Photopolymerization Kinetics of 2, 2', 4-(2-Chlorophenyl)-5-(3, 4-Dimethoxyphenyl)-4', 5'-Diphenyl-1, 1'-Two Midazole Containing Initiator System

doi:10.7517/j.issn.1674-0475.2013.01.007

Abstract

Abstract: 2, 2', 4-(2-chlorophenyl)-5-(3, 4-dimethoxyphenyl)-4', 5'-diphenyl-1, 1'-two imidazole (CZ-HABI) is a highly efficient UV initiator. Its characteristics were investigated by FTIR and ¹HNMR and UV absorption spectra. The compound photointiator systems consisted of photoinitiator 2,2',4-(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-two imidazole (CZ-HABI), photosensitizer 4,4'-bis (diethylamino)benzophenone(EMK) and hydrogen donor N-phenyl glycine (NPG). Real time infrared spectroscopy (RT-IR) was used to study the effect of polymerized kinetics of compound photointiator systems. The results indicated that basically no initiation efficient without hydrogen donor, while the effect of initiation efficient boosted greatly in the case of adding hydrogen donor. When concentration of compound photointiator systems increased, the conversion rate of the double bond can been enhanced. Its maximum polymerization rate accorded with the direct proportion relationship of R_p∝(PI)^{1/ 2}. The conversion rate of the double bond of the monomer and maximum reaction rate were enlarged accompanying with the light intensity strengthened. The final conversion rate of the double bond of diacrylate monomer was higher than that of triacrylate monomer. Initiator efficiency of complex photoinitiator system was better than conventional ITX/EDAB initiator system, and similar to initiator efficiency of 184, 1173.

Key words: photoinitiator, polymerized kinetics, photopolymerization, RT-IR

CLC Number:

WU Wen-tao, MA Gui-ping, LU Jian, FANG Da-wei, QIAN Xiao-chun, NIE Jun, WANG Ke-min. Photopolymerization Kinetics of 2, 2', 4-(2-Chlorophenyl)-5-(3, 4-Dimethoxyphenyl)-4', 5'-Diphenyl-1, 1'-Two Midazole Containing Initiator System[J]. Imaging Science and Photochemistry, 2013, 31(1): 53-62.

References

[1] Corrales T, Catalina F, Allen N S, Peinado C. Novel water soluble copolymers based on thioxanthone: photochemistry and photoinitiation activity[J]. J. Photochem. Photobiol.A, 2005,169: 95-100.
[2] 张海清,肖浦,戴明之,等.可聚合型光引发剂4-丙烯酰氧基二苯甲酮的光聚合性能研究[J].影像科学与光化学,2008,1(26): 32-38. Zhang H Q, Xiao P, Dai M Z, et al. Photopolymerizaiton of 4-aryloylbenzophenone[J]. Imaging Science and Photochemistry, 2008, 1(26): 32-38.
[3] Monroe B M, Weed G C. Photoinitiators for free-radical-initiated photoimaging systems[J]. Chem. Rev., 1993, 93: 435-444.
[4] Kennedy J P.Carbocationic Polymerization[M].New York:Wiley,1982:1-5.
[5] Frouassier J P.Photoinitation.Photopolymerization and Photocuring[M].New York: Haner,1995.
[6] Scherzer T,Decker U.The effect of temperature on the kinetics of diacrylate photopolymerization studied by Real-time FTIR spectroscopy[J]. Polymer, 2000, 41: 7681-7690.
[7] 杨建文,曾兆华,陈永烈.光固化涂料及其应用[M].北京:化学工业出版社,2003.101-116. Yang J W,Zeng Z H,Chen Y L. Radiant-curable Materials and Application[M]. Beijing:Chemical Industry Press, 2003.101-116.
[8] 路键,聂俊,等.2-(4-甲氧基苯基)-4,6-双(三氯甲基)-S-三嗪光引发剂的合成及其光聚合动力学性能研究[J].影像科学与光化学, 2011, 29(2): 99-107. Lu J, Nei J, et al. Synthesis and photopolymerization kinetics of 2- (4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine photointiiator[J]. Imaging Science and Photochemistry, 2011, 29(2): 99-107.
[9] 聂俊, 肖鸣,等.光聚合技术与应用[M].北京:化学工业出版社, 2008. Nie J,Xiao M, et al. Photopolymerization Technology and Application[M]. Beijing:Chemical Industry Press, 2008.
[10] 朱俊飞,龚灵,樊彬,等.光引发剂的研究现状及进展[J].涂料工业,2010,40(5): 74-79. Zhu J F, Gong L, Fan B, et al. Research status and progress of photoinitiator[J]. Paint & amp; Coatings Industry, 2010,40(5): 74-79.
[11] Temel G, Arsu N, Yagci Y.One-component benzoxazine type photoinitiator for free radical polymerization[J].Polym. Bull., 2006, 57: 51-56.
[12] Temel G, Aydogan B, Arsu N, Yagci Y. Synthesis and characterization of one-component polymeric photoinitiator by simultaneous double click reactions and its use in photoinduced free radical polymerization[J]. Macromolecules, 2009, 42: 6098-6106.
[13] Bruce M.Monroe Gregory C.Weed, Photoinitators for free-radical-initiated photoimaging systens[J]. Chem.Rev., 1993, 93: 435-448.
[14] 杨长吉,等.六方基双咪唑光引发体系[J]. 感光材料, 1996, 3: 18-22. Yang C J, et al. Six base pairs of imidazole light initiator system[J]. Sensitive Material, 1996, 3: 18-22.
[15] 胡建琪, 等.六方基双咪唑复合光引发体系的研究及其在液态光液态光致抗蚀剂中的应用[J]. 信息记录材料, 2008, 9: 46-51. Hu J Q, et al. Study and application on hexaarylbiimidazole compoude photoinitiator for photoresist of PCB[J]. Information Recording Materials, 2008, 9: 46-51.
[16] 李长多, 张学俊. 1,3-二烷基咪唑类离子液体的合成研究[J]. 化工中间体, 2008, 11: 62-66. Li C D, Zhang X J. The synthesis research of 1,3-dislkylimidazolium ionic liquids[J]. Chemical Intermediate, 2008, 11: 62-66.
[17] 张静,杨冬芝,聂俊.三官能度甲基丙烯酰氧基单体的合成与性能研究[J].影像科学与光化学,2008, 26(5): 403-409. Zhang J, Yang D Z, Nie J. Synthesis and characterization of trifunctional methacryloyloxy monomers[J]. Imaging Science and Photochemistry, 2008, 26(5): 403-409.
[18] 徐锦琪,高放,杨永源,等.双咪唑光敏体系紫外光引发聚合甲基丙烯酸甲酯动力学和应用研究[J].感光科学与光化学, 1998, 2(16): 1-7. Xu J Q,Gao F,Yang Y Y,et al.Kinetic and applied study of UV light photosensitive initiating polymerization of methyl methacrylate by biimidazole photosensitive system[J]. Photographic Science and Photochemistry,1998, 2(16): 1-7.
[19] 徐娟,蒋姗,等.DPPH引发丙烯酸酯单体光聚合动力学研究[J].粘结.2011, 3: 44-47. Xu J, Jiang S, et al.Photopolymerization kinetics of acrylate monomer initated with diphentyl(4-phenylthio) phenyl-Sufonium hexafluorophophate[J]. Adhesion, 2011, 3: 44-47.
[20] Odian G. Principles of Polymerziation[M]. 3rd ed. New York: Wiley, 1991.