高顺式聚异戊二烯橡胶的研究进展

doi:10.16085/j.issn.1000-6613.2015.01.028

化工进展 ›› 2015, Vol. 34 ›› Issue (1): 160-165,182.DOI: 10.16085/j.issn.1000-6613.2015.01.028

高顺式聚异戊二烯橡胶的研究进展

姚臻, 张景, 屠宇侠, 付强, 曹堃

浙江大学化工系化学工程联合国家重点实验室, 浙江杭州 310027

收稿日期:2014-05-30 修回日期:2014-08-08 出版日期:2015-01-05 发布日期:2015-01-05
通讯作者: 曹堃,教授,博士生导师,主要从事基于过程强化和系统集成的高分子先进制造技术及其产品工程应用开发。E-mail kcao@che.zju.edu.cn。
作者简介:姚臻(1972-),教授,博士生导师,主要从事聚合反应工程及高分子科学与材料研究。E-mail yaozhen@zju.edu.cn。
基金资助:
国家高技术研究发展计划项目(2012AA040306)。

Progress in the preparation of cis-rich polyisoprene

YAO Zhen, ZHANG Jing, TU Yuxia, FU Qiang, CAO Kun

State Key Laboratory of Chemical Engineering, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China

Received:2014-05-30 Revised:2014-08-08 Online:2015-01-05 Published:2015-01-05

摘要/Abstract

摘要： 顺式-1,4聚异戊二烯橡胶因其良好的性能,可代替天然橡胶应用于众多领域。本文首先介绍了顺式聚异戊二烯的国内外现有的生产工艺、催化体系及其产能等,并就目前均采用溶液聚合的工艺流程进行了评述,指出气相聚合工艺因其无需溶剂、能耗低、流程简单、操作安全、成本低、污染少等优点已引起学术界和工业界的高度重视,具有潜在的应用前景。同时,重点阐述了高顺式含量聚异戊二烯的最新研究进展,主要从对传统催化体系的改进和新型催化剂的开发两方面加以评述。其中,利用新型高定向催化体系能够得到cis-1,4含量达到99%乃至更高的顺式聚异戊二烯。钛系催化剂因其独特的优越性而被国外产业界普遍接受,且发展比较成熟。稀土系也具有较大的发展空间,近年来备受关注。未来对于高顺式聚异戊二烯的研究将主要集中于对催化体系的开发和相应工艺的改进。

关键词: 聚异戊二烯, 顺式结构, 催化剂, 溶液聚合, 气相聚合, 颗粒物料, 聚异戊二烯, 顺式结构, 催化剂, 溶液聚合, 气相聚合, 颗粒物料

Abstract: Cis -1, 4 polyisoprene rubber(PIP)can replace natural rubber in many fields because of its good application performances. In this paper, the production technology and catalytic system as well as the production capacity of PIP are systemically introduced. Based on the total existing adopt solution, polymerization processes are reviewed. Gas phase polymerization has many advantages, such as none solvent, low energy consumption, simple process, low cost, less pollution, which make it significant. Moreover, we summarize the studies on the synthesis of PIP with high content of cis-1, 4 structure, mainly from two aspects:the improvement of traditional catalytic system and the invention of new catalytic system, which can be employed to prepare cis-rich polyisoprene with 99% or more cis-1, 4 structure. Ti catalytic system has been widely accepted by industry abroad and has become mature. The rare-earth catalytic system has large development space and has attracted much attention in recent years. Study on cis-rich polyisoprene will mainly be focused on the development of catalytic system and the improvement of relevant processes in the future.

Key words: polyisoprene, cis-1, 4 structure, catalyst, solution polymerization, gas phase polymerization, particle material, polyisoprene, cis-1,4 structure, catalyst, solution polymerization, gas phase polymerization, particle material

中图分类号:

TQ333.3

姚臻, 张景, 屠宇侠, 付强, 曹堃. 高顺式聚异戊二烯橡胶的研究进展[J]. 化工进展, 2015, 34(1): 160-165,182.

YAO Zhen, ZHANG Jing, TU Yuxia, FU Qiang, CAO Kun. Progress in the preparation of cis-rich polyisoprene[J]. Chemical Industry and Engineering Progree, 2015, 34(1): 160-165,182.

参考文献

[1] 刘川. 世界异戊橡胶生产现状及我国发展前景[J]. 橡胶科技市场,2009(12):1-5.

[2] James McGraw. 合成橡胶手册[M]. 胡杰,陈为民,王桂轮译. 第16版. 北京:化学工业出版社,2008:99-100.

[3] 崔小明. 我国合成橡胶行业供需现状及未来发展分析[J]. 齐鲁石油化工,2013,4(4):340-347.

[4] 杨青. 国产稀土异戊橡胶的微观结构、基本性能及其在轮胎胎面胶的应用[D]. 北京:北京化工大学,2012.

[5] Eberstein C,Garmatter B,Reichert K H,et al. Gas phase polymerisation of butadiene[J]. Chem. Ing. Tech.,1996,68(7):820-823.

[6] Gerd S,Hugo Vernaleken. Catalyst,its manufacture and its use in the gas phase polymerisation of conjugated dienes:EP,647657[P]. 1995-04-12.

[7] Heinz R C,Peter M,Christopher E,et al. Catalyst for the gas-phase polymerisation of conjugated dienes:US,5877109[P]. 1999-03-02.

[8] Anthony B J,Barry Matrana A,Adel H F. Process for preparing a catalyst system useful in the synthesis of isoprene-butadiene rubber:US,5405815[P]. 1995-04-11.

[9] Nobuhiro T,Kazuhiro A,Chikara K. Catalyst and process for production of conjugated diene polymer using the same catalyst:JP,10182726[P]. 1998-07-07.

[10] Monika B,Joseph C K,Joseph D D. Gas phase anionic polymerization of dienes and vinyl-substituted aromatic compounds:US,5728782[P]. 1998-03-17.

[11] Angelica A M,Joseph C K. Termination of gas phase polymerizations of conjugated dienes,vinyl-substituted aromatic compounds and mixtures thereof:US,5731381[P]. 1998-03-24.

[12] Ling Jun,Ni Xufeng,Zhang Yifeng,et al. Monte Carlo simulation of gas phase polymerization of 1,3-butadiene Part Ⅰ:Modeling and programming [J]. Polymer,2000, 41(24):8703-8707.

[13] Ni Xufeng,Li Junfei,Zhang Yifeng,et al. Gas phase polymerization of 1,3-butadiene with supported neodymium-based catalyst:Investigation of molecular weight[J]. Journal of Applied Polymer Science,2004,92(3):1945-1949.

[14] Ling Jun,Ni Xufeng,Zhang Yifeng,et al. Monte Carlo simulation of gas phase polymerization of 1,3-butadiene Part Ⅱ:Kinetics optimization and confirmation[J]. Polymer International,2003,52(2):213-217.

[15] Hans Josef B,Christine M F,Ulrich N,et al. New supported catalysts,their preparation and their use for the gas phase polymerisation of conjugated dienes:EP,0727447A1[P]. 1996-08-21.

[16] Karol F J,Scarola L S,Baker E C,et al. Process for producing sticky polymers:US,4994534[P]. 1991-02-19.

[17] K J 肯,M A 阿佩斯特杰,J H 摩尔豪斯,等. 聚二烯烃的气相生产:中国,1164242A[P]. 1997-11-05.

[18] K J 肯,M A 阿佩斯特杰,J H 摩尔豪斯,等. 聚二烯烃的气相生产:中国,1158624A[P]. 1997-09-03.

[19] 倪旭峰. 双烯烃的负载型稀土催化气相聚合和杯芳烃稀土催化聚合[D]. 杭州:浙江大学,2001.

[20] Li G L,Ren C Y,Dong W M,et al. A highly active neodymium chloride isopropanol complex/modified methylaluminoxane catalyst for preparing polyisoprene with high cis-1,4 stereospecificity and narrow molecular weight distribution[J]. Chinese Journal of Polymer Science,2010,28(2):157-164.

[21] Vitorino M J,Zinck P,Visseaux M,et al. Isoprene polymerization using a neodymium phenolate pre-catalyst combined to aluminum based co-catalysts[J]. European Polymer Journal,2012,48(7):1289-1294.

[22] 李桂连,董为民,姜连升,等. 改性甲基铝氧烷和烷基铝活化的新癸酸钕催化剂催化异戊二烯聚合[J]. 催化学报,2005,26(10):879-883.

[23] 洛布里P. 催化体系与使用此体系制备弹性体的方法:中国,01821596[P].2004-03-24.

[24] Fischbach A,Meermann C,Eickerling G,et al. Discrete lanthanide aryl(alk)oxide trimethylaluminum adducts as isoprene polymerization catalysts[J]. Macromolecule,2006,39(20):6811-6816.

[25] Meermann C,Tornroos K W,Nerdal W,et al. Rare-earth metal mixed chloro/methyl compounds:Heterogeneous/Homogeneous borderline catalysts in 1,3-diene polymerization[J]. Angew. Chem. Int. Edit,2007,46(34):6508-6513.

[26] Yang Y,Liu B,Lv K,et al. Pyrrolide-supported lanthanide alkyl complexes:Influence of ligands on molecular structure and catalytic activity toward isoprene polymerization[J]. Organometallics,2007,26(18):4575-4584.

[27] Yang Y,Wang Q Y,Cui D M. Isoprene polymerization with indolide-imine supported rare-earth metal alkyl and amidinate complexes[J]. J. Polym. Sci. Pol. Chem.,2008,46(15):5251-5262.

[28] Gao W,Cui D M. Highly cis-1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichioride precursors[J]. Journal of the American Chemical Society,2008,130(14):4984-4991.

[29] Lv K,Cui D. CCC-pincer bis(carbene) lanthanide dibromides catalysis on highly cis-1,4-selective polymerization of isoprene and active species[J]. Organometallics,2010,29(13):2987-2993.

[30] Pan Y,Xu T Q,Yang G W,et al. Bis(oxazolinyl)phenyl-ligated rare-earth-metal complexes:Highly regioselective catalysts for cis-1,4-polymerization of isoprene[J]. Inorg. Chem.,2013,52(6):2802-2808.

[31] Zhang J S,Hao Z Q,Gao W,et al. Y,Lu,and Gd complexes of NCO/NCS pincer ligands:Synthesis,characterization,and catalysis in the cis-1,4-selective polymerization of isoprene[J]. Chem. Asian,2013,8(9):2079-2087.

[32] Zhang L X,Suzuki T,Luo Y,et al. Cationic alkyl rare-earth metal complexes bearing an ancillary bis(phosphinophenyl)amido ligand:A catalytic system for living cis-1,4-polymerization and copolymerization of isoprene and butadiene[J]. Angew. Chem. Int. Edit,2007,46(11):1909-1913.

[33] 崔冬梅,刘东涛,高伟,等. 催化异戊二烯或丁二烯顺1,4-选择性聚合的稀土催化体系及制法和用法:中国,200810050666.2[P]. 2008-09-10.

高顺式聚异戊二烯橡胶的研究进展

Progress in the preparation of cis-rich polyisoprene

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