香草醇基环氧树脂的合成、固化动力学及性能

doi:10.16085/j.issn.1000-6613.2022-0612

摘要/Abstract

摘要：

以可再生香草醇为原料，合成了一种生物基环氧树脂（DGEVA）。通过使用甲基六氢苯酐（MeHHPA）作为固化剂，制备了一种新型的生物基环氧树脂交联网络（DGEVA/MeHHPA）。对其非等温固化动力学、热性能、热机械性能、机械性能和微观形貌结构进行了系统的研究，并用商用的石油基双酚A型环氧树脂组成的石油基环氧树脂体系（DGEBA/MeHHPA）进行对比。结果表明：DGEVA/MeHHPA和DGEBA/MeHHPA具有相似的固化反应活性。DGEVA/MeHHPA具有可以与DGEBA/MeHHPA相媲美的综合性能：玻璃化转变温度为82.2℃；拉伸强度和拉伸模量分别是 (66.7±6)MPa和 (2.8±0.1)GPa；T_d5%、T_d10%和T_dmax分别是242.4℃、284.9℃和392.4℃。此外，DGEVA/MeHHPA在形变过程中发生了塑性变形而吸收了更多的断裂能。DGEVA刚性骨架和低分子量带来的潜在高交联密度赋予了DGEVA优异性能，具有在实际应用中替代石油基环氧树脂的应用潜力。

关键词: 香草醇, 环氧树脂, 非等温固化动力学, 机械性能, 微观形貌结构

Abstract:

A bio-based epoxy resin (DGEVA) was synthesized from renewable vanilla alcohol. A novel bio-based epoxy resin system (DGEVA/MeHHPA) was prepared by using methyl hexahydrophthalic anhydride (MeHHPA) as the curing agent. The non-isothermal curing kinetics, thermal properties, thermomechanical properties, mechanical properties and microstructure of DGEVA/MeHHPA were systematically studied, and were compared with the petroleum-based epoxy resin system (DGEBA/MeHHPA) composed of commercial petroleum-based bisphenol-A epoxy resin. The results showed that DGEVA/MeHHPA and DGEBA/MeHHPA had similar curing activity. DGEVA/MeHHPA has better comprehensive performance comparable to DGEBA/MeHHPA. Specifically, the glass transition temperature of DGEVA/MeHHPA was 82.2℃. The tensile strength and tensile modulus of DGEVA/ MeHHPA were (66.7±6)MPa and (2.8±0.1)GPa, respectively. The T_d5%, T_d10% and T_dmax of DGEVA/MeHHPA were 242.4℃, 284.9℃ and 392.4℃, respectively. In addition, DGEVA/ MeHHPA exhibited plastic deformation during deformation and absorbed more fracture energy. The excellent comprehensive performance of DGEBA/MeHHPA lay in the unique molecular structure of DGEVA, which had great application potential in the practical application of DGEVA.

Key words: vanilla alcohol, epoxy resin, non-isothermal curing kinetics, mechanical properties, micromorphology structure

中图分类号:

TQ323.5

田亚州, 胡钰婧, 李继友, 任江燕, 王立伟, 王修利, 丁颖, 程珏, 张军营. 香草醇基环氧树脂的合成、固化动力学及性能[J]. 化工进展, 2022, 41(S1): 477-484.

TIAN Yazhou, HU Yujing, LI Jiyou, REN Jiangyan, WANG Liwei, WANG Xiuli, DING Ying, CHENG Jue, ZHANG Junying. Synthesis, curing kinetics and properties of vanilla alcohol-based epoxy resin[J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 477-484.

图/表 14

图1 DGEVA的合成路线

图2 本研究用的主要化学物的化学结构

表1 DGEVA/MeHHPA和DGEBA/MeHHPA的配比

样品	DGEVA/g	DGEBA/g	MeHHPA/g	DMP 30/g
DGEVA/MeHHPA	10	—	12.2	0.05
DGEBA/MeHHPA	—	10	8.4	0.05

图3 VA和DGEVA的FTIR谱图

图4 DGEVA的1H NMR谱图和13C NMR谱图

图5 环氧/酸酐体系的反应机理

图6 环氧树脂的DSC谱图

表2 DGEVA/MeHHPA和DGEBA/MeHHPA的非等温固化反应的 Tonse、Tp及To的值

样品	升温速率/℃·min^-1	T_i/℃	T_p/℃	T_o/℃
DGEVA+MeHHPA	5	91.72	135.08	180.38
	10	91.96	149.42	194.36
	15	93.08	158.00	198.47
	20	95.53	164.16	203.31
DGEBA/MeHHPA	5	90.08	134.97	183.70
	10	93.39	148.73	201.92
	15	95.36	155.62	206.22
	20	97.51	161.69	212.67

图7 DGEVA/MeHHPA和DGEBA/MeHHPA固化体系T与β的线性拟合关系

图8 DGEVA/MeHHPA和DGEBA/MeHHPA的DSC谱图

图9 DGEVA/MeHHPA和DGEBA/MeHHPA的DMA谱图

表3 DGEVA/MeHHPA和DGEBA/MeHHPA的机械性能和热稳定性能

样品	拉伸强度/MPa	拉伸模量/GPa	断裂伸长率/%	T_d5%/℃	T_d10%/℃	T_max/℃	残炭率/%
DGEVA/MeHHPA	66.7 ± 6	2.8 ± 0.1	2.7 ± 0.5	242.4	284.9	392.4	6.7
DGEBA/MeHHPA	62.9 ± 13	2.9 ± 0.3	1.4 ± 0.4	357.4	377.4	409.9	6.2

图10 DGEVA/MeHHPA和DGEBA/MeHHPA的TGA谱图

图11 DGEVA/MeHHPA[(a)和(b)]和DGEBA/MeHHPA[(c)和(d)]的微观形貌结构

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