基于共价自适应网络的可回收再利用阻燃双马树脂研究

doi:10.19491/j.issn.1001-9278.2024.11.010

中国塑料 ›› 2024, Vol. 38 ›› Issue (11): 57-63.DOI: 10.19491/j.issn.1001-9278.2024.11.010

基于共价自适应网络的可回收再利用阻燃双马树脂研究

黎友霜, 金秋硕, 唐璟玥, 贾梦, 许博()

北京工商大学轻工科学与工程学院，北京 100048

收稿日期:2024-08-19 出版日期:2024-11-26 发布日期:2024-11-21
通讯作者: 许博（1982—），男，教授，从事阻燃材料研究，xubo@btbu.edu.cn
E-mail:xubo@btbu.edu.cn

Study on recyclable and reusable flame⁃retardant bismaleimide resin based on covalent adaptive network

LI Youshuang, JIN Qiushuo, TANG Jingyue, JIA Meng, XU Bo()

School of Light Industry Science and Engineering，Beijing Technology and Business University，Beijing 100048，China

Received:2024-08-19 Online:2024-11-26 Published:2024-11-21
Contact: XU Bo E-mail:xubo@btbu.edu.cn

摘要/Abstract

摘要：

以双马来酰亚胺树脂（BMI）为原料，向其引入阻燃交联剂DOPO⁃DBA⁃F，用来制备一种兼具自愈合与阻燃性能的改性材料。利用傅里叶红外光谱仪（FTIR）、热重分析仪（TG）、差示扫描量热仪（DSC）、偏光显微镜（PLM）、极限氧指数仪、垂直燃烧测试仪和锥形量热仪对改性材料进行了结构表征与性能测试，并利用扫描电子显微镜（SEM）对其残炭形貌进行了分析。研究结果表明，可逆Diels⁃Alder（DA）键的形成有效改善了BMI的可回收性能，并通过DSC测试研究了呋喃基团和BMI之间可逆DA的存在。同时，阻燃交联剂的引入成功提高了可逆BMI的阻燃性能，其LOI值可以达到38.5 %，UL94达到V⁃0级。

关键词: 双马来酰亚胺树脂, Diels?Alder反应, 自愈合, 阻燃

Abstract:

In this study， DOPO⁃DBA⁃F as a flame⁃retardant cross⁃linking agent was introduced into the bismaleimide resin as a raw material to prepare a modified material with both self⁃healing and flame⁃retardant properties. The structure and performance of the modified material was characterized by using Fourier⁃transform infrared spectroscopy， thermogravimetry analysis， differential scanning calorimetry （DSC）， polarized light microscopy， limiting oxygen index meter， vertical burning experiment， and cone calorimetry. The morphology of the residual char was observed by scanning electron microscopy. The results indicated that the formation of reversible Diels⁃Alder （DA） bonds effectively improved the recyclability of the bismaleimide resin. The presence of the reversible DA bonds between the furan groups and bismaleimide resin was confirmed by DSC. Meanwhile， the introduction of flame⁃retardant cross⁃linking agent successfully improved the flame⁃retardant properties of the modified material， resulting in a limiting oxygen index of 38.5 % and a UL94 V⁃0 rating in the vertical burning experiment.

Key words: bismaleimide resin, Diels?Alder reaction, self?healing, flame retardancy

中图分类号:

TQ314.24⁺8

黎友霜, 金秋硕, 唐璟玥, 贾梦, 许博. 基于共价自适应网络的可回收再利用阻燃双马树脂研究[J]. 中国塑料, 2024, 38(11): 57-63.

LI Youshuang, JIN Qiushuo, TANG Jingyue, JIA Meng, XU Bo. Study on recyclable and reusable flame⁃retardant bismaleimide resin based on covalent adaptive network[J]. China Plastics, 2024, 38(11): 57-63.

图/表 9

图1 BMI/DOPO⁃DBA⁃F的制备

Fig.1 Preparation of the BMI/DOPO⁃DBA⁃F

图2 样品的FTIR谱图与1H⁃NMR谱图

Fig.2 FTIR and 1H⁃NMR spectra of the samples

样品	T_{d，5 %}/℃	T_{d，50 %}/℃	T_peak/℃	残炭率/%
样品	T_{d，5 %}/℃	T_{d，50 %}/℃	T_peak/℃	500 ℃	600 ℃	700 ℃
DOPO⁃DBA	286	428	439	8.12	6.17	6.15
DOPO⁃DBA⁃F	102	410	452	9.92	8.35	8.97
BMI/DOPO⁃DBA⁃F	248	485	435	47.33	42.51	41.40

表1 样品的热重分析结果

Tab.1 Thermogravimetric analysis results of the samples

图3 样品的TG 与DTG曲线

Fig.3 TG and DTG curves of the samples

图4 BMI/DOPO⁃DBA⁃F的DSC曲线与FTIR谱图

Fig.4 DSC curves and FTIR spectra of the BMI/DOPO⁃DBA⁃F

图5 刀片划痕修复过程的示意图与不同温度下划痕自发热修复的PLM照片

Fig.5 Schematic diagram of the blade scratch repair process and PLM images of the scratch spontaneous thermal repair at different temperature

样品	TTI/s	PHRR/kW·m^-2	THR/MJ·m^-2	av⁃EHC/MJ·kg^-1	av⁃COY/kg·kg^-1	av⁃CO₂Y/kg·kg^-1	TSR/m²·m^-2	残炭率/%
DBA/BDM	58	358	86	24.9	0.13	2.35	2 757	23.17
BMI/DOPO⁃DBA⁃F	13	364	37	18.2	0.26	1.55	2 582	37.60

表2 样品的锥形量热测试结果

Tab.2 Cone calorimetric test results of the samples

图6 样品的阻燃性能

Fig.6 Flame retardancy of the samples

图7 BMI/DOPO⁃DBA⁃F的残炭照片、SEM照片与阻燃机理

Fig.7 Carbon residue photos of SEM images of the BMI/DOPO⁃DBA⁃F and its flame retardant mechanism

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基于共价自适应网络的可回收再利用阻燃双马树脂研究

Study on recyclable and reusable flame⁃retardant bismaleimide resin based on covalent adaptive network

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