一种硼酸酯动态交联环氧树脂的合成与性能

doi:10.11949/0438-1157.20190503

摘要/Abstract

摘要：

利用巯基与环氧的点击反应，向环氧体系中引入二醇结构，并通过硼酸酯键对其进行交联，制备了一系列不同流变性能和玻璃化转变温度的可塑环氧树脂材料。研究了不同的配方对材料性能的影响，结果表明通过改变交联剂与动态链结的比例，体系的流变性能可以被调控；另一方面，改变软硬环氧组分的比例可以使材料的玻璃化转变温度在14.6~36.5℃之间调节。制备了该可塑环氧树脂与密胺通孔泡沫的复合材料，该材料具备良好的快速自黏结性能。材料断裂后，在10 s内即可达到最大黏结强度，且经多次拆卸-黏结循环后，黏结强度可以保持在约0.06 MPa。

关键词: 聚合物, 复合材料, 流变学, 硼酸酯, 动态键

Abstract:

A series of dynamic covalent polymer networks providing various rheological properties and glass transition temperatures were prepared via firstly introducing a diol group into an epoxy molecule through a thiol-epoxy click reaction and secondly crosslinking the diol groups by dynamic borate bonds. Effect of formulation on the properties of the materials was investigated. The rheological properties of the materials can be adjusted by tuning the ratio of the crosslinking agents and the exchangeable borate bonds. Glass transition temperature of the polymer can be adjusted from 14.6℃ to 36.5℃ by changing the ratio of the fed soft and hard epoxy components. A composite material is prepared by introducing the dynamic network into an open porous melamine foam. Such a composite can be rapidly self-welded in a few seconds after it had been cut. The welding performance is found to retain 0.06 MPa after 20 disassembling-bonding cycles, showing a good repeatability.

Key words: polymers, composites, rheology, boronic esters, dynamic bonds

中图分类号:

TB 324

陈峰, 候宇坤, 赵骞. 一种硼酸酯动态交联环氧树脂的合成与性能[J]. 化工学报, 2019, 70(11): 4449-4456.

Feng CHEN, Yukun HOU, Qian ZHAO. Synthesis and properties of epoxy resin crosslinked by dynamic boronic ester bonds[J]. CIESC Journal, 2019, 70(11): 4449-4456.

图/表 10

表1 不同流变性能材料的配方

Table 1 Formulations for materials of different rheological properties

样品	m(MP)/g	m(TMB)/g	m(DBU)/g	m(PTME)/g	m(PPGDE)/g
E1	1.10	0.53	0.53	0.67	5.00
E2	1.01	0.49	0.49	0.76	5.00
E3	0.93	0.45	0.45	0.86	5.00
E4	0.85	0.41	0.41	0.95	5.00
E5	0.76	0.37	0.37	1.05	5.00

表2 不同玻璃化转变温度材料的配方

Table 2 Formulations for materials of different glass transition temperature

样品	m(MP)/g	m(TMB)/g	m(DBU)/g	m(DGOA)/g	m(DABE)/g	m(PPGDE)/g
E6	2.73	1.31	1.31	0.16	4.00	0.00
E7	3.01	1.44	1.44	0.18	4.00	0.75
E8	3.28	1.58	1.58	0.20	4.00	1.50
E9	3.55	1.71	1.71	0.21	4.00	2.26

图1 原料的分子式

Fig.1 Molecular formulas of reagents

图2 材料合成的反应机理

Fig.2 Reaction mechanism of material synthesis

图3 聚合物网链示意图

Fig.3 Diagram of polymer network

图4 样品E1~E4的流变扫频测试

Fig.4 Angular frequency sweeps of E1—E4

图5 样品E6~E9的热分析

Fig.5 DSC measurements of E6—E9

图6 密胺泡沫与材料复合前后的SEM图

Fig.6 SEM images of melamine foam before/after being composited

图7 密胺泡沫/E3复合材料的黏结行为

Fig.7 Adhesive behavior of melamine foam/E3 composite

图8 密胺泡沫/E3复合材料的力学性能

Fig.8 Mechanical properties of melamine foam/E3 composites

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