Enhanced Photopolymerization of Dimethacrylates with Ketones, Amines, and Iodonium Salts: The CQ System
Enhanced Photopolymerization of Dimethacrylates with Ketones, Amines, and Iodonium Salts: The CQ System
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DOI：
10.1002/pola.24964
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发表时间：
2011-12-01
影响因子：
--
通讯作者：
Chen, Fei
中科院分区：
文献类型：
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作者：
Cook, Wayne D.;Chen, Fei
采用dsc和紫外可见光谱研究了由脑醌（CQ）、六氟磷酸二苯基碘铵(Ph（2)IPF(6)）和N，N,3,5-四甲基苯胺（TMA）、N，N -二甲基苄胺或三乙胺组成的三组分引发体系光聚合二甲丙烯酸酯的动力学和机理。研究了单体结构对固化动力学和光漂白的影响。photodsc研究表明，当所有三种组分都存在时，聚合速率增加了五倍，并且动力学遵循以下趋势：CQ/amine/Ph(2)IPF(6) >> CQ/amine > CQ/Ph(2)IPF(6)。对于CQ/amine/Ph(2)IPF(6)和CQ/amine体系，CQ在光- dsc时间尺度上都发生了快速的光漂白，但对于不含胺的体系，在CQ光漂白前有一个诱导阶段。单体类型对光漂白速率影响的研究表明，光漂白行为与单体结构无关。提出了三种光引发机制。CQ/胺/Ph(2)IPF(6)体系的反应机理包括：被激发的CQ分子被胺还原形成酮基和氨基烷基自由基，随后胺和较小程度的酮基自由基被碘盐不可逆氧化形成起始自由基。(C) 2011 Wiley期刊公司高分子材料学报，2011,31 (4):557 - 557
The kinetics and mechanism of the photopolymerization of dimethacrylates using three-component initiation systems consisting of camphorquinone (CQ), diphenyliodonium hexafluorophosphate (Ph(2)IPF(6)), and either N,N,3,5-tetramethylaniline (TMA) or N, N-dimethylbenzylamine or triethylamine were studied by photo-DSC and UV-visible spectroscopy. The effect of monomer structure on the curing kinetics and photobleaching were also investigated. Photo-DSC studies showed fivefold increases in polymerization rate when all three components were present and the kinetics followed the trend: CQ/amine/Ph(2)IPF(6) >> CQ/amine > CQ/Ph(2)IPF(6). For both CQ/amine/Ph(2)IPF(6) and CQ/amine systems, the CQ was rapidly photobleached during the photo-DSC timescale but for the systems without amine there was an induction stage before CQ photobleaching was evident. Studies of the effect of monomer type on the photobleaching rate show that the photobleaching behavior was independent of monomer structure. Three photoinitiation mechanisms have been proposed. The reaction mechanism of the CQ/amine/Ph(2)IPF(6) system involves the reduction of the excited CQ molecule by the amine to form ketyl and aminoalkyl radicals, followed by the irreversible oxidation of the amine, and to a lesser extent, the ketyl radical by the iodonium salt, to form an initiating radical. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 50305041, 2011