{"title":"以双苯胺为原料的生物基线性聚氨酯的合成与表征","authors":"Yoshihiro Minegishi, Tadahisa Iwata, Yukiko Enomoto","doi":"10.1016/j.polymdegradstab.2025.111646","DOIUrl":null,"url":null,"abstract":"<div><div>The development of bio-based polymers with superior thermal and mechanical properties is essential for creating sustainable high-performance plastics. The synthesis of linear aromatic bio-based polyurethanes (PUs) with high thermal resistance, rigidity, and processability remains largely unexplored. Herein, we report the synthesis of a series of bio-based linear aromatic PUs from divanillin (DV)-derived diols and various diisocyanates. DV-based PUs (DVPUs) with different side-chain length (methyl or butyl) had weight-average molecular weights (<em>M</em><sub>w</sub>) ranging from 5.0 × 10<sup>3</sup> to 6.3 × 10<sup>5</sup>. Thermogravimetric analysis (TGA) found 5% decomposition temperatures (<em>T</em><sub>d, 5%</sub>) of DVPUs ranging from 242 to 310 °C. Dynamic mechanical analysis (DMA) revealed that DVPUs exhibited a glass transition temperature (<em>T</em><sub>g</sub>) of 16–167 °C. Notably, a specific DVPU prepared from DVA with methyl side-chains and hexamethylene diisocyanate (HDI) formed a transparent, self-standing film with a tensile strength of 68 MPa and a Young’s modulus of 1.4 GPa. This linear bio-based PUs have achieved high thermal stability, mechanical strength, and optical clarity. This research presents a new molecular design strategy for developing sustainable, heat-resistant aromatic polymers, significantly expanding the potential of bio-based PUs for high-performance bio-plastics.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"242 ","pages":"Article 111646"},"PeriodicalIF":7.4000,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis and characterization of bio-based linear polyurethanes derived from divanillin\",\"authors\":\"Yoshihiro Minegishi, Tadahisa Iwata, Yukiko Enomoto\",\"doi\":\"10.1016/j.polymdegradstab.2025.111646\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The development of bio-based polymers with superior thermal and mechanical properties is essential for creating sustainable high-performance plastics. The synthesis of linear aromatic bio-based polyurethanes (PUs) with high thermal resistance, rigidity, and processability remains largely unexplored. Herein, we report the synthesis of a series of bio-based linear aromatic PUs from divanillin (DV)-derived diols and various diisocyanates. DV-based PUs (DVPUs) with different side-chain length (methyl or butyl) had weight-average molecular weights (<em>M</em><sub>w</sub>) ranging from 5.0 × 10<sup>3</sup> to 6.3 × 10<sup>5</sup>. Thermogravimetric analysis (TGA) found 5% decomposition temperatures (<em>T</em><sub>d, 5%</sub>) of DVPUs ranging from 242 to 310 °C. Dynamic mechanical analysis (DMA) revealed that DVPUs exhibited a glass transition temperature (<em>T</em><sub>g</sub>) of 16–167 °C. Notably, a specific DVPU prepared from DVA with methyl side-chains and hexamethylene diisocyanate (HDI) formed a transparent, self-standing film with a tensile strength of 68 MPa and a Young’s modulus of 1.4 GPa. This linear bio-based PUs have achieved high thermal stability, mechanical strength, and optical clarity. This research presents a new molecular design strategy for developing sustainable, heat-resistant aromatic polymers, significantly expanding the potential of bio-based PUs for high-performance bio-plastics.</div></div>\",\"PeriodicalId\":406,\"journal\":{\"name\":\"Polymer Degradation and Stability\",\"volume\":\"242 \",\"pages\":\"Article 111646\"},\"PeriodicalIF\":7.4000,\"publicationDate\":\"2025-09-04\",\"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/S0141391025004756\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer Degradation and Stability","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0141391025004756","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Synthesis and characterization of bio-based linear polyurethanes derived from divanillin
The development of bio-based polymers with superior thermal and mechanical properties is essential for creating sustainable high-performance plastics. The synthesis of linear aromatic bio-based polyurethanes (PUs) with high thermal resistance, rigidity, and processability remains largely unexplored. Herein, we report the synthesis of a series of bio-based linear aromatic PUs from divanillin (DV)-derived diols and various diisocyanates. DV-based PUs (DVPUs) with different side-chain length (methyl or butyl) had weight-average molecular weights (Mw) ranging from 5.0 × 103 to 6.3 × 105. Thermogravimetric analysis (TGA) found 5% decomposition temperatures (Td, 5%) of DVPUs ranging from 242 to 310 °C. Dynamic mechanical analysis (DMA) revealed that DVPUs exhibited a glass transition temperature (Tg) of 16–167 °C. Notably, a specific DVPU prepared from DVA with methyl side-chains and hexamethylene diisocyanate (HDI) formed a transparent, self-standing film with a tensile strength of 68 MPa and a Young’s modulus of 1.4 GPa. This linear bio-based PUs have achieved high thermal stability, mechanical strength, and optical clarity. This research presents a new molecular design strategy for developing sustainable, heat-resistant aromatic polymers, significantly expanding the potential of bio-based PUs for high-performance bio-plastics.
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.