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

doi:10.19491/j.issn.1001-9278.2024.11.010

Abstract

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

CLC Number:

TQ314.24⁺8

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.

Figures/Tables 9

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

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

Tab.1. Thermogravimetric analysis results of the samples

Fig.3. TG and DTG curves of the samples

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

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

Tab.2. Cone calorimetric test results of the samples

Fig.6. Flame retardancy of the samples

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

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