有机硫化物用于自由基活性/可控聚合

Research Development of Organic Sulfides in Living/controlled Free-radical Polymerization

综述了有机硫化物用于自由基活性聚合的研究进展 ,对其机理和活性特征进行了简要的讨论。有机硫化物用于自由基活性聚合的研究工作可以追溯到上个世纪 80年代 ,N ,N 二乙基二硫代氨基甲酸酯用作光引发—转移—终止剂 (Iniferter) ,其聚合具有一定的活性特征 ,但分子量分布较宽。以二硫代羧酸酯和三硫代碳酸酯为链转移剂的可逆加成裂解链转移 (RAFT)自由基聚合的发现 ,在活性自由基聚合领域是一个重要突破。用二硫代羧酸和三硫代碳酸酯作转移剂 ,在6 0 Coγ 射线辐照下实现了St、AA、MA和MMA等单体的活性自由基聚合 。

The present paper reviews the recent progresses of organic sulfides in living free-radical polymerization, such as Iniferter, RAFT and 60Co γ-irradiation polymerization. The mechanism and living characteristics of them are discussed, respectively. In 1980′s, some sulfur compounds containing N,N-diethyldithiocarbamoyl group was firstly used as photoiniferter in living free-radical polymerization, which has some living behaviors, but the molecular weight distribution becomes broader with the conversion. RAFT uses the dithiocarbamate or trithiocarbonate derivatives as transfer agents, the polymerization has excellent living behavior, which is an important breakthrough in the development of living free-radical polymerization. Recently dithiobenzoic acid and dibenzyl trithiocarbonate are used in living free-radical polymerizations under 60Co γ-irradiation at room temperature, many monomers have been investigated, this is another new development.