Preparation and Properties of Intrinsically Flame Retardant Polydicyclopentadiene Based on Frontal Ring-opening Metathesis Polymerization

Ping Wang; Jie Xu; Xin-yun Hu; Li Yang; Wen-xiu Liu; Tian Cao; Yi-yang Zhou; Yun-sheng Ding

doi:10.11777/j.issn1000-3304.2025.25022

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Preparation and Properties of Intrinsically Flame Retardant Polydicyclopentadiene Based on Frontal Ring-opening Metathesis Polymerization

更新时间：2025-04-28

- Preparation and Properties of Intrinsically Flame Retardant Polydicyclopentadiene Based on Frontal Ring-opening Metathesis Polymerization
- Acta Polymerica Sinica Pages: 1-12(2025)
- 作者机构：
  
  1.安徽建筑大学安徽省先进建筑材料国际联合研究中心合肥 230601
  2.特种电线电缆国家地方联合工程研究中心安徽建筑大学分中心合肥 230601
  3.合肥工业大学先进功能材料与器件安徽省重点实验室合肥 230009
- 作者简介：
  
  E-mail: anjzwp@ahjzu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25022
  CLC：
- CSTR：32057.14.GFZXB.2025.7373
- Received：18 January 2025，
  
  Accepted：2025-02-27，
  
  Published Online：28 April 2025，
- 稿件说明：
移动端阅览
王平, 许杰, 胡心芸, 杨利, 刘文秀, 曹田, 周意杨, 丁运生. 基于前端开环易位聚合的本征阻燃聚双环戊二烯的制备及性能研究. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25022

Wang, P.; Xu J.; Hu, X. Y.; Yang, L.; Liu, W. X.; Cao, T.; Zhou, Y. Y.; Ding, Y. S. Preparation and properties of intrinsically flame retardant polydicyclopentadiene based on frontal ring-opening metathesis polymerization. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25022
王平, 许杰, 胡心芸, 杨利, 刘文秀, 曹田, 周意杨, 丁运生. 基于前端开环易位聚合的本征阻燃聚双环戊二烯的制备及性能研究. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25022 DOI： CSTR： 32057.14.GFZXB.2025.7373.

Wang, P.; Xu J.; Hu, X. Y.; Yang, L.; Liu, W. X.; Cao, T.; Zhou, Y. Y.; Ding, Y. S. Preparation and properties of intrinsically flame retardant polydicyclopentadiene based on frontal ring-opening metathesis polymerization. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25022 DOI： CSTR： 32057.14.GFZXB.2025.7373.

摘要

针对聚双环戊二烯(PDCPD)易燃、聚合工艺复杂且周期长的问题，将阻燃基元9

10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)引入降冰片烯结构中，设计合成了一种能够与双环戊二烯(DCPD)发生前端开环易位聚合(FROMP)的阻燃单体NB-DOPO，制备了本征阻燃PDCPD/NB-DOPO共聚物. 研究了NB-DOPO的引入对于共聚体系的前端聚合过程、动态力学性能、热稳定性能、机械性能及阻燃性能的影响，并探究PDCPD/NB-DOPO共聚物的阻燃机理. 研究结果表明NB-DOPO能够降低共聚体系的前端聚合速率，并与DCPD发生无规共聚，在保证材料固化度的同时实现可控FROMP. 当NB-DOPO的含量低于10%时，高环张力单环烯烃共聚单体的引入促进了交联点的形成，降低了共聚物交联点间分子量(

)，材料储能模量和机械性能增加. 当NB-DOPO添加量达到30%时，PDCPD/NB-DOPO的交联密度降低，但分子链中的刚性结构作为物理交联点，使得材料的机械性能保持的同时，阻燃性能明显提升，材料的极限氧指数(LOI)较PDCPD提高了38%，具有优异的综合性能.

Abstract

Polydicyclopentadiene (PDCPD) is flammable

its polymerization process is complicated and the period is long. In this paper

a flame retardant monomer NB-DOPO were designed and synthesized by introducing 9

10-dihydro-9-oxaze-10-phosphoxene-10-oxide (DOPO) into the norbornene. This monomer can be copolymerized with dicyclopentadiene (DCPD) by frontal ring-opening metathesis polymerization (FROMP) to p

repare the PDCPD/NB-DOPO copolymers with intrinsic flame retardant properties. The effects of the introduction of NB-DOPO on the FROMP process and the dynamic mechanical properties

thermal stability

mechanical properties as well as the flame-retardant properties of the copolymers were studied. On that basis

the possible flame retardant mechanism of the PDCPD/NB-DOPO copolymer was explored further. The results indicated that NB-DOPO could copolymerize with DCPD randomly

and thus the frontal polymerization velocity of the copolymerization was reduced. According to this

a controllable FROMP was achieved while maintaining a high curing degree of the material. When the content of NB-DOPO was below 10%

the introduction of NB-DOPO with high ring tension promoted the formation of cross-linking points in the system

reduced the molecular weight of cross-linking points (

)

and enhanced the storage modulus and mechanical properties of the copolymer; When the concentration of NB-DOPO reached 30%

the cross-linking density of PDCPD/NB-DOPO declined

the rigid structures in the NB-DOPO acted as physical cross-linking points

hence the mechanical properties of the material could be kept at a high level accompanied by a markedly enhanced flame retardancy. The limiting oxygen index (LOI) of the material was increased by 38% compared to that of PDCPD

and it exhibited excellent comprehensive performance.

关键词

Keywords

references

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