含杂萘联苯结构的环氧树脂固化动力学分析

doi:10.11949/0438-1157.20211019

摘要/Abstract

摘要：

采用差示扫描量热法（DSC）对含杂萘联苯结构环氧单体（3EPZ）与聚醚胺（ED-2003）的固化过程进行研究。采用Starink模型及自催化模型获得了不同转化率下体系的活化能及相关动力学参数，并建立了动力学方程。实验结果曲线与模型计算结果曲线的相关系数大于99%，表明所建立的自催化动力学模型能够较好地描述体系的固化过程。

关键词: 环氧树脂, 固化动力学, 自催化模型

Abstract:

The curing process of epoxy monomer (3EPZ) containing heteronaphthalene biphenyl structure with polyether amine (ED-2003) was investigated by differential scanning calorimetry (DSC). The activation energy and related kinetic parameters of the system at different conversion rates were obtained using the Starink model and the autocatalytic model, and the kinetic equations were established. The correlation coefficients between the experimental results and the model calculations were greater than 99%, indicating that the autocatalytic kinetic model developed can better describe the curing process of the system.

Key words: epoxy resin, curing kinetics, autocatalytic model

中图分类号:

TQ 323.5

王哲, 祖愿, 胡方圆, 蹇锡高. 含杂萘联苯结构的环氧树脂固化动力学分析[J]. 化工学报, 2022, 73(2): 681-688.

Zhe WANG, Yuan ZU, Fangyuan HU, Xigao JIAN. Kinetic analysis of curing of epoxy resin containing phthalazinone structure[J]. CIESC Journal, 2022, 73(2): 681-688.

图/表 16

图1 3EPZ与ED-2003的固化反应过程示意图

Fig.1 Schematic diagram of the curing reaction process of 3EPZ and ED-2003

图2 环氧树脂体系在不同升温速率下的DSC曲线

Fig.2 The DSC curves of epoxy resin systems at different heating rate

表1 不同升温速率下环氧树脂的固化特征温度

Table 1 The characteristic temperature of curing reaction at different heating rate

β /(K/min)	T_i/K	T_p/K	T_f/K
5	353	413	478
10	358	428	459
15	366	435	483
20	375	458	515

图3 不同升温速率下转化率与温度的关系曲线

Fig.3 The curves of conversion vs temperature at various heating rate

图4 不同转化率下ln(β/Tα1.92)与1/T之间的关系曲线

Fig.4 The curves of ln(β/Tα1.92) vs 1/T at different conversion

表2 Starink方程中的相关数据

Table 2 The relevant data of the Starink equation

转化率	斜率	活化能/(kJ/mol)
0.1	-5297	44.0
0.2	-5255	43.6
0.3	-5200	43.2
0.4	-5189	43.1
0.5	-5141	42.7
0.6	-5145	42.7
0.7	-5113	42.5
0.8	-5100	42.4
0.9	-5119	42.5

图5 表观活化能与转化率关系曲线

Fig.5 The curve of Eavsα

图6 不同升温速率下反应速率与转化率的关系曲线

Fig.6 The curves of the reaction vs conversion at different heating rate

图7 不同升温速率下ln(dα/dt)+Ea/RT与ln(1-α)的关系曲线

Fig.7 The curves of ln(dα/dt)+Ea/Rvs ln(1-α) at different heating rate

表3 经计算的体系动力学参数

Table 3 Calculated kinetic parameters for the system

β/(K/min)	lnA	n	m	相关系数(R²)
5	7.62	0.76	0.52	0.9993
10	7.65	0.67	0.53	0.9968
15	7.97	0.73	0.53	0.9954
20	7.33	0.67	0.53	0.9965
均值	7.64	0.71	0.53	—

图8 实验结果(符号)与经过DSC计算的结果(实线)对比

Fig.8 The comparison curves of the experimental results (symbols) with the calculated by DSC (solid line)

图9 自催化模型的拟合曲线与实验数据（符号）的对比

Fig.9 The comparison curves of the autocatalytic model results with experimental results (symbols)

图10 ln(β/Tp2)与1/Tp的关系曲线

Fig.10 The curve of ln(β/Tp2) vs 1/Tp

图11 lnβ与1/Tp的关系曲线

Fig.11 The curve of lnβvs 1/Tp

图12 n级模型的拟合曲线与实验数据（符号）的对比

Fig.12 The comparison curves of the n-level model results with experimental results (symbols)

图13 实验结果(符号)与经过DSC计算的结果(实线)对比

Fig.13 The comparison curves of the experimental results (symbols) with the calculated by DSC (solid line)

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