Thermolysis of RAFT-Synthesized Polymers. A Convenient Method for Trithiocarbonate Group Elimination
Thermolysis of RAFT-Synthesized Polymers. A Convenient Method for Trithiocarbonate Group Elimination
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DOI：
10.1021/ma050402x
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发表时间：
2005-05
期刊：
影响因子：
5.5
通讯作者：
A. Postma;T. P. Davis;G. Moad;M. S. O'shea
中科院分区：
文献类型：
--
作者：
A. Postma;T. P. Davis;G. Moad;M. S. O'shea
使用硫代羰基硫基 RAFT（可逆加成-断裂链转移）试剂 1-4 进行的自由基聚合可以说是活性自由基聚合最通用的方法之一，在单体和反应条件方面表现出卓越的灵活性。 RAFT 聚合的一个关键特征是初始 RAFT 试剂中存在的硫代羰基硫基团保留在聚合产物中。这些基团的保留决定了聚合物的活性特性。然而，硫代羰基硫基团的存在也意味着聚合物通常是有色的。在一些情况下，由于硫代羰基硫基团的分解和挥发性含硫化合物的放出，聚合物还可能有气味或随时间释放气味。这种颜色和气味的存在在一些应用中可能是不利的。尽管其中一些问题可以通过更合适地选择初始 RAFT 试剂而在很大程度上减轻或克服，但仍然有一些动机来开发有效的方法来处理 RAFT 制造的聚合物，以在聚合后裂解硫代羰基硫基端基。
Radical polymerization with thiocarbonylthio RAFT (reversible addition-fragmentation chain transfer) agents 1-4 is arguably one of the most versatile processes for living free radical polymerization displaying superior flexibility with respect to monomers and reaction conditions. A key feature of RAFT polymerization is that the thiocarbonylthio group(s), present in the initial RAFT agent, is (are) retained in the polymeric product(s). The retention of these groups is responsible for the polymers’ living character. However, the presence of the thiocarbonylthio groups also means that the polymers are usually colored. The polymers may also, in some cases, be odorous or release an odor over time due to decomposition of the thiocarbonylthio groups and the evolution of volatile sulfur-containing compounds. The presence of such color and odor can be disadvantageous in some applications. Even though some of these issues may be largely mitigated or overcome by more appropriate selection of the initial RAFT agent, there has nonetheless been some incentive to develop effective methods for treatment of RAFT-made polymers to cleave the thiocarbonylthio end-groups postpolymerization.