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High-fire-safety thermoplastic polyester constructed by novel sulfonate with benzimidazole structure

新型含苯并咪唑结构磺酸盐构建高火灾安全性热塑性聚酯

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Abstract

The flammability of thermoplastic polyesters and the subsequent heavy smoke and severe melt drips formed after ignition are the main obstacles hindering their widespread application. In this study, a novel ionic monomer containing sulfonate and benzimidazole was synthesized and incorporated into the main chain of poly(ethylene terephthalate) (PET, used as a model thermoplastic polyester) by melt copolymerization. The synergetic effect of ionic aggregation and carbonization endowed the obtained copolyester with high melt viscosity and excellent char-forming ability at high temperatures. The copolyester having a monomer content of 8 mol.% easily achieved the Underwriters Laboratories Inc 94 (UL-94) V-0 flammability rating without dripping and the limiting oxygen index value reached 33.0 vol.%. In addition, the total smoke production, peak heat release rate, and maximum CO production decreased by 45.2%, 60.5%, and 75.0%, respectively, compared with those of PET. In addition, the copolyester was spinnable, and showed greater adsorption efficiency (99.6%) for a cationic dye from solution compared to PET (6.5%), demonstrating the excellent affinity of the copolyester for the cationic dye. The obtained inherently fire-safe PET copolyester has great potential for applications in flame retardant textiles, artwork base materials, and decorative materials for transportation applications.

摘要

热塑性聚酯本身具有极高的易燃性, 同时在燃烧过程中还会产生浓烟以及严重的熔滴, 这已经成为阻碍其广泛应用的主要因素. 为了解决这个问题, 在本文中, 我们合成了一种全新的含磺酸盐以及苯并咪唑结构的离子单体, 并将其引入聚对苯二甲酸乙二醇酯(PET, 热塑性聚酯模型)分子链中. 由于离子聚集以及炭化能力的协同作用, 共聚酯在高温下表现出极高的熔体黏度以及优异的成炭能力. 当离子单体引入量为8 mol%时, 共聚酯能够通过UL -94 V-0级, 在测试过程中没有熔滴产生. 同时, 极限氧指数(LOI)高 达33.0 vol%. 与PET相比, 共聚酯的总产烟量, 峰值热释放速率以及最大CO释放速率分别降低了45.2%, 60.5%和75.0%. 除此之外, 共聚 酯具有可纺性, 同时阳离子染料的竭染率也由PET的6.5%提高到99.6%, 表明共聚酯与阳离子染料之间具有很好的亲和性. 这种本征阻燃的共聚酯在阻燃织物、 艺术品基材、 轨道交通与运输的装饰材料方面都有很好的应用前景.

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Acknowledgements

This work was financially supported by the National Key Research and Development Program of China (2017YFB0309001), and the National Natural Science Foundation of China (21634006 and 51827803).

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Authors and Affiliations

  1. The Collaborative Innovation Center for Eco-Friendly and Fire-Safety Polymeric Materials (MoE), State Key Laboratory of Polymer Materials Engineering, National Engineering Laboratory of Eco-Friendly Polymeric Materials (Sichuan), College of Chemistry, Sichuan University, Chengdu, 610064, China

    Wan-Shou Wu  (吴万寿), Ping-Hui Duan  (段平慧), Yin-Long Wang  (王寅龙), Li Chen  (陈力), Xiu-Li Wang  (汪秀丽) & Yu-Zhong Wang  (王玉忠)

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  1. Wan-Shou Wu  (吴万寿)
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  2. Ping-Hui Duan  (段平慧)
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  3. Yin-Long Wang  (王寅龙)
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  4. Li Chen  (陈力)
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  5. Xiu-Li Wang  (汪秀丽)
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  6. Yu-Zhong Wang  (王玉忠)
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Contributions

Author contributions Wu WS designed and synthesized the monomer, performed the experiments and tests, analyzed the results and prepared the manuscript with support from Wang XL; Wang XL and Wang YZ proposed the project and offered critical comments on the manuscript; Duan PH and Wang YL provided comments on the manuscript. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Xiu-Li Wang  (汪秀丽) or Yu-Zhong Wang  (王玉忠).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Wan-Shou Wu is a PhD student at Sichuan University under the supervision of Prof. Yu-Zhong Wang. His research interest is flame retardant polyester materials.

Xiu-Li Wang is currently a full professor at the College of Chemistry, Sichuan University. She earned her PhD degree in materials science (2003) and MSc degree in polymer chemistry and physics (1999) from Sichuan University, and BSc degree in chemistry (1994) from Sichuan University. In 2002, she joined Prof. Yu-Zhong Wang’s group and her current research interests are focused on the synthesis, structure and properties of flame-retardant materials.

Yu-Zhong Wang earned his PhD degree from Sichuan University in 1994, where he was promoted to a full Professor in 1995. He is the Director of the National Engineering Laboratory for Eco-Friendly Polymeric Materials (Sichuan). His research interests are focused on fire-retardant and functional polymeric materials, bio-based and biodegradable polymers. He has been awarded eleven National and Provincial Science & Technology awards. In 2015, he was selected as an Academician of Chinese Academy of Engineering.

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Wu, WS., Duan, PH., Wang, YL. et al. High-fire-safety thermoplastic polyester constructed by novel sulfonate with benzimidazole structure. Sci. China Mater. 64, 2067–2080 (2021). https://doi.org/10.1007/s40843-020-1605-7

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  • DOI: https://doi.org/10.1007/s40843-020-1605-7

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