苯基次磷酸盐离聚物/聚磷酸铵协效阻燃增韧改性聚乳酸

伍聪; 杨丹丹; 吴刚; 陈思翀

doi:10.11777/j.issn1000-3304.2020.20161

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苯基次磷酸盐离聚物/聚磷酸铵协效阻燃增韧改性聚乳酸

研究论文 | 更新时间：2021-01-26

- 苯基次磷酸盐离聚物/聚磷酸铵协效阻燃增韧改性聚乳酸
- Flame Retardant and Toughening Modification of Poly(lactic acid) with Phenylhypophosphate Ionomer/Ammonium Polyphosphate
- 高分子学报 2021年52卷第2期页码：176-185
- 作者机构：
  
  四川大学化学学院　成都 610064
- 作者简介：
  
  E-mail: chensichong@scu.edu.cn Si-chong Chen, E-mail: chensichong@scu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号21875147，51991351)资助项目()
- DOI：10.11777/j.issn1000-3304.2020.20161
  中图分类号：
- 纸质出版日期：2021-2-3，
  
  网络出版日期：2020-9-8，
  
  收稿日期：2020-6-23，
  
  修回日期：2020-7-29，
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伍聪, 杨丹丹, 吴刚, 陈思翀. 苯基次磷酸盐离聚物/聚磷酸铵协效阻燃增韧改性聚乳酸[J]. 高分子学报, 2021,52(2):176-185.

Cong Wu, Dan-dan Yang, Gang Wu, Si-chong Chen. Flame Retardant and Toughening Modification of Poly(lactic acid) with Phenylhypophosphate Ionomer/Ammonium Polyphosphate[J]. Acta Polymerica Sinica, 2021,52(2):176-185.
伍聪, 杨丹丹, 吴刚, 陈思翀. 苯基次磷酸盐离聚物/聚磷酸铵协效阻燃增韧改性聚乳酸[J]. 高分子学报, 2021,52(2):176-185. DOI： 10.11777/j.issn1000-3304.2020.20161.

Cong Wu, Dan-dan Yang, Gang Wu, Si-chong Chen. Flame Retardant and Toughening Modification of Poly(lactic acid) with Phenylhypophosphate Ionomer/Ammonium Polyphosphate[J]. Acta Polymerica Sinica, 2021,52(2):176-185. DOI： 10.11777/j.issn1000-3304.2020.20161.

摘要

通过将双端羟基的聚己内酯(PCL)、聚乳酸(PLA)预聚物以及苯基次磷酸离子盐扩链得到一种含苯基次磷酸盐的离子共聚物，将其与聚磷酸铵(APP)复合用于协同改性聚乳酸，离聚物中苯基次磷酸盐结构与APP具有优异的协同阻燃PLA的作用，同时该离聚物中PLA与苯基次磷酸盐结构有效提升了APP在PLA中的分散能力，最后该离聚物中PCL柔性链段有效改善了PLA的韧性，最终得到更高效阻燃性能且韧性也较好改善的PLA/PCLA-PIU/APP复合材料. 一方面，离聚物中苯基次磷酸盐结构与APP协同有效促进了PLA的成炭，形成更连续致密的炭层从而阻隔可燃气体的释放，达到更好的阻燃效果. 锥形量热、残炭的扫描电子显微镜(SEM)、能谱分析(EDS)、拉曼光谱等测试证实了这一结果，与纯PLA以及仅使用APP的PLA/APP相比，PLA/PCLA-PIU/APP的热释放速率与总热释放均降低，同时残炭的石墨化程度更高，形成了更为致密的炭层. 另一方面，力学性能测试结果表明，离聚物中PCL柔性链段的存在使得与APP复合改性后的PLA的韧性相比纯PLA和PLA/APP有较大的提升；SEM测试表明，离聚物中PLA与苯基次磷酸盐结构起到增容作用，提升了APP在PLA中的分散性.

Abstract

Poly(lactic acid) (PLA)

as a kind of aliphatic polyester derived from biomass with excellent mechanical strength

biocompatibility and biodegradability

is a kind of green polymers with promising potential application. However

the application of PLA as a commodity polyester has been restricted dramatically because of its brittleness and flammability nature. It is still a great challenge to improve flame retardancy and toughness of PLA simultaneously by a simple blending method. In this work

copolymer ionomer (PCLA-PIU) was prepared by chain extension copolymerization of hydroxyl terminated poly(

-caprolactone) (PCL)

PLA prepolymer and phenylhypophosphate

and then incorporated with ammonium polyphosphate (APP) for synergistic modification of PLA. The ionomer can act as a compatibilizer to enhance the dispersion of APP in PLA matrix because of its PLA segments and phenylhypophosphate groups. The SEM observation shows that the APP particles dispersed in PLA/PCLA-PIU/APP composite has significantly smaller size and uniform dispersity

compared to the PLA/APP

. The phenyl hypophosphate groups in the ionomer also has an excellent synergistic effect with APP for improving the flame-retardance of PLA. The flame-retardant properties and mechanism of the PLA and its composites were investigated by LOI

UL-94

Cone calorimeter test

SEM

EDS

Raman spectroscopy

etc

. Compared with neat PLA and PLA/APP

the composite PLA/PCLA-PIU

/APP

containing 10 wt% of PCLA-PIU and 10 wt% of APP

achieves the V-0 rating in UL-94 burning test with limiting oxygen index (LOI) as high as 27.6%. The heat release rate and total heat release of PLA/PCLA-PIU

/APP

are also reduced significantly to 254.9 kW/m

and 55.8 MJ/m

respectively. SEM and Raman analysis for char residues after Cone calorimeter test suggest PCLA-PIU and APP had synergistic effect on promoting charring of PLA

which result in compact char residue with high graphitization degree

therefore effectively improving the flame-retardant efficiency. Moreover

the toughness of PLA is improved effectively by the flexible PCL segments of ionomers

resulting in a PLA/PCLA-PIU/APP composite with improved flame retardancy and toughness simultaneously. The mechanical properties test results show that the toughness of the modified PLA (10.3 kJ/m

of PLA/PCLA-PIU

/APP

) is significantly improved compared to those of neat PLA (3.7 kJ/m

) and PLA/APP

(2.5 kJ/m

关键词

聚乳酸阻燃增韧聚磷酸铵离聚物

Keywords

Poly(lactic acid)Flame retardantTougheningAmmonium polyphosphateIonomer

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