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Heteroarm core cross-linked star polymers via RAFT copolymerization of styrene and bismaleimide

机译：通过苯乙烯和双聚酰亚胺的筏共聚杂体核心交联星聚合物

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We explored reversible addition-fragmentation chain transfer (RAFT) copolymerization of 1,2-bis(maleimidoethane) (BMI) with styrene (S) in the presence of polylactide macro-chain transfer agent (PLA-CTA) as a means to synthesize heteroarm core cross-linked star (CCS) polymers consisting of PLA and PS arms (PLA _( n ) PS _( n ) ). Because of the strong alternating tendency of maleimide and styrenic double bonds, copolymerization of BMI with an excess of S depleted BMI in the early stage of polymerization forming a cross-linked core. The remaining S was successively polymerized to grow PS arms from the core, completing PLA _( n ) PS _( n ) via “in–out” mechanism. Use of a stoichiometric amount of S produced PLA _( n ) , which could be used as a macro-CTA for the synthesis of more well-defined PLA _( n ) PS _( n ) . Compared with divinylbenzene, copolymerization of BMI with S was much more effective for core formation suggesting the importance of the alternating character of the copolymerization. While PLA _( n ) PS _( n ) existed as stable nanoparticles in a neutral solvent in contrast to linear PLA- b -PS, it also self-assembled to form microphase-separated structures in a selective solvent and in bulk indicating that PLA and PS arms can be intramolecularly segregated.
机译：我们探讨了苯乙烯大规模转移剂（PLA-CTA）存在于苯乙烯的苯乙烯作为合成异质的手段的苯乙烯（S）与苯乙烯的可逆附加 - 碎片链转移（BMI）共聚合由PLA和PS臂组成的核心交联星（CCS）聚合物（PLA _（n）ps _（n））。由于马来酰亚胺和苯乙烯类双键的强交替倾向，BMI的共聚在聚合的早期具有过量的S贫化BMI形成交联芯。剩余的S连续聚合以使PS臂从核心生长，通过“出局”机制完成PLA _（n）PS _（n）。使用化学计量的S产生的PLA _（n），其可以用作用于合成更明确的PLA _（n）PS _（n）的宏CTA。与二乙烯基苯相比，BMI的共聚合对于核心形成更有效，表明共聚特征的重要性。虽然PLA _（n）ps _（n）在中性溶剂中存在于与线性pla-b -ps相反的中性溶剂中的稳定纳米颗粒，但它也自组装以在选择性溶剂和块状中形成微相分离的结构，表明PLA表示PLA PS臂可以是分层分子隔离。

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