二苯甲酮/一缩二乙二醇光引发丙烯酸丁酯聚合机理

doi:10.16085/j.issn.1000-6613.2017-1032

化工进展 ›› 2018, Vol. 37 ›› Issue (01): 206-211.DOI: 10.16085/j.issn.1000-6613.2017-1032

二苯甲酮/一缩二乙二醇光引发丙烯酸丁酯聚合机理

梁爽, 杨永登, 周宏勇, 李云庆, 王家喜

河北工业大学化工学院, 天津 300130

收稿日期:2017-05-31 修回日期:2017-09-27 出版日期:2018-01-05 发布日期:2018-01-05
通讯作者: 王家喜,教授,研究方向为环境友好的化学及材料。
作者简介:梁爽(1991-),女,博士研究生。

Photopolymerization mechanism of butyl acrylate initiated by benzophenone and diethylene glycol

LIANG Shuang, YANG Yongdeng, ZHOU Hongyong, LI Yunqing, WANG Jiaxi

School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China

Received:2017-05-31 Revised:2017-09-27 Online:2018-01-05 Published:2018-01-05

摘要/Abstract

摘要： 以二苯甲酮（BP）与一缩二乙二醇（DEG）为光引发剂引发丙烯酸丁酯（BA）聚合，利用核磁共振波谱¹H NMR、¹³C NMR和液相色谱-串联质谱（Q-TOF）对产品结构进行分析。¹³C NMR结果表明，聚合物链上存在叔碳及季碳原子。Q-TOF分析结果表明，聚合物主要由DEG自由基引发，聚合度主要为6、7的链转移终止的低聚物构成，此外，链自由基可以经歧化及偶合终止。快速链转移反应及叔碳、季碳原子的存在表明聚合物的形成过程可能经历了自由基在DEG分子链上“游走”的机理。自由基在DEG链上的转移及链增长的相互竞争，导致形成多取代的聚合产物。聚合反应存在严重的氧阻聚效应，链自由基与氧气快速反应形成过氧化自由基，经终止反应及分解反应形成多1～3个氧原子的低聚物。

关键词: 光化学, 自由基, 聚合, 机理, 氢转移, 氧阻聚

Abstract: The structure of the products of butyl acrylate photopolymerization initiated by benzophenone and diethylene glycol were characterized by ¹H NMR、¹³C NMR and Q-TOF. The ¹³C NMR results indicate that there are tertiary and quaternary carbons in the polymer chain. The analysis results of Q-TOF show that the polymers are mainly composed of oligomers initiated by DEG radicals and terminated by chain transfer with polymerization degree of around 6 and 7. In addition, the chain radicals can also be terminated by disproportionation and coupling reaction. The fast chain transfer termination reaction and the presence of tertiary and quaternary carbon atoms indicate that the formation of the polymers may undergo the mechanism of free radicals migration along the DEG molecular chain. The competition between the chain transfer and the chain growth leads to the formation of multi substituted polymer products. The oxygen inhibition effect is significant in the polymerization. The chain radicals react with oxygen rapidly to form peroxide radicals, which undergo the termination and decomposition reactions to form oligomers with one to three oxygen atoms.

Key words: photochemistry, radical, polymerization, mechanism, hydrogen transfer, oxygen inhibition

中图分类号:

TQ317

梁爽, 杨永登, 周宏勇, 李云庆, 王家喜. 二苯甲酮/一缩二乙二醇光引发丙烯酸丁酯聚合机理[J]. 化工进展, 2018, 37(01): 206-211.

LIANG Shuang, YANG Yongdeng, ZHOU Hongyong, LI Yunqing, WANG Jiaxi. Photopolymerization mechanism of butyl acrylate initiated by benzophenone and diethylene glycol[J]. Chemical Industry and Engineering Progress, 2018, 37(01): 206-211.

参考文献

[1] KUGIMOTO Y,WAKABAYASHI A,DOBASHI T,et al. Preparation and characterization of composite coatings containing a quaternary ammonium salt as an anti-static agent[J].Progress in Organic Coatings,2016,92:80-84.
[2] QIN X H,OVSIANIKOV A,STAMPFL J,et al. Additive manufacturing of photosensitive hydrogels for tissue engineering applications[J].Bionanomaterials,2014,15(3/4):49-70.
[3] XIAO P,ZHANG J,DUMUR F,et al.Visible light sensitive photoinitiating systems:recent progress in cationic and radical photopolymerization reactions under soft conditions[J].Progress in Polymer Science,2015,41:32-66.
[4] YAGCI Y,JOCKUSCH S,TURRO N J.Photoinitiated polymerization:advances,challenges,and opportunities[J]. Macromolecules,2010,43:6245-6260.
[5] 唐铭,王姝.紫外光固化光敏涂料的研制[J].化工进展,2010,29(6):1116-1119. TANG Ming,WANG Shu. Preparation of UV-curable epoxy-acrylate photosemsitive coating[J]. Chemical Industry and Engineering Progress,2010,29(6):1116-1119.
[6] 解月伟,解一军,高晓哲,等. 紫外光固化可剥离胶的研究与制备[J].化工进展,2015,34(12):4301-4304. XIE Yuewei,XIE Yijun,GAO Xiaozhe,et al. Preparation of ultraviolet-irradiated strippable adhesive[J]. Chemical Industry and Engineering Progress,2015,34(12):4301-4304.
[7] ALLEN N S,CORRALES T,EDGE M,et al.Photochemistry and photopolymerization activities of novel phenylthiobenzophenone and diphenylthiophene photoinitiators[J]. Polymer,1998,39(4):903-909.
[8] SETHURAM B. Photopolymerization of acrylonitrile:benzophenone-isopropanol system as initiator[J]. Journal of Macromolecular Science Chemistry,1984,21(6/7):739-744.
[9] XIAO P,DUMUR F,THIRION D,et al.Multicolor photoinitiators for radical and cationic polymerization:monofunctional vs polyfunctional thiophene derivatives[J]. Macromolecules,2013,46(17):6786-6793.
[10] DAVIDSON R S,Gold V. Advances in physical chemistry[M]. London:Academic Press,1983.
[11] PIERRE F J. Photoinitiation,photopolymerization,and photocuring:fundamentals and applications[M]. Hanser Gardner Publications,1995.
[12] LEDWITH A,PURBRICK M D. Initiation of free-radical polymerization by photoinduced electron transfer processes[J]. Polymer,1973,14(10):521-522.
[13] TASDELEN M A,MOSZNER N,YAGCI Y. The use of poly(ethylene oxide) as hydrogen donor in type Ⅱ photoinitiated free radical polymerization[J].Polymer Bulletin,2009,63(2):173-183.
[14] WANG K M,LU Y H,CHEN P H,et al.Novel one-component polymeric benzophenone photoinitiator containing poly(ethylene glycol) as hydrogen donor[J].Materials Chemistry & Physics,2014,143(3):1391-1395.
[15] 金养智.光固化材料性能及应用手册[M].北京:化学工业出版社,2013. JIN Yangzhi. Guan guhua cailiao xingneng ji yingyong shouce[M]. Bejing:Chemical Industry Press,2013.
[16] 芮雯,冯毅凡,姜苗苗,等. 不同产地黄芪药材的UPLC/Q-TOF-MS指纹图谱研究[J].药物分析杂志,2012,32(4):607-611. RUI Wen,FENG Yifan,JIANG Miaomiao,et al. UPLC/Q-TOF-MS study on fingerpint of astragalus membranaceus obtained from 7 different origin[J]. Chinese Journal of Pharmaceutical Analysis,2012,32(4):607-611.
[17] LIGON S C,HUSAR B,WUTZEL H,et al.Strategies to reduce oxygen inhibition in photoinduced polymerization[J]. Chemical Reviews,2013,114(1):557-589.
[18] RABEK J F. Experimental and analytical methods for the investigation of radiation curing[J].Radiation Curing in Polymer Science and Technology,1993,1:329-452.

二苯甲酮/一缩二乙二醇光引发丙烯酸丁酯聚合机理

Photopolymerization mechanism of butyl acrylate initiated by benzophenone and diethylene glycol

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[2]	王谨航, 何勇, 史伶俐, 龙臻, 梁德青. 气体水合物阻聚剂研究进展[J]. 化工进展, 2023, 42(9): 4587-4602.
[3]	林晓鹏, 肖友华, 管奕琛, 鲁晓东, 宗文杰, 傅深渊. 离子聚合物-金属复合材料（IPMC）柔性电极的研究进展[J]. 化工进展, 2023, 42(9): 4770-4782.
[4]	宋伟涛, 宋慧平, 范朕连, 樊飙, 薛芳斌. 粉煤灰在防腐涂料中的研究进展[J]. 化工进展, 2023, 42(9): 4894-4904.
[5]	朱传强, 茹晋波, 孙亭亭, 谢兴旺, 李长明, 高士秋. 固体高分子脱硝剂选择性非催化还原NO _x 特性[J]. 化工进展, 2023, 42(9): 4939-4946.
[6]	白志华, 张军. 二乙烯三胺五亚甲基膦酸/Fenton体系氧化脱除NO[J]. 化工进展, 2023, 42(9): 4967-4973.
[7]	李伯耿, 罗英武, 刘平伟. 聚合物产品工程研究内容与方法的思考[J]. 化工进展, 2023, 42(8): 3905-3909.
[8]	王报英, 王皝莹, 闫军营, 汪耀明, 徐铜文. 聚合物包覆膜在金属分离回收中的研究进展[J]. 化工进展, 2023, 42(8): 3990-4004.
[9]	吕程远, 张函, 杨明旺, 杜健军, 樊江莉. 生物成像用二氧杂环丁烷余辉发光体系的研究进展[J]. 化工进展, 2023, 42(8): 4108-4122.
[10]	吴亚, 赵丹, 方荣苗, 李婧瑶, 常娜娜, 杜春保, 王文珍, 史俊. 用于复杂原油乳液的高效破乳剂开发及应用研究进展[J]. 化工进展, 2023, 42(8): 4398-4413.
[11]	于静文, 宋璐娜, 刘砚超, 吕瑞东, 武蒙蒙, 冯宇, 李忠, 米杰. 一种吲哚基超交联聚合物In-HCP对水中碘的吸附作用[J]. 化工进展, 2023, 42(7): 3674-3683.
[12]	徐沛瑶, 陈标奇, KANKALA Ranjith Kumar, 王士斌, 陈爱政. 纳米材料用于铁死亡联合治疗的研究进展[J]. 化工进展, 2023, 42(7): 3684-3694.
[13]	欧阳素芳, 周道伟, 黄伟, 贾凤. 新型耐迁移橡胶防老剂的研究进展[J]. 化工进展, 2023, 42(7): 3708-3719.
[14]	徐伟, 李凯军, 宋林烨, 张兴惠, 姚舜华. 光催化及其协同电化学降解VOCs的研究进展[J]. 化工进展, 2023, 42(7): 3520-3531.
[15]	余希希, 张金帅, 雷文, 刘承果. 基于动态共价键自修复的光固化高分子材料研究进展[J]. 化工进展, 2023, 42(7): 3589-3599.