 - 23 Aug 2019
Cited by 21 | Viewed by 4509
Abstract
MQ silicone resins represent a broad range of hydrolytic condensation products of monofunctional silane (M units) and tetrafunctional silane (Q units). In this work, a Bio-Phenol MQ silicone resin (BPMQ) was designed and synthesized by the hydrosilylation of hydrogen containing MQ silicone resin [...] Read more.
MQ silicone resins represent a broad range of hydrolytic condensation products of monofunctional silane (M units) and tetrafunctional silane (Q units). In this work, a Bio-Phenol MQ silicone resin (BPMQ) was designed and synthesized by the hydrosilylation of hydrogen containing MQ silicone resin and eugenol in the presence of chloroplatinic acid. The structure, thermal property, and antibacterial property against Escherichia coli of the modified MQ silicone resin were investigated. The results showed that BPMQ has been prepared successfully, and the thermal stability of this modified polymer improved significantly because of the introduction of phenyl in eugenol. The temperature at the maximum degradation rate increased from 250 °C to 422.5 °C, and the residual yields mass left at 600 °C were increased from 2.0% to 28.3%. In addition, its antibacterial property against Escherichia coli was also enhanced markedly without adding any other antimicrobial agents. This improved performance is ascribed to special functional groups in the structure of eugenol. The BPMQ polymer is expected to be applied to pressure-sensitive adhesives and silicone rubber products for the biomedical field due to its reinforcing effect and antioxidant quality. Full article
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13 pages, 5136 KiB  
Article
Raspberry-Like Polysilsesquioxane Particles with Hollow-Spheres-on-Sphere Structure: Rational Design, Controllable Synthesis, and Catalytic Application
by Jian Li, Fuping Dong, Liangyu Lu, Hongwei Li, Yuzhu Xiong and Chang-Sik Ha
Polymers 2019, 11(8), 1350; https://doi.org/10.3390/polym11081350 - 14 Aug 2019
Cited by 20 | Viewed by 5741
Abstract
Raspberry-like hollow-spheres-on-sphere (HSOS) particles with reactive surfaces, uniform sizes and monodisperse properties were rational designed and fabricated to immobilize gold nanoparticles for the catalytic reduction of 4-nitrophenol. HSOS polysilsesquioxane (PSQ) particles were constructed by an organic alkali catalyzed sol-gel process from trialkoxysilane precursors [...] Read more.
Raspberry-like hollow-spheres-on-sphere (HSOS) particles with reactive surfaces, uniform sizes and monodisperse properties were rational designed and fabricated to immobilize gold nanoparticles for the catalytic reduction of 4-nitrophenol. HSOS polysilsesquioxane (PSQ) particles were constructed by an organic alkali catalyzed sol-gel process from trialkoxysilane precursors with stabilized polystyrene (PS) nanoparticles as both a sacrifice template and a Pickering emulsifier. The PSQ particles were fabricated in an ice bath with methyltrimethoxysilane and mercaptopropyltrimethoxysiane as a co-precursor, tetramethylammonium hydroxide (TMAH) as a catalyst, polyvinylpyrrolidone (PVP) and sodium lignosulfonat as co-stabilizers and PS latex as a hard template. The formation mechanism of the hierarchical particles was investigated in detail by the time study through imaging the particles at regular time intervals during the reaction process. Various effect factors on the morphology were studied systematically which showed that the precursor composition, the content of PS, TMAH and PVP are the most important factors. The hierarchical structure combined with the mercaptopropyl groups on both the surface and the skeleton to make it possible to adsorb guest molecules. Au nanoparticles were immobilized on the particles for the catalytic reduction of 4-nitrophenol to 4-aminophenol. The unique PSQ colloids with hollow-spheres-on-sphere extended the family of the hierarchical structures and has shown the potential applications in separations, drug delivery and heterogeneous catalysts. Full article
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11 pages, 2191 KiB  
Article
Replicated Pattern Formation and Recognition Properties of 2,4-Dichlorophenoxyacetic Acid-Imprinted Polymers Using Colloidal Silica Array Molds
by Gita Amiria Aya, Jin Chul Yang, Suck Won Hong and Jin Young Park
Polymers 2019, 11(8), 1332; https://doi.org/10.3390/polym11081332 - 11 Aug 2019
Cited by 7 | Viewed by 3746
Abstract
Surface imprinting is an effective and simple method to fabricate and retain imprinted templates and recognizable nanocavities after template extraction. The imprinted effects can be controlled depending on the surface morphological changes. In general, a planar film has a limited area compared to [...] Read more.
Surface imprinting is an effective and simple method to fabricate and retain imprinted templates and recognizable nanocavities after template extraction. The imprinted effects can be controlled depending on the surface morphological changes. In general, a planar film has a limited area compared to a structured film with relatively higher surface-to-volume (S/V) ratio (A/A0), leading to the conventional sensing response upon the functionality of monomers in a fixed chemical composition. To increase the limited sensing properties and develop simple fabrication of porous arrays on a large area, we herein demonstrate the 2,4-dichlorophenoxyacetic acid (2,4-D, herbicide)-imprinted porous thin film lithographically patterned using photopolymerization and silica colloidal array as a master mold, derived by a unidirectional rubbing method. The resonant frequency changes with respect to the adsorption of 2,4-D molecules on a template-extracted porous poly(MAA-co-EGDMA) (MIP) film in a 10−1 mM aqueous solution of 2,4-D for 1 h, and when compared to the planar MIP film, the higher sensing response (Δf = −283 ± 7 Hz ≈ 1543 ± 38 ng/cm2) appears on the porous MIP film due to the specific recognition toward the more accessible templated cavities of the structured porous array, indicating an imprinting effect (If) value of 3.5. In addition, a higher selectivity for 2,4-D was also displayed on the porous MIP film compared to other herbicides. From these results, it was revealed that these improved sensing properties can be determined from the effects of various parameters (template functionality, film structuring, hydroxyl groups of silica colloids, etc.). Full article
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35 pages, 11117 KiB  
Review
A Review on Porous Polymeric Membrane Preparation. Part II: Production Techniques with Polyethylene, Polydimethylsiloxane, Polypropylene, Polyimide, and Polytetrafluoroethylene
by XueMei Tan and Denis Rodrigue
Polymers 2019, 11(8), 1310; https://doi.org/10.3390/polym11081310 - 5 Aug 2019
Cited by 149 | Viewed by 14797
Abstract
The development of porous polymeric membranes is an important area of application in separation technology. This article summarizes the development of porous polymers from the perspectives of materials and methods for membrane production. Polymers such as polyethylene, polydimethylsiloxane, polypropylene, polyimide, and polytetrafluoroethylene are [...] Read more.
The development of porous polymeric membranes is an important area of application in separation technology. This article summarizes the development of porous polymers from the perspectives of materials and methods for membrane production. Polymers such as polyethylene, polydimethylsiloxane, polypropylene, polyimide, and polytetrafluoroethylene are reviewed due to their outstanding thermal stability, chemical resistance, mechanical strength, and low cost. Six different methods for membrane fabrication are critically reviewed, including thermally induced phase separation, melt-spinning and cold-stretching, phase separation micromolding, imprinting/soft molding, manual punching, and three-dimensional printing. Each method is described in details related to the strategy used to produce the porous polymeric membranes with a specific morphology and separation performances. The key factors associated with each method are presented, including solvent/non-solvent system type and composition, polymer solution composition and concentration, processing parameters, and ambient conditions. Current challenges are also described, leading to future development and innovation to improve these membranes in terms of materials, fabrication equipment, and possible modifications. Full article
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10 pages, 3042 KiB  
Article
Improving Oxygen Permeability and Thermostability of Polycarbonate via Copolymerization Modification with Bio-Phenol Polysiloxane
by Xiaoyan Pang, Xin Ge, Jianye Ji, Weijie Liang, Ruoling Liu, Xunjun Chen, Guoqiang Yin and Jianfang Ge
Polymers 2019, 11(8), 1302; https://doi.org/10.3390/polym11081302 - 3 Aug 2019
Cited by 10 | Viewed by 4513
Abstract
As a new kind of functionalized polysiloxane with chemical reactivity, bio-phenol polysiloxane was synthesized through facile heterogeneous catalytic route. Bio-phenol polysiloxane/polycarbonate (Si/PC) block copolymer was synthesized via a three-step approach, and the effect of the amount of bio-phenol polysiloxane on the properties of [...] Read more.
As a new kind of functionalized polysiloxane with chemical reactivity, bio-phenol polysiloxane was synthesized through facile heterogeneous catalytic route. Bio-phenol polysiloxane/polycarbonate (Si/PC) block copolymer was synthesized via a three-step approach, and the effect of the amount of bio-phenol polysiloxane on the properties of Si/PC copolymer was then studied. The structure and morphology of Si/PC copolymer were characterized, showing that, when the amount of bio-phenol polysiloxane reached 20%, the pyrolysis temperature of Si/PC copolymer at 5% weight loss was 450.8 °C which was 76.1 °C higher than pure PC. The oxygen permeability of 20%Si/PC copolymer membrane was 502.65 cm3/m2·24h·0.1MPa, which was increased by 128.4% compared with pure PC membrane. The mechanical property and hydrophobicity of Si/PC copolymer had been improved. Full article
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12 pages, 3036 KiB  
Article
Surface-Induced ARGET ATRP for Silicon Nanoparticles with Fluorescent Polymer Brushes
by Chun-Na Yan, Lin Xu, Qing-Di Liu, Wei Zhang, Rui Jia, Cheng-Zhi Liu, Shuang-Shuang Wang, Li-Ping Wang and Guang Li
Polymers 2019, 11(7), 1228; https://doi.org/10.3390/polym11071228 - 23 Jul 2019
Cited by 14 | Viewed by 5964
Abstract
Well-defined polymer brushes attached to nanoparticles offer an elegant opportunity for surface modification because of their excellent mechanical stability, functional versatility, high graft density as well as controllability of surface properties. This study aimed to prepare hybrid materials with good dispersion in different [...] Read more.
Well-defined polymer brushes attached to nanoparticles offer an elegant opportunity for surface modification because of their excellent mechanical stability, functional versatility, high graft density as well as controllability of surface properties. This study aimed to prepare hybrid materials with good dispersion in different solvents, and to endow this material with certain fluorescence characteristics. Well-defined diblock copolymers poly (styrene)-b-poly (hydroxyethyl methyl acrylate)–co-poly (hydroxyethyl methyl acrylate- rhodamine B) grafted silica nanoparticles (SNPs-g-PS-b-PHEMA-co-PHEMA-RhB) hybrid materials were synthesized via surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP). The SNPs surfaces were modified by 3-aminopropyltriethoxysilane (KH-550) firstly, then the initiators 2-Bromoisobutyryl bromide (BIBB) was attached to SNPs surfaces through the esterification of acyl bromide groups and amidogen groups. The synthetic initiators (SNPs-Br) were further used for the SI-ARGET ATRP of styrene (St), hydroxyethyl methyl acrylate (HEMA) and hydroxyethyl methyl acrylate-rhodamine B (HEMA-RhB). The results indicated that the SI-ARGET ATRP initiator had been immobilized onto SNPs surfaces, the Br atom have located at the end of the main polymer chains, and the polymerization process possessed the characteristic of controlled/“living” polymerization. The SNPs-g-PS-b-PHEMA-co-PHEMA-RhB hybrid materials show good fluorescence performance and good dispersion in water and EtOH but aggregated in THF. This study demonstrates that the SI-ARGET ATRP provided a unique way to tune the polymer brushes structure on silica nanoparticles surface and further broaden the application of SI-ARGET ATRP. Full article
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14 pages, 3550 KiB  
Article
Design and Application of Highly Efficient Flame Retardants for Polycarbonate Combining the Advantages of Cyclotriphosphazene and Silicone Oil
by Jicheng Jiang, Yanbin Wang, Zhonglin Luo, Tianyi Qi, Yihui Qiao, Menghao Zou and Biaobing Wang
Polymers 2019, 11(7), 1155; https://doi.org/10.3390/polym11071155 - 5 Jul 2019
Cited by 27 | Viewed by 4229
Abstract
A novel flame retardant (HSPCTP) was successfully designed and incorporated into a polycarbonate (PC) matrix. Combining the advantages of cyclotriphosphazene and silicone oil, PC/HSPCTP composites passed UL-94 V-0 rating testing with only 3 wt% HSPCTP, and their LOI value increased from 25.0% to [...] Read more.
A novel flame retardant (HSPCTP) was successfully designed and incorporated into a polycarbonate (PC) matrix. Combining the advantages of cyclotriphosphazene and silicone oil, PC/HSPCTP composites passed UL-94 V-0 rating testing with only 3 wt% HSPCTP, and their LOI value increased from 25.0% to 28.4%. The findings showed that HSPCTP exhibits both gas-phase and solid-phase flame-retardant effects. Furthermore, the incorporation of HSPCTP into PC could suppress the release of smoke. Finally, the flame-retardant mechanism is discussed in depth. Full article
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16 pages, 3807 KiB  
Article
Synthesis and Characterization of Room Temperature Vulcanized Silicone Rubber Using Methoxyl-Capped MQ Silicone Resin as Self-Reinforced Cross-Linker
by Jianye Ji, Xin Ge, Xiaoyan Pang, Ruoling Liu, Shuyi Wen, Jiaqi Sun, Weijie Liang, Jianfang Ge and Xunjun Chen
Polymers 2019, 11(7), 1142; https://doi.org/10.3390/polym11071142 - 3 Jul 2019
Cited by 30 | Viewed by 9668
Abstract
Methoxyl-capped MQ silicone resin (MMQ) was first synthesized by the hydrosilylation of vinyl-containing MQ silicone resin and trimethoxysilane and then used in condensed room-temperature vulcanized (RTV) silicone rubber as a self-reinforced cross-linker. Results show that modified silicone rubber exhibits good light transmission. Compared [...] Read more.
Methoxyl-capped MQ silicone resin (MMQ) was first synthesized by the hydrosilylation of vinyl-containing MQ silicone resin and trimethoxysilane and then used in condensed room-temperature vulcanized (RTV) silicone rubber as a self-reinforced cross-linker. Results show that modified silicone rubber exhibits good light transmission. Compared with unmodified silicone rubber, the hardness, tensile strength and elongation of MMQ at the break are increased by 26.4 A, 2.68 MPa and 65.1%, respectively. In addition, the characteristic temperature of 10% mass loss is delayed from 353.5 °C to 477.1 °C, the temperature at maximum degradation rate is also delayed from 408.9 °C to 528.4 °C and the residual mass left at 800 °C is increased from 1.2% to 27.7%. These improved properties are assigned to the synergistic effect of the rigid structure of MMQ, the formation of a dense cross-linking structure in polymers and the uniform distribution of MMQ cross-linking agent in RTV silicone rubber. Full article
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16 pages, 2334 KiB  
Article
Influence of Surface Modified Nanodiamonds on Dielectric and Mechanical Properties of Silicone Composites
by Alexandra Shakun, Rafal Anyszka, Essi Sarlin, Anke Blume and Jyrki Vuorinen
Polymers 2019, 11(7), 1104; https://doi.org/10.3390/polym11071104 - 29 Jun 2019
Cited by 9 | Viewed by 3900
Abstract
Detonation nanodiamonds, also known as ultradispersed diamonds, possess versatile chemically active surfaces, which can be adjusted to improve their interaction with elastomers. Such improvements can result in decreased dielectric and viscous losses of the composites without compromising other in-rubber properties, thus making the [...] Read more.
Detonation nanodiamonds, also known as ultradispersed diamonds, possess versatile chemically active surfaces, which can be adjusted to improve their interaction with elastomers. Such improvements can result in decreased dielectric and viscous losses of the composites without compromising other in-rubber properties, thus making the composites suitable for new demanding applications, such as energy harvesting. However, in most cases, surface modification of nanodiamonds requires the use of strong chemicals and high temperatures. The present study offers a less time-consuming functionalization method at 40 °C via reaction between the epoxy-rings of the modifier and carboxylic groups at the nanodiamond surface. This allows decorating the nanodiamond surface with chemical groups that are able to participate in the crosslinking reaction, thus creating strong interaction between filler and elastomer. Addition of 0.1 phr (parts per hundred rubber) of modified nanodiamonds into the silicone matrix results in about fivefold decreased electric losses at 1 Hz due to a reduced conductivity. Moreover, the mechanical hysteresis loss is reduced more than 50% and dynamic loss tangent at ambient temperature is lowered. Therefore, such materials are recommended for the dielectric energy harvesting application, and they are expected to increase its efficiency. Full article
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11 pages, 1777 KiB  
Article
Transparent, High Glass-Transition Temperature, Shape Memory Hybrid Polyimides Based on Polyhedral Oligomeric Silsesquioxane
by Zhongxu Lan, Xueli Chen, Xiao Zhang, Chongyu Zhu, Yanlei Yu and Jia Wei
Polymers 2019, 11(6), 1058; https://doi.org/10.3390/polym11061058 - 18 Jun 2019
Cited by 29 | Viewed by 6996
Abstract
Optically transparent polyimides with excellent thermal stability and shape memory effect have potential applications in optoelectronic devices and aerospace industries. A series of optically transparent shape memory polyimide hybrid films are synthesized from 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 2,2′-bis-(trifluoromethyl)biphenyl-4,4′-diamine (TFMB) with various polyhedral oligomeric [...] Read more.
Optically transparent polyimides with excellent thermal stability and shape memory effect have potential applications in optoelectronic devices and aerospace industries. A series of optically transparent shape memory polyimide hybrid films are synthesized from 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 2,2′-bis-(trifluoromethyl)biphenyl-4,4′-diamine (TFMB) with various polyhedral oligomeric silsesquioxane (POSS) contents and then subjected to thermal imidization. The hybrid films show good optical transparency (>80% at 400 nm and >95% at 500 nm) with cutoff wavelengths ranging from 318 to 336 nm. Following the incorporation of the inorganic POSS structure, the hybrid films exhibit excellent thermal stability with glass transition temperature (Tg) ranging from 351 to 372 °C. The hybrid films possess the highest Tg compared with the previously-reported shape memory polymers. These findings show that POSS is successfully utilized to develop transparent polyimides with excellent thermal stability and shape memory effect. Full article
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12 pages, 1826 KiB  
Article
Polydimethylsiloxane/Nanodiamond Composite Sponge for Enhanced Mechanical or Wettability Performance
by Xuxin Zhao, Tao Wang, Yaoyao Li, Lei Huang and Stephan Handschuh-Wang
Polymers 2019, 11(6), 948; https://doi.org/10.3390/polym11060948 - 1 Jun 2019
Cited by 17 | Viewed by 5131
Abstract
Polydimethylsiloxane (PDMS) is widely utilized in material science, chemical engineering, and environmental science due to its excellent properties. By utilizing fillers, so-called composite materials can be obtained with enhanced mechanical, wettability, or thermal conductivity performance. Here, we present a simple, cost-effective approach to [...] Read more.
Polydimethylsiloxane (PDMS) is widely utilized in material science, chemical engineering, and environmental science due to its excellent properties. By utilizing fillers, so-called composite materials can be obtained with enhanced mechanical, wettability, or thermal conductivity performance. Here, we present a simple, cost-effective approach to vary either the mechanical properties (Young’s modulus) or surface wettability of bulk PDMS and PDMS sponges simply by adding nanodiamond filler with different surface terminations, either oxidized (oND) or hydrogenated (reduced, rND) nanodiamond. Minuscule amounts of oxidized nanodiamond particles as filler showed to benefit the compressive Young’s modulus of composite sponges with up to a 52% increase in its value, while the wettability of composite sponges was unaffected. In contrast, adding reduced nanodiamond particles to PDMS yielded inclined water contact angles on the PDMS/nanodiamond composite sponges. Finally, we show that the PDMS/rND composites are readily utilized as an absorbent for oil/water separation problems. This signifies that the surface termination of the ND particle has a crucial effect on the performance of the composite. Full article
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13 pages, 1279 KiB  
Article
Synthesis and Characterization of Silicone Contact Lenses Based on TRIS-DMA-NVP-HEMA Hydrogels
by Nguyen-Phuong-Dung Tran and Ming-Chien Yang
Polymers 2019, 11(6), 944; https://doi.org/10.3390/polym11060944 - 31 May 2019
Cited by 61 | Viewed by 12119
Abstract
In this study, silicone-based hydrogel contact lenses were prepared by the polymerization of 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane (TRIS), N,N-dimethylacrylamide (DMA), 1-vinyl-2-pyrrolidinone (NVP), and 2-hydroxyethylmethacrylate (HEMA). The properties of silicone hydrogel lenses were analyzed based on the methods such as equilibrium water content, oxygen permeability, optical transparency, [...] Read more.
In this study, silicone-based hydrogel contact lenses were prepared by the polymerization of 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane (TRIS), N,N-dimethylacrylamide (DMA), 1-vinyl-2-pyrrolidinone (NVP), and 2-hydroxyethylmethacrylate (HEMA). The properties of silicone hydrogel lenses were analyzed based on the methods such as equilibrium water content, oxygen permeability, optical transparency, contact angle, mechanical test, protein adsorption, and cell toxicity. The results showed that the TRIS content in all formulations increased the oxygen permeability and decreased the equilibrium water content, while both DMA and NVP contributed the hydrophilicity of the hydrogels. The maximum value of oxygen permeability was 74.9 barrers, corresponding to an equilibrium water content of 44.5% as well as a contact angle of 82°. Moreover, L929 fibroblasts grew on all these hydrogels, suggesting non-cytotoxicity. In general, the silicone hydrogels in this work exhibited good oxygen permeability, stiffness, and optical transparency as well as anti-protein adsorption. Hence, these silicone hydrogel polymers would be feasible for making contact lens. Full article
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12 pages, 3192 KiB  
Article
Hydrosilylation of Reactive Quantum Dots and Siloxanes for Stable Quantum Dot Films
by Changmin Lee, Eunhee Nam, Woosuk Lee and Heeyeop Chae
Polymers 2019, 11(5), 905; https://doi.org/10.3390/polym11050905 - 18 May 2019
Cited by 4 | Viewed by 4567
Abstract
The reactive acrylate-terminated CdZnSeS/ZnS quantum dots (QDs) were designed and prepared by the effective synthetic route to bond with a siloxane matrix via hydrosilylation. The conventional QD with oleic acid ligands does not have any reactivity, so the QDs were functionalized to assign [...] Read more.
The reactive acrylate-terminated CdZnSeS/ZnS quantum dots (QDs) were designed and prepared by the effective synthetic route to bond with a siloxane matrix via hydrosilylation. The conventional QD with oleic acid ligands does not have any reactivity, so the QDs were functionalized to assign reactivity for the QDs by the ligand modification of two step reactions. The oleic acid of the QDs was exchanged for hydroxyl-terminated ligands as an intermediate product by one-pot reaction. The hydroxyl-terminated QDs and acrylate-containing isocyanates were combined by nucleophilic addition reaction with forming urethane bonds and terminal acrylate groups. No degradation in quantum yield was observed after ligand exchange, nor following the nucleophilic addition reaction. The modification reactions of ligands were quantitatively controlled and their molecular structures were precisely confirmed by FT-IR and 1H-NMR. The QDs with acrylate ligands were then reacted with hydride-terminated polydimethylsiloxane (H-PDMS) to form a QD-siloxane matrix by thermal curing via hydro-silylation for the first time. The covalent bonding between the QDs and the siloxane matrix led to improvements in the stability against oxygen and moisture. Stability at 85 °C and 85% relative humidity (RH) were both improved by 22% for the QD-connected siloxane QD films compared with the corresponding values for conventional QD-embedded poly(methylmethacrylate) (PMMA) films. The photo-stability of the QD film after 26 h under a blue light-emitting diode (LED) was also improved by 45% in comparison with those of conventional QD-embedded PMMA films. Full article
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17 pages, 13787 KiB  
Article
Aluminosilicate Nanotubes Embedded Polyamide Thin Film Nanocomposite Forward Osmosis Membranes with Simultaneous Enhancement of Water Permeability and Selectivity
by She-Ji Shi, Ye-Han Pan, Shao-Fei Wang, Zheng-Wei Dai, Lin Gu and Qing-Yun Wu
Polymers 2019, 11(5), 879; https://doi.org/10.3390/polym11050879 - 14 May 2019
Cited by 20 | Viewed by 3720
Abstract
Nanocomposite membranes are strongly desired to break a trade-off between permeability and selectivity. This work reports new thin film nanocomposite (TFN) forward osmosis (FO) membranes by embedding aluminosilicate nanotubes (ANTs) into a polyamide (PA) rejection layer. The surface morphology and structure of the [...] Read more.
Nanocomposite membranes are strongly desired to break a trade-off between permeability and selectivity. This work reports new thin film nanocomposite (TFN) forward osmosis (FO) membranes by embedding aluminosilicate nanotubes (ANTs) into a polyamide (PA) rejection layer. The surface morphology and structure of the TFN FO membranes were carefully characterized by FTIR, XPS, FESEM and AFM. The ANTs incorporated PA rejection layers exhibited many open and broad “leaf-like” folds with “ridge-and-valley” structures, high surface roughness and relatively low cross-linking degree. Compared with thin film composite (TFC) membrane without ANTs, the TFN membrane with only 0.2 w/v% ANTs loading presented significantly improved FO water permeability, selectivity and reduced structural parameters. This promising performance can be mainly contributed to the special ANTs embedded PA rejection layer, where water molecules preferentially transport through the nanochannels of ANTs. Molecular dynamic simulation further proved that water molecules have much larger flux through the nanotubes of ANTs than sodium and chloride ions, which are attributed to the intrinsic hydrophilicity of ANTs and low external force for water transport. This work shows that these TFN FO membranes with ANTs decorated PA layer are promising in desalination applications due to their simultaneously enhanced permeability and selectivity. Full article
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17 pages, 11849 KiB  
Article
Effects of an Organic-Inorganic Hybrid Containing Allyl Benzoxazine and POSS on Thermal Properties and Flame Retardancy of Epoxy Resin
by Benben Liu, Huiling Wang, Xiaoyan Guo, Rongjie Yang and Xiangmei Li
Polymers 2019, 11(5), 770; https://doi.org/10.3390/polym11050770 - 1 May 2019
Cited by 21 | Viewed by 4640
Abstract
A novel organic-inorganic hybrid containing allyl benzoxazine and polyhedral oligomeric silsesquioxane (POSS) was synthesized by the thiol-ene (click) reaction. The benzoxazine (BOZ)-containing POSS (SPOSS-BOZ) copolymerized with benzoxazine/epoxy resin was used to prepare composites of SPOSS-PBZ-E nanocomposites(NPs). The polymerization behavior was monitored by FTIR [...] Read more.
A novel organic-inorganic hybrid containing allyl benzoxazine and polyhedral oligomeric silsesquioxane (POSS) was synthesized by the thiol-ene (click) reaction. The benzoxazine (BOZ)-containing POSS (SPOSS-BOZ) copolymerized with benzoxazine/epoxy resin was used to prepare composites of SPOSS-PBZ-E nanocomposites(NPs). The polymerization behavior was monitored by FTIR and non-isothermal differential scanning calorimetry (DSC), which showed that the composites had completely cured with multiple polymerization mechanisms according to the oxazine ring-opening and epoxy resin (EP) polymerization. The thermal properties of the organic–inorganic polybenzoxazine (PBZ) nanocomposites were analyzed by DSC and thermogravimetric analysis (TGA). Furthermore, the X-ray diffraction analysis and the scanning electron microscopy (SEM) micrographs of the SPOSS-PBZ-E nanocomposites indicated that SPOSS was chemically incorporated into the hybrid nanocomposites in the size range of 80–200 nm. The flame retardancy of the benzoxazine epoxy resin composites was investigated by limiting oxygen index (LOI), UL 94 vertical burn test, and cone calorimeter tests. When the amount of SPOSS reached 10% or more, the vertical burning rating of the curing system arrived at V-1, and when the SPOSS-BOZ content reached 20 wt %, the thermal stability and flame retardancy of the material were both improved. Moreover, in the cone calorimeter testing, the addition of SPOSS-BOZ hindered the decomposition of the composites and led to a reduction in the peak heat release rate (pHRR), the average heat release rate (aHRR), and the total heat release (THR) values by about 20%, 25%, and 25%, respectively. The morphologies of the chars were also studied by SEM and energy dispersive X-ray spectroscopy (EDX), and the flame-retardant mechanism of POSS was mainly a condensed-phase flame retardant. The ceramic layer was formed by the enrichment of silicon on the char surface. When there are enough POSS nanoparticles, it can effectively protect the combustion of internal polymers. Full article
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16 pages, 4204 KiB  
Article
Effect of Silane Treatment on Mechanical Properties of Polyurethane/Mesoscopic Fly Ash Composites
by Chuanrui Qin, Wei Lu, Zhenglong He, Guansheng Qi, Jinliang Li and Xiangming Hu
Polymers 2019, 11(4), 741; https://doi.org/10.3390/polym11040741 - 24 Apr 2019
Cited by 18 | Viewed by 4325
Abstract
In view of the accidents such as rock mass breakage, roof fall and coal slide in coal mines, polyurethane/mesoscopic fly ash (PU/MFA) reinforcement materials were produced from polymethylene polyphenylene isocyanate (PAPI), the polyether polyol, flame retardant, and MFA using stannous octanate as a [...] Read more.
In view of the accidents such as rock mass breakage, roof fall and coal slide in coal mines, polyurethane/mesoscopic fly ash (PU/MFA) reinforcement materials were produced from polymethylene polyphenylene isocyanate (PAPI), the polyether polyol, flame retardant, and MFA using stannous octanate as a catalyst. 3-Glycidoxypropyltrimethoxysilane (GPTMS) was grafted on MFA surface, aiming to improve the mechanical properties of PU/MFA composites. The analyses of infrared spectroscopy and compression resistance reveal that the GPTMS can be successfully attached to the surface of MFA, and the optimum modification dosage of GPTMS to MFA is 2.5 wt. % (weight percent). On this basis, the effect of GPTMS on the mechanical properties of PU/MFA reinforcement materials during the curing process was systematically investigated through a compression test, a fracture toughness test, a three-point bending test, a bond property test, and a dynamic mechanics analysis. The results show that the compression property, fracture toughness, maximum flexural strength, and bond strength of PU/MFA composites increase by 21.6%, 10.1%, 8.8%, and 19.3%, respectively, compared with the values before the modification. Furthermore, the analyses of scanning electron microscope and dynamic mechanics suggest that the coupling agent GPTMS can successfully improve the mechanical properties of PU/MFA composites because it eliminates the stress concentration and exerts a positive effect on the crosslink density and hardness of PU/MFA composites. Full article
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13 pages, 4236 KiB  
Article
Manifestation of Interactions of Nano-Silica in Silicone Rubber Investigated by Low-Frequency Dielectric Spectroscopy and Mechanical Tests
by Chao Wu, Yanfeng Gao, Xidong Liang, Stanislaw M. Gubanski, Qian Wang, Weining Bao and Shaohua Li
Polymers 2019, 11(4), 717; https://doi.org/10.3390/polym11040717 - 19 Apr 2019
Cited by 30 | Viewed by 5227
Abstract
Silicone rubber composites filled with nano-silica are currently widely used as high voltage insulating materials in power transmission and substation systems. We present a systematic study on the dielectric and mechanical performance of silicone rubber filled with surface modified and unmodified fumed nano-silica. [...] Read more.
Silicone rubber composites filled with nano-silica are currently widely used as high voltage insulating materials in power transmission and substation systems. We present a systematic study on the dielectric and mechanical performance of silicone rubber filled with surface modified and unmodified fumed nano-silica. The results indicate that the different interfaces between the silicone rubber and the two types of nano-silica introduce changes in their dielectric response when electrically stressed by a sinusoidal excitation in the frequency range of 10−4–1 Hz. The responses of pure silicone rubber and the composite filled with modified silica can be characterized by a paralleled combination of Maxwell-Wagner-Sillars interface polarization and DC conduction. In contrast, the silicone rubber composite with the unmodified nano-silica exhibits a quasi-DC (Q-DC) transport process. The mechanical properties of the composites (represented by their stress-strain characteristics) reveal an improvement in the mechanical strength with increasing filler content. Moreover, the strain level of the composite with a modified filler is improved. Full article
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15 pages, 3008 KiB  
Article
Improving the Damping Properties of Nanocomposites by Monodispersed Hybrid POSS Nanoparticles: Preparation and Mechanisms
by Wei Wei, Yingjun Zhang, Meihua Liu, Yifan Zhang, Yuan Yin, Wojciech Stanislaw Gutowski, Pengyang Deng and Chunbai Zheng
Polymers 2019, 11(4), 647; https://doi.org/10.3390/polym11040647 - 9 Apr 2019
Cited by 27 | Viewed by 5678
Abstract
In this work, a series of heptaphenyl siloxane trisilanol/polyhedral oligomeric silsesquioxane (T7-POSS) modified by polyols with different molecular weights were synthesized into liquid-like nanoparticle–organic hybrid materials using the grafted-from method. All grafted POSS nanoparticles changed from solid powders to liquid at [...] Read more.
In this work, a series of heptaphenyl siloxane trisilanol/polyhedral oligomeric silsesquioxane (T7-POSS) modified by polyols with different molecular weights were synthesized into liquid-like nanoparticle–organic hybrid materials using the grafted-from method. All grafted POSS nanoparticles changed from solid powders to liquid at room temperature. Polyurethane (PU) nanocomposites with POSS contents ranging from 1.75 to 9.72 wt % were prepared from these liquefied polyols-terminated POSS with polyepichlorohydrin (POSS–PECH). Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to characterize the morphology of the POSS–PECH/PU nanocomposites. The results showed that the polyol-terminated POSS particles overcame the nanoagglomeration effect and evenly disperse in the polymeric matrix. The damping factor (tan δ) of resultant nanocomposites increased from 0.90 to 1.16, while the glass transition temperature decreased from 15.8 to 9.4 °C when POSS contents increased from 0 to 9.75 wt %. The gel content, tensile strength and Fourier transform infrared (FTIR) analyses demonstrated that the molecular thermal movement ability of the polyurethane (PU) matrix increased with increasing POSS hybrid content. Therefore, the improvement of the damping properties of the composites was mainly due to the friction-related losses occurring in the interface region between the nanoparticles and the matrix. Full article
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14 pages, 2587 KiB  
Article
Functional Nanostructured Oligochitosan–Silica/Carboxymethyl Cellulose Hybrid Materials: Synthesis and Investigation of Their Antifungal Abilities
by Thuy N Nguyen, Thu NM Huynh, DongQuy Hoang, Dai Hai Nguyen, Quoc Hien Nguyen and Thai Hoa Tran
Polymers 2019, 11(4), 628; https://doi.org/10.3390/polym11040628 - 4 Apr 2019
Cited by 17 | Viewed by 3930
Abstract
Functional hybrid materials were successfully synthesized from low-cost waste products, such as oligochitosan (OCS) obtained from chitosan (one of the main components in crab shells) and nanosilica (nSiO2) obtained from rice husk, in a 1:1 ratio (w/w), [...] Read more.
Functional hybrid materials were successfully synthesized from low-cost waste products, such as oligochitosan (OCS) obtained from chitosan (one of the main components in crab shells) and nanosilica (nSiO2) obtained from rice husk, in a 1:1 ratio (w/w), and their dispersion in the presence of carboxymethyl cellulose at pH 7 was stable for over one month without aggregation. The molecular weights, chemical structures, morphologies, and crystallinities of the obtained materials were characterized by GPC, FTIR, TEM, and XRD, respectively. The antifungal effects of OCS, nSiO2, and the OCS/nSiO2 hybrid materials were investigated via a disk-diffusion method. The results showed that the nanohybrid materials had better resistance to Phytophthora infestans fungus than the individual components, and a concentration of the OCS2/nSiO2 hybrid material of 800 mg L−1 was the lowest concentration where the material completely inhibited Phytophthora infestans growth, as measured via an agar dilution method. This study not only creates a novel environmentally friendly material with unique synergistic effects that can replace current toxic agrochemicals but also can be considered a new platform for further research in green agricultural applications. Full article
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12 pages, 5417 KiB  
Article
POSS-Derived Synthesis and Full Life Structural Analysis of Si@C as Anode Material in Lithium Ion Battery
by Ziyu Bai, Wenmao Tu, Junke Zhu, Junsheng Li, Zhao Deng, Danpeng Li and Haolin Tang
Polymers 2019, 11(4), 576; https://doi.org/10.3390/polym11040576 - 29 Mar 2019
Cited by 14 | Viewed by 6150
Abstract
Polyhedral oligomeric silsesquioxane (POSS)-derived Si@C anode material is prepared by the copolymerization of octavinyl-polyhedral oligomeric silsesquioxane (octavinyl-POSS) and styrene. Octavinyl-polyhedral oligomeric silsesquioxane has an inorganic core (-Si8O12) and an organic vinyl shell. Carbonization of the core-shell structured organic-inorganic hybrid [...] Read more.
Polyhedral oligomeric silsesquioxane (POSS)-derived Si@C anode material is prepared by the copolymerization of octavinyl-polyhedral oligomeric silsesquioxane (octavinyl-POSS) and styrene. Octavinyl-polyhedral oligomeric silsesquioxane has an inorganic core (-Si8O12) and an organic vinyl shell. Carbonization of the core-shell structured organic-inorganic hybrid precursor results in the formation of carbon protected Si-based anode material applicable for lithium ion battery. The initial discharge capacity of the battery based on the as-obtained Si@C material Si reaches 1500 mAh g−1. After 550 charge-discharge cycles, a high capacity of 1430 mAh g−1 was maintained. A combined XRD, XPS and TEM analysis was performed to investigate the variation of the discharge performance during the cycling experiments. The results show that the decrease in discharge capacity in the first few cycles is related to the formation of solid electrolyte interphase (SEI). The subsequent rise in the capacity can be ascribed to the gradual morphology evolution of the anode material and the loss of capacity after long-term cycles is due to the structural pulverization of silicon within the electrode. Our results not only show the high potential of the novel electrode material but also provide insight into the dynamic features of the material during battery cycling, which is useful for the future design of high-performance electrode material. Full article
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16 pages, 1478 KiB  
Article
Effect of a Modified Silicone as a Thickener on Rheology of Liquid CO2 and Its Fracturing Capacity
by Qiang Li, Yanling Wang, Fuling Wang, Qingchao Li, Forson Kobina, Hao Bai and Lin Yuan
Polymers 2019, 11(3), 540; https://doi.org/10.3390/polym11030540 - 21 Mar 2019
Cited by 22 | Viewed by 3450
Abstract
The low viscosity of pure liquid CO2 hindered the development of CO2 fracturing technology. A modified silicone polymer was prepared as a CO2 thickener to investigate the effect of temperature, pressure, shear rate and thickener content (wt.%) on the apparent [...] Read more.
The low viscosity of pure liquid CO2 hindered the development of CO2 fracturing technology. A modified silicone polymer was prepared as a CO2 thickener to investigate the effect of temperature, pressure, shear rate and thickener content (wt.%) on the apparent viscosity and rheology of thickened liquid CO2. In addition, CO2 fracturing capacity was evaluated with the numerical simulation of extended finite element. The results displayed that an apparent viscosity of up to 1.3 mPa·s at 303 K and 18 MPa was attained over liquid CO2 using the thickener of 3 wt.% and Toluene of 9 wt.% as additives. Compared to the commercial linear polydimethylsiloxane, a better apparent viscosity was obtained from the mixture of this prepared thickener, Toluene and CO2. The apparent viscosity decreases with increasing temperature and shear rate. By contrast, an improving apparent viscosity was revealed with an increase in the pressure from 8 to 14 MPa and thickener content from 1 to 3 wt.%. The rheological index decreased with increasing thickener content with pressure but the rise in temperature led to an increasing rheological index. The mesh structure theory of the thickener, CO2 and Toluene molecules was in this paper gives a good explanation for the discrepancy between CO2 viscosity with the thickener content, temperature, pressure, or shear rate. Compared to pure CO2, the numerical simulation of CO2 fracturing demonstrated an excellent fracturing capacity by using the thickened CO2 fracturing fluid in shale reservoirs. This investigation could provide the basic reference for the development of CO2 fracturing technology. Full article
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18 pages, 4796 KiB  
Article
POSS Hybrid Robust Biomass IPN Hydrogels with Temperature Responsiveness
by Yi Chen, Yueyun Zhou, Wenyong Liu, Hejie Pi and Guangsheng Zeng
Polymers 2019, 11(3), 524; https://doi.org/10.3390/polym11030524 - 20 Mar 2019
Cited by 9 | Viewed by 3782
Abstract
In order to improve the performance of traditional sodium alginate (SA) hydrogels cross-linked by Ca2+ ions to meet greater application demand, a strategy was designed to structure novel SA-based gels (named OP-PN gels) to achieve both stimulus responsiveness and improved mechanical strength. [...] Read more.
In order to improve the performance of traditional sodium alginate (SA) hydrogels cross-linked by Ca2+ ions to meet greater application demand, a strategy was designed to structure novel SA-based gels (named OP-PN gels) to achieve both stimulus responsiveness and improved mechanical strength. In this strategy, the SA chains are co-cross-linked by CaCl2 and cationic octa-ammonium polyhedral oligomeric silsesquioxane (Oa-POSS) particles as the first network, and an organically cross-linked poly(N-isopropyl acrylamide) (PNIPA) network is introduced into the gels as the second network. Several main results are obtained from the synthesis and characterization of the gels. For OP-PN gels, their properties depend on the content of both uniformly dispersed Oa-POSS and PNIPA network directly. The increased Oa-POSS and PNIPA network content significantly improves both the strength and resilience of gels. Relatively, the increased Oa-POSS is greatly beneficial to the modulus of gels, and the increased PNIPA network is more favorable to advancing the tensile deformation of gels. The gels with hydrophilic PNIPA network exhibit better swelling ability and remarkable temperature responsiveness, and their volume phase transition temperature can be adjusted by altering the content of Oa-POSS. The deswelling rate of gels increases gradually with the increase of POSS content due to the hydrophobic Si–O skeleton of POSS. Moreover, the enhanced drug loading and sustained release ability of the target drug bovine serum albumin displays great potential for this hybrid gel in the biomedical field. Full article
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20 pages, 5900 KiB  
Article
Anchor Effect in Polymerization Kinetics: Case of Monofunctionalized POSS
by Agnieszka Marcinkowska, Dawid Przadka, Beata Dudziec, Katarzyna Szczesniak and Ewa Andrzejewska
Polymers 2019, 11(3), 515; https://doi.org/10.3390/polym11030515 - 19 Mar 2019
Cited by 9 | Viewed by 4012
Abstract
The effect of the anchoring group on the detailed polymerization kinetics was investigated using monomethacryloxy-heptaisobutyl POSS (1M-POSS). This compound was copolymerized with lauryl methacrylate (LM) as the base monomer, at various molar ratios. The process was initiated photochemically. The polymerization kinetics were followed [...] Read more.
The effect of the anchoring group on the detailed polymerization kinetics was investigated using monomethacryloxy-heptaisobutyl POSS (1M-POSS). This compound was copolymerized with lauryl methacrylate (LM) as the base monomer, at various molar ratios. The process was initiated photochemically. The polymerization kinetics were followed by photo-DSC and photorheology while the polymers were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). For comparison, a methacrylate containing the branched siloxy-silane group (TSM) was also studied. It was found that the modifiers with a bulky substituent have a dual effect on the termination process: (i) At low concentrations, they increase the molecular mobility by increasing the free volume fraction, which leads to an acceleration of the termination and slows the polymerization; while (ii) at higher concentrations, they retard molecular motions due to the “anchor effect” that suppresses the termination, leading to acceleration of the polymerization. The anchor effect can also be considered from a different point of view: The possibility of anchoring a monomer with a long substituent (LM) around the POSS cage, which can further enhance propagation. These conclusions were derived based on kinetic results, determination of polymerization rate coefficients, and copolymer analysis. Full article
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39 pages, 9472 KiB  
Review
Synthetic Routes to Silsesquioxane-Based Systems as Photoactive Materials and Their Precursors
by Beata Dudziec, Patrycja Żak and Bogdan Marciniec
Polymers 2019, 11(3), 504; https://doi.org/10.3390/polym11030504 - 16 Mar 2019
Cited by 51 | Viewed by 7029
Abstract
Over the past two decades, organic optoelectronic materials have been considered very promising. The attractiveness of this group of compounds, regardless of their undisputable application potential, lies in the possibility of their use in the construction of organic–inorganic hybrid materials. This class of [...] Read more.
Over the past two decades, organic optoelectronic materials have been considered very promising. The attractiveness of this group of compounds, regardless of their undisputable application potential, lies in the possibility of their use in the construction of organic–inorganic hybrid materials. This class of frameworks also considers nanostructural polyhedral oligomeric silsesquioxanes (POSSs) with “organic coronae” and precisely defined organic architectures between dispersed rigid silica cores. A significant number of papers on the design and development of POSS-based organic optoelectronic as well as photoluminescent (PL) materials have been published recently. In view of the scientific literature abounding with numerous examples of their application (i.e., as OLEDs), the aim of this review is to present efficient synthetic pathways leading to the formation of nanocomposite materials based on silsesquioxane systems that contain organic chromophores of complex nature. A summary of stoichiometric and predominantly catalytic methods for these silsesquioxane-based systems to be applied in the construction of photoactive materials or their precursors is given. Full article
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15 pages, 8094 KiB  
Article
Recycled-Oil-Based Polyurethane Modified with Organic Silicone for Controllable Release of Coated Fertilizer
by Qian Wang, Fuping Dong, Jun Dai, Qingpo Zhang, Meng Jiang and Yuzhu Xiong
Polymers 2019, 11(3), 454; https://doi.org/10.3390/polym11030454 - 10 Mar 2019
Cited by 30 | Viewed by 5175
Abstract
Fertilizer is very important for increasing food yield, but the extensive use of fertilizer will cause environmental pollution. To enhance the effectiveness of fertilizer, we developed the double organic silicone-modified recycled-oil-based polyurethane as a coating material to prepare degradable polymer coating urea for [...] Read more.
Fertilizer is very important for increasing food yield, but the extensive use of fertilizer will cause environmental pollution. To enhance the effectiveness of fertilizer, we developed the double organic silicone-modified recycled-oil-based polyurethane as a coating material to prepare degradable polymer coating urea for constant fertilizer release. The moisture, heat resistance, and sustained release properties of polyurethane coating materials were investigated by modification with hydroxyl-terminated polydimethyl silicone (HTPMS) and γ-Aminopropyl triethoxy silane (KH550). The content and distribution of the siloxane groups were effectively controlled by adjusting the content ratio of two kinds of organosilicon. Meanwhile, the organic–inorganic hybrid structure was further controlled to form three-dimensional networks with a uniform distribution and a small scale. The moisture and heat resistance of polyurethane were thus improved, resulting in reduced porosity and an excellent sustained release performance. Observably, the best sustained release property of modified polyurethane coated urea was obtained when the ratio of KH550 to HTPMS is 0.3:0.7. Full article
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13 pages, 3745 KiB  
Article
Multifunctional Silicone Rubber Nanocomposites by Controlling the Structure and Morphology of Graphene Material
by Ruben Sanchez-Hidalgo, Clara Blanco, Rosa Menendez, Raquel Verdejo and Miguel A. Lopez-Manchado
Polymers 2019, 11(3), 449; https://doi.org/10.3390/polym11030449 - 8 Mar 2019
Cited by 25 | Viewed by 4702
Abstract
Multifunctional elastomer nanocomposites have been applied in several high-tech fields. The design of materials with tailored properties capable of tuning their performance is a topical challenge. Here, we demonstrate that it is possible to modulate the mechanical and transport properties of silicone rubber [...] Read more.
Multifunctional elastomer nanocomposites have been applied in several high-tech fields. The design of materials with tailored properties capable of tuning their performance is a topical challenge. Here, we demonstrate that it is possible to modulate the mechanical and transport properties of silicone rubber nanocomposites by controlling the structure, chemical composition and morphology of the graphene material. Intrinsic graphene properties, such as remaining oxygen groups, specific surface area, and aspect ratio, among others, have a profound effect on the final properties of the nanocomposite. Thus, the thermal conductivity benefits from larger filler size and high aromatic restoration. Whereas mechanical properties and electrical conductivity require a proper balance between filler/polymer matrix interaction and a partial aromatic restoration. Full article
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14 pages, 2074 KiB  
Article
Mechanically Robust Hybrid POSS Thermoplastic Polyurethanes with Enhanced Surface Hydrophobicity
by Xiuhuan Song, Xiaoxiao Zhang, Tianduo Li, Zibiao Li and Hong Chi
Polymers 2019, 11(2), 373; https://doi.org/10.3390/polym11020373 - 20 Feb 2019
Cited by 30 | Viewed by 5124
Abstract
A series of hybrid thermoplastic polyurethanes (PUs) were synthesized from bi-functional polyhedral oligomeric silsesquioxane (B-POSS) and polycaprolactone (PCL) using 1,6-hexamethylene diisocyanate (HDI) as a coupling agent for the first time. The newly synthesized hybrid materials were fully characterized in terms of structure, morphology, [...] Read more.
A series of hybrid thermoplastic polyurethanes (PUs) were synthesized from bi-functional polyhedral oligomeric silsesquioxane (B-POSS) and polycaprolactone (PCL) using 1,6-hexamethylene diisocyanate (HDI) as a coupling agent for the first time. The newly synthesized hybrid materials were fully characterized in terms of structure, morphology, thermal and mechanical performance, as well as their toughening effect toward polyesters. Thermal gravimeter analysis (TGA) and differential scanning calorimetry (DSC) showed enhanced thermal stability by 76 °C higher in decomposition temperature (Td) of the POSS PUs, and 22 °C higher glass transition temperature (Tg) when compared with control PU without POSS. Static contact angle results showed a significant increment of 49.8° and 53.4° for the respective surface hydrophobicity and lipophilicity measurements. More importantly, both storage modulus (G’) and loss modulus (G’’) are improved in the hybrid POSS PUs and these parameters can be further adjusted by varying POSS content in the copolymer. As a biodegradable hybrid filler, the as-synthesized POSS PUs also demonstrated a remarkable effect in toughening commercial polyesters, indicating a simple yet useful strategy in developing high-performance polyester for advanced biomedical applications. Full article
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19 pages, 7871 KiB  
Article
Composites of Rigid Polyurethane Foams Reinforced with POSS
by Sylwia Członka, Anna Strąkowska, Krzysztof Strzelec, Agnieszka Adamus-Włodarczyk, Agnė Kairytė and Saulius Vaitkus
Polymers 2019, 11(2), 336; https://doi.org/10.3390/polym11020336 - 14 Feb 2019
Cited by 42 | Viewed by 5013
Abstract
Rigid polyurethane foams (RPUFs) were successfully modified with different weight ratios (0.5 wt%, 1.5 wt% and 5 wt%) of APIB-POSS and AEAPIB-POSS. The resulting foams were evaluated by their processing parameters, morphology (Scanning Electron Microscopy analysis, SEM), mechanical properties (compressive test, three-point bending [...] Read more.
Rigid polyurethane foams (RPUFs) were successfully modified with different weight ratios (0.5 wt%, 1.5 wt% and 5 wt%) of APIB-POSS and AEAPIB-POSS. The resulting foams were evaluated by their processing parameters, morphology (Scanning Electron Microscopy analysis, SEM), mechanical properties (compressive test, three-point bending test and impact strength), viscoelastic behavior (Dynamic Mechanical Analysis, DMA), thermal properties (Thermogravimetric Analysis, TGA, and thermal conductivity) and application properties (contact angle, water absorption and dimensional analysis). The results showed that the morphology of modified foams is significantly affected by the type of the filler and filler content, which resulted in inhomogeneous, irregular, large cell shapes and further affected the physical and mechanical properties of resulting materials. RPUFs modified with APIB-POSS represent better mechanical and thermal properties compared to the RPUFs modified with AEAPIB-POSS. The results showed that the best results were obtained for RPUFs modified with 0.5 wt% of APIB-POSS. For example, in comparison with unfilled foam, compositions modified with 0.5 wt% of APIB-POSS provide greater compression strength, better flexural strength and lower water absorption. Full article
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13 pages, 5260 KiB  
Article
Versatile Construction of Single-Tailed Giant Surfactants with Hydrophobic Poly(ε-caprolactone) Tail and Hydrophilic POSS Head
by Qiangyu Qian, Jun Xu, Mingzu Zhang, Jinlin He and Peihong Ni
Polymers 2019, 11(2), 311; https://doi.org/10.3390/polym11020311 - 12 Feb 2019
Cited by 9 | Viewed by 3628
Abstract
Giant surfactants refer to a new kind of amphiphile by incorporating functional molecular nanoparticles with polymer tails. As a size-amplified counterpart of small-molecule surfactants, they serve to bridge the gap between small-molecule surfactants and amphiphilic block copolymers. This work reports the design and [...] Read more.
Giant surfactants refer to a new kind of amphiphile by incorporating functional molecular nanoparticles with polymer tails. As a size-amplified counterpart of small-molecule surfactants, they serve to bridge the gap between small-molecule surfactants and amphiphilic block copolymers. This work reports the design and synthesis of single-tailed giant surfactants carrying a hydrophobic poly(ε-caprolactone) (PCL) as the tail and a hydrophilic cage-like polyhedral oligomeric silsesquioxane (POSS) nanoparticle as the head. The modular synthetic strategy features an efficient “growing-from” and “click-modification” approach. Starting from a monohydroxyl and heptavinyl substituted POSS (VPOSS-OH), a PCL chain with controlled molecular weight and narrow polydispersity was first grown by the ring-opening polymerization (ROP) of ε-CL under the catalysis of stannous octoate, leading to a PCL chain end-capped with heptavinyl substituted POSS (VPOSS-PCL). To endow the POSS head with adjustable polarity and functionality, three kinds of hydrophilic groups, including hydroxyl groups, carboxylic acids, and amine groups, were installed to the periphery of POSS molecule by a high-efficiency thiol-ene “click” reaction. The compounds were fully characterized by NMR, gel permeation chromatography (GPC), MALDI-TOF mass spectrometry, and TGA analysis. In addition, the preliminary self-assembly study of these giant surfactants was also investigated by TEM and dynamic laser light scattering (DLS), which indicated that they can form spherical nanoparticles with different diameters in aqueous solution. This work affords a straightforward and versatile way for synthesizing single-tailed giant surfactants with diverse head surface functionalities. Full article
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18 pages, 3753 KiB  
Article
Hydrolyzable Additive-Based Silicone Elastomers: A New Approach for Antifouling Coatings
by Laure Gevaux, Marlène Lejars, André Margaillan, Jean-François Briand, Robert Bunet and Christine Bressy
Polymers 2019, 11(2), 305; https://doi.org/10.3390/polym11020305 - 12 Feb 2019
Cited by 34 | Viewed by 6507
Abstract
Fouling Release Coatings are marine antifouling coatings based on silicone elastomers. Contrary to commonly used biocide-based antifouling coatings, they do not release biocides into the marine environment, however, they suffer from poor antifouling efficacy during idle periods. To improve their antifouling performances in [...] Read more.
Fouling Release Coatings are marine antifouling coatings based on silicone elastomers. Contrary to commonly used biocide-based antifouling coatings, they do not release biocides into the marine environment, however, they suffer from poor antifouling efficacy during idle periods. To improve their antifouling performances in static conditions, various amounts of hydrolyzable polymers were incorporated within a silicone matrix. These hydrolyzable polymers were chosen for the well-known hydrolytic degradation mechanism of their main chain, e.g. poly(ε-caprolactone) (PCL), or of their ester pending groups, e.g. poly(bis(trimethylsilyloxy)methylsilyl methacrylate) (PMATM2). The degradation kinetics of such hydrolyzable silicone coatings were assessed by mass loss measurements during immersion in deionized water. Coatings containing PMATM2 exhibited a maximum mass loss after 12 weeks, whereas PCL-based coatings showed no significant mass loss after 24 weeks. Dynamic contact angle measurements revealed the modifications of the coatings surface chemistry with an amphiphilic behavior after water exposure. The attachment of macrofoulers on these coatings were evaluated by field tests in the Mediterranean Sea, demonstrating the short or long-term antifouling effect of these hydrolyzable polymers embedded in the silicone matrix. The settlement of A. amphitrite barnacles on the different coatings indicated inhospitable behaviors towards larval barnacles for coatings with at least 15 wt % of additives. Full article
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15 pages, 4655 KiB  
Article
A Novel POSS-Based Copolymer Functionalized Graphene: An Effective Flame Retardant for Reducing the Flammability of Epoxy Resin
by Min Li, Hong Zhang, Wenqian Wu, Meng Li, Yiting Xu, Guorong Chen and Lizong Dai
Polymers 2019, 11(2), 241; https://doi.org/10.3390/polym11020241 - 1 Feb 2019
Cited by 24 | Viewed by 4335
Abstract
In this study, a novel copolymer, PbisDOPOMA-POSSMA-GMA (PDPG), containing methacryloisobutyl polyhedral oligomeric silsesquioxane (POSSMA), reactive glycidyl methacrylate (GMA), and bis-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide methacrylate (bisDOPOMA) and derivative functionalized graphene oxide (GO) were synthesized by a one-step grafting reaction to create a hybrid flame retardant (GO-MD-MP). GO-MD-MP [...] Read more.
In this study, a novel copolymer, PbisDOPOMA-POSSMA-GMA (PDPG), containing methacryloisobutyl polyhedral oligomeric silsesquioxane (POSSMA), reactive glycidyl methacrylate (GMA), and bis-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide methacrylate (bisDOPOMA) and derivative functionalized graphene oxide (GO) were synthesized by a one-step grafting reaction to create a hybrid flame retardant (GO-MD-MP). GO-MD-MP was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). Flame-retardant epoxy resin (EP) composites were prepared by adding various amounts of GO-MD-MP to the thermal-curing epoxy resin of diglycidyl ether of bisphenol A (DGEBA, trade name E-51). The thermal properties of the EP composites were remarkably enhanced by adding the GO-MD-MP, and the residue char of the epoxy resin also increased greatly. With the incorporation of 4 wt % GO-MD-MP, the limiting oxygen index (LOI) value was enhanced to 31.1% and the UL-94 V-0 rating was easily achieved. In addition, the mechanical strength of the epoxy resin was also improved. Full article
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15 pages, 2482 KiB  
Article
New Triphenylamine-Based Oligomeric Schiff Bases Containing Tetraphenylsilane Moieties in the Backbone
by Patricio A. Sobarzo, Alexis F. González, Eduardo Schott, Luis H. Tagle, Alain Tundidor-Camba, Carmen González-Henríquez, Ignacio A. Jessop and Claudio A. Terraza
Polymers 2019, 11(2), 216; https://doi.org/10.3390/polym11020216 - 27 Jan 2019
Cited by 17 | Viewed by 4517
Abstract
Three new triphenylamine-based oligomeric Schiff bases (polySB1, polySB2 and polySB3) containing tetraphenylsilane core (TPS-core) in the main chain were obtained from TPS-core-based diamines and bis(4-formylphenyl)phenylamine by a high-temperature polycondensation reaction. These new oligomers were structurally characterized by FT-IR, NMR and elemental analysis. All [...] Read more.
Three new triphenylamine-based oligomeric Schiff bases (polySB1, polySB2 and polySB3) containing tetraphenylsilane core (TPS-core) in the main chain were obtained from TPS-core-based diamines and bis(4-formylphenyl)phenylamine by a high-temperature polycondensation reaction. These new oligomers were structurally characterized by FT-IR, NMR and elemental analysis. All polySBs were highly soluble in common organic solvents, such as chloroform, tetrahydrofuran and chlorobenzene. Samples showed moderate molecular average molecular weight (Mw) and a high thermal stability above 410 °C. Likewise, polySBs showed absorption near 400 nm in the UV-vis range and photoluminescence. The HOMO levels and band-gap values were found in the ranges of −6.06 to −6.18 eV and 2.65–2.72 eV, respectively. The lowest band-gap value was observed for polySB2, which could be attributed to a more effective π-conjugation across the main chain. The results suggest that silicon-containing polySBs are promising wide-band-gap semiconductors materials for optoelectronic applications. Full article
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13 pages, 3143 KiB  
Article
Blends of Cyanate Ester and Phthalonitrile–Polyhedral Oligomeric Silsesquioxane Copolymers: Cure Behavior and Properties
by Xiaodan Li, Fei Zhou, Ting Zheng, Ziqiao Wang, Heng Zhou, Haoran Chen, Lin Xiao, Dongxing Zhang and Guanhui Wang
Polymers 2019, 11(1), 54; https://doi.org/10.3390/polym11010054 - 1 Jan 2019
Cited by 7 | Viewed by 4821
Abstract
Blends of cyanate ester and phthalonitrile–polyhedral oligomeric silsesquioxane copolymers were prepared, and their cure behavior and properties were compared via differential scanning calorimetry (DSC) analysis, thermogravimetric (TG) analysis, dynamic mechanical analysis, Fourier-transform far-infrared (FTIR) spectroscopy, and rheometric studies. The copolymer blends showed high [...] Read more.
Blends of cyanate ester and phthalonitrile–polyhedral oligomeric silsesquioxane copolymers were prepared, and their cure behavior and properties were compared via differential scanning calorimetry (DSC) analysis, thermogravimetric (TG) analysis, dynamic mechanical analysis, Fourier-transform far-infrared (FTIR) spectroscopy, and rheometric studies. The copolymer blends showed high chemical reactivity, low viscosity, and good thermal stability (TG temperatures were above 400 °C). The glass-transition temperature of the blends increased by at least 140 °C compared to cyanate ester resin. The blends are suitable for preparing carbon-fiber-reinforced composite materials via a winding process and a prepreg lay-up process with a molding technique. The FTIR data showed that the polymerization products contained triazine-ring structures that were responsible for the superior thermal properties. Full article
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2018

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15 pages, 1972 KiB  
Article
Developing a Polypropylene Fabric, Silica Fume, and Redispersible Emulsion Powder Cementitious Composite for Dynamic Water Environment
by Jinquan Liu, Xiaofei Li, Pooya Saffari, Qichao Liang, Ling Li and Weizhong Chen
Polymers 2019, 11(1), 47; https://doi.org/10.3390/polym11010047 - 30 Dec 2018
Cited by 12 | Viewed by 3463
Abstract
In the dynamic water environment, grouting requires a material with higher strength and anti-washout performance to prevent groundwater inrush. This study aims to develop a dynamic water slurry by mixing polypropylene fiber (PP fiber), silica fume (SF) and the polymer material of redispersible [...] Read more.
In the dynamic water environment, grouting requires a material with higher strength and anti-washout performance to prevent groundwater inrush. This study aims to develop a dynamic water slurry by mixing polypropylene fiber (PP fiber), silica fume (SF) and the polymer material of redispersible emulsion powder (REP) to the Portland cement. Towards this aim, a series of tests, including strength, gel time, bleeding rate, fluidity, and anti-washout, were conducted to evaluate the effects of SF, PP fiber, and REP on the slurry properties. The test results show that: (1) SF displays significant effects on strength, gel time, fluidity, and bleeding rate of cement slurry. Differently, PP fiber mainly affects the stress–strain behavior of the slurry and can improve the ductility significantly. (2) By mixing SF and fiber simultaneously, the slurry strength can increase by about 30%, and its strain can extend by more than 70%. Meanwhile, the composite slurry possesses great anti-washout properties at a low flow velocity (v ≤ 0.4 m/s), and the grouting retention rate (GRR) can reach up to 98.7%. However, the GRR decreases to a maximum value of 31.3% when v = 0.6 m/s. (3) By mixing the REP into the fiber-SF composite slurry, the GRR can further increase, reaching more than 60% even when v = 0.6 m/s. As a result, the developed fiber-SF cementitious composite slurry, which when mixed with REP, presents a favorable performance in the dynamic water environment. Full article
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16 pages, 4667 KiB  
Article
Self-Healable Supramolecular Vanadium Pentoxide Reinforced Polydimethylsiloxane-Graft-Polyurethane Composites
by Ali Sabri Berkem, Ahmet Capoglu, Turgut Nugay, Erol Sancaktar and Ilke Anac
Polymers 2019, 11(1), 41; https://doi.org/10.3390/polym11010041 - 29 Dec 2018
Cited by 6 | Viewed by 5345
Abstract
The self-healing ability can be imparted to the polymers by different mechanisms. In this study, self-healing polydimethylsiloxane-graft-polyurethane (PDMS-g-PUR)/Vanadium pentoxide (V2O5) nanofiber supramolecular polymer composites based on a reversible hydrogen bonding mechanism are prepared. V2O5 [...] Read more.
The self-healing ability can be imparted to the polymers by different mechanisms. In this study, self-healing polydimethylsiloxane-graft-polyurethane (PDMS-g-PUR)/Vanadium pentoxide (V2O5) nanofiber supramolecular polymer composites based on a reversible hydrogen bonding mechanism are prepared. V2O5 nanofibers are synthesized via colloidal route and characterized by XRD, SEM, EDX, and TEM techniques. In order to prepare PDMS-g-PUR, linear aliphatic PUR having one –COOH functional group (PUR-COOH) is synthesized and grafted onto aminopropyl functionalized PDMS by EDC/HCl coupling reaction. PUR-COOH and PDMS-g-PUR are characterized by 1H NMR, FTIR. PDMS-g-PUR/V2O5 nanofiber composites are prepared and characterized by DSC/TGA, FTIR, and tensile tests. The self-healing ability of PDMS-graft-PUR and composites are determined by mechanical tests and optical microscope. Tensile strength data obtained from mechanical tests show that healing efficiencies of PDMS-g-PUR increase with healing time and reach 85.4 ± 1.2 % after waiting 120 min at 50 °C. The addition of V2O5 nanofibers enhances the mechanical properties and healing efficiency of the PDMS-g-PUR. An increase of healing efficiency and max tensile strength from 85.4 ± 1.2% to 95.3 ± 0.4% and 113.08 ± 5.24 kPa to 1443.40 ± 8.96 kPa is observed after the addition of 10 wt % V2O5 nanofiber into the polymer. Full article
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20 pages, 4053 KiB  
Article
PCL/POSS Nanocomposites: Effect of POSS Derivative and Preparation Method on Morphology and Properties
by Mónica Cobos, Johnny R. Ramos, Dailyn J. Guzmán, M. Dolores Fernández and M. Jesús Fernández
Polymers 2019, 11(1), 33; https://doi.org/10.3390/polym11010033 - 26 Dec 2018
Cited by 22 | Viewed by 5345
Abstract
The incorporation of polyhedral oligomeric silsesquioxanes (POSS) molecules as nanoparticles into polymers can provide improved physico-chemical properties. The enhancement depends on the extent of dispersion of the nanofiller, which is determined by the compatibility with the polymer that is by the POSS type, [...] Read more.
The incorporation of polyhedral oligomeric silsesquioxanes (POSS) molecules as nanoparticles into polymers can provide improved physico-chemical properties. The enhancement depends on the extent of dispersion of the nanofiller, which is determined by the compatibility with the polymer that is by the POSS type, and the processing method. In this study, poly(ε-caprolactone)/POSS derivatives nanocomposites (PCL/POSS) were obtained via solution-casting and melt compounding. Two amino-derivatives containing different alkyl substituents, and ditelechelic POSS-containing hybrid PCL masterbatch were used as nanofillers. The effect of preparation method, POSS content and type on the morphology, thermal, mechanical, and surface properties of nanocomposites were studied. Morphological analysis evidenced the formation of POSS crystalline aggregates, self-assembled POSS molecules of submicrometer size dispersed in the polymer matrix. The best dispersion was achieved using the ditelechelic POSS-containing hybrid PCL masterbatch, and comparing the two amino-POSS derivatives, the one with longer alkyl chain of substituents exhibited better degree of dispersion independent of preparation method. DSC analysis showed the role of POSS derivatives as nucleating agents for PCL. The incorporation of POSS derivatives into the PCL matrix improved thermal stability. The preparation method, POSS type and content had influence on mechanical properties of nanocomposites. POSS nanoparticles enhanced the surface hydrophobicity of PCL. Full article
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17 pages, 5530 KiB  
Review
Functional Polyimide/Polyhedral Oligomeric Silsesquioxane Nanocomposites
by Mohamed Gamal Mohamed and Shiao Wei Kuo
Polymers 2019, 11(1), 26; https://doi.org/10.3390/polym11010026 - 25 Dec 2018
Cited by 140 | Viewed by 9685
Abstract
The preparation of hybrid nanocomposite materials derived from polyhedral oligomeric silsesquioxane (POSS) nanoparticles and polyimide (PI) has recently attracted much attention from both academia and industry, because such materials can display low water absorption, high thermal stability, good mechanical characteristics, low dielectric constant, [...] Read more.
The preparation of hybrid nanocomposite materials derived from polyhedral oligomeric silsesquioxane (POSS) nanoparticles and polyimide (PI) has recently attracted much attention from both academia and industry, because such materials can display low water absorption, high thermal stability, good mechanical characteristics, low dielectric constant, flame retardance, chemical resistance, thermo-redox stability, surface hydrophobicity, and excellent electrical properties. Herein, we discussed the various methods that have been used to insert POSS nanoparticles into PI matrices, through covalent chemical bonding and physical blending, as well as the influence of the POSS units on the physical properties of the PIs. Full article
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14 pages, 3210 KiB  
Article
Synthesis and Characterization of Konjac Glucomannan/Carrageenan/Nano-silica Films for the Preservation of Postharvest White Mushrooms
by Rongfei Zhang, Xiangyou Wang, Juan Wang and Meng Cheng
Polymers 2019, 11(1), 6; https://doi.org/10.3390/polym11010006 - 21 Dec 2018
Cited by 35 | Viewed by 5533
Abstract
In this study, the konjac glucomannan (KGM)/carrageenan (KC)/nano-silica film was prepared and characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The preservation quality of white mushrooms (Agaricus bisporus) packed using the films was also [...] Read more.
In this study, the konjac glucomannan (KGM)/carrageenan (KC)/nano-silica film was prepared and characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The preservation quality of white mushrooms (Agaricus bisporus) packed using the films was also determined. The nano-silica dosage was found to affect the properties of the nanocomposite KGM/KC films. The results indicated that the properties of the films were significantly improved with the addition of nano-silica. The water vapor permeability, water solubility, moisture absorption, and light transmittance of KGM/KC/nano-silica films were significantly affected by the nano-silica dosage. In this study, the optimal nano-silica dosage to incorporate into the film in order to achieve excellent performance was 0.3%. Strong intermolecular hydrogen bonds were also observed between KGM/KC and nano-silica in the KGM/KC/nano-silica film by FTIR. In addition, the KGM/KC/nano-silica film markedly reduced the browning index, delayed the weight loss and softening, and extended the shelf life of mushrooms during storage at 4 °C. The KGM/KC film modified using nano-silica can provide a potential method for improving the preservation quality of white mushrooms during storage. Full article
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22 pages, 6629 KiB  
Article
Enhanced Photovoltaic Performance in D-π-A Copolymers Containing Triisopropylsilylethynyl-Substituted Dithienobenzodithiophene by Modulating the Electron-Deficient Units
by Junfeng Tong, Lili An, Jie Lv, Pengzhi Guo, Xunchang Wang, Chunyan Yang and Yangjun Xia
Polymers 2019, 11(1), 12; https://doi.org/10.3390/polym11010012 - 21 Dec 2018
Cited by 22 | Viewed by 3739
Abstract
Three alternated D-π-A type 5,10-bis(triisopropylsilylethynyl)dithieno[2,3-d:2′,3′-d′]-benzo[1,2-b:4,5-b′]dithiophene (DTBDT-TIPS)-based semiconducting conjugated copolymers (CPs), PDTBDT-TIPS-DTBT-OD, PDTBDT-TIPS-DTFBT-OD, and PDTBDT-TIPS-DTNT-OD, bearing different A units, including benzothiadiazole (BT), 5,6-difluorinated-BT (FBT) and naphtho[1,2-c:5,6-c′]-bis[1,2,5]thiadiazole (NT), were designed and synthesized to [...] Read more.
Three alternated D-π-A type 5,10-bis(triisopropylsilylethynyl)dithieno[2,3-d:2′,3′-d′]-benzo[1,2-b:4,5-b′]dithiophene (DTBDT-TIPS)-based semiconducting conjugated copolymers (CPs), PDTBDT-TIPS-DTBT-OD, PDTBDT-TIPS-DTFBT-OD, and PDTBDT-TIPS-DTNT-OD, bearing different A units, including benzothiadiazole (BT), 5,6-difluorinated-BT (FBT) and naphtho[1,2-c:5,6-c′]-bis[1,2,5]thiadiazole (NT), were designed and synthesized to investigate the impact of the variation in electron-deficient units on the properties of these photovoltaic polymers. It was exhibited that the down-shifted highest occupied molecular orbital energy level (EHOMO), the enhanced aggregation in both the chlorobenzene solution and the solid film, as well as the better molecular planarity, were achieved using methods involving fluorination and the replacement of BT with NT on the polymer backbone. The absorption profile was little changed upon fluorination; however, it was greatly broadened during replacement of BT with NT. Consequently, the optimized photovoltaic device based on the PDTBDT-TIPS-DTNT-OD exhibited synchronous enhancements in the open-circuit voltage (VOC) of 0.88 V, the short-circuit current density (JSC) of 7.21 mA cm−2, and the fill factor (FF) of 52.99%, resulting in a drastic elevation in the PCE by 129% to 3.37% compared to that of the PDTBDT-TIPS-DTBT-OD. This was triggered by PDTBDT-TIPS-DTNT-OD’s broadened absorption, deepened EHOMO, improved coplanarity, and enhanced SCLC mobility (which increased 3.9 times), as well as a favorable morphology of the active layer. Unfortunately, the corresponding PCE deteriorated after incorporating fluorine into the BT, due to the oversized aggregation and large phase separation morphology in the blend films, severely impairing its JSC. Our preliminary results demonstrated that the replacement of BT with NT in a D-π-A type polymer backbone was an effective strategy of tuning the molecular structure to achieve highly efficient polymer solar cells (PSCs). Full article
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13 pages, 3684 KiB  
Article
Fabrication and Characterization of Isotropic and Anisotropic Magnetorheological Elastomers, Based on Silicone Rubber and Carbonyl Iron Microparticles
by Jesús G. Puente-Córdova, M. Edgar Reyes-Melo, Luis M. Palacios-Pineda, Imperio A. Martínez-Perales, Oscar Martínez-Romero and Alex Elías-Zúñiga
Polymers 2018, 10(12), 1343; https://doi.org/10.3390/polym10121343 - 5 Dec 2018
Cited by 53 | Viewed by 5443
Abstract
This article focuses on studying the rheological behavior of isotropic and anisotropic magnetorheological elastomers (MREs), made of carbonyl iron microparticles dispersed into a silicone–rubber matrix by considering 20 and 30 wt % of microparticles. Sample sets were prepared for each composition, with and [...] Read more.
This article focuses on studying the rheological behavior of isotropic and anisotropic magnetorheological elastomers (MREs), made of carbonyl iron microparticles dispersed into a silicone–rubber matrix by considering 20 and 30 wt % of microparticles. Sample sets were prepared for each composition, with and without the application of an external magnetic field. Experimental measurements of the material rheology behavior were carried out by a shear oscillatory rheometer at constant temperature, to determine both the shear storage modulus (G′) and shear loss modulus (G′′) for all characterized samples. Then, experimental data collected from the isotropic and the anisotropic material samples were used to plot the Cole-Cole diagrams to quantify the interfacial adhesion between carbonyl iron microparticles and the silicone-rubber matrix. Furthermore, the Fractional Zener Model (FZM) with two spring-pots in series is used for quantitative analysis of collected experimental data. Full article
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10 pages, 2427 KiB  
Article
Surface Hydrophobic Modification of Microcrystalline Cellulose by Poly(methylhydro)siloxane Using Response Surface Methodology
by Yulin Xie, Siquan Cai, Zhen Hou, Weihua Li, Yan Wang, Xinxiang Zhang and Wenbin Yang
Polymers 2018, 10(12), 1335; https://doi.org/10.3390/polym10121335 - 3 Dec 2018
Cited by 18 | Viewed by 4277
Abstract
Poly(methylhydro)siloxane (PMHS) and n-hexane were used as modifiers and solvents, respectively, to prepare surface modification of microcrystalline cellulose (MCC). The response surface methodology was used to optimize the effects of reaction conditions on hydrophobicity of MCC. The optimal reaction conditions were determined as [...] Read more.
Poly(methylhydro)siloxane (PMHS) and n-hexane were used as modifiers and solvents, respectively, to prepare surface modification of microcrystalline cellulose (MCC). The response surface methodology was used to optimize the effects of reaction conditions on hydrophobicity of MCC. The optimal reaction conditions were determined as follows: the concentration of PMHS was 0.0275% (the mass ratio of PMHS to MCC), the reaction time was 20 min, and the drying temperature was 70 °C. Under the optimum reaction conditions, the water contact angle of modified MCC was 141.5°. It is feasible to optimize and select the reaction conditions of modified MCC by Design-Expert, and the predicted value of the mathematical model is in good agreement with the experimental value. Surface chemical characteristics were investigated using X-ray photoelectron spectroscopy (XPS). These analyses confirmed that the PMHS chains were attached to MCC. Due to the introduction of a large amount of methyl groups, the reaction between MCC and PMHS leads to an improvement in its hydrophobicity. Full article
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10 pages, 2764 KiB  
Article
Fluoroalkyl POSS with Dual Functional Groups as a Molecular Filler for Lowering Refractive Indices and Improving Thermomechanical Properties of PMMA
by Kazunari Ueda, Kazuo Tanaka and Yoshiki Chujo
Polymers 2018, 10(12), 1332; https://doi.org/10.3390/polym10121332 - 2 Dec 2018
Cited by 13 | Viewed by 4474
Abstract
The dual-functionalized polyhedral oligomeric silsesquioxane (POSS) derivatives, which have the seven fluorinated alkanes and the single acrylate ester on the silica cube, were designed as a filler for lowering the refractive index (RI) and improving thermomechanical properties in poly(methyl methacrylate) (PMMA). The desired [...] Read more.
The dual-functionalized polyhedral oligomeric silsesquioxane (POSS) derivatives, which have the seven fluorinated alkanes and the single acrylate ester on the silica cube, were designed as a filler for lowering the refractive index (RI) and improving thermomechanical properties in poly(methyl methacrylate) (PMMA). The desired dual-functionalized POSS fillers were prepared, and because of its high miscibility, homogeneous films were readily obtained, by the casting method, with the mixture solutions containing the modified POSS and the polymers. From optical measurements, it was found that the larger effects of lowering the RIs of the PMMA matrices were observed from the modified POSS than those of the octa-substituted POSS derivatives with the homogeneous substituents. It should be mentioned that the degradation temperatures and the storage moduli were able to be greatly elevated by loading the present POSS fillers. Finally, it was demonstrated that the methacrylate ester-tethered POSS should be the most effective filler for modulating PMMA (Δn = −0.020, ΔTd20 = +53 °C, ΔE’/E’ = +72%). Full article
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13 pages, 3103 KiB  
Article
Reduced Graphene Oxide Embedded with MQ Silicone Resin Nano-Aggregates for Silicone Rubber Composites with Enhanced Thermal Conductivity and Mechanical Performance
by Weijie Liang, Xin Ge, Jianfang Ge, Tiehu Li, Tingkai Zhao, Xunjun Chen, Yaozhen Song, Yingde Cui, Muhammad Khan, Jianye Ji, Xiaoyan Pang and Ruoling Liu
Polymers 2018, 10(11), 1254; https://doi.org/10.3390/polym10111254 - 12 Nov 2018
Cited by 40 | Viewed by 6197
Abstract
With developments of the electronics industry, more components are being included in electronic devices, which has led to challenges in thermal management. Using reduced graphene oxide embedded with MQ silicone resin (RGO/MQ) nano-aggregates as the composite filler and silicone rubber (SR) as the [...] Read more.
With developments of the electronics industry, more components are being included in electronic devices, which has led to challenges in thermal management. Using reduced graphene oxide embedded with MQ silicone resin (RGO/MQ) nano-aggregates as the composite filler and silicone rubber (SR) as the matrix, a simple approach is designed to prepare RGO/MQ/SR composites. Reduced graphene oxide (RGO) was first used as a substrate for the growth of MQ silicone resin by hybridization, forming sandwich-like micro structured RGO/MQ nano-aggregates successfully. Then, RGO/MQ was integrated into α,ω-dihydroxylpolydimethylsiloxane based on the in situ solvent-free blending method, followed by condensation and vulcanization, fabricating the final RGO/MQ/SR composites. The effective strategy could enhance the adaptability between graphene and silicone matrix under external stimuli at room temperature by embedding nanoscale MQ into the interface of graphene/silicone as the buffer layer. Obvious improvements were found in both thermal conductivity and mechanical properties due to excellent dispersion and interfacial compatibility of RGO/MQ in the host materials. These attractive results suggest that this RGO/MQ/SR composite has potential as a thermal interface material for heat dissipation applications. Full article
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10 pages, 2199 KiB  
Article
Actuation Behavior of Multilayer Graphene Nanosheets/Polydimethylsiloxane Composite Films
by Chunmei Zhang, Tianliang Zhai, Chao Zhan, Qiuping Fu and Chao Ma
Polymers 2018, 10(11), 1243; https://doi.org/10.3390/polym10111243 - 9 Nov 2018
Cited by 12 | Viewed by 5004
Abstract
The graphene nanosheets (GNS)/polydimethylsiloxane (PDMS) composite films with out-of-plane dielectric actuation behavior were prepared through a layer-by-layer spin coating process. The GNS-PDMS/PDMS composite films with 1~3 layers of GNS-PDMS films were spin coated on top of the PDMS film. The dielectric, mechanical, and [...] Read more.
The graphene nanosheets (GNS)/polydimethylsiloxane (PDMS) composite films with out-of-plane dielectric actuation behavior were prepared through a layer-by-layer spin coating process. The GNS-PDMS/PDMS composite films with 1~3 layers of GNS-PDMS films were spin coated on top of the PDMS film. The dielectric, mechanical, and electromechanical actuation properties of the composite films were investigated. The dielectric constant of the GNS-PDMS3/PDMS composite film at 1 kHz is 5.52, which is 1.7 times that of the GNS-PDMS1/PDMS composite film. The actuated displacement of the GNS-PDMS/PDMS composite films is greatly enhanced by increasing the number of GNS-PDMS layers. This study provides a novel alternative approach for fabricating high-performance actuators with out-of-plane actuation behavior. Full article
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10 pages, 3820 KiB  
Article
Facile Route for Bio-Phenol Siloxane Synthesis via Heterogeneous Catalytic Method and its Autonomic Antibacterial Property
by Xiaoyan Pang, Xin Ge, Jianye Ji, Weijie Liang, Xunjun Chen and Jianfang Ge
Polymers 2018, 10(10), 1151; https://doi.org/10.3390/polym10101151 - 16 Oct 2018
Cited by 7 | Viewed by 3548
Abstract
Eugenol, used as bio-phenol, was designed to replace the hydrogen atom of hydrogenterminated siloxane by hydrosilylation reaction under the presence of alumina-supported platinum catalyst (Pt-Al2O3), silica-supported platinum catalyst (Pt-SiO2) and carbon nanotube-supported platinum catalyst (Pt-CNT), respectively. The [...] Read more.
Eugenol, used as bio-phenol, was designed to replace the hydrogen atom of hydrogenterminated siloxane by hydrosilylation reaction under the presence of alumina-supported platinum catalyst (Pt-Al2O3), silica-supported platinum catalyst (Pt-SiO2) and carbon nanotube-supported platinum catalyst (Pt-CNT), respectively. The catalytic activities of these three platinum catalysts were measured by nuclear magnetic resonance hydrogen spectrometer (1H NMR). The properties of bio-phenol siloxane were characterized by Fourier transform infrared spectrometer (FT–IR), UV-visible spectrophotometer (UV) and thermogravimeter (TGA), and its antibacterial property against Escherichia coli was also studied. The results showed that the catalytic activity of the catalyst Pt-CNT was preferable. When the catalyst concentration was 100 ppm, the reaction temperature was 80 °C and reaction time was 6 h, the reactant conversion rate reached 97%. After modification with bio-phenol, the thermal stability of the obtained bio-phenol siloxane was improved. For bio-phenol siloxane, when the ratio of weight loss reached 98%, the pyrolysis temperature was raised to 663 °C which was 60 °C higher than hydrogenterminated siloxane. Meanwhile, its autonomic antibacterial property against Escherichia coli was improved significantly. Full article
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16 pages, 5511 KiB  
Article
Thermal Stability and Flame Retardancy of Polypropylene Composites Containing Siloxane-Silsesquioxane Resins
by Arkadiusz Niemczyk, Katarzyna Dziubek, Beata Sacher-Majewska, Krystyna Czaja, Justyna Czech-Polak, Rafał Oliwa, Joanna Lenża and Mariusz Szołyga
Polymers 2018, 10(9), 1019; https://doi.org/10.3390/polym10091019 - 13 Sep 2018
Cited by 32 | Viewed by 6073
Abstract
A novel group of silsesquioxane derivatives, which are siloxane-silsesquioxane resins (S4SQ), was for the first time examined as possible flame retardants in polypropylene (PP) materials. Thermal stability of the PP/S4SQ composites compared to the S4SQ resins and neat PP was estimated using thermogravimetric [...] Read more.
A novel group of silsesquioxane derivatives, which are siloxane-silsesquioxane resins (S4SQ), was for the first time examined as possible flame retardants in polypropylene (PP) materials. Thermal stability of the PP/S4SQ composites compared to the S4SQ resins and neat PP was estimated using thermogravimetric (TG) analysis under nitrogen and in air atmosphere. The effects of the non-functionalized and n-alkyl-functionalized siloxane-silsesquioxane resins on thermostability and flame retardancy of PP materials were also evaluated by thermogravimetry-Fourier transform infrared spectrometry (TG-FTIR) and by cone calorimeter tests. The results revealed that the functionalized S4SQ resins may form a continuous ceramic layer on the material surface during its combustion, which improves both thermal stability and flame retardancy of the PP materials. This beneficial effect was observed especially when small amounts of the S4SQ fillers were applied. The performed analyses allowed us to propose a possible mechanism for the degradation of the siloxane-silsesquioxane resins, as well as to explain their possible role during the combustion of the PP/S4SQ composites. Full article
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10 pages, 2573 KiB  
Article
Cellulose Nanofiber/Carbon Nanotube Conductive Nano-Network as a Reinforcement Template for Polydimethylsiloxane Nanocomposite
by Chuchu Chen, Xiangting Bu, Qian Feng and Dagang Li
Polymers 2018, 10(9), 1000; https://doi.org/10.3390/polym10091000 - 7 Sep 2018
Cited by 49 | Viewed by 7320
Abstract
Both cellulose nanofiber (CNF) and carbon nanotube (CNT) are nanoscale fibers that have shown reinforcing effects in polymer composites. It’s worth noting that CNF and CNT could form a three-dimensional nano-network via mixing and vacuum filtration, which exhibit excellent mechanical strength and electrical [...] Read more.
Both cellulose nanofiber (CNF) and carbon nanotube (CNT) are nanoscale fibers that have shown reinforcing effects in polymer composites. It’s worth noting that CNF and CNT could form a three-dimensional nano-network via mixing and vacuum filtration, which exhibit excellent mechanical strength and electrical conductivity. In this study, the developed CNF/CNT film was applied as a nano-network template and immersed into polydimethylsiloxane (PDMS) solutions. By controlling the immersed polydimethylsiloxane pre-polymer concentration, the PDMS/CNF/CNT nanocomposite with various PDMS contents were fabricated after a curing process. Morphological images showed that the CNF/CNT nano-network was well-preserved inside the PDMS, which resulted in significantly improved mechanical strength. While increasing the PDMS content (~71.3 wt %) gave rise to decreased tensile strength, the PDMS-30/CNF/CNT showed a fracture strain of 7.5%, which was around seven fold higher than the rigid CNF/CNT and still kept a desirable strength—Young’s modulus and conductivity of 18.3 MPa, 805 MPa, and 0.8 S/cm, respectively. Therefore, with the enhanced mechanical properties and the electrical conductivity, the prepared PDMS/CNF/CNT composite films may offer promising and broad prospects in the field of flexible devices. Full article
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14 pages, 4877 KiB  
Article
A Novel Synthetic UV-Curable Fluorinated Siloxane Resin for Low Surface Energy Coating
by Chunfang Zhu, Haitao Yang, Hongbo Liang, Zhengyue Wang, Jun Dong, Lei Xiong, Jianping Zhou, Junjun Ke, Xi Xu and Weixian Xi
Polymers 2018, 10(9), 979; https://doi.org/10.3390/polym10090979 - 3 Sep 2018
Cited by 16 | Viewed by 7392
Abstract
Low surface energy materials have attracted much attention due to their properties and various applications. In this work, we synthesized and characterized a series of ultraviolet (UV)-curable fluorinated siloxane polymers with various fluorinated acrylates—hexafluorobutyl acrylate, dodecafluoroheptyl acrylate, and trifluorooctyl methacrylate—grafted onto a hydrogen-containing [...] Read more.
Low surface energy materials have attracted much attention due to their properties and various applications. In this work, we synthesized and characterized a series of ultraviolet (UV)-curable fluorinated siloxane polymers with various fluorinated acrylates—hexafluorobutyl acrylate, dodecafluoroheptyl acrylate, and trifluorooctyl methacrylate—grafted onto a hydrogen-containing poly(dimethylsiloxane) backbone. The structures of the fluorinated siloxane polymers were measured and confirmed by proton nuclear magnetic resonance and Fourier transform infrared spectroscopy. Then the polymers were used as surface modifiers of UV-curable commercial polyurethane (DR-U356) at different concentrations (1, 2, 3, 4, 5, and 10 wt %). Among three formulations of these fluorinated siloxane polymers modified with DR-U356, hydrophobic states (91°, 92°, and 98°) were obtained at low concentrations (1 wt %). The DR-U356 resin is only in the hydrophilic state at 59.41°. The fluorine and siloxane element contents were investigated by X-ray photoelectron spectroscopy and the results indicated that the fluorinated and siloxane elements were liable to migrate to the surface of resins. The results of the friction recovering assays showed that the recorded contact angles of the series of fluorinated siloxane resins were higher than the original values after the friction-annealing progressing. Full article
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13 pages, 3920 KiB  
Article
New Polyhedral Oligomeric Silsesquioxanes-Based Fluorescent Ionic Liquids: Synthesis, Self-Assembly and Application in Sensors for Detecting Nitroaromatic Explosives
by Wensi Li, Dengxu Wang, Dongdong Han, Ruixue Sun, Jie Zhang and Shengyu Feng
Polymers 2018, 10(8), 917; https://doi.org/10.3390/polym10080917 - 15 Aug 2018
Cited by 10 | Viewed by 4670
Abstract
In this paper, two different models of hybrid ionic liquids (ILs) based on polyhedral oligomeric silsesquioxanes (POSSs) have been prepared. Additionally, these ILs based on POSSs (ILs-POSSs) exhibited excellent thermal stabilities and low glass transition temperatures. 1H, 13C, and 29Si [...] Read more.
In this paper, two different models of hybrid ionic liquids (ILs) based on polyhedral oligomeric silsesquioxanes (POSSs) have been prepared. Additionally, these ILs based on POSSs (ILs-POSSs) exhibited excellent thermal stabilities and low glass transition temperatures. 1H, 13C, and 29Si nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) were used to confirm the structures of the IL-POSSs. Furthermore, the spherical vesicle structures of two IL-POSSs were observed and were caused by self-assembly behaviors. In addition, we found it very meaningful that these two ILs showed lower detection limits of 2.57 × 10−6 and 3.98 × 10−6 mol/L for detecting picric acid (PA). Moreover, the experimental data revealed that the products have high sensitivity for detecting a series of nitroaromatic compounds—including 4-nitrophenol, 2,4-dinitrophenol, and PA—and relatively comprehensive explosive detection in all of the tests of IL-POSSs with nitroaromatic compounds thus far. Additionally, the data indicate that these two new ILs have great potential for the detection of explosives. Therefore, our work may provide new materials including ILs as fluorescent sensors in detecting nitroaromatic explosives. Full article
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10 pages, 1937 KiB  
Article
The Rediscovery of POSS: A Molecule Rather than a Filler
by Ignazio Blanco
Polymers 2018, 10(8), 904; https://doi.org/10.3390/polym10080904 - 11 Aug 2018
Cited by 82 | Viewed by 6417
Abstract
The use of polyhedral oligomeric silsesquioxanes (POSSs) for making polymer composites has grown exponentially since the last few years of the 20th century. In comparison with the other most commonly used fillers, POSSs possess the advantage of being molecules. Thus, this allows us [...] Read more.
The use of polyhedral oligomeric silsesquioxanes (POSSs) for making polymer composites has grown exponentially since the last few years of the 20th century. In comparison with the other most commonly used fillers, POSSs possess the advantage of being molecules. Thus, this allows us to combine their nano-sized cage structures, which have dimensions that are similar to those of most polymer segments and produce a particular and exclusive chemical composition. These characteristics linked with their hybrid (inorganic–organic) nature allow researchers to modify POSS according to particular needs or original ideas, before incorporating them into polymers. In this present study, we first start with a brief introduction about the reasons for the rediscovery of these nanoparticles over the last 25 years. Starting from the form of POSS that is most widely used in literature (octaisobutyl POSS), this present study aims to evaluate how the reduction of symmetry through the introduction of organic groups favors their dispersion in polystyrene matrix without compromising their solubility. Full article
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14 pages, 3286 KiB  
Article
Preparation and Characterization of Highly Ordered Mercapto-Modified Bridged Silsesquioxane for Removing Ammonia-Nitrogen from Water
by Derong Lin, Yichen Huang, Yuanmeng Yang, Xiaomei Long, Wen Qin, Hong Chen, Qing Zhang, Zhijun Wu, Suqing Li, Dingtao Wu, Lijiang Hu and Xingwen Zhang
Polymers 2018, 10(8), 819; https://doi.org/10.3390/polym10080819 - 25 Jul 2018
Cited by 3 | Viewed by 3554
Abstract
In acidic conditions, mesoporous molecular sieves SBA-15 and SBA-15-SH were synthesized. Structural characterization was carried out by powder X-ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), 13C CP MAS-NMR, 29Si CP MAS-NMR and [...] Read more.
In acidic conditions, mesoporous molecular sieves SBA-15 and SBA-15-SH were synthesized. Structural characterization was carried out by powder X-ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), 13C CP MAS-NMR, 29Si CP MAS-NMR and nitrogen adsorption–desorption (BET). The results showed that in SBA-15-SH, the direct synthesis method made the absorption peak intensity weaker than that of SBA-15, while the post-grafted peak intensity did not change. Their spectra were different due to the C-H stretching bands of Si-O-Si and propyl groups. But their structure was still evenly distributed and was still hexangular mesoporous structure. Their pore size increased, and the H-SBA-15-SH had larger pore size. The adsorption of ammonia-nitrogen by molecular sieve was affected by the relative pressure and the concentration of ammonia-nitrogen, in which the adsorption capacity of G-SBA-15-SH was the largest and the adsorption capacity of SBA-15 was the smallest. Full article
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11 pages, 2374 KiB  
Review
Polysiloxanes in Theranostics and Drug Delivery: A Review
by Ignazio Blanco
Polymers 2018, 10(7), 755; https://doi.org/10.3390/polym10070755 - 9 Jul 2018
Cited by 49 | Viewed by 6287
Abstract
One of the historical problems of medicine is that often, diagnosis and therapy do not interface, at best. Moreover, especially in some areas, such as oncology, the stress for the organism during the two phases (diagnosis and therapy) can become excessive, and be [...] Read more.
One of the historical problems of medicine is that often, diagnosis and therapy do not interface, at best. Moreover, especially in some areas, such as oncology, the stress for the organism during the two phases (diagnosis and therapy) can become excessive, and be fatal to the success of the treatment. The extraordinary progress of nanotechnology in the last 25 years has offered the opportunity to build a nanoplatform able to ferry drugs, and loads onto them both imaging and therapeutic functions, thus creating nanosystems capable of diagnosis, drug delivery, and monitoring of therapeutic response. The purpose of this unusual, and up to recent times, unimaginable, marriage between diagnosis and therapeutics is the reaching of protocols more specific to individuals. The dual use of particles/device lead to a personalized medicine. Due to their biocompatibility, versatility, physical and chemical resistance, and ability to be functionalized, silica nanoparticles and polysiloxanes are the heart and the shield of this nanoplatform, respectively. In this short review, I analyze the applications of these silicon-based materials in the field of controlled drug delivery. Full article
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12 pages, 2476 KiB  
Article
Sol-Gel Synthesis, Spectroscopic and Thermal Behavior Study of SiO2/PEG Composites Containing Different Amount of Chlorogenic Acid
by Michelina Catauro, Elisabetta Tranquillo, Roberta Risoluti and Stefano Vecchio Ciprioti
Polymers 2018, 10(6), 682; https://doi.org/10.3390/polym10060682 - 19 Jun 2018
Cited by 54 | Viewed by 5631
Abstract
In this work, new phenol-based materials have been synthesized by the sol-gel method, in which different amounts of the phenolic antioxidant chlorogenic acid (CGA) (from 5 wt % to 20 wt %) were embedded in two different silica matrices: pure silica and silica-based [...] Read more.
In this work, new phenol-based materials have been synthesized by the sol-gel method, in which different amounts of the phenolic antioxidant chlorogenic acid (CGA) (from 5 wt % to 20 wt %) were embedded in two different silica matrices: pure silica and silica-based hybrids materials, containing 50 wt % of polyethylene glycol (PEG). The incorporation of CGA in different sol-gel matrices might protect them from degradation, which could cause the loss of their properties. The two series of materials were chemically characterized by Fourier transform infrared (FTIR) spectroscopy. In addition, the thermal behavior of both series of materials containing CGA was studied by thermogravimetry under both air and inert N2 flowing gas atmosphere. The bioactivity was evaluated by soaking the synthesized hybrids in a simulated body fluid, showing that the bioactivity of the silica matrix is not modified by the presence of PEG and CGA. Full article
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13 pages, 2045 KiB  
Article
Structural and Thermoanalytical Characterization of 3D Porous PDMS Foam Materials: The Effect of Impurities Derived from a Sugar Templating Process
by José González-Rivera, Rossella Iglio, Giuseppe Barillaro, Celia Duce and Maria Rosaria Tinè
Polymers 2018, 10(6), 616; https://doi.org/10.3390/polym10060616 - 5 Jun 2018
Cited by 79 | Viewed by 12793
Abstract
Polydimethylsiloxane (PDMS) polymers are extensively used in a wide range of research and industrial fields, due to their highly versatile chemical, physical, and biological properties. Besides the different two-dimensional PDMS formulations available, three-dimensional PDMS foams have attracted increased attention. However, as-prepared PDMS foams [...] Read more.
Polydimethylsiloxane (PDMS) polymers are extensively used in a wide range of research and industrial fields, due to their highly versatile chemical, physical, and biological properties. Besides the different two-dimensional PDMS formulations available, three-dimensional PDMS foams have attracted increased attention. However, as-prepared PDMS foams contain residual unreacted low molecular weight species that need to be removed in order to obtain a standard and chemically stable material for use as a scaffold for different decorating agents. We propose a cleaning procedure for PDMS foams obtained using a sugar templating process, based on the use of two different solvents (hexane and ethanol) as cleaning agents. Thermogravimetry coupled with Fourier Transform Infrared Spectroscopy (TG-FTIR) for the analysis of the evolved gasses was used to characterize the thermal stability and decomposition pathway of the PDMS foams, before and after the cleaning procedure. The results were compared with those obtained on non-porous PDMS bulk as a reference. Micro-CT microtomography and scanning electron microscopy (SEM) analyses were employed to study the morphology of the PDMS foam. The thermogravimetric analysis (TGA) revealed a different thermal behaviour and crosslinking pathway between bulk PDMS and porous PDMS foam, which was also influenced by the washing process. This information was not apparent from spectroscopic or morphological studies and it would be very useful for planning the use of such complex and very reactive systems. Full article
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14 pages, 11213 KiB  
Article
Hyperbranched Polysiloxanes Based on Polyhedral Oligomeric Silsesquioxane Cages with Ultra-High Molecular Weight and Structural Tuneability
by Ning Liu, Jianyi Yu, Yaoyong Meng and Yuzhou Liu
Polymers 2018, 10(5), 496; https://doi.org/10.3390/polym10050496 - 4 May 2018
Cited by 9 | Viewed by 5366
Abstract
Hyperbranched siloxane-based polymers with ultra-high molecular weight were synthesized by the Piers–Rubinsztajn reaction between octakis(dimethylsiloxy) octasilsesquioxane with different dialkoxysilanes, using tris(pentafluorophenyl) borane as the catalyst. The origin of the high molecular weight is explained by the high reactivity of the catalyst and strain [...] Read more.
Hyperbranched siloxane-based polymers with ultra-high molecular weight were synthesized by the Piers–Rubinsztajn reaction between octakis(dimethylsiloxy) octasilsesquioxane with different dialkoxysilanes, using tris(pentafluorophenyl) borane as the catalyst. The origin of the high molecular weight is explained by the high reactivity of the catalyst and strain energy of isolated small molecule in which all eight silane groups close into rings on the sides of a single cubic cage. The structural tuneability was further demonstrated by use of methyl(3-chloropropyl)diethoxysilane, which generates a polymer with similar ultra-high molecular weight. Introduction of phosphonate groups through the chloropropyl sites later leads to functionalized polymers which can encapsulate various transition metal nanoparticles. Full article
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18 pages, 2308 KiB  
Article
Synthesis, Characterization and Microstructure of New Liquid Poly(methylhydrosiloxanes) Containing Branching Units SiO4/2
by Jerzy J. Chruściel, Marzena Fejdyś and Witold Fortuniak
Polymers 2018, 10(5), 484; https://doi.org/10.3390/polym10050484 - 28 Apr 2018
Cited by 15 | Viewed by 6828
Abstract
Six liquid branched poly(methylhydrosiloxanes) of new random structures (PMHS-Q), containing quadruple branching units SiO4/2 (Q), both MeHSiO (DH) and Me2SiO (D) chain building units (or only mers MeHSiO), and terminal groups Me3SiO0.5 (M) were prepared [...] Read more.
Six liquid branched poly(methylhydrosiloxanes) of new random structures (PMHS-Q), containing quadruple branching units SiO4/2 (Q), both MeHSiO (DH) and Me2SiO (D) chain building units (or only mers MeHSiO), and terminal groups Me3SiO0.5 (M) were prepared by a hydrolytic polycondensation method of appropriate organic chlorosilanes and tetraethyl ortosilicate (TEOS), in diethyl ether medium at temperature below 0 °C. Volatile low molecular weight siloxanes were removed by a vacuum distillation at 150–155 °C. Yields of PMHS-Q reached from 55–69 wt%. Their dynamic viscosities were measured in the Brookfield HBDV+IIcP cone-plate viscometer and ranged from 10.7–13.1 cP. Molecular weights (MW) of PMHS-Q (Mn = 2440–6310 g/mol, Mw = 5750–10,350 g/mol) and polydispersities of MW (Mw/Mn = 2.0–2.8) were determined by a size exclusion chromatography (SEC). All polymers were characterized by FTIR, 1H- and 29Si-NMR, and an elemental analysis. A microstructure of siloxane chains was proposed on a basis of 29Si-NMR results and compared with literature data. Full article
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12 pages, 2107 KiB  
Article
High-Performance and Simply-Synthesized Ladder-Like Structured Methacrylate Siloxane Hybrid Material for Flexible Hard Coating
by Yun Hyeok Kim, Gwang-Mun Choi, Jin Gyu Bae, Yong Ho Kim and Byeong-Soo Bae
Polymers 2018, 10(4), 449; https://doi.org/10.3390/polym10040449 - 17 Apr 2018
Cited by 36 | Viewed by 10549
Abstract
A high performance ladder-like structured methacrylate siloxane hybrid material (LMSH) was fabricated via simple hydrolytic sol–gel reaction, followed by free-radical polymerization. A structurally ordered siloxane backbone, the ladder-like structure, which is an essential factor for high performance, could be achieved by a short [...] Read more.
A high performance ladder-like structured methacrylate siloxane hybrid material (LMSH) was fabricated via simple hydrolytic sol–gel reaction, followed by free-radical polymerization. A structurally ordered siloxane backbone, the ladder-like structure, which is an essential factor for high performance, could be achieved by a short period of sol–gel reaction in only 4 h. This results in superior optical (Transmittance > 90% at 550 nm), thermal (T5 wt % decomposition > 400 ℃ ), mechanical properties(elastic recovery = 0.86, hardness = 0.6 GPa) compared to the random- and even commercialized cage-structured silsesquioxane, which also has ordered structure. It was investigated that the fabricated ladder-like structured MSH showed the highest overall density of organic/inorganic co-networks that are originated from highly ordered siloxane network, along with high conversion rate of polymerizable methacrylate groups. Our findings suggest a potential of the ladder-like structured MSH as a powerful alternative for the methacrylate polysilsesquioxane, which can be applied to thermally stable and flexible optical coatings, even with an easier and simpler preparation process. Full article
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12 pages, 5824 KiB  
Article
Non-Leachable Hydrophilic Additives for Amphiphilic Coatings
by Guillaume Gillet, Fabrice Azemar, Fabienne Faÿ, Karine Réhel and Isabelle Linossier
Polymers 2018, 10(4), 445; https://doi.org/10.3390/polym10040445 - 16 Apr 2018
Cited by 6 | Viewed by 6020
Abstract
Amphiphilic surfaces are particularly effective at inhibiting the adhesion of microorganisms (bacteria, cells, microalgae, etc.) in liquid media. The aim of this study is to determine the best hydrophilic linker to promote bonding between poly(ethylene glycol) (PEG) as a hydrophilic additive and poly(dimethyl [...] Read more.
Amphiphilic surfaces are particularly effective at inhibiting the adhesion of microorganisms (bacteria, cells, microalgae, etc.) in liquid media. The aim of this study is to determine the best hydrophilic linker to promote bonding between poly(ethylene glycol) (PEG) as a hydrophilic additive and poly(dimethyl siloxane) (PDMS) as the hydrophobic matrix. Various parameters have been studied (molecular weight, linker type, and polymer end-group), as well as the efficiency of the linking, the capacity of PEG to access to the surface of the film, and overall film homogeneity. According to the results, a PDMS linker paired with a PEG moiety allows for compatibilization of the compounds during cross-linking. This compatibilization seems to provide a good bonding with the matrix and a good surface access to the hydrophilic moiety. Therefore, this structure comprising a linking function attached to the PDMS–PEG copolymer has high potential as a non-releasable additive for amphiphilic coating applications. Full article
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20 pages, 52323 KiB  
Article
Effect of Polysiloxanes on Roughness and Durability of Basalt Fibres–Reinforced Cement Mortar
by Danuta Barnat-Hunek, Grzegorz Łagód, Stanisław Fic and Monika Jarosz-Hadam
Polymers 2018, 10(4), 420; https://doi.org/10.3390/polym10040420 - 9 Apr 2018
Cited by 25 | Viewed by 4464
Abstract
The influence of roughness and the way it affects the adhesion properties and surface free energy (SFE) of polysiloxanes hydrophobised basalt fibres–reinforced cement mortars were determined in this article. The physical properties of mortars were investigated in the experimental part, which also explored [...] Read more.
The influence of roughness and the way it affects the adhesion properties and surface free energy (SFE) of polysiloxanes hydrophobised basalt fibres–reinforced cement mortars were determined in this article. The physical properties of mortars were investigated in the experimental part, which also explored the impact of hydrophobisation and basalt fibres (BF) addition on SFE, frost resistance, contact angle (CA), and roughness. A device capable of calculating all parameters was used to indicate the surface roughness and 3D topography. Prior to and after conducting surface and weight hydrophobisation, the contact angle of mortars was specified. Subsequently, it was used for carrying out SFE calculation by means of Neumann’s method, enabling us to characterize the adhesion properties and wettability of mortars. The research indicated that the surface roughness was substantially decreased, in turn raising the frost resistance. The corrosion resistance drops when the surface roughness, water absorption, and number of fibres in the mortar increase. The SEM images presenting the structure of polysiloxane coating and mortars were provided. Full article
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12 pages, 24838 KiB  
Article
Improving the Mechanical and Electrical Properties of Ceramizable Silicone Rubber/Halloysite Composites and Their Ceramic Residues by Incorporation of Different Borates
by Jianhua Guo, Xuming Chen and Yong Zhang
Polymers 2018, 10(4), 388; https://doi.org/10.3390/polym10040388 - 1 Apr 2018
Cited by 32 | Viewed by 5692
Abstract
Ceramizable silicone rubber (MVQ)/halloysite (HNT) composites were fabricated by incorporation of three different borates, including sodium tetraborate decahydrate, ammonium pentaborate, and zinc borate into MVQ matrix, respectively. The composites without any borates were also prepared as control. The effect of the borates on [...] Read more.
Ceramizable silicone rubber (MVQ)/halloysite (HNT) composites were fabricated by incorporation of three different borates, including sodium tetraborate decahydrate, ammonium pentaborate, and zinc borate into MVQ matrix, respectively. The composites without any borates were also prepared as control. The effect of the borates on the mechanical and electrical properties of MVQ/HNT composites was investigated. The ceramic residues were obtained from the decomposition of the composites after sintering at 1000 °C. The effect of the borates on the linear shrinkage, weight loss, and flexural and impact strength of the residues was also studied. The fracture surfaces of the composites and their corresponding residues were observed by SEM. The proposed ceramizable mechanism of the composites by incorporation of different borates was revealed by XRD analysis. Full article
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12 pages, 9472 KiB  
Article
A Study on Mechanical Characteristics of Phosphor Film Containing Methyl Silicone Resin Based on Crosslinking Reaction Analysis
by Jeong Yeon Park, Young Bae Ko, Moonwoo La and Gil Sang Yoon
Polymers 2018, 10(4), 370; https://doi.org/10.3390/polym10040370 - 26 Mar 2018
Viewed by 3886
Abstract
This study reveals a methodological research for predicting mechanical properties of phosphor films through the chemical crosslinking reaction of methyl silicone resin during fabrication of the phosphor films. Crosslinking point according to the type of methyl silicone resins was verified through the magnitude [...] Read more.
This study reveals a methodological research for predicting mechanical properties of phosphor films through the chemical crosslinking reaction of methyl silicone resin during fabrication of the phosphor films. Crosslinking point according to the type of methyl silicone resins was verified through the magnitude of the absorption peak of the functional group and the curing reaction heat. Then, we measured mechanical properties of the fabricated phosphor films. As a result, it was figured out that the number of the crosslinking point was directly proportional to the total curing reaction heat, and also affected the mechanical properties of the phosphor films. Based on the correlation of curing reaction heat and crosslinking point of the methyl silicone resins and mechanical properties of the fabricated phosphor films, we proposed a methodology that can understand and control the phosphor films in advance of finishing the fabrication of the final phosphor products. Full article
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11 pages, 13667 KiB  
Article
POSS Dental Nanocomposite Resin: Synthesis, Shrinkage, Double Bond Conversion, Hardness, and Resistance Properties
by Yizhi Liu, Xiaorong Wu, Yi Sun and Weili Xie
Polymers 2018, 10(4), 369; https://doi.org/10.3390/polym10040369 - 26 Mar 2018
Cited by 29 | Viewed by 5528
Abstract
Nanocomposite dental resins with 0, 2, 5, and 10 wt % methacryl polyhedral oligomeric silsesquioxane (POSS) as filler in the resin matrix were prepared by a light curing method.The atomic force microscopy (AFM), fourier transform infrared spectroscopy (FTIR), nanoindentation, and nanoscratch tests were [...] Read more.
Nanocomposite dental resins with 0, 2, 5, and 10 wt % methacryl polyhedral oligomeric silsesquioxane (POSS) as filler in the resin matrix were prepared by a light curing method.The atomic force microscopy (AFM), fourier transform infrared spectroscopy (FTIR), nanoindentation, and nanoscratch tests were carried out to study the effect of POSS contents on the compatibility, double bond conversion, volumetric shrinkage, hardness, modulus, and resistance of the dental resins. POSS was very uniformly dispersed and showed a good compatibility with the matrix. The double bond conversion increased and the volume reduced with the addition of POSS. As the POSS addition increased, the mechanical properties increased initially. Small addition of POSS remarkably enhanced the hardness and scratch resistance of the resin matrix. Full article
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12 pages, 5498 KiB  
Article
PNIPAM-MAPOSS Hybrid Hydrogels with Excellent Swelling Behavior and Enhanced Mechanical Performance: Preparation and Drug Release of 5-Fluorouracil
by Peihong Li, Xiaoman Hou, Lijie Qu, Xueyan Dai and Chunling Zhang
Polymers 2018, 10(2), 137; https://doi.org/10.3390/polym10020137 - 31 Jan 2018
Cited by 37 | Viewed by 6596
Abstract
Poly(N-isopropylacrylamide) (PNIPAM) is a widely-studied polymers due to its excellent temperature sensitivity. PNIPAM-MAPOSS hybrid hydrogel, based on the introduction of acrylolsobutyl polyhedral oligomeric silsesquioxane (MAPOSS) into the PNIPAM matrix in the presence of polyethylene glycol, was prepared via radical polymerization. The [...] Read more.
Poly(N-isopropylacrylamide) (PNIPAM) is a widely-studied polymers due to its excellent temperature sensitivity. PNIPAM-MAPOSS hybrid hydrogel, based on the introduction of acrylolsobutyl polyhedral oligomeric silsesquioxane (MAPOSS) into the PNIPAM matrix in the presence of polyethylene glycol, was prepared via radical polymerization. The modified hydrogels exhibited a thick, heterogeneous porous structure. PEG was used as a pore-forming agent to adjust the pore size. MAPOSS reduced the swelling ratios of gels, and decreased the LCST, causing the hydrogels to shrink at lower temperatures. However, its hydrophobicity helped to improve the temperature response rate. The incorporation of rigid MAPOSS into the polymer network greatly increased the compressive modulus of the hydrogel. It is worth noting that, by adjusting the amount of MAPOSS and PEG, the hydrogel could have both ideal mechanical properties and swelling behavior. In addition, hydrogel containing 8.33 wt % MAPOSS could achieve stable and sustained drug release. Thus, the prepared PNIPAM-MAPOSS hybrid hydrogel can serve as drug carrier for 5-fluorouracil and may have potential application in other biomedical fields. Full article
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13 pages, 3373 KiB  
Article
A New Route for Preparation of Hydrophobic Silica Nanoparticles Using a Mixture of Poly(dimethylsiloxane) and Diethyl Carbonate
by Iryna Protsak, Evgeniy Pakhlov, Valentyn Tertykh, Zi-Chun Le and Wen Dong
Polymers 2018, 10(2), 116; https://doi.org/10.3390/polym10020116 - 26 Jan 2018
Cited by 28 | Viewed by 9222
Abstract
Organosilicon layers chemically anchored on silica surfaces show high carbon content, good thermal and chemical stability and find numerous applications as fillers in polymer systems, thickeners in dispersing media, and as the stationary phases and carriers in chromatography. Methyl-terminated poly(dimethylsiloxanes) (PDMSs) are typically [...] Read more.
Organosilicon layers chemically anchored on silica surfaces show high carbon content, good thermal and chemical stability and find numerous applications as fillers in polymer systems, thickeners in dispersing media, and as the stationary phases and carriers in chromatography. Methyl-terminated poly(dimethylsiloxanes) (PDMSs) are typically considered to be inert and not suitable for surface modification because of the absence of readily hydrolyzable groups. Therefore, in this paper, we report a new approach for surface modification of silica (SiO2) nanoparticles with poly(dimethylsiloxanes) with different lengths of polymer chains (PDMS-20, PDMS-50, PDMS-100) in the presence of diethyl carbonate (DEC) as initiator of siloxane bond splitting. Infrared spectroscopy (IR), elemental analysis (CHN), transmission electron microscopy (TEM), atomic force microscopy (AFM), rotational viscosity and contact angle of wetting were employed for the characterization of the raw fumed silica and modified silica nanoparticles. Elemental analysis data revealed that the carbon content in the grafted layer is higher than 8 wt % for all modified silicas, but it decreases significantly after sample treatment in polar media for silicas which were modified using neat PDMS. The IR spectroscopy data indicated full involvement of free silanol groups in the chemisorption process at a relatively low temperature (220 °C) for all resulting samples. The contact angle studies confirmed hydrophobic surface properties of the obtained materials. The rheology results illustrated that fumed silica modified with mixtures of PDMS-x/DEC exhibited thixotropic behavior in industrial oil (I-40A), and exhibited a fully reversible nanostructure and shorter structure recovery time than nanosilicas modified with neat PDMS. The obtained results from AFM and TEM analysis revealed that the modification of fumed silica with mixtures of PDMS-20/DEC allows obtaining narrow particle size distribution with uniform dispersity and an average particle size of 15–17 nm. The fumed silica nanoparticles chemically modified with mixtures of PDMS-x/DEC have potential applications such as nanofillers of various polymeric systems, thickeners in dispersing media, and additives in coatings. Full article
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10 pages, 2201 KiB  
Article
Quartz Microcrystal-Hybridized Organosilicone Encapsulant with Enhanced Optical and Thermal Performances
by Xin Chen, Yancong Feng, Xiao Wang, En Li, Yao Wang, Lingling Shui, Hao Li, Nan Li and Guofu Zhou
Polymers 2018, 10(1), 84; https://doi.org/10.3390/polym10010084 - 16 Jan 2018
Cited by 3 | Viewed by 4247
Abstract
Encapsulant is one determining factor underpinning the device lifetimes of organic optoelectronics. However, encapsulant seriously needs improvement in optical, thermal, and mechanical properties, especially to develop organic light emitting diodes. In this study, we prepared an in situ crosslinked organosilane composite containing benzyloxy [...] Read more.
Encapsulant is one determining factor underpinning the device lifetimes of organic optoelectronics. However, encapsulant seriously needs improvement in optical, thermal, and mechanical properties, especially to develop organic light emitting diodes. In this study, we prepared an in situ crosslinked organosilane composite containing benzyloxy and glycidyl-modified quartz microcrystal (mQMC) as high performance encapsulant. In the present work, methylphenylsilanediol (MPSD) was introduced as a novel crosslinker to impart appropriate structural strength. Along with increasing mQMC fillers, this organosilane system shows improved properties, such as refractive index, thermal stability, and storage modulus. Specifically, these hybridized mQMCs in the organosilane framework may facilitate an approximate two-fold increase (0.238 W/(m·K)) in overall thermal conductivity at the determined concentration. Full article
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2017

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5282 KiB  
Article
Plateau-Shaped Flexible Polymer Microelectrode Array for Neural Recording
by Jun-Min Kim, Changkyun Im and Woo Ram Lee
Polymers 2017, 9(12), 690; https://doi.org/10.3390/polym9120690 - 8 Dec 2017
Cited by 21 | Viewed by 7708
Abstract
Conventional polymer multielectrode arrays (MEAs) have limitations resulting from a high Young’s modulus, including low conformability and gaps between the electrodes and neurons. These gaps are not a problem in soft tissues such as the brain, due to the repopulation phenomenon. However, gaps [...] Read more.
Conventional polymer multielectrode arrays (MEAs) have limitations resulting from a high Young’s modulus, including low conformability and gaps between the electrodes and neurons. These gaps are not a problem in soft tissues such as the brain, due to the repopulation phenomenon. However, gaps can result in signal degradation when recording from a fiber bundle, such as the spinal cord. Methods: We propose a method for fabricating flexible polydimethylsiloxane (PDMS)-based MEAs featuring plateau-shaped microelectrodes. The proposed fabrication technique enables the electrodes on the surface of MEAs to make a tight connection to the neurons, because the wire of the MEA is fabricated to be plateau-shaped, as the Young’s modulus of PDMS is similar to soft tissues and PDMS follows the curvature of the neural tissue due to its high conformability compared to the other polymers. Injury caused by the movement of the MEAs can therefore be minimized. Each electrode has a diameter of 130 μm and the 8-channel array has a center-to-center electrode spacing of 300 μm. The signal-to-noise ratio of the plateau-shaped electrodes was larger than that of recessed electrodes because there was no space between the electrode and neural cell. Reliable neural recordings were possible by adjusting the position of the electrode during the experiment without trapping air under the electrodes. Simultaneous multi-channel neural recordings were successfully achieved from the spinal cord of rodents. We describe the fabrication technique, electrode 3D profile, electrode impedance, and MEA performance in in vivo experiments in rodents. Full article
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2964 KiB  
Article
Effect of Zinc Oxide Modified Silica Particles on the Molecular Dynamics of Carboxylated Acrylonitrile-Butadiene Rubber Composites
by Magdalena Gaca, Joanna Pietrasik, Marian Zaborski, Lidia Okrasa, Gisèle Boiteux and Olivier Gain
Polymers 2017, 9(12), 645; https://doi.org/10.3390/polym9120645 - 25 Nov 2017
Cited by 16 | Viewed by 5485
Abstract
This work examines the molecular dynamics of carboxylated acrylonitrile-butadiene rubber crosslinked with zinc oxide modified silica particles. ZnO/SiO2 with the wide range of ZnO concentrations were used as both a crosslinking agent and filler. A series of thermal measurements were applied to [...] Read more.
This work examines the molecular dynamics of carboxylated acrylonitrile-butadiene rubber crosslinked with zinc oxide modified silica particles. ZnO/SiO2 with the wide range of ZnO concentrations were used as both a crosslinking agent and filler. A series of thermal measurements were applied to the characterization of the samples: differential scanning calorimetry, dynamical mechanical thermal analysis, and dielectric relaxation spectroscopy. A complementary experimental technique, which is equilibrium swelling in solvents, confirms the presence of ionic crosslinks, which are created between zinc ions and the functional carboxyl groups of the rubber, within the structure of the vulcanizates. These interactions influenced not only the affinity of the vulcanizates to solvents, but also their dynamic mechanical and dielectric properties. In these investigations, the influence of concentration of ZnO on the surface of the ZnO/SiO2 on the properties of the vulcanizates are described. Full article
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12853 KiB  
Article
Polymeric Amines and Ampholytes Derived from Poly(acryloyl chloride): Synthesis, Influence on Silicic Acid Condensation and Interaction with Nucleic Acid
by Elena N. Danilovtseva, Uma Maheswari Krishnan, Viktor A. Pal’shin and Vadim V. Annenkov
Polymers 2017, 9(11), 624; https://doi.org/10.3390/polym9110624 - 16 Nov 2017
Cited by 10 | Viewed by 9429
Abstract
Polymeric amines are intensively studied due to various valuable properties. This study describes the synthesis of new polymeric amines and ampholytes by the reaction of poly(acryloyl chloride) with trimethylene-based polyamines containing one secondary and several (1–3) tertiary amine groups. The polymers contain polyamine [...] Read more.
Polymeric amines are intensively studied due to various valuable properties. This study describes the synthesis of new polymeric amines and ampholytes by the reaction of poly(acryloyl chloride) with trimethylene-based polyamines containing one secondary and several (1–3) tertiary amine groups. The polymers contain polyamine side chains and carboxylic groups when the polyamine was in deficiency. These polymers differ in structure of side groups, but they are identical in polymerization degree and polydispersity, which facilitates the study of composition-properties relationships. The structure of the obtained polymers was confirmed with 13C nuclear magnetic resonance infrared spectroscopy, and acid-base properties were studied with potentiometry titration. Placement of the amine groups in the side chains influences their acid-base properties: protonation of the amine group exerts a larger impact on the amine in the same side chain than on the amines in the neighboring side chains. The obtained polymers are prone to aggregation in aqueous solutions tending to insolubility at definite pH values in the case of polyampholytes. Silicic acid condensation in the presence of new polymers results in soluble composite nanoparticles and composite materials which consist of ordered submicrometer particles according to dynamic light scattering and electron microscopy. Polymeric amines, ampholytes, and composite nanoparticles are capable of interacting with oligonucleotides, giving rise to complexes that hold promise for gene delivery applications. Full article
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7894 KiB  
Article
Aggregation Behavior of Nano-Silica in Polyvinyl Alcohol/Polyacrylamide Hydrogels Based on Dissipative Particle Dynamics
by Qinghua Wei, Yanen Wang, Yingfeng Zhang and Xiongbiao Chen
Polymers 2017, 9(11), 611; https://doi.org/10.3390/polym9110611 - 14 Nov 2017
Cited by 19 | Viewed by 7545
Abstract
Due to the aggregation behavior of nano-silica in aqueous solution, the use of nano-silica without surface modification for synthesizing hydrogels is still a challenging task. This paper presents our study on the use of dissipative particle dynamics simulations to discover the aggregation behavior [...] Read more.
Due to the aggregation behavior of nano-silica in aqueous solution, the use of nano-silica without surface modification for synthesizing hydrogels is still a challenging task. This paper presents our study on the use of dissipative particle dynamics simulations to discover the aggregation behavior of nano-silica in polyvinyl alcohol (PVA)/polyacrylamide (PAM) blended hydrogels. By simulations, we aimed at investigating the effects of such factors as nano-silica content, polymer component ratio, temperature and shear rate on the aggregation behavior of nano-silica in terms of the mesoscopic morphologies and the relative concentration distribution functions. Our results reveal that the dispersion of nano-silica is seen if the nano-silica content is increased to 1.5%, and the aggregation of nano-silica becomes noticeable in blended hydrogels with an increase in the nano-silica content. This finding agrees well with the experimental results obtained by means of scanning electron microscopy. Furthermore, it is also found that the dispersion of nano-silica becomes more uniform with an increase in PAM content, temperature and shear rate. These findings greatly enrich our understanding of the aggregation behavior of nano-silica in PVA/PAM blended hydrogels. Full article
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20672 KiB  
Review
Fifty Years of Hydrosilylation in Polymer Science: A Review of Current Trends of Low-Cost Transition-Metal and Metal-Free Catalysts, Non-Thermally Triggered Hydrosilylation Reactions, and Industrial Applications
by Robin J. Hofmann, Matea Vlatković and Frank Wiesbrock
Polymers 2017, 9(10), 534; https://doi.org/10.3390/polym9100534 - 20 Oct 2017
Cited by 112 | Viewed by 20945
Abstract
Hydrosilylation reactions, the (commonly) anti-Markovnikov additions of silanes to unsaturated bonds present in compounds such as alkenes and alkynes, offer numerous unique and advantageous properties for the preparation of polymeric materials, such as high yields and stereoselectivity. These reactions require to be catalyzed, [...] Read more.
Hydrosilylation reactions, the (commonly) anti-Markovnikov additions of silanes to unsaturated bonds present in compounds such as alkenes and alkynes, offer numerous unique and advantageous properties for the preparation of polymeric materials, such as high yields and stereoselectivity. These reactions require to be catalyzed, for which platinum compounds were used in the initial stages. Celebrating the 50th anniversary of hydrosilylations in polymer science and, concomitantly, five decades of continuously growing research, hydrosilylation reactions have advanced to a level that renders them predestined for transfer into commercial products on the large scale. Facing this potential transfer, this review addresses and discusses selected current trends of the scientific research in the area, namely low-cost transition metal catalysts (focusing on iron, cobalt, and nickel complexes), metal-free catalysts, non-thermally triggered hydrosilylation reactions (highlighting stimuli such as (UV-)light), and (potential) industrial applications (highlighting the catalysts used and products manufactured). This review focuses on the hydrosilylation reactions involving alkene reactants. Full article
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6044 KiB  
Article
Dielectric and Carrier Transport Properties of Silicone Rubber Degraded by Gamma Irradiation
by Daomin Min, Chenyu Yan, Yin Huang, Shengtao Li and Yoshimichi Ohki
Polymers 2017, 9(10), 533; https://doi.org/10.3390/polym9100533 - 20 Oct 2017
Cited by 50 | Viewed by 9161
Abstract
Silicone rubber (SiR) is used as an insulating material for cables installed in a nuclear power plant. Gamma rays irradiated SiR sheets for various periods at temperatures of 145 and 185 °C, and the resultant changes were analyzed by examining complex permittivity spectra [...] Read more.
Silicone rubber (SiR) is used as an insulating material for cables installed in a nuclear power plant. Gamma rays irradiated SiR sheets for various periods at temperatures of 145 and 185 °C, and the resultant changes were analyzed by examining complex permittivity spectra and surface potential decay characteristics. Three different processes, namely, instantaneous polarization, electrode polarization due to the accumulation of ions to form double charge layers at dielectric/electrode interfaces, and DC conduction caused by directional hopping of ions, contribute to the complex permittivity. By fitting the spectra to theoretical equations, we can obtain the dielectric constant at high frequencies, concentration and diffusion coefficient of ions and DC conductivity for the pristine and degraded samples. The instantaneous polarization becomes active with an increase of dose and ageing temperature. The thermal expansion coefficient estimated from the temperature dependence of dielectric constant at high frequencies becomes smaller with an increase in dose, which is in good agreement with the experimental results of the swelling ratio. Additionally, trap distributions are calculated from surface potential decay measurements and analyzed to explain the variation in conductivity. Trap energy increases firstly, and then decreases with an increase in dose, leading to a similar change in DC conductivity. It is concluded that generations of both oxidative products and mobile ions, as well as the occurrence of chain scission and crosslinking are simultaneously induced by gamma rays. Full article
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5250 KiB  
Article
Supported Ionic Liquid Silica as Curing Agent for Epoxy Composites with Improved Mechanical and Thermal Properties
by Chongrui Zhang, Xiaoqian Mi, Junyu Tian, Junheng Zhang and Tiwen Xu
Polymers 2017, 9(10), 478; https://doi.org/10.3390/polym9100478 - 29 Sep 2017
Cited by 22 | Viewed by 6486
Abstract
The present study aims to improve the mechanical properties of epoxy composite by incorporating supported ionic liquid silica (IL-silica). The IL-silica not only showed improved interfacial interaction and reinforcement, but also served as cure agent of epoxy composites. The differential scanning calorimetry analysis [...] Read more.
The present study aims to improve the mechanical properties of epoxy composite by incorporating supported ionic liquid silica (IL-silica). The IL-silica not only showed improved interfacial interaction and reinforcement, but also served as cure agent of epoxy composites. The differential scanning calorimetry analysis revealed that epoxy composites could be successfully cured with IL-silica without any routine curing agents. IL-silica/epoxy composites presented higher mechanical and thermal properties compared with epoxy composite containing un-functionalized silica (u-silica). The dynamic mechanical analysis showed that the storage modulus of composites significantly increased with the addition of IL-silica in comparison to that with added u-silica, as well as the variation of Tg parameter. The incorporation of IL-silica simultaneously enhanced the tensile strength, toughness, and thermal stability of the epoxy composites. The considerable improvements in mechanical and thermal properties are ascribed to the improved dispersion of IL-silica and the enhanced interfacial interactions between epoxy matrix and IL-silica by strong covalent bonding, which results in an effective load transfer. Full article
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2297 KiB  
Article
Synthesis of Polystyrene–Polyphenylsiloxane Janus Particles through Colloidal Assembly with Unexpected High Selectivity: Mechanistic Insights and Their Application in the Design of Polystyrene Particles with Multiple Polyphenylsiloxane Patches
by Daniel Mann, Stefanie Voogt, Helmut Keul, Martin Möller, Marcel Verheijen and Pascal Buskens
Polymers 2017, 9(10), 475; https://doi.org/10.3390/polym9100475 - 28 Sep 2017
Cited by 11 | Viewed by 5742
Abstract
Janus particles are of great research interest because of their reduced symmetry, which provides them with unique physical and chemical properties. Such particles can be prepared from spherical structures through colloidal assembly. Whilst colloidal assembly has the potential to be a low cost [...] Read more.
Janus particles are of great research interest because of their reduced symmetry, which provides them with unique physical and chemical properties. Such particles can be prepared from spherical structures through colloidal assembly. Whilst colloidal assembly has the potential to be a low cost and scalable process, it typically lacks selectivity. As a consequence, it results in a complex mixture of particles of different architectures, which is tedious to purify. Very recently, we reported the colloidal synthesis of Au semishells, making use of polystyrene–polyphenylsiloxane Janus particles as an intermediate product (Chem. Commun. 2017, 53, 3898–3901). Here, we demonstrate that these Janus particles are realized through colloidal assembly of spherical glucose-functionalized polystyrene particles and an emulsion of phenyltrimethoxysilane in aqueous ammonia, followed by interfacial polycondensation to form the polyphenylsiloxane patch. Both the polystyrene spheres and the emulsion of Ph-TMS in aqueous ammonia are stabilized by a surfmer—a reactive surfactant. The colloidal assembly reported in this manuscript proceeds with an unexpected high selectivity, which makes this process exceptionally interesting for the synthesis of Janus particles. Furthermore, we report insights into the details of the mechanism of formation of these Janus particles, and apply those to adapt the synthesis conditions to produce polystyrene particles selectively decorated with multiple polyphenylsiloxane patches, e.g., raspberry particles. Full article
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2915 KiB  
Article
Computational Thermomechanical Properties of Silica–Epoxy Nanocomposites by Molecular Dynamic Simulation
by Xiaoxing Zhang, Hao Wen and Yunjian Wu
Polymers 2017, 9(9), 430; https://doi.org/10.3390/polym9090430 - 8 Sep 2017
Cited by 62 | Viewed by 8207
Abstract
Silica–epoxy nanocomposite models were established to investigate the influence of silane coupling agent on the structure and thermomechanical properties of the nanocomposites through molecular dynamics simulation. Results revealed that incorporating silica nanoparticles into a polymer matrix could improve thermomechanical properties of the composites [...] Read more.
Silica–epoxy nanocomposite models were established to investigate the influence of silane coupling agent on the structure and thermomechanical properties of the nanocomposites through molecular dynamics simulation. Results revealed that incorporating silica nanoparticles into a polymer matrix could improve thermomechanical properties of the composites and increase their glass transition temperature and thermal conductivity. Their thermomechanical properties were further enhanced through silane coupling agent modification on the surface of fillers. Compared with that of pure epoxy, the glass transition temperatures of the silica–epoxy composites with grafting ratios of 5% and 10% increased by 17 and 28 K, respectively. The thermal conductivities of the two models at room temperature respectively increased by 60.0% and 67.1%. At higher temperature 450 K, thermal conductivity of the nanocomposite model with a high grafting ratio of 10% demonstrated a considerable increase of approximately 50% over the pure epoxy resin (EP) model. The elastic and shear modulus of the nanocomposite models decreased at temperatures below their glass transition temperatures. These observations were further addressed in the interpretation from three aspects: segmental mobility capability, radial distribution function, and free volume fraction. Our computational results are largely consistent with existing experimental data, and our simulation model got fully validated. Full article
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3086 KiB  
Article
Cure Behavior and Thermomechanical Properties of Phthalonitrile–Polyhedral Oligomeric Silsesquioxane Copolymers
by Xiaodan Li, Baifeng Yu, Dongxing Zhang, Jing Lei and Zhu Nan
Polymers 2017, 9(8), 334; https://doi.org/10.3390/polym9080334 - 3 Aug 2017
Cited by 13 | Viewed by 6608
Abstract
Phthalonitrile–polyhedral oligomeric silsesquioxane (POSS) copolymers were prepared by adding two different POSS cage mixtures: epoxycyclohexyl POSS (EP0408) and N-phenylaminopropyl POSS (AM0281). The cure behavior and properties of these polymers were analyzed and compared using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic [...] Read more.
Phthalonitrile–polyhedral oligomeric silsesquioxane (POSS) copolymers were prepared by adding two different POSS cage mixtures: epoxycyclohexyl POSS (EP0408) and N-phenylaminopropyl POSS (AM0281). The cure behavior and properties of these polymers were analyzed and compared using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), Fourier transform far infrared (FTIR) measurements, and rheometric studies. The POSS-containing polymers showed higher chemical reactivity, better thermal stability and better mechanical performance in comparison to their unmodified counterparts. All the polymers showed water absorption below 1.5%. As revealed by FTIR measurements, the polymerization products contained triazine ring structures that were responsible for the superior thermal properties exhibited by these POSS-containing polymers. Full article
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3956 KiB  
Article
Facile Synthesis and Self-Assembly of Amphiphilic Polyether-Octafunctionalized Polyhedral Oligomeric Silsesquioxane via Thiol-Ene Click Reaction
by Yong Xia, Sha Ding, Yuejun Liu and Zhengjian Qi
Polymers 2017, 9(7), 251; https://doi.org/10.3390/polym9070251 - 28 Jun 2017
Cited by 10 | Viewed by 9744
Abstract
We demonstrated here a facile and efficient synthesis of polyhedral oligomeric silsesquioxane-based amphiphilic polymer by thiol-ene click chemistry. The properties of polyhedral oligomeric silsesquioxane (POSS)–PEG amphiphilic polymers were studied in detail by a combination of 1H NMR, 13C NMR, 29Si [...] Read more.
We demonstrated here a facile and efficient synthesis of polyhedral oligomeric silsesquioxane-based amphiphilic polymer by thiol-ene click chemistry. The properties of polyhedral oligomeric silsesquioxane (POSS)–PEG amphiphilic polymers were studied in detail by a combination of 1H NMR, 13C NMR, 29Si NMR FT-IR, GPC, and TG analysis. The newly-designed thiol-ene protocol obtains only anti-Markovnikov addition POSS-based amphiphilic polymers when compared with platinum-catalysed hydrosilylation method. The critical micelle concentration (CMC) of the resulting polymers are in the range of 0.011 to 0.050 mg/mL, and dynamic light scattering (DLS) results revealed that the obtained amphiphilic polymers can self-assemble into nanoparticles in aqueous solutions with a bimodal (two peaks) distribution. Furthermore, the specific polymer showed obvious thermo-sensitive behaviour at 45.5 °C. Full article
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1836 KiB  
Communication
A Rapid One-Pot Synthesis of Novel High-Purity Methacrylic Phosphonic Acid (PA)-Based Polyhedral Oligomeric Silsesquioxane (POSS) Frameworks via Thiol-Ene Click Reaction
by K. Karuppasamy, K. Prasanna, Dhanasekaran Vikraman, Hyun-Seok Kim, A. Kathalingam, Liviu Mitu and Hee Woo Rhee
Polymers 2017, 9(6), 192; https://doi.org/10.3390/polym9060192 - 27 May 2017
Cited by 11 | Viewed by 8161
Abstract
Herein, we demonstrate a facile methodology to synthesis a novel methacrylic phosphonic acid (PA)-functionalized polyhedral oligomeric silsesquioxanes (POSSs) via thiol-ene click reaction using octamercapto thiol-POSS and ethylene glycol methacrylate phosphate (EGMP) monomer. The presence of phosphonic acid moieties and POSS-cage structure in POSS-S-PA [...] Read more.
Herein, we demonstrate a facile methodology to synthesis a novel methacrylic phosphonic acid (PA)-functionalized polyhedral oligomeric silsesquioxanes (POSSs) via thiol-ene click reaction using octamercapto thiol-POSS and ethylene glycol methacrylate phosphate (EGMP) monomer. The presence of phosphonic acid moieties and POSS-cage structure in POSS-S-PA was confirmed by Fourier transform infrared (FT-IR) and nuclear magnetic resonance (1H, 29Si and 31P-NMR) analyses. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrum of POSS-S-PA acquired in a dithranol matrix, which has specifically designed for intractable polymeric materials. The observed characterization results signposted that novel organo-inorganic hybrid POSS-S-PA would be an efficacious material for fuel cells as a proton exchange membrane and high-temperature applications due to its thermal stability of 380 °C. Full article
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2016

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1347 KiB  
Article
Study on Hydrogen Sensitivity of Ziegler–Natta Catalysts with Novel Cycloalkoxy Silane Compounds as External Electron Donor
by Hongming Li, Jing Wang, Lei He, Feng Nan, Fan Wang, Wantai Yang, Mingge Zhang, Tianxu Sun, Qigu Huang and Jianjun Yi
Polymers 2016, 8(12), 433; https://doi.org/10.3390/polym8120433 - 16 Dec 2016
Cited by 9 | Viewed by 8724
Abstract
Two novel cycloalkoxy silane compounds (ED1 and ED2) were synthesized and used as the external electron donors (EEDs) in Ziegler–Natta catalysts with diethyl 2,3-diisopropylsuccinate as internal electron donor. The results indicated that the Ziegler–Natta catalysts using ED1 and ED2 as EEDs had high [...] Read more.
Two novel cycloalkoxy silane compounds (ED1 and ED2) were synthesized and used as the external electron donors (EEDs) in Ziegler–Natta catalysts with diethyl 2,3-diisopropylsuccinate as internal electron donor. The results indicated that the Ziegler–Natta catalysts using ED1 and ED2 as EEDs had high catalytic activities and good stereoselectivities. The melt flow rate (MFR) and gel permeation chromatography (GPC) results revealed that the obtained polypropylene has higher MFR and lower average molecular weights than the commercial EED cyclohexyl methyl dimethoxysilane. The differential scanning calorimetry (DSC) results indicated that new isospecific active centers formed after the introduction of new external donors. The work implied that the novel EEDs could improve the hydrogen sensitivities of the catalyst system and obtain polymers with high melt flow rate. Full article
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30526 KiB  
Article
Physical and Mechanical Evaluation of Silicone-Based Double-Layer Adhesive Patch Intended for Keloids and Scar Treatment Therapy
by Barbara Mikolaszek, Marzena Jamrógiewicz, Krystyna Mojsiewicz-Pieńkowska, Maria Żebrowska, Małgorzata Sznitowska and Justyna Strankowska
Polymers 2016, 8(11), 398; https://doi.org/10.3390/polym8110398 - 22 Nov 2016
Cited by 8 | Viewed by 7294
Abstract
Growing interest in silicone elastomers for pharmaceutical purposes is due to both their beneficial material effect for scar treatment and their potential as drug carriers. Regarding their morphological structure, silicone polymers possess unique properties, which enable a wide range of applicability possibilities. The [...] Read more.
Growing interest in silicone elastomers for pharmaceutical purposes is due to both their beneficial material effect for scar treatment and their potential as drug carriers. Regarding their morphological structure, silicone polymers possess unique properties, which enable a wide range of applicability possibilities. The present study focused on developing a double-layer adhesive silicone film (DLASil) by evaluating its physical and mechanical properties, morphology, and stability. DLASil suitability for treatment of scars and keloids was evaluated by measurement of tensile strength, elasticity modulus, and elongation. The results indicated that mechanical and physical properties of the developed product were satisfying. Full article
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3328 KiB  
Communication
Stabilization of Inverse Miniemulsions by Silyl-Protected Homopolymers
by Sarah Wald, Frederik R. Wurm, Katharina Landfester and Daniel Crespy
Polymers 2016, 8(8), 303; https://doi.org/10.3390/polym8080303 - 12 Aug 2016
Cited by 3 | Viewed by 6493
Abstract
Inverse (water-in-oil) miniemulsions are an important method to encapsulate hydrophilic payloads such as oligonucleotides or peptides. However, the stabilization of inverse miniemulsions usually requires block copolymers that are difficult to synthesize and/or cannot be easily removed after transfer from a hydrophobic continuous phase [...] Read more.
Inverse (water-in-oil) miniemulsions are an important method to encapsulate hydrophilic payloads such as oligonucleotides or peptides. However, the stabilization of inverse miniemulsions usually requires block copolymers that are difficult to synthesize and/or cannot be easily removed after transfer from a hydrophobic continuous phase to an aqueous continuous phase. We describe here a new strategy for the synthesis of a surfactant for inverse miniemulsions by radical addition–fragmentation chain transfer (RAFT) polymerization, which consists in a homopolymer with triisopropylsilyl protecting groups. The protecting groups ensure the efficient stabilization of the inverse (water-in-oil, w/o) miniemulsions. Nanocapsules can be formed and the protecting group can be subsequently cleaved for the re-dispersion of nanocapsules in an aqueous medium with a minimal amount of additional surfactant. Full article
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1985 KiB  
Article
Synthesis of Monodisperse Silica Particles Grafted with Concentrated Ionic Liquid-Type Polymer Brushes by Surface-Initiated Atom Transfer Radical Polymerization for Use as a Solid State Polymer Electrolyte
by Takashi Morinaga, Saika Honma, Takeo Ishizuka, Toshio Kamijo, Takaya Sato and Yoshinobu Tsujii
Polymers 2016, 8(4), 146; https://doi.org/10.3390/polym8040146 - 16 Apr 2016
Cited by 17 | Viewed by 9281
Abstract
A polymerizable ionic liquid, N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide (DEMM-TFSI), was polymerized via copper-mediated atom transfer radical polymerization (ATRP). The polymerization proceeded in a living manner producing well-defined poly(DEMM-TFSI) of target molecular weight up to about 400 K (including [...] Read more.
A polymerizable ionic liquid, N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide (DEMM-TFSI), was polymerized via copper-mediated atom transfer radical polymerization (ATRP). The polymerization proceeded in a living manner producing well-defined poly(DEMM-TFSI) of target molecular weight up to about 400 K (including a polycation and an counter anion). The accurate molecular weight as determined by a GPC analysis combined with a light scattering measurement, and the molecular weight values obtained exhibited good agreement with the theoretical values calculated from the initial molar ratio of DEMM-TFSI and the monomer conversion. Surface-initiated ATRP on the surface of monodisperse silica particles (SiPs) with various diameters was successfully performed, producing SiPs grafted with well-defined poly(DEMM-TFSI) with a graft density as high as 0.15 chains/nm2. Since the composite film made from the silica-particle-decorated polymer brush and ionic liquid shows a relatively high ionic conductivity, we have evaluated the relationship between the grafted brush chain length and the ionic conductivity. Full article
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7041 KiB  
Article
Synchronously Tailoring Strain Sensitivity and Electrical Stability of Silicone Elastomer Composites by the Synergistic Effect of a Dual Conductive Network
by Nanying Ning, Sishu Wang, Liqun Zhang, Yonglai Lu, Ming Tian and Tung W. Chan
Polymers 2016, 8(4), 100; https://doi.org/10.3390/polym8040100 - 31 Mar 2016
Cited by 14 | Viewed by 5690
Abstract
The use of conductive polymer composites (CPCs) as strain sensors has been widely investigated. A wide range of strain sensitivities and high repeatability are vital for different applications of CPCs. In this study, the relations of the conductive filler network and the strain-sensing [...] Read more.
The use of conductive polymer composites (CPCs) as strain sensors has been widely investigated. A wide range of strain sensitivities and high repeatability are vital for different applications of CPCs. In this study, the relations of the conductive filler network and the strain-sensing behavior and electrical stability under fatigue cycles were studied systematically for the first time based on the conductive polymethylvinylsiloxane (PMVS) composites filled with both carbon nanotubes arrays (CNTAs) and carbon black (CB). It was proved that the composites could be fabricated with large strain-sensing capability and a wide range of strain sensitivities by controlling the volume ratio of CNTA/CB and their amounts. Additionally, the CNTA/CB/PMVS composite with 3 vol % content of fillers showed high sensitivity (GF is 10 at 60% strain), high repeatability (the relative standard deviation (RSD) of the max R/R0 value is 3.58%), and electrical stability under fatigue cycles (value range of R/R0 is 1.62 to 1.82) at the same time due to the synergistic effects of the dual conductive network of CNTAs and CB. This could not be achieved by relying on a single CNTA or CB conductive network. This study may provide guidance for the preparation of high performance CPCs for applications in strain sensors. Full article
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2865 KiB  
Article
Stability Study of Flexible 6,13-Bis(triisopropylsilylethynyl)pentacene Thin-Film Transistors with a Cross-Linked Poly(4-vinylphenol)/Yttrium Oxide Nanocomposite Gate Insulator
by Jin-Hyuk Kwon, Xue Zhang, Shang Hao Piao, Hyoung Jin Choi, Jin-Hyuk Bae and Jaehoon Park
Polymers 2016, 8(3), 88; https://doi.org/10.3390/polym8030088 - 16 Mar 2016
Cited by 14 | Viewed by 7473
Abstract
We investigated the electrical and mechanical stability of flexible 6,13-bis(triisopropylsilylehtynyl)pentacene (TIPS-pentacene) thin-film transistors (TFTs) that were fabricated on polyimide (PI) substrates using cross-linked poly(4-vinylphenol) (c-PVP) and c-PVP/yttrium oxide (Y2O3) nanocomposite films as gate insulators. Compared with the electrical characteristics [...] Read more.
We investigated the electrical and mechanical stability of flexible 6,13-bis(triisopropylsilylehtynyl)pentacene (TIPS-pentacene) thin-film transistors (TFTs) that were fabricated on polyimide (PI) substrates using cross-linked poly(4-vinylphenol) (c-PVP) and c-PVP/yttrium oxide (Y2O3) nanocomposite films as gate insulators. Compared with the electrical characteristics of TIPS-pentacene TFTs with c-PVP insulators, the TFTs with c-PVP/Y2O3 nanocomposite insulators exhibited enhancements in the drain current and the threshold voltage due to an increase in the dielectric capacitance. In electrical stability experiments, a gradual decrease in the drain current and a negative shift in the threshold voltage occurred during prolonged bias stress tests, but these characteristic variations were comparable for both types of TFT. On the other hand, the results of mechanical bending tests showed that the characteristic degradation of the TIPS-pentacene TFTs with c-PVP/Y2O3 nanocomposite insulators was more critical than that of the TFTs with c-PVP insulators. In this study, the detrimental effect of the nanocomposite insulator on the mechanical stability of flexible TIPS-pentacene TFTs was found to be caused by physical adhesion of TIPS-pentacene molecules onto the rough surfaces of the c-PVP/Y2O3 nanocomposite insulator. These results indicate that the dielectric and morphological properties of polymeric nanocomposite insulators are significant when considering practical applications of flexible electronics operated at low voltages. Full article
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2015

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12745 KiB  
Article
Influence of pH, Temperature and Sample Size on Natural and Enforced Syneresis of Precipitated Silica
by Sebastian Wilhelm and Matthias Kind
Polymers 2015, 7(12), 2504-2521; https://doi.org/10.3390/polym7121528 - 1 Dec 2015
Cited by 40 | Viewed by 14520
Abstract
The production of silica is performed by mixing an inorganic, silicate-based precursor and an acid. Monomeric silicic acid forms and polymerizes to amorphous silica particles. Both further polymerization and agglomeration of the particles lead to a gel network. Since polymerization continues after gelation, [...] Read more.
The production of silica is performed by mixing an inorganic, silicate-based precursor and an acid. Monomeric silicic acid forms and polymerizes to amorphous silica particles. Both further polymerization and agglomeration of the particles lead to a gel network. Since polymerization continues after gelation, the gel network consolidates. This rather slow process is known as “natural syneresis” and strongly influences the product properties (e.g., agglomerate size, porosity or internal surface). “Enforced syneresis” is the superposition of natural syneresis with a mechanical, external force. Enforced syneresis may be used either for analytical or preparative purposes. Hereby, two open key aspects are of particular interest. On the one hand, the question arises whether natural and enforced syneresis are analogous processes with respect to their dependence on the process parameters: pH, temperature and sample size. On the other hand, a method is desirable that allows for correlating natural and enforced syneresis behavior. We can show that the pH-, temperature- and sample size-dependency of natural and enforced syneresis are indeed analogous. It is possible to predict natural syneresis using a correlative model. We found that our model predicts maximum volume shrinkages between 19% and 30% in comparison to measured values of 20% for natural syneresis. Full article
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8876 KiB  
Article
Stable Failure-Inducing Micro-Silica Aqua Epoxy Bonding Material for Floating Concrete Module Connection
by Jang-Ho Jay Kim, Young-Jun You, Youn-Ju Jeong and Ji-Hun Choi
Polymers 2015, 7(11), 2389-2409; https://doi.org/10.3390/polym7111520 - 24 Nov 2015
Cited by 5 | Viewed by 6698
Abstract
Many recent studies in the development of floating concrete structures focused on a connection system made of modules. In the connection system, the modules are designed to be attached by pre-stressing (PS) while floating on the water, which exposes them to loads on [...] Read more.
Many recent studies in the development of floating concrete structures focused on a connection system made of modules. In the connection system, the modules are designed to be attached by pre-stressing (PS) while floating on the water, which exposes them to loads on the surface of the water. Therefore, the development of a pre-connection material becomes critical to ensure successful bonding of floating concrete modules. Micro-silica mixed aqua-epoxy (MSAE) was developed for this task. To find the proper MSAE mix proportion, 0% to 4% micro-silica was mixed in a standard mixture of aqua-epoxy for material testing. Also, the effect of micro-silica on the viscosity of the aqua epoxy was evaluated by controlling the epoxy silane at proportions of 0%, ±5%, and ±10%. After completion of the performance tests of the MSAE, we evaluated the effect of MSAE in a connected structure. The plain unreinforced concrete module joint specimens applied with MSAE at thicknesses of 5, 10, and 20 mm were prepared to be tested. Finally, we evaluated the performance of MSAE-applied reinforced concrete (RC) module specimens connected by PS tendons, and these were compared with those of continuous RC and non-MSAE-applied beams. The results showed that the mix of micro-silica in the aqua-epoxy changed the performance of the aqua-epoxy and the mix ratio of 2% micro-silica gave a stable failure behavior. The flexural capacity of concrete blocks bonded with MSAE changed according to the bond thickness and was better than that of concrete blocks bonded with aqua-epoxy without micro-silica. Even though MSAE insignificantly increases the load-carrying capacity of the attached concrete module structure, the stress concentration reduction effect stabilized the failure of the structure. Full article
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3486 KiB  
Article
Preparation and Characterization of Novel PVC/Silica–Lignin Composites
by Łukasz Klapiszewski, Franciszek Pawlak, Jolanta Tomaszewska and Teofil Jesionowski
Polymers 2015, 7(9), 1767-1788; https://doi.org/10.3390/polym7091482 - 15 Sep 2015
Cited by 54 | Viewed by 12934
Abstract
An advanced SiO2–lignin hybrid material was obtained and tested as a novel poly(vinyl chloride) (PVC) filler. The processing of compounds of poly(vinyl chloride) in the form of a dry blend with silica–lignin hybrid material and, separately, with the two components from which that [...] Read more.
An advanced SiO2–lignin hybrid material was obtained and tested as a novel poly(vinyl chloride) (PVC) filler. The processing of compounds of poly(vinyl chloride) in the form of a dry blend with silica–lignin hybrid material and, separately, with the two components from which that material was prepared, was performed in a Brabender mixing chamber. An analysis was made of processing (mass melt flow rate, MFR), thermal (thermogravimetric analysis, Congo red and Vicat softening temperature test) and tensile properties of the final PVC composites with fillers in a range of concentrations between 2.5 wt % and 10 wt %. Additionally, the effects of filler content on the fusion characteristics of PVC composites were investigated. The homogeneity of dispersion of the silica–lignin hybrid material in the PVC matrix was determined by optical microscopy and SEM. Finally, it should be noted that it is possible to obtain a PVC composite containing up to 10 wt % of silica–lignin filler using a melt processing method. The introduction of hybrid filler into the PVC matrix results in a homogeneous structure of the composites and positive processing and functional properties, especially thermal stability and Vicat softening temperature. Full article
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3022 KiB  
Article
Stable Poly(methacrylic acid) Brush Decorated Silica Nano-Particles by ARGET ATRP for Bioconjugation
by Marcello Iacono and Andreas Heise
Polymers 2015, 7(8), 1427-1443; https://doi.org/10.3390/polym7081427 - 6 Aug 2015
Cited by 13 | Viewed by 8645
Abstract
The synthesis of polymer brush decorated silica nano-particles is demonstrated by activator regeneration by electron transfer atom transfer radical polymerization (ARGET ATRP) grafting of poly(tert-butyl methacrylate). ATRP initiator decorated silica nano-particles were obtained using a novel trimethylsiloxane derivatised ATRP initiator obtained [...] Read more.
The synthesis of polymer brush decorated silica nano-particles is demonstrated by activator regeneration by electron transfer atom transfer radical polymerization (ARGET ATRP) grafting of poly(tert-butyl methacrylate). ATRP initiator decorated silica nano-particles were obtained using a novel trimethylsiloxane derivatised ATRP initiator obtained by click chemistry. Comparison of de-grafted polymers with polymer obtained from a sacrificial initiator demonstrated good agreement up to 55% monomer conversion. Subsequent mild deprotection of the tert-butyl ester groups using phosphoric acid yielded highly colloidal and pH stable hydrophilic nano-particles comprising approximately 50% methacrylic acid groups. The successful bio-conjugation was achieved by immobilization of Horseradish Peroxidase to the polymer brush decorated nano-particles and the enzyme activity demonstrated in a conversion of o-phenylene diamine dihydrochloride assay. Full article
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