聚(ε-己内酯-co-1,2-丙二醇草酸酯)的合成及其性能

Synthesis and Properties of Poly(ε-caprolactone-co-1, 2-propanediol oxalate)

摘要

以环状1,2-丙二醇草酸酯（1,2-POx）为改性单体，与ε-己内酯（CL）进行本体开环共聚，制备了一系列聚（ε-己内酯-co-1,2-丙二醇草酸酯）（P（CL-co-POx））。系统考察了P（CL-co-POx）的聚合条件、理化性能、力学性能及降解性能。结果表明，P（CL-co-POx）的单体转化率超过94%，数均分子量（M_n）可达131.5×10³，结晶度为39.0%，兼具良好的力学性能（拉伸强度26.9 MPa、断裂伸长率1 928%）与可控的降解性能（降解28 d后失重率达66%）。本研究为设计兼具优异力学性能与可控降解性能的脂肪族聚酯提供了有效途径。

Abstract

A series of poly(ε-caprolactone-co-1,2-propylene glycol oxalate) (P(CL-co-POx)) copolymers were synthesized via bulk ring-opening copolymerization of ε-caprolactone (CL) with cyclic 1,2-propylene glycol oxalate (1,2-POx) as a modifying monomer. The polymerization behavior, physicochemical properties, mechanical properties, and degradation performance of P(CL-co-POx) were systematically investigated. Results demonstrated that the monomer conversion exceeded 94%, the number-average molecular weight (M _n) reached up to 131.5×10³, and the crystallinity was determined to be 39.0%. The copolymer exhibited favorable mechanical properties with a tensile strength of 26.9 MPa and an elongation at break of 1 928%, as well as excellent degradability, showing a mass loss of 66% after 28 d of degradation. This strategy provides an effective route for designing aliphatic polyesters with superior mechanical performance and tunable degradability.

关键词

可降解聚合物 / 共聚酯 / ε-己内酯 / 环状1,2-丙二醇草酸酯 / 开环聚合

Key words

degradable polymer / copolyester / ε-caprolactone / cyclic 1,2-propylene glycol oxalate / ring-opening copolymerization

参考文献

[1] SHI C, QUINN E C, DIMENT W T, CHEN E Y . Recyclable and (bio)degradable polyesters in a circular plastics economy [J]. Chemical Reviews, 2024, 124(7): 4393-4478.

[2] HAQUE F M, ISHIBASHI J S A, LIDSTON C A L, SHAO H, BATES F S, CHANG A B, COATES G W, CRAMER C J, DAUENHAUER P J, DICHTEL W R, ELLISON C J, GORMONG E A, HAMACHI L S, HOYE T R, JIN M, KALOW J A, KIM H J, KUMAR G, LASALLE C J, LIFFLAND S, LIPINSKI B M, PANG Y, PARVEEN R, PENG X, POPOWSKI Y, PREBIHALO E A, REDDI Y, REINEKE T M, SHEPPARD D T, SWARTZ J L, TOLMAN W B, VLAISAVLJEVICH B, WISSINGER J, XU S, HILLMYER M A . Defining the macromolecules of tomorrow through synergistic sustainable polymer research [J]. Chemical Reviews, 2022, 122(6): 6322-6373.

[3] SUN Y, AN Z, GAO Y, HU R, LIU Y, LU H, LU X B, PANG X, QIN A, SHEN Y, TAO Y, WANG Y Z, WANG J, WU G, WU G P, XU T Q, ZHANG X H, ZHANG Y, ZHANG Z, ZHU J B, HONG M, LI Z . New sustainable polymers with on—demand depolymerization property [J]. Science China Chemistry, 2024, 67(9): 2803-2841.

[4] JADAUN J S, BANSAL S, SONTHALIA A, RAI A K, SINGH S P . Biodegradation of plastics for sustainable environment [J]. Bioresource Technology, 2022, 347: 126697.

[5] JAMBECK J R, GEYER R, WILCOX C, SIEGLER T R, PERRYMAN M, ANDRADY A, NARAYAN R, LAW K L . Marine pollution: Plastic waste inputs from land into the ocean [J]. Science, 2015, 347(6223): 768-771.

[6] JEHANNO C, ALTY J, ROOSEN M, DE MEESTER S, DOVE A P, CHEN E Y X, LEIBFARTH F A, SARDON H . Critical advances and future opportunities in upcycling commodity polymers [J]. Nature, 2022, 603: 803-814.

[7] SAMIR A, ASHOUR F H, HAKIM A A A, BASSYOUNI M . Recent advances in biodegradable polymers for sustainable applications [J]. npj Materials Degradation, 2022, 6(1): 68.

[8] QIN B, ZHANG X . On depolymerization [J]. CCS Chemistry, 2024, 6(2): 297-312.

[9] HONG M, CHEN E Y X . Completely recyclable biopolymers with linear and cyclic topologies via ring—opening polymerization of γ—butyrolactone [J]. Nature Chemistry, 2016, 8(1): 42-49.

[10] 冯西敏, 耿晓维, 张成建, 张兴宏 . 多功能单分子催化丙交酯开环聚合和共聚合 [J]. 功能高分子学报, 2025, 38(6): 471-480.

[11] FENG X M, GENG X W, ZHANG C J, ZHANG X H . Multifunctional monomolecular catalysis for ring—opening polymerization and copolymerization of lactide [J]. Journal of Functional Polymers, 2025, 38(6): 471-480.

[12] WOODRUFF M A, HUTMACHER D W . The return of a forgotten polymer—polycaprolactone in the 21st century [J]. Progress in Polymer Science, 2010, 35(10): 1217-1256.

[13] SONG M, LI S, ZHU G, GUO J . Compatibilisation and toughening of PLA/PCL blends via modified chitosan linking amorphous regions: 4D printing and shape memory processes [J]. Polymer Testing, 2023, 125: 108105.

[14] RANGEL A L R, COLAÇO L, NGUYEN N T, GROSSET J F, EGLES C, MIGONNEY V . Adapting mechanical characterization of a biodegradable polymer to physiological approach of anterior cruciate ligament functions [J]. IRBM, 2020, 43(1): 39-48.

[15] PFAU M R, MCKINZEY K G, ROTH A A, GRUNLAN M A . PCL—Based shape memory polymer semi—IPNs: The role of miscibility in tuning the degradation rate [J]. Biomacromolecules, 2020, 21(6): 2493-2501.

[16] TERZI M, CELESTRE V, TANG P, MADSEN J, DAUGAARD A E . Accelerating polyester hydrolysis through blending with bio—based poly(4—hydroxyphenylacetate) multiblock copolymers [J]. European Polymer Journal, 2025, 228: 113841.

[17] BARTNIKOWSKI M, DARGAVILLE T R, IVANOVSKI S, HUTMACHER D W . Degradation mechanisms of polycaprolactone in the context of chemistry, geometry and environment [J]. Progress in Polymer Science, 2019, 96: 1-20.

[18] LANG F, FEI F, SUN C, WU S . Highly efficient degradation of polybutylene succinate (PBS) and polycaprolactone (PCL) by a recombinant marine fungal cutinase [J]. Applied and Environmental Microbiology, 2025, 91(9): e0083325.

[19] SHEN J, YUAN W, BADV M, MOSHAVERINIA A, WEISS P S . Modified poly(ε—caprolactone) with tunable degradability and improved biofunctionality for regenerative medicine [J]. ACS Mater Au, 2023, 3(5): 540-547.

[20] 谢美昌, 刘悦洋, 向洪平, 章明秋 . 基于动态共价化学的弹性体可控降解与回收研究进展 [J]. 功能高分子学报, 2025, 38(1): 1-12.

[21] XIE M C, LIU Y Y, XIANG H P, ZHANG M Q . Research progress on controllable degradation and recycling of elastomers based on dynamic covalent chemistry [J]. Journal of Functional Polymers, 2025, 38(1): 1-12.

[22] ANDERSON R J, FINE R L, RAPAGNANI R M, TONKS I A . Ring—opening copolymerizations of a CO₂—derived δ—valerolactone with ε—caprolactone and L—lactide [J]. Macromolecules, 2024, 57(13): 6248-6254.

[23] WENG C, DING Z, QIU W, WANG B, TANG X . Achieving exceptional thermal and hydrolytic resistance in chemically circular polyesters via in—chain 1, 3—cyclobutane rings [J]. Angewandte Chemie International Edition, 2024, 63(24): e202401682.

[24] MURCIA VALDERRAMA M A, van PUTTEN R J, GRUTER G J M . The potential of oxalic— and glycolic acid based polyesters (review). Towards CO₂ as a feedstock (Carbon Capture and Utilization—CCU) [J]. European Polymer Journal, 2019, 119: 445-468.

[25] CAROTHERS W H, NATTA F J V . Studies on polymerization and ring formation: Ⅲ. Glycol esters of carbonic acid [J]. Journal of the American Chemical Society, 2002, 52(1): 314-326.

[26] IAKIMOV N P, BUDYNINA E M, BERKOVICH A K . Polymerization of six—membered propylene oxalate [J]. European Polymer Journal, 2024, 220: 113410.

[27] LUAN Q, HU H, OUYANG X, JIANG X, LIN C, ZHU H, SHI T, ZHAO Y L, WANG J, ZHU J . New modifications of PBAT by a small amount of oxalic acid: Fast crystallization and enhanced degradation in all natural environments [J]. Journal of Hazardous Materials, 2024, 465: 133475.

[28] HU H, LIN C, LUAN Q, JIANG X, ZHANG X, WANG Q, DONG Y, WEI J, WANG J, ZHU J . Synergistic modification of PBT with diglycolic acid and succinic acid: Fast crystallization and high strength—toughness copolyesters for environmentally degradable packaging [J]. ACS Sustainable Chemistry & Engineering, 2023, 11(38): 14068-14080.

[29] TU Z, LU Y, SANG L, ZHANG Y, LI Y, WEI Z . Kilogram—scale preparation of poly(ethylene oxalate) toward marine—degradable plastics [J]. Macromolecules, 2023, 56(8): 3149-3159.

[30] GARCIA J J, MILLER S A . Polyoxalates from biorenewable diols via oxalate metathesis polymerization [J]. Polymer Chemistry, 2014, 5(3): 955-961.

[31] TU Z, WANG B, LU Y, WANG L, LI Y, SANG L, ZHANG Y, WEI Z . Incorporation of large—scale prepared poly(ethylene oxalate) into biodegradable poly(butylene adipate— co—terephthalate) blown films with enhanced mechanical and barrier performance [J]. ACS Sustainable Chemistry & Engineering, 2023, 11(26): 9833-9845.

[32] TU Z, WANG L, LU Y, LI Y, SANG L, ZHANG Y, WEI E . Rapid marine degradable poly(butylene oxalate) by introducing promotion building blocks [J]. Journal of Hazardous Materials, 2024, 462: 132791.

[33] LIU Y, LI Z, ZHAO D, SHEN Y, LI Z . A polycondensation—depolymerization strategy enables closed—loop recyclable polyoxalates via ring—opening polymerization of six—membered cyclic oxalates [J]. Chemical Science, 2026, 17(7): 3733-3742.

[34] DAI J, XIONG W, DU M R, WU G, CAI Z, ZHU J B . A facile approach towards high—performance poly(thioether—thioester)s with full recyclability [J]. Science China Chemistry, 2023, 66(1): 251-258.

基金资助

国家自然科学基金(U24A20558)

国家自然科学基金(22031005)