{"title":"Biomass-derived poly(lactic acid) and poly(3-methyl-1,5-pentanediol sebacate) alternating multiblock copolymers with improved marine biodegradability and mechanical properties","authors":"Atsuki Takagi , Yu-I Hsu , Hiroshi Uyama","doi":"10.1016/j.polymdegradstab.2025.111301","DOIUrl":null,"url":null,"abstract":"<div><div>The reliance on fossil resources and the mismanagement of waste owing to the rapid increase in plastic production have led to serious environmental problems, particularly global marine pollution. In recent years, poly(lactic acid) (PLA) has been widely used as a biomass plastic to replace petroleum-based materials. However, the biodegradation of PLA is limited to composting environments and its brittle nature limits its application. This study aimed to synthesize a biomass-based PLA and poly(3-methyl-1,5-pentanediol sebacic acid) (PMPDSe)-diol copolymer and evaluate its marine biodegradability and mechanical properties. PLA was copolymerized with PMPDSe-diol to obtain the triblock copolymer PLA-PMPDSe-PLA, which was then chain-extended with hexamethylene diisocyanate to form an alternating multiblock (PLA-<em>alt</em>-PMPDSe) copolymer. Because of their regular arrangement, the thermal and mechanical properties could be controlled by varying the length of the PLA chains, compared with random multiblock (PLA-<em>ran</em>-PMPDSe) copolymers. In particular, when 61 % or 71 % PLA was included, the films had higher elongation at break (331 %–518 %) and toughness than PLA and PLA-<em>ran</em>-PMPDSe copolymers. Biodegradability was the highest when 54 % PLA was used, and the films disintegrated in compost and seawater. In seawater, the molecular weight decreased to 45 % in three months, and the biodegradability was confirmed to be >17 % in two months. Furthermore, the PLA-<em>alt</em>-PMPDSe copolymer exhibited a contact angle of over 83°, which is equivalent to that of PLA and could be used as a film. This polymer has a wide range of applications and will contribute to the development of sustainable bioplastics and address plastic waste.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"236 ","pages":"Article 111301"},"PeriodicalIF":6.3000,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer Degradation and Stability","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0141391025001314","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0
Abstract
The reliance on fossil resources and the mismanagement of waste owing to the rapid increase in plastic production have led to serious environmental problems, particularly global marine pollution. In recent years, poly(lactic acid) (PLA) has been widely used as a biomass plastic to replace petroleum-based materials. However, the biodegradation of PLA is limited to composting environments and its brittle nature limits its application. This study aimed to synthesize a biomass-based PLA and poly(3-methyl-1,5-pentanediol sebacic acid) (PMPDSe)-diol copolymer and evaluate its marine biodegradability and mechanical properties. PLA was copolymerized with PMPDSe-diol to obtain the triblock copolymer PLA-PMPDSe-PLA, which was then chain-extended with hexamethylene diisocyanate to form an alternating multiblock (PLA-alt-PMPDSe) copolymer. Because of their regular arrangement, the thermal and mechanical properties could be controlled by varying the length of the PLA chains, compared with random multiblock (PLA-ran-PMPDSe) copolymers. In particular, when 61 % or 71 % PLA was included, the films had higher elongation at break (331 %–518 %) and toughness than PLA and PLA-ran-PMPDSe copolymers. Biodegradability was the highest when 54 % PLA was used, and the films disintegrated in compost and seawater. In seawater, the molecular weight decreased to 45 % in three months, and the biodegradability was confirmed to be >17 % in two months. Furthermore, the PLA-alt-PMPDSe copolymer exhibited a contact angle of over 83°, which is equivalent to that of PLA and could be used as a film. This polymer has a wide range of applications and will contribute to the development of sustainable bioplastics and address plastic waste.
期刊介绍:
Polymer Degradation and Stability deals with the degradation reactions and their control which are a major preoccupation of practitioners of the many and diverse aspects of modern polymer technology.
Deteriorative reactions occur during processing, when polymers are subjected to heat, oxygen and mechanical stress, and during the useful life of the materials when oxygen and sunlight are the most important degradative agencies. In more specialised applications, degradation may be induced by high energy radiation, ozone, atmospheric pollutants, mechanical stress, biological action, hydrolysis and many other influences. The mechanisms of these reactions and stabilisation processes must be understood if the technology and application of polymers are to continue to advance. The reporting of investigations of this kind is therefore a major function of this journal.
However there are also new developments in polymer technology in which degradation processes find positive applications. For example, photodegradable plastics are now available, the recycling of polymeric products will become increasingly important, degradation and combustion studies are involved in the definition of the fire hazards which are associated with polymeric materials and the microelectronics industry is vitally dependent upon polymer degradation in the manufacture of its circuitry. Polymer properties may also be improved by processes like curing and grafting, the chemistry of which can be closely related to that which causes physical deterioration in other circumstances.