基于 3-Methylene-1,5-dioxepan-2-one 的聚（共轭酯）的合成及后功能化,Biomacromolecules

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基于 3-Methylene-1,5-dioxepan-2-one 的聚（共轭酯）的合成及后功能化
Biomacromolecules ( IF 5.5 ) Pub Date : 2022-11-16 , DOI: 10.1021/acs.biomac.2c01015
Zhaoyue Li ₁ , Yilin Qian ₁ , Yihuan Lai ₁ , Fu-Sheng Du ₁ , Zi-Chen Li ₁

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聚（α-亚甲基酯）是一种有吸引力的功能性脂肪族聚酯，代表了制造各种可生物降解和生物医学聚合物的平台。在此，我们报告了基于 Baylis-Hillman 反应合成的七元 α-亚甲基内酯（3-methylene-1,5-dioxepan-2-one, MDXO）的受控开环聚合 (ROP)。MDXO 的化学选择性 ROP 在 60 °C 下由磷酸二苯酯 (DPP) 或在 130 °C 下由辛酸亚锡 (Sn(Oct) ₂ ) 催化，生成具有线性结构和易于调节摩尔数的 α-亚甲基聚酯 (PMDXO)大量的。MDXO与ε-己内酯或1,5-二氧杂环庚烷-2-酮的开环共聚也在DPP或Sn(Oct) _{2催化下进行}提供具有受单体和催化剂种类影响的不同组成和序列结构的共聚物。PMDXO 是一种可缓慢结晶的聚合物，其玻璃化转变温度为 ca。−33 °C，其熔化温度和热函受热历史的显着影响。共聚物的热性能取决于它们的组成和序列结构。最后，简要探讨了以三乙胺为催化剂的基于硫醇-迈克尔加成反应的PMDXO后改性。在优化条件下，PMDXO 可以进行双重改性以提供具有不同功能的可生物降解聚酯。

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Synthesis and Post-Functionalization of Poly(conjugated ester)s Based on 3-Methylene-1,5-dioxepan-2-one

Poly(α-methylene ester)s are an attractive type of functional aliphatic polyesters that represent a platform for the fabrication of various biodegradable and biomedical polymers. Herein, we report the controlled ring-opening polymerization (ROP) of a seven-membered α-methylene lactone (3-methylene-1,5-dioxepan-2-one, MDXO) that was synthesized based on the Baylis–Hillman reaction. The chemoselective ROP of MDXO was catalyzed by diphenyl phosphate (DPP) at 60 °C or stannous octoate (Sn(Oct)₂) at 130 °C, generating α-methylene-containing polyester (PMDXO) with a linear structure and easily tunable molar mass. The ring-opening copolymerization of MDXO with ε-caprolactone or 1,5-dioxepan-2-one was also performed under the catalysis of DPP or Sn(Oct)₂ to afford copolymers with different compositions and sequence structures that are influenced by the kinds of monomers and catalysts. PMDXO is a slowly crystallizable polymer with a glass transition temperature of ca. −33 °C, and its melting temperature and enthalpy are significantly influenced by the thermal history. The thermal properties of the copolymers are dependent on their composition and sequence structure. Finally, the post-modification of PMDXO based on the thiol-Michael addition reaction was briefly explored using triethylamine as a catalyst. Given the optimized condition, PMDXO could be dually modified to afford biodegradable polyesters with different functionalities.

更新日期：2022-11-16

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