二硫代水杨酸衍生物对光固化材料性能的影响

doi:10.11949/0438-1157.20220484

摘要/Abstract

摘要：

设计、合成了一种二硫代水杨酸衍生物(MAPBS)，详细研究了MAPBS对丙烯酸酯类单体光聚合动力学及其聚合物膜体积收缩、耐热性能及硬度的影响。研究结果表明，在365 nm LED光源照射下，MAPBS能够引发甲基丙烯酸酯类单体聚合和降低聚合物膜体积收缩。随着MAPBS含量的增加，光聚合体系的双键转化率和聚合速率随之增加，分别达到64.9%和1.19%/s，而体积收缩呈现先降低再增加的趋势，聚合物膜热稳定性略微降低，硬度略有增加。MAPBS兼具引发和降低体积收缩的双重功能，在LED光聚合体系表现出一定的应用潜力。

关键词: 光化学, 合成, 聚合, LED 光聚合, 体积收缩, 二硫化合物

Abstract:

A dithiosalicylic acid derivative (MAPBS) was designed and synthesized. The effects of MAPBS on the photopolymerization kinetics of methacrylate monomers, and the volume shrinkage, thermostability and hardness of polymer films were investigated in detail. The results show that MAPBS can initiate the polymerization of methacrylate monomers and reduce the volume shrinkage of polymer films under 365 nm LED irradiation. With the increase of MAPBS content, the double bond conversion and photopolymerization rate are increased to 64.9% and 1.19%/s, respectively, while the volume shrinkage is decreased initially and followed by an increase. Furthermore, the thermostability of polymer films is slightly reduced, while their hardness is increased a little. MAPBS has the dual functions of initiating polymerization and reducing volume shrinkage, and certain application potential in LED photopolymerization system.

Key words: photochemistry, synthesis, polymerization, LED photopolymerization, volume shrinkage, disulfide

中图分类号:

O 625.7

鞠小兵, 李雪纯, 孙芳. 二硫代水杨酸衍生物对光固化材料性能的影响[J]. 化工学报, 2022, 73(9): 4187-4193.

Xiaobing JU, Xuechun LI, Fang SUN. Effect on dithiosalicylic acid derivative on properties of photocuring materials[J]. CIESC Journal, 2022, 73(9): 4187-4193.

图/表 10

图1 MAPBS合成路线

Fig.1 Synthesis route of MAPBS

图2 MAPBS在无水乙腈溶液中的紫外-可见吸收光谱（浓度：1 × 10-4 mol/L）

Fig.2 UV-Vis absorption spectra of MAPBS in anhydrous acetonitrile (concentration: 1 × 10-4 mol/L)

表1 MAPBS的摩尔消光系数（ε）

Table 1 Molar extinction coefficients （ε） of MAPBS

波长/nm	摩尔消光系数（ε）/(L/(mol·cm))
220	35700
250	16970
312	8380
365	30
385	0

图3 无水乙腈溶液中MAPBS在365 nm LED点光源照射后的ESR谱图及其拟合谱图（捕捉剂：PBN）

Fig.3 ESR spectrum of MAPBS in anhydrous acetonitrile solution after irradiation with 365 nm LED point light source and its fitted spectrum (the capture agent: PBN)

图4 在阻氧条件下MAPBS和CQ/ DMAEMA引发单体的光聚合动力学（365 nm LED，光照强度：100 mW/cm2）

Fig.4 Photopolymerization kinetics of monomers initiated by MAPBS and CQ/ DMAEMA in the absence of oxygen (365 nm LED, light intensity: 100 mW/cm2)

图5 含有MAPBS聚合物膜的体积收缩率（365 nm LED，光照强度：100 mW/cm2）

Fig.5 Volume shrinkage of polymer films with MAPBS (365 nm LED, light intensity: 100 mW/cm2)

图6 MAPBS降低体积收缩可能的机理（365 nm LED，光照强度：100 mW/cm2）

Fig.6 Possible mechanism of MAPBS reducing volume shrinkage (365 nm LED, light intensity: 100 mW/cm2)

图7 MAPBS体系固化膜的热失重及失重速率曲线

Fig.7 Thermogravimetric curves and mass loss rate curves of polymer films with MAPBS

表2 MAPBS体系固化膜的热失重数据

Table 2 Thermogravimetric data of polymer films with MAPBS

体系	MAPBS含量/ %(质量分数)	T_5%/℃	T_max1/℃	T_max2/℃
MAPBS-0%	0	292.7	343.4	422.6
MAPBS-2.5%	2.5	279.3	322.4	438.0
MAPBS-5.0%	5.0	278.2	319.0	434.8
MAPBS-7.5%	7.5	278.0	313.1	431.2
MAPBS-10.0%	10.0	278.1	310.5	429.4

图8 含有MAPBS体系聚合物膜的硬度

Fig.8 Hardness of polymer films with MAPBS

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