AAB-Sequence Living Radical Chain Copolymerization of Naturally Occurring Limonene with Maleimide: An End-to-End Sequence-Regulated Copolymer
AAB-Sequence Living Radical Chain Copolymerization of Naturally Occurring Limonene with Maleimide: An End-to-End Sequence-Regulated Copolymer
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DOI：
10.1021/ja1042353
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发表时间：
2010-07-28
影响因子：
15
通讯作者：
Kamigaito, Masami
中科院分区：
文献类型：
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作者：
Satoh, Kotaro;Matsuda, Masaru;Kamigaito, Masami
与具有完全序列调控结构的天然大分子（如蛋白质和DNA）相比，链生长聚合中的序列控制仍然是合成聚合物化学中最具挑战性的课题之一。在这里，我们报道了天然存在的(+)-d-柠檬烯(L)和马来酰亚胺(M)在氟醇中进行了定量和高选择性的1:2序列调控自由基共聚，产生了高玻璃化转变温度（220-250℃）的手性共聚物，源自单体的特定刚性循环结构。此外，通过可控/活性自由基聚合与可逆加成-裂解链转移（RAFT）剂（C- s）结合，得到端到端序列调控的共聚物[C-(M-M-L)(n)- m - s]，其链端和主链重复单元高度有序，分子量可控。
Sequence control in chain-growth polymerization is still one of the most challenging topics in synthetic polymer chemistry in contrast to natural macromolecules with completely sequence-regulated structures like proteins and DNA. Here, we report the quantitative and highly selective 1:2 sequence-regulated radical copolymerization of naturally occurring (+)-d-limonene (L) and a maleimide (M) in fluoroalcohol giving chiral copolymers with high glass transition temperatures (220-250 degrees C) originating from the specific rigid cyclic structures of the monomers. Furthermore, the combination with a reversible addition-fragmentation chain transfer (RAFT) agent (C-S) via the controlled/living radical polymerization resulted in end-to-end sequence-regulated co-polymers [C-(M-M-L)(n)-M-S] with both highly sequenced chain ends and main-chain repeating units as well as controlled molecular weights.