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。     

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.     

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     

碳酸二甲酯的生产技术

采用非光气法生产DMC的甲醇氯化羰基化合成工艺是DMC合成技术的重大改进。文中重点介绍了这一生产技术及其发展。     

聚碳酸酯的技术与市场现状及发展趋势

论述了聚碳酸酯技术现状,界面光气法是生产聚碳酸酯的传统技术,存在环境污染重、原料毒性大等问题.分析了二氧化碳甲醇法和甲醇羰基氧化法等主要非光气法技术路线特点及生产装置现状,指出非光气法是未来的发展方向.将聚碳酸酯与常用塑料品种进行性能比较,分析其应用领域及与其性能相似的竞争品种,指出聚碳酸酯合金可以兼具有两种或者更多品种树脂优点,是今后主要的应用形式.研究了国内市场供需平衡关系,预测聚碳酸酯在国内面临较好的发展机遇,同时提出国内聚碳酸酯产业发展存在的问题及建议.     

非光气法生产聚碳酸酯工业路线研究进展

综述了由甲醇、一氧化碳、二氧化碳、环氧丙烷、尿素等出发,采用非光气工艺路线依次合成碳酸二甲酯、碳酸二苯酯及高质量聚碳酸酯(PC)的清洁生产工艺.重点对非光气法合成的各种生产工艺与传统的光气法进行比较,指出非光气法PC生产工艺路线已显示出明显优势,具有无污染、原子利用率高、产品品质好等优点.     

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。     

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。     

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。     

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.     

Polycarbonate-polystyrene block copolymers and their application as compatibilzing agents in polymer blends

The synthesis of a block copolymer with polystyrene (PS) and polycarbonate (PC) segments is described. It is produced by anionic polymerization of the styrene and endcapping with a hydroxyl group followed by subsequent reaction with phosgene and bisphenol-A. The polystyrene/polycarbonate block copolymer was used as a compatibilizing agent for blends of poly(ethylene terephthalate) (PET) and poly(p- phenylene oxide) (PPO). The block copolymer reduced the dimensions of the dispersed phase. The uniaxial mechanical properties of the compatibilized blends were improved by 5 to 10 wt% loadings of the copolymer.     

Precipitative polymerization for polycarbonate: A simultaneous reaction–precipitation technique

A novel phenomenon, termed precipitative polymerization, is described. In it, the BPA—phosgene reaction is conducted with simultaneous precipitation of polycarbonate granules. Very low organic-to-aqueous phase ratio and high pH medium are primarily required to cause this in-situ precipitation.     

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     

聚碳酸酯合成技术进展

综述了聚碳酸酯(PC)已经实现工业化的4种合成聚合工艺,按照各生产工艺的流程和特点对其进行了阐述。同时,介绍了非光气法缩聚阶段的关键设备。非光气法PC生产工艺已经在竞争中逐步占据优势,未来需要进一步优化酯交换反应和缩聚反应阶段的反应器设计。     

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。     

Mathematical modeling and analysis of an interfacial polycarbonate polymerization in a continuous multizone tubular reactor

A detailed mathematical model is presented to describe the steady state behavior of a continuous multizone tubular reactor for the synthesis of aromatic polycarbonate by interfacial polycondensation mechanism. In this process, bisphenol‐A dissolved in a dispersed aqueous phase reacts with phosgene dissolved in a continuous organic phase and hence, the reaction initiates at the interface of the two phases. A liquid‐liquid mass transfer process is incorporated into a reaction kinetic model to calculate the reaction rates and polymer molecular weight distribution. The kinetic model has also been used in developing a steady state multizone tubular reactor model for continuous production of polycarbonate. The model simulations are compared with proprietary plant data and excellent agreement has been obtained. POLYM. ENG. SCI., 58:438–446, 2018. © 2017 Society of Plastics Engineers     

Synthesis of Polycarbonate Precursors over Titanosilicate Molecular Sieves

A novel catalytic application of titanosilicate molecular sieves (TS-1 and TiMCM-41), in the synthesis of polycarbonate precursors like cyclic carbonates and dimethyl and diphenyl carbonates, avoiding toxic chemicals like phosgene or CO, is reported. Cyclic carbonates were prepared, over TS-1 and TiMCM-41, in high yields, by cycloaddition of CO₂ to epoxides, like epichlorohydrin, propylene oxide and styrene oxide, at low temperatures and pressures. Further, transesterification of the cyclic carbonates with methanol and phenol, over TiMCM-41, yielded other polycarbonate precursors like dimethyl carbonate (DMC) and diphenyl carbonate (DPC). The cyclic carbonates could also be synthesized from the olefins in the same reactor by reacting the olefins, in the presence of TiMCM-41, with a mixture of an epoxidizing agent (like H₂O₂ or tert-butyl hydroperoxide) and CO₂.