Alternating Graft Copolymer Carrying PLA Graft Chains at Every Other Unit: Sequence Impacts on Crystallization Behaviors,ACS Macro Letters

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Alternating Graft Copolymer Carrying PLA Graft Chains at Every Other Unit: Sequence Impacts on Crystallization Behaviors
ACS Macro Letters ( IF 5.1 ) Pub Date : 2024-08-02 , DOI: 10.1021/acsmacrolett.4c00290
Aoto Ishikawa ₁ , Makoto Ouchi ₁

Affiliation

Alternating graft copolymers were precisely synthesized via selective cyclopolymerization of pendant-transformable divinyl monomer (1), post-polymerization modification via aminolysis with alkylamine, and ring-opening polymerization of l-lactide (LLA) from the hydroxy pendant group in alternating sequence. The poly(LLA) (PLLA) graft chain on the alternating copolymer gave a higher crystallization degree on the isothermal treatment than that on the random counterpart likely because of the periodic sequence. The comonomer pendant group from alkylamine in the aminolysis reaction in the alternating sequence affected the crystallization behaviors, and the oligoethylene glycol (OEG) group promoted the crystallization thanks to the larger free volume effect. As for the stereocomplex formation of the racemic mixture of enantiomeric PLLA and poly(d-lactide) (PDLA) chains, the alternating graft copolymer gave a higher degree of stereocomplex crystallization in the mixture with the enantiomer homopolymer than the random analogue.

中文翻译：

每隔一个单元交替携带 PLA 接枝链的接枝共聚物：序列对结晶行为的影响

通过选择性环化可侧链转化的二乙烯基单体（ 1 ）、通过烷基胺氨解进行聚合后改性、以及羟基侧基的L-丙交酯（LLA）的开环聚合，以交替顺序精确合成交替接枝共聚物。交替共聚物上的聚（LLA）（PLLA）接枝链在等温处理中比无规对应物上的结晶度更高，这可能是由于周期序列的原因。交替顺序氨解反应中烷基胺的共聚单体侧基影响结晶行为，而低聚乙二醇（OEG）基团由于更大的自由体积效应而促进结晶。至于对映体PLLA和聚( d-丙交酯)(PDLA)链的外消旋混合物的立体络合物形成，交替接枝共聚物在与对映体均聚物的混合物中比无规类似物产生更高程度的立体络合物结晶。

更新日期：2024-08-02

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