ArnSnOm靶向催化二甲氧基碳酸双酚A二酯合成和缩聚及反应机理研究

The reaction of dimethyl carbonate (DMC) with bisphenol A into Bisphenol A polycarbonate (PC) provides a main green method for PC synthesis. As for the bottleneck problems in PC synthesis from DMC and bisphenol A (BPA), such as the difficult bis-methylcarbonate of bisphenol-A (BMBPA) synthesis, BPA methylation and BMBPA decomposition. Herein, ArnSnOm type catalysts were prepared, and BMBPA selective synthesis and its orientation polymerization were promoted by π-d in ArnSnOm, π-π between ArnSnOm and substrates, and the presence of CO2 which restrains BMBPA decomposition. Catalyst were characterized, and carbonate group adsorption types over catalyst were studied, The relations between carbonate group adsorption type and reaction process were established. The effects of π-d and π-π on promotion transesterification, restraining side reactions and BMBPA orientation polymerization were exploited. The role of CO2 on BMBPA synthesis and condensation was studied, and carbonate group decomposition mechanism was investigated. This research project will provide theoretical guidance for catalyst design and selective reaction.

开发碳酸二甲酯（DMC）法合成聚碳酸酯(PC)是实现绿色低能耗制备PC的重要途径。针对中间体二甲氧基碳酸双酚A二酯（BMBPA）合成中，DMC与双酚Ａ(BPA)酯交换反应效率低，BPA易烷基化，而BMBPA高温分解不利于缩聚等难题，本课题提出制备芳基氧化锡（ArnSnOm）催化剂，利用ArnSnOm中芳基与Sn之间的π-d作用，ArnSnOm与BPA或BMBPA之间的π-π作用，CO2抑制碳酸酯分解作用等，实现BMBPA高效合成和定向缩聚。表征DMC在ArnSnOm上的活化方式，研究ArnSnOm结构对DMC活化方式的影响规律，探索DMC活化方式与酯交换反应之间的关系；研究ArnSnOm中芳基与Sn之间的π-d作用规律，表征ArnSnOm与BPA或BMBPA之间的π-π作用方式，揭示ArnSnOm在BMPBA靶向合成及其定向缩聚中的作用机理；阐释BMBPA分解的影响因素和CO2作用成效。

开发碳酸二甲酯（DMC）法合成聚碳酸酯(PC)是实现绿色低能耗制备PC的重要途径。针对中间体二甲氧基碳酸双酚A二酯（BMBPA）合成过程中，DMC与双酚Ａ酯交换反应效率低，双酚Ａ易发生烷基化，而BMBPA高温分解不利于缩聚等难题，本课题制备了芳基有机氧化锡（ArnSnOm）催化剂，利用芳基和Sn之间的π-d作用，催化剂与反应底物之间的π-π作用，并利用CO2抑制碳酸酯分解等，实现了BMBPA或其他聚酯中间体高效合成和定向缩聚。系统表征催化剂，研究DMC在催化剂表面的活化形态，建立DMC的活化方式与反应途径之间的定性关系；研究催化剂与反应底物之间的π-π靶向堆积作用，以及芳基与Sn之间的π-d作用，揭示催化剂在BMPBA或其他聚酯中间体靶向合成及其定向缩聚中的作用机理；阐释BMBPA或其他聚酯中间体分解和重排的反应机制，以及CO2抑制分解的具体作用机理；为催化剂设计和靶向催化反应提供理论指导。基于以上理论研究开发了聚碳酸酯和碳酸二正丁酯的DMC法合成技术，实现了部分碳酸酯产品的工业化生产。项目期间发表论文6篇，申请专利4项，授权2项。