Sequence-Controlled Copolymerization of 6-/7-Membered Cyclic Carbonates with l-Lactide: Wide-Range Regulation of Copolymer Properties

IF 5.7 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2026-10-12 DOI:10.1021/acs.macromol.6c01662

Shuming Dai,Mingqian Wang,Zhiqiang Ding,Honggang Xia,Dongbin Wang,Zhe Ma,Bin Wang

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Abstract

The synthesis of sequence-controlled poly(lactide-carbonate) copolymers via ring-opening copolymerization (ROCOP) of l-lactide (l-LA) with cyclic carbonates under industrially relevant conditions (in bulk and melt) is highly challenging owing to the lack of highly active and thermally stable catalysts. Herein, we systematically investigated the melt and bulk ROCOPs of l-LA with 6-membered trimethylene carbonate (TMC) and 7-membered cyclic 1,4-butylene carbonate (CBC), respectively, using the (amidoalkyl)pyridine–phenolate aluminum methyl complexes as catalysts. The kinetic differentiation and reactivity ratios for l-LA/TMC and l-LA/CBC monomer mixtures were determined in solution polymerization to deeply understand the catalyst-dependent ROCOP behavior. Poly(LA-TMC) and poly(LA-CBC) copolymers with varying comonomer incorporation ratios and tunable sequence length of PLA segments were further synthesized under bulk and melt conditions with different catalysts. The thermal/mechanical properties and degradation behavior of the resulting poly(LA-TMC) and poly(LA-CBC) samples were thoroughly investigated to elucidate the significant effects of comonomer distribution and chain sequences on material properties. Notably, the aluminum complexes exhibited a higher degree of control over the ROCOP process compared with stannous octoate (Sn(Oct)2), affording poly(LA-TMC) and poly(LA-CBC) copolymers with higher molecular weights and superior thermal/mechanical properties under identical conditions. This systematic investigation of the relationships between catalyst/monomer structure, chain composition, and material properties provides valuable insights into the development of high-performance aliphatic copolyesters and the optimization of their practical application performance.

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6-/7元环碳酸盐与l-丙交酯的序控共聚：共聚物性能的大范围调控

由于缺乏高活性和热稳定的催化剂，在工业相关条件下（散装和熔融）通过l-丙交酯（l-LA）与环状碳酸盐的开环共聚（ROCOP）合成顺序控制的聚（丙交酯-碳酸酯）共聚物极具挑战性。本文以（氨基烷基）吡啶-酚酸铝甲基配合物为催化剂，系统地研究了l-LA与6元碳酸三亚甲基（TMC）和7元环1,4-碳酸丁烯（CBC）的熔体和体rocop。在溶液聚合中测定l-LA/TMC和l-LA/CBC单体混合物的动力学分化和反应性比，以深入了解催化剂依赖的ROCOP行为。在不同催化剂和体化条件下，进一步合成了不同单体掺入比和可调PLA段序列长度的Poly（LA-TMC）和Poly（LA-CBC）共聚物。研究了聚（LA-TMC）和聚（LA-CBC）样品的热/力学性能和降解行为，以阐明共聚单体分布和链序列对材料性能的显著影响。值得注意的是，与八酸锡（Sn(Oct)2）相比，铝配合物对ROCOP过程的控制程度更高，在相同的条件下，聚（LA-TMC）和聚（LA-CBC）共聚物具有更高的分子量和更优越的热/机械性能。对催化剂/单体结构、链组成和材料性能之间关系的系统研究为高性能脂肪族共聚酯的开发和其实际应用性能的优化提供了有价值的见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.