Oxygen inhibition in thiol-acrylate photopolymerizations
Oxygen inhibition in thiol-acrylate photopolymerizations
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DOI：
10.1002/pola.21304
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发表时间：
2006-03-15
影响因子：
--
通讯作者：
Bowman, CN
中科院分区：
文献类型：
--
作者：
O'Brien, AK;Cramer, NB;Bowman, CN
表征了氧对硫醇-丙烯酸酯光聚合的总体影响。特别考虑了硫醇单体的化学组成、官能度和浓度对氧抑制程度的影响。随着硫醇浓度的增加，氧的抑制程度大大降低，这是因为过氧基向硫醇的链转移。将1，6-己二醇二丙烯酸酯与烷基硫醇(1，6-己烷二硫醇)的共聚反应与丙酸硫醇(乙二醇二硫代丙酸酯)的共聚反应进行比较，发现丙酸酯体系在有氧的情况下活性更强，聚合程度更高。此外，还考虑了乙二醇二硫代丙酸酯与化学成分相似的四官能团丙酸酯(季戊四醇四硫代丙酸酯)进行比较时的官能度。在相同的硫醇浓度下，官能度越高的硫醇聚合速度越快，这是因为聚合物体系的粘度增加，从而限制了氧的扩散，降低了氧的整体抑制程度。因此，对硫醇单体的选择如何影响硫醇-丙烯酸酯光聚合中氧的抑制程度提供了初步的见解。(C)2006年威利期刊公司。
The overall effects of oxygen on thiol-acrylate photopolymerizations were characterized. Specially, the choice of thiol monomer chemistry, functionality, and Concentration on the extent of oxygen inhibition were considered. As thiol concentration was increased, the degree of oxygen inhibition was greatly reduced because of chain transfer from the peroxy radical to the thiol. When comparing the copolymerization of 1,6-hexanediol diacrylate with the alkane-based thiol (1,6-hexane dithiol) to the copolymerization with the propionate thiol (glycol dimercaptopropionate), it was found that the propionate system was much more reactive and polymerized to a greater extent in the presence of oxygen. In addition, the functionality was considered where the glycol dimercaptopropionate was compared to a tetrafunctional propionate of similar chemistry (pentaerythritol tetrakis(mercaptopropionate)). Given the same thiol concentration, the higher functionality thiol imparted a faster polymerization rate, due to the increased polymer system viscosity, which limited oxygen diffusion and decreased the extent of overall oxygen inhibition. Thus, preliminary insight is provided into how thiol monomer choice affects the extent of oxygen inhibition in thiol-acrylate photopolymerization. (c) 2006 Wiley Periodicals, Inc.