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Advances in Flame Retardant Polymeric Materials II
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Advances in Flame Retardant Polymeric Materials II

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Applications".

Deadline for manuscript submissions: closed (31 December 2022) | Viewed by 38554

Special Issue Editors

Dr. Jelena Vasiljević

E-Mail Website
Guest Editor
Faculty of Natural Sciences and Engineering, University of Ljubljana, Ljubljana, Slovenia
Interests: sol-gel coatings; dispersion coatings; flame retardants; flame retardant polymers; thermal stability; flammability; polymer composites; polymer nanocomposites; water and oil repellency; multifunctionality; antimicrobial activity; functional protective textiles; textile finishing; surface modification
Special Issues, Collections and Topics in MDPI journals
Dr. Ivan Jerman

E-Mail Website
Guest Editor
Assistant Professor, Department of Material Chemistry, National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia
Interests: synthesis of polyhedral oligomeric silsesquioxane; sol-gel thin films; modification of pigments; spectrally selective paint coatings; high solar absorptivity coatings for concentrated solar power; textile finishing; flame retardant polymers; surface treatments; nanocoatings; electrochromic materials; cotton fabric; organic functional trialkoxysilane; surface functionalization; multifunctional properties; flame retardant; photocatalytic degradation; antibacterial; nanoparticles; repellent; few-layer graphene; pathogen-repellent coating
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

This Special Issue of Polymers aims to broaden and deepen the scientific and technological knowledge with the most recent advances in the preparation, performance, and application of flame-retardant polymeric materials with respect to the concept of long-term environmental, economic, and social sustainability.

Flame-retardant natural and synthetic polymeric materials play a crucial role in building the fire-safe urban world. At the same time, the demand for minimizing potential health and environmental impacts requires considering the toxicology, safety, and circularity parameters at the beginning of the design process of flame-retardant systems. This drives development of new flame retardants and flame-retardant materials, ensuring that fire safety is not compromised at the expense of the targeted sustainability. In that respect, an interdisciplinary approach for the development of flame-retardant systems with improved persistent, bioaccumulative, and toxic profiles, lowered heat and smoke release, and reduced smoke toxicity is of high importance.

We invite the research community to contribute to this Special Issue by submitting comprehensive reviews or original research articles. The topics of interest include but are not limited to:

  • Flame-retardant co-monomers and co-polymers;
  • New polymeric flame retardants and their application;
  • Flame-retardant polymers by reactive extrusion;
  • Multi-component flame-retardant systems;
  • Bio-based flame retardants and their application;
  • Flame-retardant composites;
  • Nano-dispersed flame-retardant systems;
  • Flame-retardant systems for surface treatments and coatings;
  • Flame-retardant systems for film- and fiber-forming polymers;
  • Fundamentals of thermal stability, heat transfer, smoke release, and flame-retardant mechanisms;
  • Flame retardancy of recycled polymers;
  • Assessment of the toxicity of combustion products;
  • Assessment of the migration/leaching of flame retardant from polymer;
  • Assessment of the physical/chemical recyclability of flame-retardant polymer;
  • Assessment of the biodegradation of flame-retardant polymer;
  • Life cycle analysis (LCA) of flame-retardant polymeric materials;
  • Structure modelling of flame-retardant molecules.

Prof. Dr. Ivan Jerman
Dr. Jelena Vasiljević
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • flame retardants
  • additives
  • composites
  • nanocomposites
  • coatings
  • films
  • fibrers
  • adhesives
  • foams
  • polymerization
  • reactive extrusion
  • synergism
  • flame- retardant mechanism
  • thermal stability
  • heat transfer
  • smoke release
  • recycling
  • toxicity
  • migration
  • leaching
  • biodegradation
  • life cycle analysis

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Published Papers (13 papers)

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Research

19 pages, 2840 KiB  
Article
Ferrocene-Based Terpolyamides and Their PDMS-Containing Block Copolymers: Synthesis and Physical Properties
by Irrum Mushtaq, Erum Jabeen, Zareen Akhter, Fatima Javed, Azfar Hassan, Muhammad Saif Ullah Khan, Faheem Ullah and Faiz Ullah Shah
Polymers 2022, 14(23), 5087; https://doi.org/10.3390/polym14235087 - 23 Nov 2022
Cited by 1 | Viewed by 2280
Abstract
Aromatic polyamides are well-known as high-performance materials due to their outstanding properties making them useful in a wide range of applications. However, their limited solubility in common organic solvents restricts their processability and becomes a hurdle in their applicability. This study is focused [...] Read more.
Aromatic polyamides are well-known as high-performance materials due to their outstanding properties making them useful in a wide range of applications. However, their limited solubility in common organic solvents restricts their processability and becomes a hurdle in their applicability. This study is focused on the synthesis of processable ferrocene-based terpolyamides and their polydimethylsiloxane (PDMS)-containing block copolymers, using low-temperature solution polycondensation methodology. All the synthesized materials were structurally characterized using FTIR and 1H NMR spectroscopic techniques. The ferrocene-based terpolymers and block copolymers were soluble in common organic solvents, while the organic analogs were found only soluble in sulfuric acid. WXRD analysis showed the amorphous nature of the materials, while the SEM analysis exposed the modified surface of the ferrocene-based block copolymers. The structure–property relationship of the materials was further elucidated by their water absorption and thermal behavior. These materials showed low to no water absorption along with their high limiting oxygen index (LOI) values depicting their good flame-retardant behavior. DFT studies also supported the role of various monomers in the polycondensation reaction where the electron pair donation from HOMO of diamine monomer to the LUMO of acyl chloride was predicted, along with the calculation of various other parameters of the representative terpolymers and block copolymers. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials II)
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17 pages, 4282 KiB  
Article
Environmentally Friendly Hybrid Organic–Inorganic Halogen-Free Coatings for Wood Fire-Retardant Applications
by Georgia C. Lainioti, Vasilis Koukoumtzis, Konstantinos S. Andrikopoulos, Lazaros Tsantaridis, Birgit Östman, George A. Voyiatzis and Joannis K. Kallitsis
Polymers 2022, 14(22), 4959; https://doi.org/10.3390/polym14224959 - 16 Nov 2022
Cited by 8 | Viewed by 2164
Abstract
Wood and wood-based products are extensively used in the building sector due to their interesting combination of properties. Fire safety and fire spread, however, are of utmost concern for the protection of buildings. Therefore, in timber structures, wood must be treated with fire-retardant [...] Read more.
Wood and wood-based products are extensively used in the building sector due to their interesting combination of properties. Fire safety and fire spread, however, are of utmost concern for the protection of buildings. Therefore, in timber structures, wood must be treated with fire-retardant materials in order to improve its reaction to fire. This article highlights the flame retardancy of novel hybrid organic–inorganic halogen-free coatings applied on plywood substrates. For this purpose, either a huntite-rich mineral (H5) or its modified nano-Mg (OH)2 type form (H5-m), acting as an inorganic (nano) filler, was functionalized with reactive oligomers (ROs) and incorporated into a waterborne polymeric matrix. A water-soluble polymer (P (SSNa-co-GMAx)), combining its hydrophilic nature with functional epoxide groups, was used as the reactive oligomer in order to enhance the compatibility between the filler and the matrix. Among various coating compositions, the system composed of 13% polymeric matrix, 73% H5 and 14% ROs, which provided the best coating quality and flame retardancy, was selected for the coating of plywood on a larger scale in one or two layers. The results indicated that the novel plywood coating systems with the addition of ecological coating formulations (WF-13, WF-14 and WF-15), prepared at two layers, reached Euroclass B according to EN13501-1, which is the best possible for fire systems applied to wood. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials II)
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10 pages, 2884 KiB  
Article
Thermal Degradation of Organophosphorus Flame Retardants
by Bob A. Howell
Polymers 2022, 14(22), 4929; https://doi.org/10.3390/polym14224929 - 15 Nov 2022
Cited by 24 | Viewed by 2430
Abstract
The development of new organophosphorus flame retardants for polymeric materials is spurred by relatively low toxicity, effectiveness, and demand for replacement of more traditional materials. To function, these compounds must decompose in a degrading polymer matrix to form species which promote modification of [...] Read more.
The development of new organophosphorus flame retardants for polymeric materials is spurred by relatively low toxicity, effectiveness, and demand for replacement of more traditional materials. To function, these compounds must decompose in a degrading polymer matrix to form species which promote modification of the solid phase or generate active radical moieties that escape to the gas phase and interrupt combustion propagating reactions. An understanding of the decomposition process for these compounds may provide insight into the nature of flame retardant action which they may offer and suggest parameters for the synthesis of effective new organophosphorus flame retardants. The thermal degradation of a series of organophosphorus esters varying in the level of oxygenation at phosphorus—alkyl phosphate, aryl phosphate, phosphonate, phosphinate—has been examined. Initial degradation in all cases corresponds to elimination of a phosphorus acid. However, the facility with which this occurs is strongly dependent on the level of oxygenation at phosphorus. For alkyl phosphates elimination occurs rapidly at relatively low temperature. The same process occurs at somewhat higher temperature for aryl phosphates. Elimination of a phosphorus acid from phosphonate or phosphinate occurs more slowly and at much higher temperature. Further, the acids formed from elimination rapidly degrade further to evolve volatile species. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials II)
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14 pages, 5050 KiB  
Article
Flexible Polyurethane Foams Reinforced by Functionalized Polyhedral Oligomeric Silsesquioxanes: Structural Characteristics and Evaluation of Thermal/Flammability Properties
by Edyta Hebda, Artur Bukowczan, Sławomir Michałowski and Krzysztof Pielichowski
Polymers 2022, 14(21), 4743; https://doi.org/10.3390/polym14214743 - 5 Nov 2022
Cited by 6 | Viewed by 2155
Abstract
In this work, we report on flexible toluene diisocyanate (TDI)-based polyurethane foams (FPUFs) chemically modified by POSS moieties, i.e., octa (3-hydroxy-3-methylbutyldimethylsiloxy) POSS (OCTA-POSS) and 1,2-propanediolizo-butyl POSS (PHI-POSS). The influence of silsesquioxane on the PU foaming process, structure, morphology, physicochemical, and mechanical properties, as [...] Read more.
In this work, we report on flexible toluene diisocyanate (TDI)-based polyurethane foams (FPUFs) chemically modified by POSS moieties, i.e., octa (3-hydroxy-3-methylbutyldimethylsiloxy) POSS (OCTA-POSS) and 1,2-propanediolizo-butyl POSS (PHI-POSS). The influence of silsesquioxane on the PU foaming process, structure, morphology, physicochemical, and mechanical properties, as well as flammability, was examined. FT-IR analysis provided evidence for the chemical incorporation of the nanofiller into the foam structure. It was found that the addition of POSS increases the apparent density of the foam and its compressive strength. The XRD and SEM-EDS techniques showed the uniform distribution of POSS in the FPUF with agglomeration depending on the kind and content of the introduced POSS moieties. The analysis of the thermogravimetric and microcalorimetry data revealed an improved resistance to the burning of FPUFs containing reactive POSS, as evidenced by the reduced rate of heat release (HRR). Importantly, the mechanical properties tests showed that the incorporation of silsesquioxane nanoparticles into the polyurethane structure via covalent bonds strengthens the foam integrity. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials II)
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19 pages, 30180 KiB  
Article
Mode of Action of Zn-DOPOx and Melamine Polyphosphate as Flame Retardants in Glass Fiber-Reinforced Polyamide 66
by Johannes Klitsch, Rudolf Pfaendner, Claudia Fasel and Frank Schönberger
Polymers 2022, 14(18), 3709; https://doi.org/10.3390/polym14183709 - 6 Sep 2022
Cited by 1 | Viewed by 1932
Abstract
In this study, the flame retardant effect of the Zn salt of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Zn-DOPOx), melamine polyphosphate (MPP) and their mixture was investigated towards the mode of action in glass fiber-reinforced polyamide 66 (PA 66 GF). The flammability was evaluated using UL 94 V [...] Read more.
In this study, the flame retardant effect of the Zn salt of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Zn-DOPOx), melamine polyphosphate (MPP) and their mixture was investigated towards the mode of action in glass fiber-reinforced polyamide 66 (PA 66 GF). The flammability was evaluated using UL 94 V and cone calorimetry. Influence on char formation was analyzed by SEM. Thermal decomposition of Zn-DOPOx and MPP was studied by TGA and ATR-FTIR. The release of gaseous PA 66 decomposition products was investigated using TGA-DTA-FTIR. Combining Zn-DOPOx and MPP leads to an improvement in flame retardancy, most pronounced for equal parts of weight. Mode of action changes significantly for Zn-DOPOx:MPP (1:1) compared to the sole components and a strong interaction between Zn-DOPOx and MPP is revealed, resulting in a more open char structure. Fuel dilution as well as less exothermic decomposition are essential for the mode of action of the combination. Through low HRR values and high CO/CO2 ratio during cone calorimetry measurements, a significant increase in gas phase activity was proven. Therefore, it is concluded that Zn-DOPOx:MPP (1:1) leads to a significant increase in flame retardancy through a combination of mode of actions in the gas and condensed phase resulting from the change in thermal stability. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials II)
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24 pages, 5157 KiB  
Article
It Takes Two to Tango: Synergistic Expandable Graphite–Phosphorus Flame Retardant Combinations in Polyurethane Foams
by Yin Yam Chan and Bernhard Schartel
Polymers 2022, 14(13), 2562; https://doi.org/10.3390/polym14132562 - 23 Jun 2022
Cited by 25 | Viewed by 4395
Abstract
Due to the high flammability and smoke toxicity of polyurethane foams (PUFs) during burning, distinct efficient combinations of flame retardants are demanded to improve the fire safety of PUFs in practical applications. This feature article focuses on one of the most impressive halogen-free [...] Read more.
Due to the high flammability and smoke toxicity of polyurethane foams (PUFs) during burning, distinct efficient combinations of flame retardants are demanded to improve the fire safety of PUFs in practical applications. This feature article focuses on one of the most impressive halogen-free combinations in PUFs: expandable graphite (EG) and phosphorus-based flame retardants (P-FRs). The synergistic effect of EG and P-FRs mainly superimposes the two modes of action, charring and maintaining a thermally insulating residue morphology, to bring effective flame retardancy to PUFs. Specific interactions between EG and P-FRs, including the agglutination of the fire residue consisting of expanded-graphite worms, yields an outstanding synergistic effect, making this approach the latest champion to fulfill the demanding requirements for flame-retarded PUFs. Current and future topics such as the increasing use of renewable feedstock are also discussed in this article. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials II)
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16 pages, 6234 KiB  
Article
Synthesis of New S-Triazine Bishydrazino and Bishydrazido-Based Polymers and Their Application in Flame-Retardant Polypropylene Composites
by Ali Aldalbahi, Bander S. AlOtaibi, Badr M. Thamer and Ayman El-Faham
Polymers 2022, 14(4), 784; https://doi.org/10.3390/polym14040784 - 17 Feb 2022
Cited by 4 | Viewed by 2730
Abstract
In this study six new s-triazine bishydrazino and bishydrazido-based polymers were synthesized via condensation of bishydrazino s-triazine derivatives with terephthaldehyde or via nucleophilic substitution of dichloro-s-triazine derivatives with terephthalic acid hydrazide. The synthesized polymers were characterized by different techniques. The new polymers displayed [...] Read more.
In this study six new s-triazine bishydrazino and bishydrazido-based polymers were synthesized via condensation of bishydrazino s-triazine derivatives with terephthaldehyde or via nucleophilic substitution of dichloro-s-triazine derivatives with terephthalic acid hydrazide. The synthesized polymers were characterized by different techniques. The new polymers displayed good thermal behavior with great values in terms of limited oxygen indexed (LOI) 27.50%, 30.12% for polymers 5b,c (bishydrazino-s-triazine based polymers) and 27.23%, 29.86%, 30.85% for polymers 7a–c (bishydrazido-s-triazine based polymers) at 800 °C. Based on the LOI values, these polymers could be classified as flame retardant and self-extinguishing materials. The thermal results also revealed that the type of substituent groups on the triazine core has a considerable impact on their thermal behavior. Accordingly, the prepared polymers were mixed with ammonium polyphosphate (APP) in different proportions to form an intumescent flame-retardant (IFRs) system and were introduced into polypropylene (PP) to improve the flame-retardancy of the composites. The best results were obtained with a mass ratio of APP: 5a–c or 7a–c of 2:1, according to the vertical burning study (UL-94). In addition, the presence of 25% “weight ratio” of IFR in the composite showed great impact and passed UL-94 V-0 and V-1 tests. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials II)
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16 pages, 31664 KiB  
Article
Flame-Retardant Performance Evaluation of Functional Coatings Filled with Mg(OH)2 and Al(OH)3
by Elpida Piperopoulos, Giuseppe Scionti, Mario Atria, Luigi Calabrese and Edoardo Proverbio
Polymers 2022, 14(3), 372; https://doi.org/10.3390/polym14030372 - 18 Jan 2022
Cited by 19 | Viewed by 2813
Abstract
In the shipbuilding sector (cruises, ferries, etc.), the design and control constraints applied to improve the fire safety conditions of naval vessels are acquiring important relevance. Research activities have aimed at enhancing the fire resistance of structures and surface coatings to make ships’ [...] Read more.
In the shipbuilding sector (cruises, ferries, etc.), the design and control constraints applied to improve the fire safety conditions of naval vessels are acquiring important relevance. Research activities have aimed at enhancing the fire resistance of structures and surface coatings to make ships’ working environments safer, trying to combine performance, durability and low costs. In this context, the aim of this paper is to develop and optimize flame-retardant coatings for naval applications. In particular, in an acrylic carrier, Mg(OH)2 and Al(OH)3 fillers were added to exalt the fire resistance capabilities of the coatings. Furthermore, the effect of the particle size of the hydroxides on the coatings’ fire resistance was investigated. The coatings were studied by structural (XRD), thermo-physical (TG) and morphological (SEM) characterization to evaluate their thermal stability and the damage level due to fire exposition. Specifically, fire reaction tests were applied at different fire exposure times (15 s, 30 s) to estimate the fire resistance of the proposed coatings compared to the commercial reference. The results show that the coatings based on aluminum and magnesium hydroxides exhibit favorable fire resistance. Particularly, effective performances were observed for short times of exposure to direct flames. Furthermore, the temperature monitoring of the steel alloy support during the test allowed us to evaluate the degree of insulation of the coating, highlighting a better result for the specimen filled with Mg(OH)2, making this product promising for its optimization in this context. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials II)
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14 pages, 3871 KiB  
Article
A Novel Self-Assembled Graphene-Based Flame Retardant: Synthesis and Flame Retardant Performance in PLA
by Peixin Yang, Hanguang Wu, Feifei Yang, Jie Yang, Rui Wang and Zhiguo Zhu
Polymers 2021, 13(23), 4216; https://doi.org/10.3390/polym13234216 - 1 Dec 2021
Cited by 21 | Viewed by 3185
Abstract
In this study, a novel flame retardant (PMrG) was developed by self-assembling melamine and phytic acid (PA) onto rGO, and then applying it to the improvement of the flame resistance of PLA. PMrG simultaneously decreases the peak heat release rate (pHRR) and the [...] Read more.
In this study, a novel flame retardant (PMrG) was developed by self-assembling melamine and phytic acid (PA) onto rGO, and then applying it to the improvement of the flame resistance of PLA. PMrG simultaneously decreases the peak heat release rate (pHRR) and the total heat release (THR) of the composite during combustion, and enhances the LOI value and the time to ignition (TTI), thus significantly improving the flame retardancy of the composite. The flame retardant mechanism of the PMrG is also investigated. On one hand, the dehydration of PA and the decomposition of melamine in PMrG generate non-flammable volatiles, such as H2O and NH3, which dilute the oxygen concentration around the combustion front of the composite. On the other hand, the rGO, melamine, and PA components in PMrG create a synergistic effect in promoting the formation of a compact char layer during the combustion, which plays a barrier role and effectively suppresses the release of heat and smoke. In addition, the PMrGs in PLA exert a positive effect on the crystallization of the PLA matrix, thus playing the role of nucleation agent. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials II)
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16 pages, 5138 KiB  
Article
Halogen-Free Flame Retardant Polypropylene Fibers with Modified Intumescent Flame Retardant: Preparation, Characterization, Properties and Mode of Action
by Qibin Xu, Lei Wu, Xiang Yan, Shengchang Zhang, Linan Dong, Zexi Su, Tianhaoyue Zhong, Chunhui Jiang, Yuan Chen, Mengjin Jiang and Pengqing Liu
Polymers 2021, 13(15), 2553; https://doi.org/10.3390/polym13152553 - 31 Jul 2021
Cited by 12 | Viewed by 3192
Abstract
A novel intumescent flame retardant (IFR) agent designated as Dohor-6000A has been used to prepare halogen-free flame retardant polypropylene (PP) fibers via melting spinning. Before being blended with PP resin, a surface modification of Dohor-6000A was carried out to improve its compatibility with [...] Read more.
A novel intumescent flame retardant (IFR) agent designated as Dohor-6000A has been used to prepare halogen-free flame retardant polypropylene (PP) fibers via melting spinning. Before being blended with PP resin, a surface modification of Dohor-6000A was carried out to improve its compatibility with the PP matrix. The rheological behavior of flame retardant Dohor-6000A/PP resin, the structure, morphology, mechanical properties, flammability of the Dohor-6000A/PP fibers were studied in detail, as well as the action mode of flame retardant. X-ray diffraction (XRD) showed that the addition of Dohor-6000A did not damage the crystal as well as the orientation structure of PP matrix, which was helpful to the maintenance of mechanical properties. The presence of the IFR significantly improved the flame retardant performance and thermal stability of PP fibers. When the content of Dohor-6000A reached 25%, the fibers displayed a limiting oxygen index (LOI) value of 29.1% and good melt-drop resistance. Moreover, the peak heat release rate (PHRR) and total heat release (THR) from microscale combustion colorimetry (MCC) tests were decreased by 26.0% and 16.0% in comparison with the same conditions for pure PP fibers. In the condensed phase, the IFR promoted a carbonization process and promoted the formation of a glassy or stable foam protective layer on the surface of the polymer matrix. In addition, the IFR decomposed endothermically to release of non-combustible gases such as NH3 and CO2 which dilutes the combustible gases in the combustion zone. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials II)
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19 pages, 5193 KiB  
Article
Benzoxazine Monomers and Polymers Based on 3,3′-Dichloro-4,4′-Diaminodiphenylmethane: Synthesis and Characterization
by Viktoria V. Petrakova, Vyacheslav V. Kireev, Denis V. Onuchin, Igor A. Sarychev, Vyacheslav V. Shutov, Anastasia A. Kuzmich, Natalia V. Bornosuz, Mikhail V. Gorlov, Nikolay V. Pavlov, Alexey V. Shapagin, Ramil R. Khasbiullin and Igor S. Sirotin
Polymers 2021, 13(9), 1421; https://doi.org/10.3390/polym13091421 - 28 Apr 2021
Cited by 14 | Viewed by 3927
Abstract
To reveal the effect of chlorine substituents in the ring of aromatic amine on the synthesis process of benzoxazine monomer and on its polymerization ability, as well as to develop a fire-resistant material, a previously unreported benzoxazine monomer based on 3,3′-dichloro-4,4′-diaminodiphenylmethane was obtained [...] Read more.
To reveal the effect of chlorine substituents in the ring of aromatic amine on the synthesis process of benzoxazine monomer and on its polymerization ability, as well as to develop a fire-resistant material, a previously unreported benzoxazine monomer based on 3,3′-dichloro-4,4′-diaminodiphenylmethane was obtained in toluene and mixture toluene/isopropanol. The resulting benzoxazine monomers were thermally cured for 2 h at 180 °C, 4 h at 200 °C, 2 h at 220 °C. A comparison between the rheological, thermal and fire-resistant properties of the benzoxazines based on 3,3′-dichloro-4,4′-diaminodiphenylmethane and, for reference, 4,4′-diaminodimethylmethane was made. The effect of the reaction medium on the structure of the oligomeric fraction and the overall yield of the main product were studied and the toluene/ethanol mixture was found to provide the best conditions; however, in contrast to most known diamine-based benzoxazines, synthesis in the pure toluene is also possible. The synthesized monomers can be used as thermo- and fire-resistant binders for polymer composite materials, as well as hardeners for epoxy resins. Chlorine-containing polybenzoxazines require more severe conditions for polymerization but have better fire resistance. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials II)
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16 pages, 3773 KiB  
Article
Fire Behavior of Thermally Thin Materials in Cone Calorimeter
by Marouane El Gazi, Rodolphe Sonnier, Stéphane Giraud, Marcos Batistella, Shantanu Basak, Loïc Dumazert, Raymond Hajj and Roland El Hage
Polymers 2021, 13(8), 1297; https://doi.org/10.3390/polym13081297 - 15 Apr 2021
Cited by 18 | Viewed by 3180
Abstract
In this study, a representative set of thermally thin materials including various lignocellulosic and synthetic fabrics, dense wood, and polypropylene sheets were tested using a cone calorimeter at different heat fluxes. Time-to-ignition, critical heat flux, and peak of heat release rate (pHRR) were [...] Read more.
In this study, a representative set of thermally thin materials including various lignocellulosic and synthetic fabrics, dense wood, and polypropylene sheets were tested using a cone calorimeter at different heat fluxes. Time-to-ignition, critical heat flux, and peak of heat release rate (pHRR) were the main parameters considered. It appears that the flammability is firstly monitored by the sample weight. Especially, while the burning rate of thermally-thin materials does never reach a steady state in cone calorimeter, their pHRR appears to be mainly driven by the fire load (i.e., the product of sample weight and effective heat of combustion) with no or negligible influence of textile structure. A simple phenomenological model was proposed to calculate the pHRR taking into account only three parameters, namely heat flux, sample weight, and effective heat of combustion. The model allows predicting easily the peak of heat release rate, which is often considered as the main single property informing about the fire hazard. It also allows drawing some conclusions about the flame retardant strategies to reduce the pHRR.. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials II)
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17 pages, 5700 KiB  
Article
New Insights into Antibacterial and Antifungal Properties, Cytotoxicity and Aquatic Ecotoxicity of Flame Retardant PA6/DOPO-Derivative Nanocomposite Textile Fibers
by Jelena Vasiljević, Danaja Štular, Gabriela Kalčíková, Janja Zajc, Matic Šobak, Andrej Demšar, Brigita Tomšič, Barbara Simončič, Marija Čolović, Vid Simon Šelih and Ivan Jerman
Polymers 2021, 13(6), 905; https://doi.org/10.3390/polym13060905 - 15 Mar 2021
Cited by 7 | Viewed by 3057
Abstract
The aim of this study was to evaluate the antibacterial and antifungal activity, cytotoxicity, leaching, and ecotoxicity of novel flame retardant polyamide 6 (PA6) textile fibers developed by our research group. The textile fibers were produced by the incorporation of flame-retardant bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide [...] Read more.
The aim of this study was to evaluate the antibacterial and antifungal activity, cytotoxicity, leaching, and ecotoxicity of novel flame retardant polyamide 6 (PA6) textile fibers developed by our research group. The textile fibers were produced by the incorporation of flame-retardant bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivative (PHED) in the PA6 matrix during the in situ polymerization process at concentrations equal to 10 and 15 wt% (PA6/10PHED and PA6/15PHED, respectively). Whilst the nanodispersed PHED provided highly efficient flame retardancy, its biological activity led to excellent antibacterial activity against Escherichia coli and Staphylococcus aureus, as well as excellent antifungal activity against Aspergillus niger and Candida albicans. The results confirmed leaching of the PHED, but the tested leachates did not cause any measurable toxic effect to the duckweed Lemna minor. The in vitro cytotoxicity of the leached PHED from the PA6/15PHED sample was confirmed for human cells from adipose tissue in direct and prolonged contact. The targeted biological activity of the organophosphinate flame retardant could be beneficial for the development of PA6 textile materials with multifunctional properties and the low ecotoxicity profile, while the PHED’s leaching and cytotoxicity limit their application involving the washing processes and direct contact with the skin. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials II)
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