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。     

碳酸二甲酯市场现状及技术进展

目前,全球碳酸二甲酯(DMC)的产量约为12万t/a。生产方法有光气法、酯交换法、甲醇氧化羰基法和二氧化碳-甲醇直接合成法。我国DMC产量不足3万t/a,主要采用酯交换法和甲醇液相氧化羰基法。DMC可作为羰基化试剂代替剧毒物质光气用于合成聚碳酸酯、异氰酸酯、杀虫剂西维因等,用作甲基化试剂代替致癌物硫酸二甲酯合成苯甲醚。     

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。     

碳酸二甲酯市场现状及技术进展

目前,全球碳酸二甲酯(DMC)的产量约为12万t/a.生产方法有光气法、酯交换法、甲醇氧化羰基法和二氧化碳-甲醇直接合成法.我国DMC产量不足3万t/a,主要采用酯交换法和甲醇液相氧化羰基法.DMC可作为羰基化试剂代替剧毒物质光气用于合成聚碳酸酯、异氰酸酯、杀虫剂西维因等,用作甲基化试剂代替致癌物硫酸二甲酯合成苯甲醚.     

碳酸二甲酯市场现状及技术进展

目前,全球碳酸二甲酯(DMC)的产量约为12万t/a.生产方法有光气法、酯交换法、甲醇氧化羰基法和二氧化碳-甲醇直接合成法.我国DMC产量不足3万t/a,主要采用酯交换法和甲醇液相氧化羰基法.DMC可作为羰基化试剂代替剧毒物质光气用于合成聚碳酸酯、异氰酸酯、杀虫剂西维因等,用作甲基化试剂代替致癌物硫酸二甲酯合成苯甲醚.     

芳香聚碳酸酯合成工艺进展

本文介绍了聚碳酸酯的 3种合成工艺 ,即界面缩聚法、非光气法、氧化羰基化法。界面缩聚法工艺易于生成较高分子量聚合物 ,产品适于作片材 ,界面聚合聚碳酸酯在某些终端应用上具有一定优势 ,较长一段时期内不会退出市场 ;非光气法产品纯度较高、光学性能好、透明度高 ,适合光学应用 ,但高温下稳定性相对较低 ,不适用于注模 ;氧化羰基化法具有前两种方法没有的优点 ,是一种安全高效的绿色工艺 ,原料来源广泛、廉价 ,三废少、产品质量高 ,在 2 1世纪必将有大的发展前途。     

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.     

聚碳酸酯生产工艺现状分析

对聚碳酸酯进行简单介绍,系统综述了聚碳酸酯的生产工艺现状,包括光气法和酯交换法。重点阐述了非光气熔融酯交换法生产工艺,并对目前一些创新工艺进行了简单介绍。非光气熔融酯交换法因不使用光气,绿色环保,备受人们青睐,是未来聚碳酸酯行业主要的发展方向。     

聚碳酸酯的合成方法及其研究进展

综述了聚碳酸酯的合成方法,重点概述了光气法和熔融酯交换法。光气法是目前工业化大规模生产的主要方法,绿色熔融酯交换法是环境友好的合成方法,文中对这两种方法的优缺点进行了对比和分析。最后对研究报道的其它合成方法进行了简要的介绍,并对未来的发展趋势进行了展望。     

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     

界面缩聚法合成四溴双酚A聚碳酸酯的工艺研究

以光气和四溴双酚A(TBBPA)为原料经光气界面缩聚,合成了四溴双酚A聚碳酸酯,并对四溴双酚A与光气投料比、催化剂种类及其用量、分子量调节剂用量4个因素进行考察。优化工艺条件为:四丁基氢氧化铵为催化剂,对叔丁基酚(TBP)为分子量调节剂,n(四溴双酚A)∶n(光气)=1∶1.3,n(四溴双酚A)∶n(对叔丁基酚)=1∶0.028,n(四溴双酚A)∶n(四丁基氢氧化铵)=1∶0.022。该方法操作简单,产品分子量分布窄,易于工业化生产。     

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     

Phosgene-free approaches to catalytic synthesis of diphenyl carbonate and its intermediates

Diphenyl carbonate (DPC) is considered as a substitution for phosgene to synthesize polycarbonate resins. Conventional production of DPC involves reactions of phosgene and phenol. However, the phosgene process has drawbacks such as environmental and safety problems associated with using highly toxic phosgene as the reagent, which results in the formation of chlorine salts, and copious amounts of methylene chloride as the solvent. For these reasons, environmentally friendly processes for DPC production without using phosgene have been proposed and developed in the past decades. So far, the most promising alternatives appear to be the transesterification of dimethyl carbonate (DMC) and phenol, the direct oxidative carbonylation of phenol, and transesterification of dialkyl oxalates and phenol. This paper attempts to review recent literature concerning process design and catalytic chemistry for these phosgene-free approaches. The advantages and disadvantages are discussed for each reaction. Strategies to overcome potential problems are provided. The perspectives to improve catalytic efficiency of phosgene-free process are proposed.     

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.     

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。     

A convenient laboratory preparation of aromatic polycarbonate

Summary An experimentally simple method for the synthesis of aromatic polycarbonates is described. Reaction of commercially available p-nitrophenyl chloroformate with bisphenol A afforded BPA polycarbonate in good yields with M _n= 26,000 g/mol. This laboratory procedure avoids the use of phosgene or phosgene equivalents in the laboratory. The process requires the use of 2 equivalents of triethylamine and a catalytic amount of 4-dimethylaminopyridine. Received: 31 July 2001/ Revised version: 16 November 2001/ Accepted: 28 November 2001