Synthesis of Six-membered Cyclic Carbonates <italic style="font-style: italic">via</italic> a Polycondensation-depolymerization Tandem Strategy

Wei-ning Liu; Ming-qian Wang; Zhi-qiang Ding; Bin Wang

doi:10.11777/j.issn1000-3304.2025.25094

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Synthesis of Six-membered Cyclic Carbonates via a Polycondensation-depolymerization Tandem Strategy

Research Article | 更新时间：2025-10-14

- Synthesis of Six-membered Cyclic Carbonates via a Polycondensation-depolymerization Tandem Strategy
- Acta Polymerica Sinica Vol. 56, Issue 10, Pages: 1706-1715(2025)
- 作者机构：
  
  天津大学材料科学与工程学院天津 300350
- 作者简介：
  
  Bin Wang, E-mail: binwang@tju.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25094
  CLC：
- CSTR：32057.14.GFZXB.2025.7426
- Received：10 April 2025，
  
  Accepted：23 May 2025，
  
  Published Online：14 August 2025，
  
  Published：20 October 2025
- 稿件说明：
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刘伟宁, 王明倩, 丁志强, 王彬. “缩聚-解聚”法合成六元环碳酸酯. 高分子学报, 2025, 56(10), 1706-1715

Liu, W. N.; Wang, M. Q.; Ding, Z. Q.; Wang, B. Synthesis of six-membered cyclic carbonates via a polycondensation-depolymerization tandem strategy. Acta Polymerica Sinica, 2025, 56(10), 1706-1715
刘伟宁, 王明倩, 丁志强, 王彬. “缩聚-解聚”法合成六元环碳酸酯. 高分子学报, 2025, 56(10), 1706-1715 DOI： 10.11777/j.issn1000-3304.2025.25094. CSTR： 32057.14.GFZXB.2025.7426.

Liu, W. N.; Wang, M. Q.; Ding, Z. Q.; Wang, B. Synthesis of six-membered cyclic carbonates via a polycondensation-depolymerization tandem strategy. Acta Polymerica Sinica, 2025, 56(10), 1706-1715 DOI： 10.11777/j.issn1000-3304.2025.25094. CSTR： 32057.14.GFZXB.2025.7426.

摘要

脂肪族六元环碳酸酯是一类具有广泛应用前景的单体，可用于合成聚碳酸酯、脂肪族共聚酯以及非异氰酸酯基聚氨酯等功能材料. 针对目前环碳酸酯单体合成效率低、反应条件苛刻的问题，本研究建立了“缩聚-解聚”串联反应合成功能性环碳酸酯单体的新方法. 由1

3-二醇化合物与碳酸二烷基酯缩合聚合制备低分子量聚碳酸酯，然后再经催化解聚转化成六元环碳酸酯单体. 重点考察了不同催化剂对聚碳酸酯解聚行为的影响. 结果表明，Lewis酸的解聚效率较低，碱金属醇盐展现出最优的催化活性，产物收率达94.2%. 研究发现，碱金属醇盐催化的解聚过程遵循无规断链与端基环化机理，受聚合物分子量、投料比和反应温度等因素影响. “缩聚-解聚”法具有良好的官能团耐受性，能够用于合成结构多样的功能性六元环碳酸酯. 本研究将为新型功能性六元环碳酸酯单体的设计、合成及相应聚碳酸酯材料的开发提供实验与理论基础.

Abstract

Aliphatic six-membered cyclic carbonates are a class of monomers with broad application potential

serving as key precursors in the synthesis of polycarbonates

aliphatic copolyesters

and non-isocyanate polyurethanes. To address the current challenges of low synthetic efficiency and demanding reaction conditions in cyclic carbonate monomer production

this study developed a novel "polycondensation-depolymerization" tandem strategy for the synthesis of functional cyclic carbonate monomers. This method involves the polycondensation of 1

3-diols with dialkyl carbonates to form low-molecular-weight polycarbonates

followed by catalytic depolymerization into six-membered cyclic carbonates. This study systematically investigated the influence of different catalysts on the depolymerization behavior of polycarbonate. The results demonstrate that Lewis acids exhibit low depolymerization efficiency

whereas alkali metal alkoxides exhibit superior catalytic activity with high monomer efficiency (94.2%). Mechanistic studies revealed that alkali metal alkoxide-catalyzed depolymerization follows a random chain scission coupled with an end-group cyclization mechanism

with the reaction efficiency being significantly influenced by the polymer molecular weight

feed ratio

and reaction temperature. The "polycondensation-depolymerization" approach demonstrates excellent functional group tolerance

enabling the synthesis of structurally diverse six-membered cyclic carbonates. This study provides both experimental and theoretical foundations for the design and synthesis of novel functional cyclic carbonate monomers and the development of advanced polycarbonate materials.

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Synthesis of Six-membered Cyclic Carbonates via a Polycondensation-depolymerization Tandem Strategy

DOI：10.11777/j.issn1000-3304.2025.25094

摘要

Abstract

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