{"title":"异山梨醇合成聚碳酸酯的机理和动力学:鉴定末端基团的反应性","authors":"Jun-Yao Shen, Xin-Yi Gao, Wen-Ze Guo, Jie Jiang, Jin-Jin Li, Ling Zhao, Zhen-Hao Xi, Wei-Kang Yuan","doi":"10.1002/aic.18529","DOIUrl":null,"url":null,"abstract":"<p>Challenges in the mechanistic and kinetic study on the polymerization with multiple functional monomers hinder the scale-up for the controllable reaction process. Herein, poly (isosorbide carbonate) synthesized from isosorbide (ISB) was employed to investigate the reaction behavior of functional monomers during polymerization. DFT calculations not only determined the energetically preferable pathways but also provided explanations for the significant differences between terminal groups at the molecular level. Subsequently, the characteristic absorption bands were detected from 1000 to 1100 cm<sup>−1</sup> for hydroxyls on ISB, providing a quantitative measure for asymmetric hydroxyls. The reaction network indicated that the reactivity was dominated by the types of terminal groups instead of the chain length. Thereafter, a functional group model with six kinetic parameters was built, acting a crucial role in reaction control and reactor design. This method can be promoted to other functional monomers, conducing to the industrialization of high-performance polymers.</p>","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":null,"pages":null},"PeriodicalIF":3.5000,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Mechanism and kinetics of polycarbonate synthesized from isosorbide: Identification on the reactivity of terminal groups\",\"authors\":\"Jun-Yao Shen, Xin-Yi Gao, Wen-Ze Guo, Jie Jiang, Jin-Jin Li, Ling Zhao, Zhen-Hao Xi, Wei-Kang Yuan\",\"doi\":\"10.1002/aic.18529\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Challenges in the mechanistic and kinetic study on the polymerization with multiple functional monomers hinder the scale-up for the controllable reaction process. Herein, poly (isosorbide carbonate) synthesized from isosorbide (ISB) was employed to investigate the reaction behavior of functional monomers during polymerization. DFT calculations not only determined the energetically preferable pathways but also provided explanations for the significant differences between terminal groups at the molecular level. Subsequently, the characteristic absorption bands were detected from 1000 to 1100 cm<sup>−1</sup> for hydroxyls on ISB, providing a quantitative measure for asymmetric hydroxyls. The reaction network indicated that the reactivity was dominated by the types of terminal groups instead of the chain length. Thereafter, a functional group model with six kinetic parameters was built, acting a crucial role in reaction control and reactor design. This method can be promoted to other functional monomers, conducing to the industrialization of high-performance polymers.</p>\",\"PeriodicalId\":120,\"journal\":{\"name\":\"AIChE Journal\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.5000,\"publicationDate\":\"2024-07-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"AIChE Journal\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/aic.18529\",\"RegionNum\":3,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"ENGINEERING, CHEMICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"AIChE Journal","FirstCategoryId":"5","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/aic.18529","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}
Mechanism and kinetics of polycarbonate synthesized from isosorbide: Identification on the reactivity of terminal groups
Challenges in the mechanistic and kinetic study on the polymerization with multiple functional monomers hinder the scale-up for the controllable reaction process. Herein, poly (isosorbide carbonate) synthesized from isosorbide (ISB) was employed to investigate the reaction behavior of functional monomers during polymerization. DFT calculations not only determined the energetically preferable pathways but also provided explanations for the significant differences between terminal groups at the molecular level. Subsequently, the characteristic absorption bands were detected from 1000 to 1100 cm−1 for hydroxyls on ISB, providing a quantitative measure for asymmetric hydroxyls. The reaction network indicated that the reactivity was dominated by the types of terminal groups instead of the chain length. Thereafter, a functional group model with six kinetic parameters was built, acting a crucial role in reaction control and reactor design. This method can be promoted to other functional monomers, conducing to the industrialization of high-performance polymers.
期刊介绍:
The AIChE Journal is the premier research monthly in chemical engineering and related fields. This peer-reviewed and broad-based journal reports on the most important and latest technological advances in core areas of chemical engineering as well as in other relevant engineering disciplines. To keep abreast with the progressive outlook of the profession, the Journal has been expanding the scope of its editorial contents to include such fast developing areas as biotechnology, electrochemical engineering, and environmental engineering.
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