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使用戊二酸锌催化剂对环氧丙烷和一氧化碳进行催化链转移共聚

Catalytic Chain Transfer Copolymerization of Propylene Oxide and CO using Zinc Glutarate Catalyst.

作者信息

Marbach Jakob, Höfer Theresa, Bornholdt Nick, Luinstra Gerrit A

机构信息

University of Hamburg Institute of Technical and Macromolecular Chemistry Bundesstraße 45 20146 Hamburg Germany.

出版信息

ChemistryOpen. 2019 Jun 11;8(7):828-839. doi: 10.1002/open.201900135. eCollection 2019 Jul.

Abstract

Oligo and poly(propylene ether carbonate)-polyols with molecular weights from 0.8 to over 50 kg/mol and with 60-92 mol % carbonate linkages were synthesized by chain transfer copolymerization of carbon dioxide (CO) and propylene oxide (PO) mediated by zinc glutarate. -monitoring of the polymerization revealed that the CTA controlled copolymerization has an induction time which is resulting from reversible catalyst deactivation by the CTA. Latter is neutralized after the first monomer additions. The outcome of the chain transfer reaction is a function of the carbonate content, . CO pressure, most likely on account of differences in mobility (diffusion) of the various polymers. Melt viscosities of poly(ether carbonate)diols with a carbonate content between 60 and 92 mol % are reported as function of the molecular weight, showing that the mobility is higher when the ether content is higher. The procedure of PO/CO catalytic chain copolymerization allows tailoring the glass temperature and viscosity.

摘要

通过戊二酸锌介导的二氧化碳(CO₂)和环氧丙烷(PO)的链转移共聚反应,合成了分子量在0.8至50多千克/摩尔之间、碳酸酯键含量为60 - 92摩尔%的低聚物和聚(聚丙烯醚碳酸酯)多元醇。对聚合反应的监测表明,链转移剂(CTA)控制的共聚反应有一个诱导期,这是由CTA使催化剂可逆失活导致的。在首次加入单体后,CTA被中和。链转移反应的结果是碳酸酯含量的函数。CO₂压力的影响,很可能是由于各种聚合物在流动性(扩散)方面的差异。报道了碳酸酯含量在60至92摩尔%之间的聚(醚碳酸酯)二醇的熔体粘度与分子量的关系,结果表明醚含量越高,流动性越高。PO/CO₂催化链共聚反应的过程允许调整玻璃化温度和粘度。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00fd/6604238/8b5df0499007/OPEN-8-828-g020.jpg

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