丁香酚环氧有机硅树脂的制备及其固化动力学研究

doi:10.11949/0438-1157.20221001

摘要/Abstract

摘要：

利用丁香酚环氧和环四硅氧烷硅氢加成得到新型生物基环氧树脂D4EUEP，通过核磁共振氢谱和飞行时间质谱表征其准确结构。使用非等温DSC对D4EUEP/33DDS固化体系进行分析，采用双参数自催化模型和Málek判据建立了该体系固化动力学模型。模型计算结果与实验结果相关系数大于99%，证明该模型可以较好地描述D4EUEP/33DDS体系的固化过程。通过AICM方法研究了体系的有效活化能与转化率之间的关系，揭示了微观反应机理的变化，并通过Vyazovkin法对D4EUEP/33DDS体系进行了等温固化预测。

关键词: 环氧树脂, 固化动力学, 自催化, 动力学模型, 生物质

Abstract:

A novel eugenol-based siloxane epoxy resin (D4EUEP) was synthesized from eugenol glycidyl ether and tetramethyl-cyclotetrasiloxane. The molecular structure was characterized by ¹H NMR and MALDI-TOF. The non-isothermal curing behavior of D4EUEP/33DDS system was characterized with differential scanning calorimetry (DSC), showing the relationship between temperature and heat rate. The isoconversional Šesták–Berggren model and Málek method were used to analyze the curing kinetics and established curing kinetic model. All the kinetic parameters were acquired and the explicit rate equations were constructed. The curing kinetic prediction was made in great coincidence with the experimental data. On the other hand, advanced isoconversional method (AICM) revealed the relationship between the conversion and activation energy and discussed the microscopic mechanisms during the curing process. Vyazovkin method was also used to predict the isothermal curing process in different temperature.

Key words: epoxy resin, curing kinetics, autocatalysis, kinetic modeling, biomass

中图分类号:

TQ 322.4

郑杰元, 张先伟, 万金涛, 范宏. 丁香酚环氧有机硅树脂的制备及其固化动力学研究[J]. 化工学报, 2023, 74(2): 924-932.

Jieyuan ZHENG, Xianwei ZHANG, Jintao WAN, Hong FAN. Synthesis and curing kinetic analysis of eugenol-based siloxane epoxy resin[J]. CIESC Journal, 2023, 74(2): 924-932.

图/表 13

图1 环四硅氧烷丁香酚环氧合成路线

Fig.1 Synthesis of D4EUEP

图2 D4EUEP 结构表征

Fig.2 Structure characterized of D4EUEP

图3 Málek判据流程图

Fig.3 Procedures of Málek method

图4 D4EUEP/33DDS体系固化不同升温速率下的DSC曲线

Fig.4 DSC thermographs for D4EUEP/33DDS non-isothermal reaction systems at various heating rates

表1 固化反应特征参数

Table 1 Characteristic parameters for curing systems

β/(℃/min)	ΔH/(J/g)	T_i/℃	T_p/℃
3.0	240.5	135.2	162.6
4.5	241.8	139.7	175.3
6.7	244.6	145.8	186.3
10.0	246.9	151.4	198.6

图5 固化体系转化率与温度关系曲线

Fig.5 Plots of conversion α as a function of curing temperature at various heating rates

图6 固化体系ln(β/Tp2)与-1/Tp关系

Fig.6 Plots of ln(β/Tp2) against -1/Tp for curing system

图7 固化体系在不同升温速率下转化率α与dα/dt、y(α)、z(α)函数曲线

Fig.7 Plots of dα/dt-α,y(α)-α and z(α)-α at different heating rates

表2 不同升温速率下转化率特征峰值

Table 2 Characteristic peak conversion values αp， αM and αp∞ at various heating rates

β/(℃/min)	α_p	α_M	α $_{p}^{\infty}$
3.0	0.367	0.233	0.398
4.5	0.377	0.222	0.400
6.7	0.385	0.237	0.424
10.0	0.409	0.231	0.442

表2 不同升温速率下转化率特征峰值

Table 2 Characteristic peak conversion values αp， αM and αp∞ at various heating rates

β/(℃/min)	α_p	α_M	α $_{p}^{\infty}$
3.0	0.367	0.233	0.398
4.5	0.377	0.222	0.400
6.7	0.385	0.237	0.424
10.0	0.409	0.231	0.442

图8 固化体系中ln[(dα/dt)exp(Ea/RT)]对ln[αm/n (1-α)]的线性拟合关系

Fig.8 Plots of ln[(dα/dt)exp(Ea/RT)] against ln[αm/n (1-α)]

图9 固化动力学模型预测结果与实验结果比较

Fig.9 Comparison of predicated rates from SB(m, n) model and experimental rates

图10 固化体系活化能与转化率关系

Fig.10 Variation of the effective activation energy with conversion

图11 不同温度下转化率-时间关系预测曲线

Fig.11 Predicted conversion vs time relationships under isothermal curing conditions

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