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Copolymerization and Dark Polymerization Studies for Photopolymerization of Novel Acrylic Monomers

机译：新型丙烯酸单体光聚合的共聚和暗聚合研究

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摘要

The copolymerization behavior and the dark polymerization kinetics of highly reactive novel acrylic monomers were compared to traditional acrylate monomers. Copolymerization of thiol functionalities with novel acrylic monomers was characterized, and it was observed that the inclusion of secondary functionalities such as carbamates, carbonates, and cyclic carbonates, in acrylic monomers significantly alters the relative reactivity of the novel acrylates with thiols. While traditional aliphatic acrylates exhibited propagation to chain transfer ratios ranging between 0.8 (± 0.1)–1.5(± 0.2), the novel acrylates characterized by secondary functionalities exhibited much higher propagation to chain transfer ratios ranging from 2.8(± 0.2)–4(± 0.2). In the dark polymerization studies, the kinetics of the novel acrylates were evaluated following cessation of the UV light. The novel acrylates exhibited extensive polymerization in the dark compared to most traditional acrylates and diacrylates. For instance, cyclic carbonate acrylate was observed to attain 35 % additional conversion in the dark when the UV light was extinguished at 35 % conversion, whereas traditional acrylates such as hexyl acrylate attained only 3 % additional conversion when the UV light was extinguished at 35 %, and a diacrylate such as HDDA attained 15 % additional conversion when the UV light was extinguished at 40 % conversion. Also, through choice of appropriate monomers, the dark polymerization studies were performed such that the polymerization rate was approximately the same at the point the light was extinguished for all these monomers. The copolymerization and dark polymerization studies support the hypothesis that the nature of the propagating species in the novel acrylates is altered as compared to traditional acrylic monomers and polymerizations.
机译：将高反应性新型丙烯酸单体与传统的丙烯酸酯单体的共聚行为和暗聚合动力学进行了比较。表征了硫醇官能团与新型丙烯酸单体的共聚，并且观察到，丙烯酸单体中包含仲官能团，例如氨基甲酸酯，碳酸酯和环状碳酸酯，显着改变了新型丙烯酸酯与硫醇的相对反应性。传统的脂肪族丙烯酸酯的传播链转移率范围为0.8（±0.1）–1.5（±0.2），而具有次级功能的新型丙烯酸酯具有更高的传播链转移率范围为2.8（±0.2）–4（± 0.2）。在黑暗聚合研究中，在停止紫外线后评估了新型丙烯酸酯的动力学。与大多数传统的丙烯酸酯和二丙烯酸酯相比，新型丙烯酸酯在黑暗中表现出广泛的聚合作用。例如，观察到环状碳酸盐丙烯酸酯在35％的紫外线被熄灭时在黑暗中获得了35％的额外转化率，而传统的丙烯酸酯（如丙烯酸己酯）在35％的紫外线被熄灭时仅获得了3％的额外转化率。 ，当以40％的转化率熄灭紫外线时，诸如HDDA之类的二丙烯酸酯获得了15％的额外转化率。另外，通过选择合适的单体，进行了暗聚合研究，使得对于所有这些单体，在熄灭光的点聚合速率大致相同。共聚和深色聚合研究支持以下假设：与传统的丙烯酸单体和聚合反应相比，新型丙烯酸酯中的繁殖物种性质发生了变化。

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