Syntheses and UV curing properties of urethane acrylates

doi:10.16085/j.issn.1000-6613.2018-1377

Abstract

Abstract:

Ethylene carbonate reacted with 1,6-hexanediamine and isophoronediamine to produce two carbamate diols, respectively. Six different urethane acrylate mixtures were obtained by the reaction of those carbamate diols with 1,6-hexanediol diacrylate(HDDA)，neopentyl glycol diacrylate (NPGDA) and trimethylolpropane triacrylate (TMPTA) in the absence of solvent through Oxa-Michael addition and transesterification. The structure of the reaction products was investigated by FTIR and high resolution mass spectrometry，and the UV curing kinetics of the synthesized urethane acrylates was studied by FTIR. The properties of cured film were evaluated. The results showed that the urethane acrylate resin could be UV cured within 30s under promotion of initiated by 3% (total mass fraction) of 2-hydroxy-2-methyl-1-phenylpropan-1-one(1173)under irradiation of UV light，forming to form a smooth, transparent or translucent film with good flexibility (0.5—2.5mm). The gelation rate and the pencil hardness of the film was 92%—96% and 4—5H，respectively. The adhesion of film to the glass was 0—1 level.

Key words: UV curing, Oxa-Michael addition, transesterification, urethane acrylate, polymerization, kinetics, film

摘要：

利用碳酸亚乙酯与1,6-己二胺、异佛尔酮二胺反应，制备出两种含氨基甲酸酯基的二元醇，基于氨基甲酸酯二元醇与1,6-己二醇二丙烯酸酯（HDDA）、新戊二醇二丙烯酸酯（NPGDA）及三羟甲基丙烷三丙烯酸酯（TMPTA）本体条件下的Oxa-Michael加成反应及酯交换反应，合成出6种含氨基甲酸酯基的丙烯酸酯混合物。利用FTIR及高分辨质谱分析了产物结构，用FTIR考察了所合成氨基甲酸酯基丙烯酸酯光固化过程的动力学,测定了光固化膜的性能。结果表明，在含占总质量分数3% 的2-羟基-2-甲基-1-苯基-1-丙酮（1173）光引发剂的引发下，氨基甲酸酯基丙烯酸酯能在30s内固化形成表面平整、柔韧性（0.5~2.5mm）良好、透明或半透明的膜；固化膜的凝胶率及铅笔硬度分别为92%~96%、4~5H，对玻璃的附着力为0~1级。

关键词: UV光固化, Oxa-Michael加成, 酯交换, 氨基甲酸酯丙烯酸酯, 聚合, 动力学, 膜

CLC Number:

TQ637

ZOU Jianjun, LU Ting, WANG Jiaxi. Syntheses and UV curing properties of urethane acrylates[J]. Chemical Industry and Engineering Progress, 2019, 38(04): 1947-1952.

邹建军, 鲁婷, 王家喜. 氨基甲酸酯基丙烯酸酯的合成及其光固化性能[J]. 化工进展, 2019, 38(04): 1947-1952.

Figures/Tables 7

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m/z(PUA1-1)		分子式（M+Na）	结构式^①	分子式（M+Na）	m/z(PUA2-1)
计算值	测量值	分子式（M+Na）	结构式^①	分子式（M+Na）	计算值	测量值
195.0992	195.0979	C₉H₁₆O₃Na		C₉H₁₆O₃Na	195.0992	195.0999
249.1076	249.1097	C₁₂H₁₈O₄Na		C₁₂H₁₈O₄Na	249.1076	249.1079
367.2091	367.2085	C₁₈H₃₂O₆Na		C₁₈H₃₂O₆Na	367.2091	367.2102
369.1625	369.1632	C₁₅H₂₆N₂O₇Na		C₁₉H₃₂N₂O₇Na	423.2102	423.2108
421.2194	421.2197	C₂₁H₃₄O₇Na		C₂₁H₃₄O₇Na	421.2194	421.2207
541.2734	541.2732	C₂₄H₄₂N₂O₁₀ Na		C₂₈H₄₈N₂O₁₀Na	595.3201	595.3208
595.2845	595.2837	C₂₇H₄₄N₂O₁₁ Na		C₃₁H₅₀N₂O₁₁Na	649.3307	649.3316
713.3838	713.3831	C₃₃H₅₈N₂O₁₃Na		C₃₇H₆₄N₂O₁₃Na	767.4301	767.4311
767.3942	767.3937	C₃₆H₆₀N₂O₁₄Na		C₄₀H₆₆N₂O₁₄Na	821.4406	821.4401

m/z(PUA1-1)		分子式（M+Na）	结构式^①	分子式（M+Na）	m/z(PUA2-1)
计算值	测量值	分子式（M+Na）	结构式^①	分子式（M+Na）	计算值	测量值
195.0992	195.0979	C₉H₁₆O₃Na		C₉H₁₆O₃Na	195.0992	195.0999
249.1076	249.1097	C₁₂H₁₈O₄Na		C₁₂H₁₈O₄Na	249.1076	249.1079
367.2091	367.2085	C₁₈H₃₂O₆Na		C₁₈H₃₂O₆Na	367.2091	367.2102
369.1625	369.1632	C₁₅H₂₆N₂O₇Na		C₁₉H₃₂N₂O₇Na	423.2102	423.2108
421.2194	421.2197	C₂₁H₃₄O₇Na		C₂₁H₃₄O₇Na	421.2194	421.2207
541.2734	541.2732	C₂₄H₄₂N₂O₁₀ Na		C₂₈H₄₈N₂O₁₀Na	595.3201	595.3208
595.2845	595.2837	C₂₇H₄₄N₂O₁₁ Na		C₃₁H₅₀N₂O₁₁Na	649.3307	649.3316
713.3838	713.3831	C₃₃H₅₈N₂O₁₃Na		C₃₇H₆₄N₂O₁₃Na	767.4301	767.4311
767.3942	767.3937	C₃₆H₆₀N₂O₁₄Na		C₄₀H₆₆N₂O₁₄Na	821.4406	821.4401

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