Advance in Polymer-Based Flame Retardant Materials

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

Deadline for manuscript submissions: closed (5 July 2023) | Viewed by 16861

Special Issue Editors


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Guest Editor
School of Energy, Materials and Chemical Engineering, Hefei University, 99 Jinxiu Avenue, Hefei, Anhui 230601, China
Interests: polymer composites; nanomaterials; flame retardant; surface engineering

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Guest Editor
School of Mechanical and Manufacturing Engineering, The University of New South Wales, Sydney 2052, Australia
Interests: computational fluid dynamics; computational heat transfer; heat and mass transfer operations; composite materials; fire management; biomaterials; simulation and modelling; composite and hybrid materials; other artificial intelligence
Special Issues, Collections and Topics in MDPI journals
College of Textile Science and Engineering, Jiangnan University, 1800 Lihu Road, Wuxi 214122, China
Interests: aerogels; intelligent materials; flame-retardant fiber materials; two-dimensional nanoparticles
Special Issues, Collections and Topics in MDPI journals

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Guest Editor
Laboratory of Polymer Materials and Engineering, NingboTech University, Ningbo 315100, China
Interests: rare-earth based flame retardant; polymer nanocomposites; thermal degradation

Special Issue Information

Dear Colleagues,

Multifunctional polymers and high-performance building materials such as thermal insulations (PU, EPS) are widely applied in modern infrastructures. This ranges from urban areas (e.g., high-rise, metro, residential and commercial) to rural areas (e.g., mining, energy storage, marine industries). Nonetheless, fire incidents caused by these highly flammable polymers have increased dramatically over the last decade. While fire retardants and fire protection systems can be utilised, the amount of fire toxicity/smoke and halogenated compound emissions are often overlooked. This Special Issues aims to investigate the state of the art and further perspectives of upcoming advanced fire retardant materials, as well as recent developments in multi-scale fire modelling approaches.

Prof. Dr. Wei Yang
Dr. Anthony Chun Yin Yuen
Dr. Dong Wang
Prof. Dr. Shiya Ran
Guest Editors

Manuscript Submission Information

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Keywords

  • polymer composites
  • bio-based materials
  • multifunctional materials
  • thermal degradation
  • flame retardant
  • molecular dynamics

Published Papers (7 papers)

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Research

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33 pages, 9725 KiB  
Article
Novel Macromolecular and Biobased Flame Retardants Based on Cellulose Esters and Phosphorylated Sugar Alcohols
by Matay Kaplan, Michael Ciesielski, Sabine Fuchs, Christoffer Getterle, Frank Schönberger and Rudolf Pfaendner
Polymers 2023, 15(15), 3195; https://doi.org/10.3390/polym15153195 - 27 Jul 2023
Viewed by 1407
Abstract
The increasing demand to provide sustainably produced plastic materials requires, a.o., the development of biobased flame retardants (FRs) for applications where flame retardancy is essential. To meet those challenging new sustainability requirements, a set of novel phosphorus-containing cellulose esters were synthesized by an [...] Read more.
The increasing demand to provide sustainably produced plastic materials requires, a.o., the development of biobased flame retardants (FRs) for applications where flame retardancy is essential. To meet those challenging new sustainability requirements, a set of novel phosphorus-containing cellulose esters were synthesized by an efficient two-step procedure. In the first step, cellulose was treated with acrylic anhydride to synthesize acrylate-functionalized cellulose esters—more specifically, cellulose acrylate butyrate (CeAcBu) and propionate (CeAcPr). Subsequently, phosphorylated anhydro erythritol (PAHE), synthesized from the sugar alcohol erythritol, was added to the acrylate-functionalized cellulose esters via Phospha-Michael addition. For comparison a cellulose ester based on 6H-Dibenzo[c,e][1,2]oxaphosphorin-6-on (DOPO) was prepared analogously. The acrylate-functionalized cellulose esters and novel FRs were characterized by NMR spectroscopy. TGA investigations of PAHE-functionalized CeAcBu revealed an onset temperature of decomposition (2% mass loss) of approx. 290 °C. The novel PAHE-based FR was incorporated into a polypropylene-polyethylene copolymer (PP-co-PE) together with poly-tert-butylphenol disulfide (PBDS) (8 wt.%/2 wt.%) as a synergist. The PP-PE samples achieved V2 classification in the UL 94 V test. In addition, specimens of a rapeseed oil-based polyamide containing PAHE-functionalized CeAcBu at 20 wt.% loading yielded a V2 rating with short burning times. Full article
(This article belongs to the Special Issue Advance in Polymer-Based Flame Retardant Materials)
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13 pages, 3964 KiB  
Article
Highly Efficient Flame-Retardant and Enhanced PVA-Based Composite Aerogels through Interpenetrating Cross-Linking Networks
by Ningjing Wu, Shanshan Deng, Fei Wang, Mohan Wang, Mingfeng Xia, Hongli Cui and Haoyi Jia
Polymers 2023, 15(3), 657; https://doi.org/10.3390/polym15030657 - 27 Jan 2023
Cited by 5 | Viewed by 1807
Abstract
Poly(vinyl alcohol) (P)/alginate (A)/MMT (M) (PAM) composite aerogels was modified through interpenetrating cross-linking of methyltriethoxysilane (Ms) or γ-aminopropyltriethoxysilane (K) and calcium ion (Ca2+) as a cross-linking agent, respectively. The compressive moduli of the cross-linked PAM/MsCa and PAM/KCa aerogels greatly increased to [...] Read more.
Poly(vinyl alcohol) (P)/alginate (A)/MMT (M) (PAM) composite aerogels was modified through interpenetrating cross-linking of methyltriethoxysilane (Ms) or γ-aminopropyltriethoxysilane (K) and calcium ion (Ca2+) as a cross-linking agent, respectively. The compressive moduli of the cross-linked PAM/MsCa and PAM/KCa aerogels greatly increased to 17.4 and 22.1 MPa, approximately 10.5- and 8.2-fold of that of PAM aerogel, respectively. The limited oxygen index (LOI) values for PAM/MsCa and PAM/KCa composite aerogels increased from 27.0% of PAM aerogel to 40.5% and 56.8%. Compared with non-cross-linked PAM aerogel, the peak heat release rate (PHRR) of PAM/MsCa and PAM/KCa composite aerogels dramatically decreased by 34% and 74%, respectively, whereas the PAM/KCa aerogel presented better flame retardancy and lower smoke toxicity than the PAM/MsCa aerogel because of the release of more inert gases and the barrier action of more compact char layer during the combustion. The highly efficient flame-retardant PAM-based composite aerogels with excellent mechanical properties are promising as a sustainable alternative to traditional petroleum-based foams. Full article
(This article belongs to the Special Issue Advance in Polymer-Based Flame Retardant Materials)
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17 pages, 3517 KiB  
Article
Synergistic Enhancement of Flame Retardancy Behavior of Glass-Fiber Reinforced Polylactide Composites through Using Phosphorus-Based Flame Retardants and Chain Modifiers
by Ceren Yargici Kovanci, Mohammadreza Nofar and Abbas Ghanbari
Polymers 2022, 14(23), 5324; https://doi.org/10.3390/polym14235324 - 6 Dec 2022
Cited by 6 | Viewed by 2001
Abstract
Flame retardancy properties of neat PLA can be improved with different phosphorus-based flame retardants (FRs), however, developing flame retardant PLA-based engineering composites with maintained mechanical performance is still a challenge. This study proposes symbiosis approaches to enhance the flame retardancy behavior of polylactide [...] Read more.
Flame retardancy properties of neat PLA can be improved with different phosphorus-based flame retardants (FRs), however, developing flame retardant PLA-based engineering composites with maintained mechanical performance is still a challenge. This study proposes symbiosis approaches to enhance the flame retardancy behavior of polylactide (PLA) composites with 20 wt% short glass fibers (GF). This was first implemented by exploring the effects of various phosphorus-based FRs up to 5 wt% in neat PLA samples. Among the used phosphorus-based FRs, the use of only 3 wt% of diphosphoric acid-based FR (P/N), melamine coated ammonium polyphosphate (APPcoated), and APP with melamine synergist (APP/Mel) resulted in achieving the V0 value in a vertical burning test in the neat PLA samples. In addition to their superior efficiency in improving the flame retardancy of neat PLA, P/N had the least negative effect on the final mechanical performance of PLA samples. When incorporated in PLA composites with 20 wt% GF, however, even with the use of 30 wt% P/N, the V0 value could not be obtained due to the candlewick effect. To resolve this issue, the synergistic effect of P/N and aromatic polycarbodiimide (PCDI) cross-linker or Joncryl epoxy-based chain-extender (CE) on the flame retardancy characteristics of composites was examined. Due to the further chain modification, which also enhances the melt strength of PLA, the dripping of composites in the vertical burning test terminated and the V0 value could be reached when using only 1 wt% PCDI or CE. According to the scanning electron microscopic analysis, the use of noted chain modifiers further homogenized the distribution and refined the particle size of P/N within the PLA matrix. Hence this could synergistically contribute to the enhancements of the fire resistance performance of the PLA composites. Such incorporation of P/N and chain modifiers further leads to the enhancement of the mechanical performance of PLA composites and hence the resultant product can be proposed as a promising durable bioplastic engineering product where fire risk exists. Full article
(This article belongs to the Special Issue Advance in Polymer-Based Flame Retardant Materials)
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10 pages, 4066 KiB  
Article
Flame Retardancy and Thermal Degradation Behaviors of Thiol-Ene Composites Containing a Novel Phosphorus and Silicon-Containing Flame Retardant
by Fangyi Wu, Xiaohui Bao and Jiangbo Wang
Polymers 2022, 14(4), 820; https://doi.org/10.3390/polym14040820 - 20 Feb 2022
Cited by 8 | Viewed by 2194
Abstract
In this article, a novel phosphorus and silicon-containing flame retardant (DOPO-V-PA) was synthesized via condensation reaction and then added into thiol-ene (TE) to prepare a flame-retardant composite. The results of cone calorimeter measurement demonstrated that, compared with pure TE, 22.7% and 53.2% reduction [...] Read more.
In this article, a novel phosphorus and silicon-containing flame retardant (DOPO-V-PA) was synthesized via condensation reaction and then added into thiol-ene (TE) to prepare a flame-retardant composite. The results of cone calorimeter measurement demonstrated that, compared with pure TE, 22.7% and 53.2% reduction of TE/DOPO-V-PA (thiol-ene/9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-vinyltrimethoxysilane-phenyltrimethoxysilane-(3-aminopropyl)trimethoxysilane copolymer) was found for the peak heat release rate (PHRR) and total heat release (THR), respectively. The thermal degradation of TE composites was investigated by the TGA measurement under non-isothermal conditions, and kinetic parameters were both calculated by the Kissinger and Flynn-Wall-Ozawa methods. It was indicated that the activation energies of TE at conversions exceeding 50% were enhanced by the incorporation of DOPO-V-PA for the whole conversion range. Full article
(This article belongs to the Special Issue Advance in Polymer-Based Flame Retardant Materials)
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12 pages, 5510 KiB  
Article
DOPO/Silicon/CNT Nanohybrid Flame Retardants: Toward Improving the Fire Safety of Epoxy Resins
by Yingzhe Zhang, Congling Shi, Xiaodong Qian, Jingyun Jing and Longzhe Jin
Polymers 2022, 14(3), 565; https://doi.org/10.3390/polym14030565 - 30 Jan 2022
Cited by 8 | Viewed by 2784
Abstract
Novel DOPO/silicon/CNT nanohybrid flame retardants (FR-CNTs) were synthesized and FR-CNTs were introduced into epoxy resins through thermal curing process. The SEM and TEM results indicate that CNTs distribute uniformly in epoxy resins due to the good dispersion of CNTs in DOPO/silicon/CNT nanohybrid flame [...] Read more.
Novel DOPO/silicon/CNT nanohybrid flame retardants (FR-CNTs) were synthesized and FR-CNTs were introduced into epoxy resins through thermal curing process. The SEM and TEM results indicate that CNTs distribute uniformly in epoxy resins due to the good dispersion of CNTs in DOPO/silicon/CNT nanohybrid flame retardants. The thermal stability and flame-retardant properties of EP/FR-CNTs composites are improved, which is attributed to the good dispersion of DOPO/silicon/CNT nanohybrid. The cone calorimeter results demonstrate that FR-CNTs can reduce peak heat release and the release of toxic gas effectively compared with EP/CNTs and EP/CNT/FR composites. The char-residue analysis indicates that the improved flame-retardant properties are due to the char-reinforcing effects and the catalyzing charring effect of FR-CNTs, which provides enough time for flame retardants to trap radicals. Generally, the char layers, which act as insulating barrier, can reduce the releasing of flammable gases and protect the underlying epoxy resins from the heat source. Full article
(This article belongs to the Special Issue Advance in Polymer-Based Flame Retardant Materials)
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15 pages, 5198 KiB  
Article
A Novel Synergistic Flame Retardant of Hexaphenoxycyclotriphosphazene for Epoxy Resin
by Jiawei Jiang, Siqi Huo, Yi Zheng, Chengyun Yang, Hongqiang Yan, Shiya Ran and Zhengping Fang
Polymers 2021, 13(21), 3648; https://doi.org/10.3390/polym13213648 - 23 Oct 2021
Cited by 16 | Viewed by 2341
Abstract
Hexaphenoxycyclotriphosphazene (HPCP) is a common flame retardant for epoxy resin (EP). To improve the thermostability and fire safety of HPCP-containing EP, we combined UiO66-NH2 (a kind of metal-organic frame, MOF) with halloysite nanotubes (HNTs) by hydrothermal reaction to create a novel synergistic [...] Read more.
Hexaphenoxycyclotriphosphazene (HPCP) is a common flame retardant for epoxy resin (EP). To improve the thermostability and fire safety of HPCP-containing EP, we combined UiO66-NH2 (a kind of metal-organic frame, MOF) with halloysite nanotubes (HNTs) by hydrothermal reaction to create a novel synergistic flame retardant (H-U) of HPCP for EP. For the EP containing HPCP and H-U, the initial decomposition temperature (T5%) and the temperature of maximum decomposition rate (Tmax) increased by 11 and 17 °C under nitrogen atmosphere compared with those of the EP containing only HPCP. Meanwhile, the EP containing HPCP and H-U exhibited better tensile and flexural properties due to the addition of rigid nanoparticles. Notably, the EP containing HPCP and H-U reached a V-0 rating in UL-94 test and a limited oxygen index (LOI) of 35.2%. However, with the introduction of H-U, the flame retardant performances of EP composites were weakened in the cone calorimeter test, which was probably due to the decreased height of intumescent residual char. Full article
(This article belongs to the Special Issue Advance in Polymer-Based Flame Retardant Materials)
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Review

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15 pages, 1605 KiB  
Review
Recent Advances in Zinc Hydroxystannate-Based Flame Retardant Polymer Blends
by Wei-Hao Pan, Wen-Jie Yang, Chun-Xiang Wei, Ling-Yun Hao, Hong-Dian Lu and Wei Yang
Polymers 2022, 14(11), 2175; https://doi.org/10.3390/polym14112175 - 27 May 2022
Cited by 12 | Viewed by 2765
Abstract
During the combustion of polymeric materials, plenty of heat, smoke, and toxic gases are produced that may cause serious harm to human health. Although the flame retardants such as halogen- and phosphorus-containing compounds can inhibit combustion, they cannot effectively reduce the release of [...] Read more.
During the combustion of polymeric materials, plenty of heat, smoke, and toxic gases are produced that may cause serious harm to human health. Although the flame retardants such as halogen- and phosphorus-containing compounds can inhibit combustion, they cannot effectively reduce the release of toxic fumes. Zinc hydroxystannate (ZHS, ZnSn(OH)6) is an environmentally friendly flame retardant that has attracted extensive interest because of its high efficiency, safety, and smoke suppression properties. However, using ZHS itself may not contribute to the optimal flame retardant effect, which is commonly combined with other flame retardants to achieve more significant efficiency. Few articles systematically review the recent development of ZHS in the fire safety field. This review aims to deliver an insight towards further direction and advancement of ZHS in flame retardant and smoke suppression for multiple polymer blends. In addition, the fire retarded and smoke suppression mechanism of ZHS will be demonstrated and discussed in depth. Full article
(This article belongs to the Special Issue Advance in Polymer-Based Flame Retardant Materials)
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