Polymers

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3371 KiB

Open AccessArticle

Synthesis of Well-Defined Poly(N-H Benzamide-co-N-Octyl Benzamide)s and the Study of their Blends with Nylon 6

by Chih-Feng Huang, Miao-Jia Chen, Ching-Hsuan Lin and Yeo-Wan Chiang

Polymers 2017, 9(5), 172; https://doi.org/10.3390/polym9050172 - 13 May 2017

Cited by 6 | Viewed by 4974

We synthesized a series of copolybenzamides (PBA) through chain-growth condensation polymerization (CGCP) of 4-(octylamino)benzoate (M4OB) and methyl 3-(4-(octyloxy)benzylamino) benzoate (M3OOB) co-monomers. Well-defined copolybenzamides with close to theoretical molecular weights (Mn ≈ 10,000–13,000) and narrow molecular weight distributions (Mw/Mn < 1.40) were obtained. Selective [...] Read more.

We synthesized a series of copolybenzamides (PBA) through chain-growth condensation polymerization (CGCP) of 4-(octylamino)benzoate (M4OB) and methyl 3-(4-(octyloxy)benzylamino) benzoate (M3OOB) co-monomers. Well-defined copolybenzamides with close to theoretical molecular weights (Mn ≈ 10,000–13,000) and narrow molecular weight distributions (Mw/Mn < 1.40) were obtained. Selective removals of the protecting group (i.e., 4-(octyloxy)benzyl group) from the affording P(M3OOB-co-M4OB) copolybenzamides were subsequently performed to obtain P(M3NH-co-M4OB) copolymers. These novel N-H-containing copolybenzamides (named as PNHBA) can not only provide hydrogen bonds for polymer-polymer blends but also have good solubility in organic solvents. Miscibility of the PNHBA and Nylon 6 blends was investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), FT-IR, contact angle analysis, transmission electron microscope (TEM), and dynamic mechanical analysis (DMA). This study illustrates a novel type of copolybenzamide with controlled molecular weight and narrow molecular weight distribution through an effective synthetic strategy, and can be applied to a practical blend of Nylon 6 with good miscibility. Full article

(This article belongs to the Special Issue Polymer Blends 2017)

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3757 KiB

Open AccessArticle

Coumarin- and Carboxyl-Functionalized Supramolecular Polybenzoxazines Form Miscible Blends with Polyvinylpyrrolidone

by Ruey-Chorng Lin, Mohamed Gamal Mohamed, Tao Chen and Shiao-Wei Kuo

Polymers 2017, 9(4), 146; https://doi.org/10.3390/polym9040146 - 21 Apr 2017

Cited by 20 | Viewed by 7898

Abstract

In this study, we synthesized a novel multifunctional benzoxazine monomer (Coumarin-COOH BZ), possessing both coumarin and COOH groups, through the reaction of 4-methyl-7-hydroxycoumarin, 4-aminobenzoic acid, and paraformaldehyde in 1,4-dioxane, with the structure confirmed using ¹H and ¹³C nuclear magnetic resonance and [...] Read more.

In this study, we synthesized a novel multifunctional benzoxazine monomer (Coumarin-COOH BZ), possessing both coumarin and COOH groups, through the reaction of 4-methyl-7-hydroxycoumarin, 4-aminobenzoic acid, and paraformaldehyde in 1,4-dioxane, with the structure confirmed using ¹H and ¹³C nuclear magnetic resonance and Fourier transform infrared (FTIR) spectroscopy. Differential scanning calorimetry (DSC), FTIR spectroscopy, and thermogravimetric analysis were then employed to monitor the thermal curing behavior of Coumarin-COOH BZ and its blends with poly(N-vinyl-2-pyrrolidone) (PVP), both before and after photodimerization of the coumarin moieties. DSC revealed a single glass transition temperature for each Coumarin-COOH BZ/PVP blend composition; a large positive deviation based on the Kwei equation suggested that strong hydrogen bonding existed between the Coumarin-COOH BZ and PVP segments, confirmed through FTIR spectroscopic analyses. The thermal properties improved (i.e., increased glass transition and thermal degradation temperatures) as a result of the increased crosslinking density after photodimerization under UV exposure. Full article

(This article belongs to the Special Issue Polymer Blends 2017)

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12951 KiB

Open AccessArticle

Crystal Structure Evolution of UHMWPE/HDPE Blend Fibers Prepared by Melt Spinning

by Fei Wang, Lichao Liu, Ping Xue and Mingyin Jia

Polymers 2017, 9(3), 96; https://doi.org/10.3390/polym9030096 - 9 Mar 2017

Cited by 30 | Viewed by 10485

Abstract

Ultra-high molecular weight polyethylene (UHMWPE) and high-density polyethylene (HDPE) blend fibers with the highest tensile strength of 1.13 GPa were prepared by a melt spinning process. The mechanical behavior and crystal structure of the as-spun filaments and fibers were studied by differential scanning [...] Read more.

Ultra-high molecular weight polyethylene (UHMWPE) and high-density polyethylene (HDPE) blend fibers with the highest tensile strength of 1.13 GPa were prepared by a melt spinning process. The mechanical behavior and crystal structure of the as-spun filaments and fibers were studied by differential scanning calorimetry (DSC), scanning electron microscopy (SEM), X-ray diffraction (XRD), sound velocity orientation testing, and tensile testing. The orientation degree, crystallinity, tensile strength, and initial modulus of the fibers increased with the increasing of the draw ratios. The grain size was shortened in the radial direction and elongated in the axial direction. The results suggested that the improvement of the tensile strength and initial modulus was a result of the compact crystal structure formed by slender grains composed of highly oriented molecular chains. Blending with HDPE could improve the formation of a slender and compact crystal structure, and the tensile strength and initial modulus of the blend fibers were higher. Full article

(This article belongs to the Special Issue Polymer Blends 2017)

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10497 KiB

Open AccessArticle

Preparation of R_F-(VM-SiO₂)_n-R_F/AM-Cellu Nanocomposites, and Use Thereof for the Modification of Glass and Filter Paper Surfaces: Creation of a Glass Thermoresponsive Switching Behavior and an Efficient Separation Paper Membrane

by Hideo Sawada, Yuki Suto, Tomoya Saito, Yuri Oikawa, Katsumi Yamashita, Satoshi Yamada, Masashi Sugiya and Jun-ichi Suzuki

Polymers 2017, 9(3), 92; https://doi.org/10.3390/polym9030092 - 4 Mar 2017

Cited by 6 | Viewed by 6945

Abstract

Fluoroalkyl end-capped vinyltrimethoxysilane oligomeric silica/alkyl-modified cellulose (AM-Cellu) nanocomposites [R_F-(CH₂-CHSiO₂)_n-R_F/AM-Cellu; n = 2, 3; R_F = CF(CF₃)OC₃F₇] were prepared by the sol-gel reactions of the corresponding oligomer [...] Read more.

Fluoroalkyl end-capped vinyltrimethoxysilane oligomeric silica/alkyl-modified cellulose (AM-Cellu) nanocomposites [R_F-(CH₂-CHSiO₂)_n-R_F/AM-Cellu; n = 2, 3; R_F = CF(CF₃)OC₃F₇] were prepared by the sol-gel reactions of the corresponding oligomer [R_F-(CH₂-CHSi(OMe)₃)_n-R_F] in the presence of AM-Cellu. The nanocomposites thus obtained were applied to the surface modification of glass to exhibit a highly oleophobic/superhydrophilic characteristic on the modified surface at 20 °C. Interestingly, a temperature dependence of contact angle values of dodecane and water was observed on the modified surface at 20~70 °C, and the dodecane contact angle values were found to decrease with increasing the temperatures from 20 to 70 °C to provide from highly oleophobic to superoleophilic characteristics on the surface. On the other hand, the increase of the water contact angle values was observed with the increase in the temperatures under similar conditions to supply superhydrophilic to superhydrophobic characteristics on the modified surface. The corresponding nanocomposites were also applied to the surface modification of the filter paper under similar conditions to afford a superoleophilic/superhydrophobic characteristic on the surface. It was demonstrated that the modified filter paper is effective for the separation membrane for W/O emulsion to isolate the transparent colorless oil. Full article

(This article belongs to the Special Issue Polymer Blends 2017)

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1974 KiB

Open AccessArticle

Superiorly Plasticized PVC/PBSA Blends through Crotonic and Acrylic Acid Functionalization of PVC

by Arturo Salazar Avalos, Minna Hakkarainen and Karin Odelius

Polymers 2017, 9(3), 84; https://doi.org/10.3390/polym9030084 - 1 Mar 2017

Cited by 25 | Viewed by 10307

Abstract

Superior plasticization efficiency was achieved by a grafting from functionalization of the PVC backbone. This was deduced to a synergistic effect of internal plasticization and improved intermolecular interactions between PVC and an oligomeric poly(butylene succinate-co-adipate) (PBSA) plasticizer. A mild grafting process [...] Read more.

Superior plasticization efficiency was achieved by a grafting from functionalization of the PVC backbone. This was deduced to a synergistic effect of internal plasticization and improved intermolecular interactions between PVC and an oligomeric poly(butylene succinate-co-adipate) (PBSA) plasticizer. A mild grafting process for functionalization of the PVC chain by crotonic acid (CA) or acrylic acid (AA) was used. The formation of PVC-g-CA and PVC-g-AA was confirmed by FTIR and ¹H NMR. Grafting with the seemingly similar monomers, CA and AA, resulted in different macromolecular structures. AA is easily homopolymerized and long hydrophilic poly(acrylic acid) grafts are formed resulting in branched materials. Crotonic acid does not easily homopolymerize; instead, single crotonic acid units are located along the PVC chain, leading to basically linear PVC chains with pendant crotonic acid groups. The elongation of PVC-g-CA and PVC-g-AA in comparison to pure PVC were greatly increased from 6% to 128% and 167%, respectively, by the grafting reactions. Blending 20% (w/w) PBSA with PVC, PVC-AA or PVC-CA further increased the elongation at break to 150%, 240% and 320%, respectively, clearly showing a significant synergistic effect in the blends with functionalized PVC. This is a clearly promising milestone towards environmentally friendly flexible PVC materials. Full article

(This article belongs to the Special Issue Polymer Blends 2017)

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2278 KiB

Open AccessArticle

Optical Properties and Amplified Spontaneous Emission of Novel MDMO-PPV/C500 Hybrid

by Rasha A. Abumosa, Bandar Ali Al-Asbahi and Mohamad Saleh AlSalhi

Polymers 2017, 9(2), 71; https://doi.org/10.3390/polym9020071 - 17 Feb 2017

Cited by 4 | Viewed by 5717

Abstract

The influence of the solvent nature on optical properties of poly[2-methoxy-5-3,7-dimethyloctyloxy-1,4-phenylenevinylene] (MDMO-PPV)/Coumarine 500 (C500) have been investigated. In addition, the amplified spontaneous emission (ASE) from MDMO-PPV and efficient energy transfer between the MDMO-PPV and C500 has been verified. The MDMO-PPV was dissolved in [...] Read more.

The influence of the solvent nature on optical properties of poly[2-methoxy-5-3,7-dimethyloctyloxy-1,4-phenylenevinylene] (MDMO-PPV)/Coumarine 500 (C500) have been investigated. In addition, the amplified spontaneous emission (ASE) from MDMO-PPV and efficient energy transfer between the MDMO-PPV and C500 has been verified. The MDMO-PPV was dissolved in aromatic and nonaromatic solvents, while the solution blending method was employed to prepare the MDMO-PPV:C500 hybrid. The quantum yield of the MDMO-PPV was found to increase with the reduction of a few factors such as polarity index of the solvent, absorption cross section (σ_a), emission cross section (σ_e), and extinction coefficient (ε_max). The fluorescence spectra of the MDMO-PPV appears from two vibronic band transitions (0-0, 0-1) and the ASE occurs at 0-1 transition, which was verified by the ASE from MDMO-PPV. The MDMO-PPV in toluene exhibited the best ASE efficiency due to its high quantum yield compared with other solvents. Strong overlap between the absorption spectrum of MDMO-PPV and emission spectrum of C500 confirmed the efficient energy transfer between them. Moreover, the ASE for energy transfer of the MDMO-PPV:C500 hybrid was proved. Full article

(This article belongs to the Special Issue Polymer Blends 2017)

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6999 KiB

Open AccessArticle

Crystallization of Poly(ε-caprolactone) in Poly(vinylidene fluoride)/Poly(ε-caprolactone) Blend

by Yang Kong, Yangmin Ma, Lele Lei, Xuechuan Wang and Haijun Wang

Polymers 2017, 9(2), 42; https://doi.org/10.3390/polym9020042 - 28 Jan 2017

Cited by 24 | Viewed by 6033

Abstract

The crystallization behavior of poly(ε-caprolactone) (PCL) in a poly(vinylidene fluoride) (PVDF)/PCL blend as well as on a highly orientated PVDF substrate was studied by means of POM, DSC and TEM. The results show that the miscibility of the PVDF/PCL blend and the spherulitic [...] Read more.

The crystallization behavior of poly(ε-caprolactone) (PCL) in a poly(vinylidene fluoride) (PVDF)/PCL blend as well as on a highly orientated PVDF substrate was studied by means of POM, DSC and TEM. The results show that the miscibility of the PVDF/PCL blend and the spherulitic morphology of PVDF varies with the blend ratio. For all the compositions, the pre-existing PVDF crystals accelerated the crystallization of PCL because the PVDF exhibits very strong nucleation ability toward PCL as reflected by the occurrence of heteroepitaxy and the transcrystallization of PBA on the PVDF substrate. This is associated with the perfect lattice matching between the PBA and PVDF crystals. Full article

(This article belongs to the Special Issue Polymer Blends 2017)

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4199 KiB

Open AccessArticle

Investigations on Green Blends Comprising Biodegradable Polymer and Ionic Liquid

by Li-Ting Lee and Chun-Ting Yang

Polymers 2016, 8(12), 444; https://doi.org/10.3390/polym8120444 - 21 Dec 2016

Cited by 9 | Viewed by 5641

Abstract

The green blends of an ionic liquid, 1-ethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide {[EPrI][TFSI]}, and a biodegradable polymer, poly(3-hydroxybutyrate) (PHB), were investigated in this study. The influence of an ionic liquid on the crystallization behaviors of a biodegradable polymer was explored. In the blends, the presence of [...] Read more.

The green blends of an ionic liquid, 1-ethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide {[EPrI][TFSI]}, and a biodegradable polymer, poly(3-hydroxybutyrate) (PHB), were investigated in this study. The influence of an ionic liquid on the crystallization behaviors of a biodegradable polymer was explored. In the blends, the presence of [EPrI][TFSI] decreased the T_g and T_m of PHB. Incorporating [EPrI][TFSI] in the blends reduced the degree of crystallinity of PHB, inferring that the [EPrI][TFSI] weakened the crystallization of PHB. It further showed retarded isothermal and non-isothermal crystallization for PHB with the presence of [EPrI][TFSI]. The smaller K and 1/t_0.5 estimated by the Avrami equation for the blends indicated that [EPrI][TFSI] weakened the isothermal crystallization of PHB with exhibiting the slower crystallization rate. The present study also discussed non-isothermal crystallization of the blends. We found that the Mo model, which is generally used to discuss the non-isothermal crystallization, adequately described the non-isothermal behaviors of the [EPrI][TFSI]/PHB blends. By increasing the [EPrI][TFSI] content, the rate-related parameter F(T) systematically increased, inferring a decreased crystallization rate of PHB with the addition of [EPrI][TFSI] in the blends. The FTIR results suggested an ion–dipole interaction between [EPrI][TFSI] and PHB. This proposes the occurrence of possible complexation between [EPrI][TFSI] and PHB. Full article

(This article belongs to the Special Issue Polymer Blends 2017)

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3192 KiB

Open AccessArticle

Isothermal Cold Crystallization, Heat Resistance, and Tensile Performance of Polylactide/Thermoplastic Polyester Elastomer (PLA/TPEE) Blends: Effects of Annealing and Reactive Compatibilizer

by Sisi Wang, Sujuan Pang, Lisha Pan, Nai Xu and Tan Li

Polymers 2016, 8(12), 417; https://doi.org/10.3390/polym8120417 - 8 Dec 2016

Cited by 21 | Viewed by 7360

Abstract

The combined influences of crystallinity and reactive compatibilizer—a multifunctional epoxide (ADR)—on morphology, tensile performance, and heat resistance of polylactide/thermoplastic polyester elastomer (PLA/TPEE) (80/20) blends were investigated. Annealing involved an isothermal cold crystallization of PLA matrix was performed to increase crystallinity of the samples. [...] Read more.

The combined influences of crystallinity and reactive compatibilizer—a multifunctional epoxide (ADR)—on morphology, tensile performance, and heat resistance of polylactide/thermoplastic polyester elastomer (PLA/TPEE) (80/20) blends were investigated. Annealing involved an isothermal cold crystallization of PLA matrix was performed to increase crystallinity of the samples. First, isothermal cold crystallization kinetics were investigated using differential scanning calorimetry measurement. It was found that the addition of ADR decreased the crystallization rate of the samples. The maximum crystallinity of the annealed samples also decreased from 40% to 34% while ADR loading increased from zero to 1.0 phr. Furthermore, influence of crystallinity on mechanical performances of the PLA/TPEE sample was researched. The heat resistance of the sample showed a significant enhancement while increasing its crystallinity. Meanwhile, the tensile ductility of the crystallized PLA/TPEE sample became very poor due to the embrittlement with increased crystallinity and the incompatibility between PLA and TPEE. However, the annealed PLA/TPEE/ADR samples with high crystallinity kept a higher tensile ductility because ADR greatly improved the interfacial compatibility. Differences in tensile fracture behaviors of the quenched and annealed PLA/TPEE samples with and without ADR were discussed in detail. At last, crystallized PLA/TPEE/ADR blends with excellent heat resistance and high tensile ductility were obtained by annealing and reactive compatibilization. Full article

(This article belongs to the Special Issue Polymer Blends 2017)

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9907 KiB

Open AccessArticle

Miscibility, Morphology and Crystallization Behavior of Poly(Butylene Succinate-co-Butylene Adipate)/Poly(Vinyl Phenol)/Poly(l-Lactic Acid) Blends

by Pengfei Si, Faliang Luo and Fahai Luo

Polymers 2016, 8(12), 421; https://doi.org/10.3390/polym8120421 - 6 Dec 2016

Cited by 9 | Viewed by 5511

Abstract

Amorphous poly(vinyl phenol) (PVPh) is introduced into poly(butylene succinate-co-butylene adipate)/poly(l-lactic acid) (PBSA/PLLA) blends via solution casting. Fourier transform infrared spectroscopy (FTIR) analysis verifies that intermolecular hydrogen bonding formed in PBSA/PVPh/PLLA blends. The miscibility between PBSA and PLLA is improved [...] Read more.

Amorphous poly(vinyl phenol) (PVPh) is introduced into poly(butylene succinate-co-butylene adipate)/poly(l-lactic acid) (PBSA/PLLA) blends via solution casting. Fourier transform infrared spectroscopy (FTIR) analysis verifies that intermolecular hydrogen bonding formed in PBSA/PVPh/PLLA blends. The miscibility between PBSA and PLLA is improved with PVPh incorporation as evidenced by approaching T_gs of the two components. When PVPh content reaches up to 50 wt %, the blend sample exhibits only one T_g, meaning complete miscibility between PBSA and PLLA. The improved miscibility of PBSA/PLLA blends is further confirmed by scanning electron microscope (SEM). Typical “see-island” phase separation structure for PBSA/PLLA blend transforms into homogenous phase structure for blend samples with 5 wt % PVPh and above. Non-isothermal crystallization analysis shows that the crystallization temperature and crystallization enthalpy of PBSA decrease with PVPh addition, and those of PLLA also show a decreasing trend. Isothermal crystallization rate of PBSA in blend samples distinctly decreases with PVPh incorporation, whereas that of PLLA in blend samples increases slightly with PVPh addition. Wide angle X-ray diffraction (WAXD) analysis indicated that PLLA in blend samples remained partly crystallized, while PBSA turned into amorphous state with increasing PVPh contents. Full article

(This article belongs to the Special Issue Polymer Blends 2017)

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