具有确定相分离行为的聚酰胺酯基嵌段共聚物的一步合成,Macromolecules

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具有确定相分离行为的聚酰胺酯基嵌段共聚物的一步合成
Macromolecules ( IF 5.1 ) Pub Date : 2023-10-12 , DOI: 10.1021/acs.macromol.3c01305
Tianle Gao ₁ , Feng Li ₂ , Ryota Suzuki ₁ , Huan Li _{1,

3} , Takuya Yamamoto ₂ , Xiaochao Xia _{2,

4} , Takuya Isono ₂ , Toshifumi Satoh _{2,

5}

Affiliation

我们开发了一种基于N-甲苯磺酰基氮丙啶（TAz）/环状酸酐开环共聚（ROCOP）、环状碳酸酯开环聚合（ROP）和环氧化物/酸酐ROCOP的自切换一步聚合体系。该系统使用磷腈基催化剂来合成化学结构多样的嵌段共聚物。通过结合 TAz/酸酐 ROCOP 的两个催化循环合成了“块状”聚（酰胺酯）。然后通过将TAz/酸酐ROCOP分别与环状碳酸酯ROP和环氧化物/酸酐ROCOP结合来合成“真正的”嵌段聚(酰胺酯)-b-聚碳酸酯和聚(酰胺酯) -b-聚酯。差示扫描量热法揭示了“真实”嵌段共聚物的两个玻璃化转变温度，小角 X 射线散射测量证实了微相分离，说明了两种共聚物嵌段之间极性的显着差异。这些结果证实了对合成共聚物上每个嵌段的化学结构和性能的精确控制。该方法还能够全面同步调整共聚物嵌段的化学结构，这是共聚物合成领域备受关注的挑战。

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One-Step Synthesis of Poly(amide ester)-Based Block Copolymers with Defined Phase Separation Behavior

We developed a self-switchable, one-step polymerization system based on N-tosylaziridine (TAz)/cyclic anhydride ring-opening copolymerization (ROCOP), cyclic carbonate ring-opening polymerization (ROP), and epoxide/anhydride ROCOP. This system uses a phosphazene-based catalyst for the synthesis of chemical structurally diverse block copolymers. “Block-like” poly(amide ester)s were synthesized by combining two catalytic cycles of TAz/anhydride ROCOP. “Real” block poly(amide ester)-b-polycarbonate and poly(amide ester)-b-polyester were then synthesized by combining TAz/anhydride ROCOP with cyclic carbonate ROP and epoxide/anhydride ROCOP, respectively. Differential scanning calorimetry revealed two glass transition temperatures for the “real” block copolymers, and small-angle X-ray scattering measurements confirmed microphase separation, illustrating a significant difference in polarity between the two blocks of copolymers. These results confirm the precise control of the chemical structure and properties of each block on the synthesized copolymers. This method also enables the comprehensive and synchronous adjustment of the chemical structures of copolymer blocks, a challenge that has received much attention in the field of copolymer synthesis.

更新日期：2023-10-12

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