| 有机二硫化物引发MMA光聚合的研究 |
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| 引用本文： | 李妙贞,常志英,张耀坤,王尔鑑,冯新德. 有机二硫化物引发MMA光聚合的研究[J]. 影像科学与光化学, 1984, 2(4): 46-53. DOI: 10.7517/j.issn.1674-0475.1984.04.46 |
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| 作者姓名： | 李妙贞 常志英 张耀坤 王尔鑑 冯新德 |
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| 作者单位： | 1. 中国科学院感光化学研究所;2. 北京大学化学系 |
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| 摘 要： | 本文对各种有机二硫化物引发甲基丙烯酸甲酯(MMA)的光聚合反应进行了动力学研究,实验结果表明,二硫化物的结构对聚合速度Rp有很大影响,各种二硫化物的引发反应活性可以排列如下:(p-CH3C6H4S)2>(t-C4H9S)2>(C6H5CH2S)2,(n-C12H25S)2和((C2H5)2NC2H4S)2。二甲苯二硫化物(DMDS)引发反应的效果可以和安息香醚类相比拟。发现Rp和溶剂的性质有很大关系,并且和[MMA]以及[DMDS]0.1(N2气氛下)或[DMDS]0.2(O2气氛下)成正比,测得的DMDS的单线态和三线态能量分别为Es72.2kcal/mol和ET 57.3kcal/mol,它们比一般烯类单体的能量低,这说明DMDS适于用作烯类光聚合的引发剂。从所得结果讨论了引发聚合的反应机理。
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| 收稿时间： | 1983-10-27 |
PHOTOPOLYMERIZATION OF MMA INITIATED BY DISULFIDES |
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| LI MIAO-ZHEN,CHANG ZHI-YING,ZHANG YAO-KUN,WANG ER-JIAN,FENG XIN-DE. PHOTOPOLYMERIZATION OF MMA INITIATED BY DISULFIDES[J]. Imaging Science and Photochemistry, 1984, 2(4): 46-53. DOI: 10.7517/j.issn.1674-0475.1984.04.46 |
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| Authors: | LI MIAO-ZHEN CHANG ZHI-YING ZHANG YAO-KUN WANG ER-JIAN FENG XIN-DE |
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| Affiliation: | 1. Institute of Photographic Chemistry, Academia Sinica;2. Department of Chemistry, Peking University |
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| Abstract: | Photopolymerization of methyl methacrylate (MMA) has been studied kinetically using several organic disulfides as photoinitiator. Experimental results show that the structural effect of disul’fides on polymerization rate Rp is quite obvious. The initiation activities of various disulfides may be arranged in following order (P-CH3C6S)2 > (t-C4H9S)2>(C6H5CH2S)2, (n-C12H25S)2 and ((C2H5)2NC2H4S)2. The initiation efficiency of di-toluene disulfide (DMDS)can bear comparison with benzoin ethers. The RP was found to depend highly on the nature of solvents and is proportional to [MMA] and [DMDS]0.1(N2) or [DMDS]0.2(O2). The singlet and triplet energy of DMDS have been determined to be Es72.2kcal/mol and ET57.3kcal/mol, respectively, which considerably lower than that of conventional vinyl monomers.It indicates that DMDS is qualified as photoinitiator for vinyl polymerization. From the results obtained the initiation mechanism of polymerization is proposed and discussed. |
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