ATRP-RCM Synthesis of Cyclic Diblock Copolymers
ATRP-RCM Synthesis of Cyclic Diblock Copolymers
复制标题
DOI：
10.1021/ma801363n
复制
发表时间：
2008-11-11
期刊：
影响因子：
5.5
通讯作者：
Tezuka, Yasuyuki
中科院分区：
文献类型：
--
作者：
Adachi, Kaoru;Honda, Satoshi;Tezuka, Yasuyuki
将原子转移自由基聚合（ATRP）和闭环复分解（RCM）技术相结合，发展了一种合成环状二嵌段共聚物的通用方法。因此，首先，由两个不同的丙烯酸酯链段组成的A-B型烯丙基-遥爪二嵌段共聚物，即，分别以烯丙基溴为引发剂和烯丙基三丁基锡烷为封端剂，通过丙烯酸甲酯（MA）的原子转移自由基聚合（ATRP），加入第二单体BA，制备了聚（MA）-b-聚（BA）。或者，使用具有2-溴异丁酰基端基的聚（EO）大分子引发剂，通过BA的ATRP，随后用烯丙基三丁基锡烷进行封端反应，制备由聚（BA）和聚（环氧乙烷）（聚（EO））链段组成的A-B-A型烯丙基-遥爪三嵌段共聚物。在Grubbs催化剂存在下，烯丙基遥爪嵌段共聚物在稀释条件下进行RCM，得到相应的A-B型环状二嵌段共聚物。
A versatile synthetic means for cyclic diblock copolymers has been developed by the combination of atom transfer radical polymerization (ATRP) and ring-closing metathesis (RCM) techniques. Thus, first, an A-B type allyl-telechelic diblock copolymer comprised of two different acrylate ester segments, i.e., poly(methyl acrylate)-b-poly(n-butyl acrylate), poly(MA)-b-poly(BA), was prepared via the ATRP of MA, followed by the addition of the second monomer, BA, with allyl bromide as an initiator and with allyltributylstannane as an end-capping reagent, respectively. Alternatively, an A-B-A type allyl-telechelic triblock copolymer comprised of poly(BA) and poly(ethylene oxide), poly(EO), segments was prepared via the ATRP of BA using a poly(EO) macroinitiator having 2-bromoisobutyryl end groups, followed by the end-capping reaction with allyltributylstannane. The subsequent RCM of the allyl-telechelic block copolymers under dilution in the presence of Grubbs catalyst could afford the corresponding A-B type cyclic diblock copolymers.