顺序双重热固化的硫醇-丙烯酸酯-环氧树脂三维网络的构建及性能

doi:10.11949/0438-1157.20220689

摘要/Abstract

摘要：

在常温下，叔胺催化的巯基-丙烯酸酯和巯基-环氧反应活性的差异明显，具有可控顺序固化特征。以四(3-巯基丙酸)季戊四醇酯(SH4)、对苯二甲醇二缩水甘油醚(BOB)或2，5-呋喃二甲醇二缩水甘油醚(BOF)、1，4-环己烷二甲醇二丙烯酸酯(CHDMDA)构建了硫醇-丙烯酸酯-环氧顺序双重热固化体系，并研究氢键对体系固化过程及性能的影响。采用FTIR、流变分析、DSC、DMA、万能材料试验机和硬度仪表征了一重固化后的中间态材料和二重固化后的终态材料的热性能、流变性能、力学性能及常温适用期。结果表明，氢键的存在会延缓双重固化反应的进行，提高终态材料的力学性能。此外，此顺序双重热固化体系所产生的两阶段材料流变性能、热性能和力学性能可调控，中间态材料可在室温24 h保持性能稳定。可控顺序双重固化赋予热固性聚合物方便的复杂形状加工成型、高性能于一身，以及更广泛的应用范围，如形状记忆致动器和压敏胶膜，突破了热固性塑料在形状设计与加工上的局限性。

关键词: 双重固化, 点击化学, 硫醇, 丙烯酸酯, 环氧, 聚合物, 聚合, 制备

Abstract:

At room temperature, the differences in the reactivity of thiol-acrylate and thiol-epoxy catalyzed by tertiary amines are obvious and have controlled sequential curing characteristics. In this paper, a thiol-acrylate-epoxy sequential dual thermal curing system was constructed with pentaerythritol tetra(3-mercaptopropionate) (SH4), 1,4-bis[(2-oxiranylmethoxy)-methyl]-benzene (BOB) or 2,5-bis[(2-oxiranylmethoxy)-methyl]-furan (BOF), and 1,4-cyclohexanediylbis(methylene) diacrylate (CHDMDA), and the effect of hydrogen bonding on the curing process and properties of the system was investigated. FTIR, rheological analysis, DSC, DMA, universal material testing machine and hardness tester were used to characterize the thermal properties, rheological properties, mechanical properties and ambient temperature service period of the intermediate material after the first stage curing and the final material after the second stage curing. The results show that the presence of hydrogen bonding delays the dual curing reaction and improves the mechanical properties of final material. In addition, the rheological, thermal and mechanical properties of the two-stage materials produced by this sequential dual thermal curing system can be regulated, and the intermediate materials can maintain stable properties at room temperature for 24 h. Controlled sequential dual curing gives thermoset polymers easy complex shape processing molding, high performance, and a broader range of applications such as shape memory actuators and pressure sensitive adhesive films, breaking the limitations of thermoset plastics in shape design and processing.

Key words: dual-curing, click chemistry, thiol, acrylate, epoxy, polymers, polymerization, preparation

中图分类号:

O 633.4

刘佳宁, 马嘉浩, 张军营, 程珏. 顺序双重热固化的硫醇-丙烯酸酯-环氧树脂三维网络的构建及性能[J]. 化工学报, 2022, 73(9): 4173-4186.

Jianing LIU, Jiahao MA, Junying ZHANG, Jue CHENG. Construction and properties of sequential dual thermal curing thiol-acrylate-epoxy 3D network[J]. CIESC Journal, 2022, 73(9): 4173-4186.

图/表 18

图1 BOF和BOB的合成路线

Fig.1 Synthetic route for BOF and BOB

表1 硫醇-丙烯酸酯-环氧树脂三维网络的配方组成

Table 1 Formulations of thiol-acrylate-epoxy 3D networks

Sample	r_acrylate	SH4/%	Epoxy/%	Acrylate/%
S4BOB-A00	0	47.80	52.20	0
S4BOB-A02	0.2	48.07	42.00	9.93
S4BOB-A04	0.4	48.35	31.68	19.97
S4BOB-A06	0.6	48.63	21.24	25.03
S4BOB-A08	0.8	48.91	10.68	30.13
S4BOF-A00	0	47.61	52.39	40.41
S4BOF-A02	0.2	47.92	42.19	0
S4BOF-A04	0.4	48.23	31.85	9.90
S4BOF-A06	0.6	48.55	21.37	19.92
S4BOF-A08	0.8	48.87	10.76	30.08
S4A10	1	49.20	0	40.37

图2 BOB和BOF的FTIR谱图、1H NMR谱图、MS谱图

Fig.2 FTIR spectrum, 1H NMR spectrum, MS spectrum of BOB and BOF

图3 硫醇-丙烯酸酯-环氧树脂三维网络的顺序双重固化过程

Fig.3 Formation process of sequential dual-curing 3D network of thiol-acrylate-epoxy resin

图4 由DMAP催化的丙烯酸酯迈克尔加成固化反应机理

Fig.4 Curing mechanism of thiol-acrylate Michael reaction catalyzed by DMAP

图5 由DMAP催化的巯基-环氧固化反应机理

Fig.5 Curing mechanism of thiol-epoxy reaction catalyzed by DMAP

图6 S4A10、S4BOF-A00和S4BOB-A00的等温DSC曲线和等温FTIR曲线

Fig.6 Isothermal DSC curves and isothermal FTIR tracing curves of S4A10, S4BOF-A00 and S4BOB-A00

图7 S4BOB-A00和S4BOF-A00体系固化前后的FTIR光谱

Fig.7 FTIR spectrum of S4BOB-A00 and S4BOF-A00 systems before and after curing

图8 S4BOF-A04的等温FTIR追踪曲线和流变曲线

Fig.8 Isothermal FTIR tracing curves and rheological curves of S4BOF-A04

图9 S4BOB和S4BOF体系的30℃等温流变分析曲线

Fig.9 Isothermal rheological analysis curves of S4BOB and S4BOF systems at 30℃

表2 S4BOB和S4BOF体系第一固化阶段的流变性能

Table 2 Rheological properties of S4BOB and S4BOF systems in the first curing stage

Sample	r_acrylate	G'/Pa	G"/Pa	Gel point/min
S4BOB-A02	0.2	1.40×10^-3	3.00	>150.0
S4BOB-A04	0.4	2.21×10⁵	7.19×10²	25.5
S4BOB-A06	0.6	1.18×10⁶	6.68×10³	16.0
S4BOB-A08	0.8	1.76×10⁶	1.99×10⁴	13.0
S4BOF-A02	0.2	2.94×10^-4	6.00	>150.0
S4BOF-A04	0.4	6.10×10⁴	9.81×10³	29.0
S4BOF-A06	0.6	7.70×10⁵	7.95×10³	19.0
S4BOF-A08	0.8	1.54×10⁶	5.05×10⁴	17.0

图10 中间态(int)与终态(fin)材料的DSC曲线和中间态与终态材料的Tg随racrylate的函数关系

Fig.10 DSC curves of intermediate (int) and final (fin) materials and function diagram of Tg and racrylate of intermediate and final materials

图11 S4BOB和S4BOF体系的DMA曲线及S4BOB与S4BOF体系的应力-应变曲线

Fig.11 DMA curves of S4BOB system and S4BOF system and stress-strain curves of S4BOB and S4BOF systems

表3 终态材料的热机械性能和力学性能

Table 3 Thermomechanical properties and mechanical properties of final materials

Sample	T_g_-DMA/℃	E′ at T_g_-DMA+30℃/MPa	Tensile strength/MPa	Elongation at break/%	Young’s modulus/MPa
S4BOB-A00	9.65	6.38	0.76	17.05	5.17
S4BOB-A02	12.45	9.29	1.39	20.04	7.53
S4BOB-A04	13.77	10.59	4.22	44.14	14.79
S4BOB-A06	17.06	11.95	6.00	60.57	9.03
S4BOB-A08	22.16	12.29	8.00	66.26	118.55
S4BOF-A00	10.97	10.23	3.02	44.15	8.01
S4BOF-A02	14.07	10.89	4.59	52.94	9.51
S4BOF-A04	16.44	12.28	9.82	66.25	14.77
S4BOF-A06	15.73	12.14	11.51	106.92	8.22
S4BOF-A08	20.03	13.22	15.98	86.97	277.34
S4A10	44.21	18.63	14.19	12.06	722.26

图12 S4BOB-A04和S4BOF-A04中间态材料在室温下的剩余反应热和硬度随时间的变化规律

Fig.12 The time dependence of residual heat and hardness of S4BOB-A04 and S4BOF-A04 intermediate materials at room temperature

图13 形状记忆致动器的制备、形状编程和形状恢复

Fig.13 Preparation, shape programming and shape recovery of shape memory actuator

图14 压敏胶膜的制备及黏接过程

Fig.14 Preparation of pressure sensitive film and bonding process

表4 S4BOB和S4BOF体系的黏接性能

Table 4 Bonding properties of S4BOB and S4BOF systems

Sample	Shear strength/MPa
	Aluminum substrate		Glass substrate
	int-materials	fin-materials	int-materials	fin-materials
S4BOB-A02	0.42	6.72	1.18	2.38
S4BOF-A08	0.33	8.26	1.68	2.75

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