One-Pot Synthesis of PS-b-PEO-b-PtBA Triblock Copolymers via Combination of SET-LRP and ``Click'' Chemistry Using Copper(0)/PMDETA as Catalyst System
One-Pot Synthesis of PS-b-PEO-b-PtBA Triblock Copolymers via Combination of SET-LRP and ``Click'' Chemistry Using Copper(0)/PMDETA as Catalyst System
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DOI：
10.1021/ma102621k
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发表时间：
2011-01
期刊：
影响因子：
5.5
通讯作者：
Rongkuan Jing;Guowei Wang;Yannan Zhang;Junlian Huang
中科院分区：
文献类型：
--
作者：
Rongkuan Jing;Guowei Wang;Yannan Zhang;Junlian Huang
以Cu（0）/N，N，N′，N′′，N′′-五甲基二乙烯三胺（PMDETA）为催化剂，采用单电子转移活性自由基聚合（SET-LRP）和“点击”化学相结合的方法，合成了聚苯乙烯-嵌段-聚环氧乙烷-嵌段-聚丙烯酸叔丁酯（PS-b-PEO-b-PtBA）三嵌段共聚物。以2-（1-乙氧基乙氧基）乙醇钾为引发剂，通过环氧乙烷（EO）的阴离子开环聚合（ROP），合成了羟基被乙氧基乙基保护、羟基具有活性的α，ω-杂官能化PEO。通过对端基的进一步修饰，得到了含炔基和溴基的PEO。同时，通过原子转移自由基聚合（ATRP）合成了端溴聚苯乙烯（PS−Br），在过量叠氮化钠存在下，在N，N-二甲基甲酰胺（DMF）中通过亲核取代反应将端溴基团转化为叠氮基团。最后，在Cu（0）/PMDETA催化剂存在下，PEO的溴端基发生了断裂。
Triblock copolymers of polystyrene-block-poly(ethylene oxide)-block-poly(tert-butyl acrylate) (PS-b-PEO-b-PtBA) were prepared via combination of single electron transfer living radical polymerization (SET-LRP) with “click” chemistry using Cu(0)/N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) as catalyst system. The α,ω-heterofunctionalized PEO with an ethoxyethyl-protected hydroxyl group and an active hydroxyl group was synthesized via anionic ring-opening polymerization (ROP) of ethylene oxide (EO) using potassium 2-(1-ethoxyethoxy)ethoxide as initiator. After further modifications of the end groups, the PEO with alkyne and bromine groups was obtained. Meanwhile, bromine-terminated polystyrene (PS−Br) was synthesized by atom transfer radical polymerization (ATRP), then the bromine end groups were transformed to azide groups by nucleophilic substitution reaction in N,N-dimethylformamide (DMF) in the presence of excessive sodium azide. Lastly, in the presence of Cu(0)/PMDETA, bromine end group of PEO...