Hanxu Zhu , Han Hu , Qingyang Luan , Chen Lin , Juanfang Xu , Jinggang Wang , Wu Bin Ying , Jin Zhu
{"title":"由完全生物基双吡咯烷酮单体制成的高结晶性、耐热性和可生物降解的共聚聚酯","authors":"Hanxu Zhu , Han Hu , Qingyang Luan , Chen Lin , Juanfang Xu , Jinggang Wang , Wu Bin Ying , Jin Zhu","doi":"10.1016/j.giant.2024.100276","DOIUrl":null,"url":null,"abstract":"<div><p>Improving the heat resistance of bio-based and biodegradable polyesters is of great significance to extend their applications. Herein, N,N’-trans-1,4-cyclohexane-bis(pyrrolidone-4-methyl carboxylate) (T-CBPMC) was prepared through efficient Michael-addition reaction between dimethyl itaconate and trans-1,4-cyclohexanediamine. The obtained T-CBPMC was copolymerized into aliphatic poly(butylene succinate) (PBS), and a series of PBSPs copolymers with T-CBPMC (BP) molar percentages between 41−80 mol % and weight average molecular weight (<em>M<sub>w</sub></em>) values ranging between 5.77*10<sup>4</sup> and 6.67*10<sup>4</sup> g/mol were prepared. BP units efficiently facilitated the melting temperature (203-251 °C) and isothermal-crystallization rate (t<sub>1/2</sub> < 20 s) of PBSPs, endowing the highest heat resistance among commercial biodegradable polyesters, which helps maintain stable in pasteurization, high-temperature disinfection, and microwave environments. Moreover, these copolymers displayed remarkable mechanical, gas barrier properties and degradability. PBSP40-PBSP60 obtained high elastic modulus (335–872 MPa) and tensile strength (24.7–31.5 MPa), and good toughness simultaneously. Multiple-ring structures and large steric hindrance of BP units resulted in superior O<sub>2</sub> barrier performance than that of non-degradable PET films. Importantly, the PBSP copolyesters showed obvious degradation in water environments and relatively better enzymatic degradation. It was interesting to find that even with 70 % of the BP units, the PBSP copolyesters still retained hydrolysis ability. The resulting PBSP copolyesters open the way for alternative candidates of biodegradable packaging materials with rapid crystallization, high heat-resistance and gas barrier.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":null,"pages":null},"PeriodicalIF":5.4000,"publicationDate":"2024-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666542524000419/pdfft?md5=d9808b7b5ce1ac0abad9a74a0e77ee7c&pid=1-s2.0-S2666542524000419-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Highly crystalline, heat resistant and biodegradable copolyesters from fully bio-based bis(pyrrolidone) monomer\",\"authors\":\"Hanxu Zhu , Han Hu , Qingyang Luan , Chen Lin , Juanfang Xu , Jinggang Wang , Wu Bin Ying , Jin Zhu\",\"doi\":\"10.1016/j.giant.2024.100276\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Improving the heat resistance of bio-based and biodegradable polyesters is of great significance to extend their applications. Herein, N,N’-trans-1,4-cyclohexane-bis(pyrrolidone-4-methyl carboxylate) (T-CBPMC) was prepared through efficient Michael-addition reaction between dimethyl itaconate and trans-1,4-cyclohexanediamine. The obtained T-CBPMC was copolymerized into aliphatic poly(butylene succinate) (PBS), and a series of PBSPs copolymers with T-CBPMC (BP) molar percentages between 41−80 mol % and weight average molecular weight (<em>M<sub>w</sub></em>) values ranging between 5.77*10<sup>4</sup> and 6.67*10<sup>4</sup> g/mol were prepared. BP units efficiently facilitated the melting temperature (203-251 °C) and isothermal-crystallization rate (t<sub>1/2</sub> < 20 s) of PBSPs, endowing the highest heat resistance among commercial biodegradable polyesters, which helps maintain stable in pasteurization, high-temperature disinfection, and microwave environments. Moreover, these copolymers displayed remarkable mechanical, gas barrier properties and degradability. PBSP40-PBSP60 obtained high elastic modulus (335–872 MPa) and tensile strength (24.7–31.5 MPa), and good toughness simultaneously. Multiple-ring structures and large steric hindrance of BP units resulted in superior O<sub>2</sub> barrier performance than that of non-degradable PET films. Importantly, the PBSP copolyesters showed obvious degradation in water environments and relatively better enzymatic degradation. It was interesting to find that even with 70 % of the BP units, the PBSP copolyesters still retained hydrolysis ability. 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Highly crystalline, heat resistant and biodegradable copolyesters from fully bio-based bis(pyrrolidone) monomer
Improving the heat resistance of bio-based and biodegradable polyesters is of great significance to extend their applications. Herein, N,N’-trans-1,4-cyclohexane-bis(pyrrolidone-4-methyl carboxylate) (T-CBPMC) was prepared through efficient Michael-addition reaction between dimethyl itaconate and trans-1,4-cyclohexanediamine. The obtained T-CBPMC was copolymerized into aliphatic poly(butylene succinate) (PBS), and a series of PBSPs copolymers with T-CBPMC (BP) molar percentages between 41−80 mol % and weight average molecular weight (Mw) values ranging between 5.77*104 and 6.67*104 g/mol were prepared. BP units efficiently facilitated the melting temperature (203-251 °C) and isothermal-crystallization rate (t1/2 < 20 s) of PBSPs, endowing the highest heat resistance among commercial biodegradable polyesters, which helps maintain stable in pasteurization, high-temperature disinfection, and microwave environments. Moreover, these copolymers displayed remarkable mechanical, gas barrier properties and degradability. PBSP40-PBSP60 obtained high elastic modulus (335–872 MPa) and tensile strength (24.7–31.5 MPa), and good toughness simultaneously. Multiple-ring structures and large steric hindrance of BP units resulted in superior O2 barrier performance than that of non-degradable PET films. Importantly, the PBSP copolyesters showed obvious degradation in water environments and relatively better enzymatic degradation. It was interesting to find that even with 70 % of the BP units, the PBSP copolyesters still retained hydrolysis ability. The resulting PBSP copolyesters open the way for alternative candidates of biodegradable packaging materials with rapid crystallization, high heat-resistance and gas barrier.
期刊介绍:
Giant is an interdisciplinary title focusing on fundamental and applied macromolecular science spanning all chemistry, physics, biology, and materials aspects of the field in the broadest sense. Key areas covered include macromolecular chemistry, supramolecular assembly, multiscale and multifunctional materials, organic-inorganic hybrid materials, biophysics, biomimetics and surface science. Core topics range from developments in synthesis, characterisation and assembly towards creating uniformly sized precision macromolecules with tailored properties, to the design and assembly of nanostructured materials in multiple dimensions, and further to the study of smart or living designer materials with tuneable multiscale properties.