聚碳酸酯合成技术综述

简单介绍聚碳酸酯的结构、性能及应用情况,综述了包括光气界面缩聚法、间接光气法、甲醇液相羰基化法、甲醇气相羰基化法、二氧化碳一甲醇法等合成聚碳酸酯的工艺技术情况,阐明了完全非光气工艺是聚碳酸酯合成技术发展的方向,并对聚碳酸酯发展的前景进行了展望,同时对我国聚碳酸酯工业的发展提出了几点建议。     

非光气法聚碳酸酯的合成方法

概述了聚碳酸酯的结构及性能,并简要介绍了其应用、产能分布及工业生产技术现状,认为非光气法合成聚碳酸酯是主流趋势,重点阐述了氧化羰基化法、碳酸二苯酯酯交换缩聚法以及碳酸二甲酯法三种非光气法合成聚碳酸酯的技术路线及其合成工艺的特点,并从原料、催化剂、工艺等方面对其工业化前景进行了分析。我国碳酸二甲酯产能高,聚碳酸酯缺口大,指出以碳酸二甲酯为原料合成聚碳酸酯是我国未来的发展方向。     

聚碳酸酯生产技术进展

聚碳酸酯的生产工艺主要有界面缩聚工艺(光气法)和熔融缩聚工艺(非光气法),出于环境方面的考虑,非光气路线一直在被研究开发.综述了国内外聚碳酸酯生产工艺的研究进展及新技术的开发应用情况,并对我国今后的发展提出了建议.     

聚碳酸酯合成技术进展

综述了聚碳酸酯的国内外合成技术进展情况。介绍了目前工业生产中采用的界面光气法、溶液光气法、普通熔融酯交换法及非光气熔融法生产工艺 ,讨论了苯酚氧化羰基化法与双酚A氧化羰基化法合成聚碳酸酯的最新研究动态。对我国聚碳酸酯工业的发展提出了建议     

聚碳酸酯技术现状及发展趋势

文章介绍了聚碳酸酯的生产工艺技术及进展情况。详细描述了各大公司的非光气工艺，并且介绍了界面缩聚工艺和非光气工艺的技术经济性比较，阐明了非光气生产聚碳酸酯工艺是一种全封闭、无污染、无副产物、符合环境要求的绿色环保工艺，已成为聚碳酸酯工艺技术的发展方向。     

非光气熔融酯交换合成聚碳酸酯的研究进展

非光气熔融酯交换缩聚法相对于传统光气界面缩聚法合成聚碳酸酯有着成本较低、无污染、不使用溶剂等优势并且作为新一代绿色环保型工艺已经受到了世界各国的关注。本文着重从非光气熔融酯交换缩聚法合成聚碳酸酯的反应动力学机理、催化剂和非光气法的工艺条件上进行了阐述,为今后从事开发非光气熔融酯交换缩聚法的工作者指明出一定的道路。     

聚碳酸酯生产技术及其在建筑行业的应用

综述了界面缩聚法、熔融酯交换法和非光气熔融酯交换法合成聚碳酸酯的工艺生产过程及原料使用情况,并简述了以环状单硫代碳酸酯、二氧化碳、生物基等为原料的其他聚碳酸酯新合成方法及聚碳酸酯在建筑领域的应用情况,详细介绍了几种聚碳酸酯板材的制备方法.     

光气法生产聚碳酸酯的工艺流程

综述了光气法生产聚碳酸酯的工艺流程，主要包括溶液缩聚法和界面缩聚法；详细介绍了光气界面缩聚法制备聚碳酸酯的原料配制、聚合反应过程及后处理过程；最后概括了光气化法界面缩合成聚碳酸酯反应过程的影响因素，主要有原料物质的量比、有机相惰性溶剂的选择及回收、反应过程的pH值、胶液萃取精制工艺的操作及分子量控制剂的选择等。     

非光气法生产碳酸二甲酯

本文介绍了非光气法（酯交换法、甲醇氧化羰基化法）生产碳酸二甲酯的原理及工艺路线。     

聚碳酸酯技术现状及市场分析

针对聚碳酸酯光气法和非光气法生产工艺,阐述了几种聚碳酸酯装备过程的优缺点,着重介绍了非光气法制备技术,并对其绿色环保、投资少、竞争力强等特点进行了探讨;通过国内外聚碳酸酯的供需市场情况以及生产规模分析,提出了盲目开发建设的弊端和加强改性产品研究的思路。     

Polycarbonate aus o,o,o′,o′-tetramethyl-substituierten bisphenolen

Highmolecular polycarbonates can be synthesized by interfacial polycondensation from o,o,o′,o′-tetramethylsubstituted bisphenols and phosgene although the phenolic OH-groups are greatly hindered sterically by the methyl groups. For the synthesis of these polycarbonates it is necessary to use high concentrations of the catalyst, high pH-values, a good excess amount of phosgene and a long condensation period. The polycarbonates are characterized by high second order transition temperatures, excellent hydrolytical stability, low refractive indexes and a good thermoplastic processability. Particularly the polycarbonate from 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane has a well balanced combination of properties, among which is a good compatibility with bisphenol-A-polycarbonate, polystyrene and polyvinylchloride.     

The interfacial polycarbonate reactions. I. Defining the critical process parameters

Polycarbonate is prepared by the interfacial phosgenation and polycondensation of bisphenol A (BPA) in methylene chloride with caustic using triethylamine as a catalyst. In a typical batch reactor, where phosgenation and oligomerization proceed simultaneously, the critical process parameters are intermingled and are difficult to determine. Therefore, a semicontinuous process consisting of a series of static mixers for continuous phosgenation, followed by a batch reactor for oligomerization and polycondensation, was developed for better understanding of the reaction mechanisms. Phosgene hydrolysis was reduced greatly going from a batch to a continuous reactor (excess phosgene was reduced from 30 to 5%). Variables which influence the composition of intermediates are linear velocity, organic to aqueous volume ratio, PH (BPA to NaOH ratio), and phosgene to BPA ratio. These variables also affect BPA conversion, amount of phosgene hydrolysis, terminator capping efficiency, molecular weight, and molecular weight distribution of the resulted polycarbonate. Oligomerization takes place at the interface, and monochloroformates (HO-B_n-OCOCI) which contain both hydrophilic and lipophilic end groups, stay at the interface and, hence, react preferentially. Oligomers are analyzed by a newly developed HPLC technique.     

替代光气的硒催化合成新方法

新催化合成方法具有环境友好性和原子经济性,已成为未来化学工业发展的关键技术。含肽化合物是有用的农用和医用化学品,其工业生产方法大都采用光气作羰基化试剂,光气的高毒性和苛刻的操作条件有诸多的不便。以非金属硒作催化剂、CO为羰基化试剂,可一步催化合成非对称脲类化合物或其衍生物。通过硒催化羰基化,还可以合成咪唑啉酮、(?)唑烷酮、环脲等;采用CO/H2O/Se催化体系,可以高选择性制备(取代)苯胺。本文介绍了二级胺、一级胺和4-氨基吡啶为共试剂的硝基化合物的羰基化反应情况。     

双酚A聚碳酸酯合成新方法的研究进展

介绍了双酚A聚碳酸酯不同于工业生产中常用的光气法和熔融酯交换法的3种新的合成方法,即固相缩聚法、开环聚合法、完全非光气法的实施方法、主要特点及其新进展,探讨了各种方法存在的主要问题以及对生成的聚合物结构和性能的影响。固相缩聚是由预聚物结晶后在固相缩聚,可以获得结晶型双酚A聚碳酸酯并提高聚合物质量;开环聚合法首先合成环状碳酸酯低聚物再开环聚合得到聚合物,可以获得很高分子质量聚合物;完全非光气法在合成过程中完全避免了光气的使用,环境友好,聚合物质量高,很有发展前景。     

Comparison of polycarbonate precursors synthesized from catalytic reactions of bisphenol‐A with diphenyl carbonate,dimethyl carbonate,or carbon monoxide

Transesterification of bisphenol‐A with diphenyl carbonate or dimethyl carbonate, and direct oxidative carbonylation of bisphenol‐A were compared to obtain polycarbonate precursors for phosgene‐free polycarbonate synthesis. The melt‐transesterification of bisphenol‐A and diphenyl carbonate occurred readily to produce reactive precursors without a significant equilibrium constraint. On the other hand, the transesterification of bisphenol‐A and dimethyl carbonate showed a serious equilibrium limitation in obtaining reactive polycarbonate precursors leading to high molecular weight polymers, and coproduced a significant amount of methylated bisphenol‐A. The direct oxidative carbonylation of bisphenol‐A with CO produced diphenolic‐ended oligomers and a significant amount of by‐products, which are the least reactive in the subsequent polycondensation step of the phosgene‐free polycarbonate process. A novel method to synthesize the reactive polycarbonate precursors was proposed that employed the coupled oxidative carbonylation of both bisphenol‐A and phenol. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 937–947, 2002     

MDI生产现状和研究进展

二苯甲烷二异氰酸酯（MDI）是氯碱工业高附加值耗氯产品之一,一种重要的合成有机材料。本文介绍了二苯甲烷二异氰酸酯（MDI）的生产现状和需求,可以通过光气法、硝基苯还原羰基化法、碳酸二甲酯法等方法合成。介绍了甲苯二异氰酸酯不同生产工艺的优缺点,并对其发展前景作了简要评述,对今后的研究动态作了展望。     

双酚A型聚碳酸酯合成工艺研究进展

介绍了光气法、酯交换法和氧化羰化法合成聚碳酸酯的工艺及催化剂 ,分析了三种方法的优缺点 ,侧重探讨了催化剂的选择     

Sulfur containing polymers

Summary Copolymers containing -S-CO-S-and/or -O-CO-S-groups have been synthesized mainly by interfacial polycondensation.Different chemical structures were obtained by reacting 1,3-benzene dithiol (BDT) respectively with phosgene alone, phosgene and bisphenol-A (BPA), bischloroformate of BPA, BPA polycarbonate oligomers and by reacting phosgene with the products of BPA polycarbonate degraded with BDT. The chemical structures of the copolymers were investigated by IR, ¹H-NMR and ¹³C-NMR; molecular weights were determined by viscometry and vapor pressure osmometry. Although no attempt was made to find the optimum conditions for high molecular weight, some copolymers with fairly high mol. weight were obtained.