碳酸酯绿色合成技术研究进展

碳酸酯是一类重要的有机化工中间体和精细化学品原料。传统的以剧毒光气为原料制备碳酸酯方法已基本被淘汰,该文重点介绍氧化羰化法合成碳酸二甲酯、酯交换法合成碳酸二苯酯等绿色合成路线的技术研究进展。     

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.     

合成碳酸二苯酯的多相催化剂研究进展

酯交换法合成碳酸二苯酯包括碳酸二甲酯和苯酚酯交换合成碳酸二苯酯及草酸二甲酯和苯酚酯交换合成碳酸二苯酯。对酯交换法和氧化羰基合成法中所用的多相催化剂研究进展进行了系统阐述,主要包括金属氧化物,分子筛,以分子筛和SiO2、活性炭及复合型金属氧化物为载体的催化剂。并进一步对各工艺过程及所用催化剂的优缺点进行了评论,认为开发多相催化剂是今后碳酸二苯酯合成研究的重点方向。     

Halogen‐free solvent for oxidative carbonylation of bisphenol A to polycarbonate

Halogen‐free solvents for oxidative carbonylation of bisphenol A to polycarbonate using carbon monoxide were investigated. Tetrahydorofuran, γ‐butyrolacton, and acetophenone, which dissolve both bisphenol A and polycarbonate, gave a polycarbonate yield that was lower than using a halogenated solvent of dichloromethane. On the other hand, propylene carbonate that has a carbonate bond gave a polycarbonate yield the same as using dichloromethane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

碳酸二甲酯的制备和应用

综述碳酸二甲酯的制法，性质和用途。     

碳酸二甲酯生产技术及应用前景

详细介绍了光气法、甲醇氧化羰基化法、酯交换法和尿素醇解法等合成碳酸二甲酯的工艺路线,并从技术、生产、市场需求等几方面对碳酸二甲酯的发展前景进行了分析,指出只有加大新型生产工艺和下游产品的开发及产业化力度,加快产品结构的调整与升级,努力降低投资及成本,才能推进碳酸二甲酯产业的发展。     

碳酸二苯酯的合成工艺进展

讨论了光气法、酯交换法及氧化羰化法合成碳酸二苯酯的工艺路线及相关催化剂。重点讨论酯交换法催化剂的选择及反应装置的设计开发,对氧化羰化法则侧重于催化剂的研究开发。     

Melt polymerization of bisphenol‐A and diphenyl carbonate in a semibatch reactor

The effect of thermodynamic phase equilibrium on the kinetics of semibatch melt polycondensation of bisphenol‐A and diphenyl carbonate was studied for the synthesis of polycarbonate. In the melt‐polymerization process, a partial loss of diphenyl carbonate occurs as the reaction by‐product phenol is removed from the reactor. To obtain a high molecular weight polymer under high temperature and low‐pressure conditions, a stoichiometric mol ratio of the two reactive end groups needs to be maintained during the polymerization. In this work, vapor–liquid equilibrium data for a binary mixture of phenol and diphenyl carbonate are reported and they are used in conjunction with the Wilson equation to calculate the exact amounts of diphenyl carbonate and phenol returned from a reflux column to the reactor. A good agreement between the reactor model simulations and the experimental polymerization data was obtained. It was also observed that diphenyl carbonate is quickly consumed during the early stage of polymerization and the fraction of evaporated diphenyl carbonate refluxed to the reactor is essentially constant during this period. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1253–1266, 2001     

非光气法催化合成碳酸二苯酯研究进展

综述了近年来酯交换法、苯酚氧化羰化法、草酸二甲酯和苯酚交换、脱羰法和尿素酚解法4种非光气法催化合成碳酸二苯酯（DPC）的研究进展,包括每种合成法所使用的催化剂、反应条件、反应物的转化率和产物的收率,指出了每种合成法的优缺点,并从原料来源的难易、催化剂制备的成本、产物的收率、生产工艺的复杂性、能耗等方面进行分析比较,指出选用酯交换法和尿素酚解法生产碳酸二苯酯较为有利,这两种合成法可能是未来研究的重点。     

非光气法生产碳酸二甲酯

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、工艺路线及研究进展，对其发展前景进行了分析和预测。     

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.     

酯交换合成碳酸二苯酯催化剂的研究进展

对近年来碳酸二甲酯和苯酚酯交换合成碳酸二苯酯的催化剂体系进行了较为系统的概述,包括均相催化剂体系(碱或碱金属化合物、Lewis酸、锡和钛的有机化合物等)和多相催化剂体系(各种负载型、金属氧化物、水滑石等),认为开发有机锡、有机钛配合物催化剂以及将其固载化是碳酸二甲酯与苯酚酯交换反应合成碳酸二苯酯催化剂研究的重要方向.     

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。     

合成碳酸二甲酯的催化剂研究进展

碳酸二甲酯以其优良的性质在化学反应和石油产品中得到了广泛应用.作者介绍了合成碳酸二甲酯的4种方法,包括甲醇氧化羰基化法、酯交换法、尿素醇解法和二氧化碳-甲醇合成方法.重点介绍了每种方法使用的催化剂对碳酸二甲酯的选择性及对副产品的影响.综述了负载型分子筛催化剂在催化合成碳酸二甲酯研究进展.研究负载型分子筛催化剂催化合成碳...     

酯交换法合成碳酸甲乙酯催化剂的研究进展

碳酸甲乙酯（EMC）是一种环境友好型的不对称碳酸酯,因其独特的结构性质被广泛用作溶剂或有机合成中间体,特别是随着锂离子电池的迅猛发展,其作为电池电解液主要成分市场需求量急增。文中简单介绍了光气法、氧化羰化法和酯交换法合成碳酸甲乙酯的研究进展。重点针对最具发展前景的酯交换法合成EMC工艺路线中所用催化剂进行了综述;讨论和分析了该路线所用催化剂的类型、结构、性质及性能,并对当前研究中存在的问题进行了归纳和分析总结。最后本文分析并展望了酯交换法合成EMC催化剂的研究方向及新型合成工艺发展趋势,提出研发经济、高效、稳定且制备工艺简单的非均相催化剂,并与反应精馏技术耦合是今后的主要发展趋势,期望为EMC的高效合成提供参考和借鉴。     

苄胺与碳酸二甲酯甲基化反应体系热力学分析

采用Benson和Joback基团贡献法对苄胺与碳酸二甲酯反应体系进行了热力学分析,计算了反应体系的焓变、熵变、吉布斯自由能变及反应平衡常数,讨论了反应温度对苄胺与碳酸二甲酯甲基化反应和甲氧羰基化反应的影响.计算结果表明,在373.15-453.15 K之间,甲基化反应为吸热反应,且反应为自发过程,反应平衡常数K(O)...     

PPO–PC block‐copolymers used as compatibilizers in PS/PC blends

Block‐copolymers containing poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) and polycarbonate of bisphenol A (PC) segments were employed as compatibilizers in polystyrene (PS)/PC blends. Block‐copolymers were prepared starting from oligomeric diols‐terminated PPO and PC. The poly(phenylene ethers) was obtained by oxidative coupling of 2,6‐dimethyl‐phenol in presence of tetramethyl bisphenol A. The copolymers were obtained with a chain extension reaction between the starting oligomers using bischloroformate of bisphenol A or phosgene as coupling agent. PS/PC blends, cast from chloroform solutions or mixed by melt, were studied by differential scanning calorimeter (DSC), dynamic‐mechanical thermal analysis (DMTA), and optical microscopy (OP). The thermal and morphological analyses showed a clear compatibilization effect between PS and PC, if PPO–PC copolymer is added when blending is performed in the melt; in addition, also mechanical properties are increased when compared with blends without PPO–PC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4654–4660, 2006     

碳酸二甲酯和乙酸苯酯合成碳酸二苯酯催化剂研究进展

综述了碳酸二甲酯和乙酸苯酯合成碳酸二苯酯工艺路线及其反应机理,并对该反应的催化剂体系进行了系统的概述,包括均相催化剂体系(锡和钛的有机化合物等)和多相催化剂体系(MoO3和WO3等金属氧化物)。并分析了以锡、钛以及金属氧化物作催化剂时合成碳酸二苯酯的优势和劣势;指出固载化的有机锡/有机钛与其他金属氧化物的复合化合物是今后碳酸二甲酯和乙酸苯酯合成碳酸二苯酯催化剂的重要研究方向。     

非光气法合成碳酸二甲酯催化剂研究进展

本文综述了酯交换法，甲醇氧化羰基化法及CO2直接合成法等合成碳酸二甲酯催化剂的研究与开发状况，并指出了今后研究发展方向。     

酯交换法合成聚碳酸酯催化剂性能考察

以双酚A和碳酸二苯酯为原料,采用非光气熔融酯交换法合成聚碳酸酯。考察了氢氧化钾、氢氧化钠、四丁基氢氧化铵、碳酸钠、吡啶以及复合催化剂对聚碳酸酯合成反应速率及聚碳酸酯分子量和色差的影响。研究表明,氢氧化钾作为催化剂较适合于聚碳酸酯合成工艺,使用复合催化剂可以得到分子量较高、色差较低的聚碳酸酯。