聚烯烃类弹性体——现状与进展

doi:10.16085/j.issn.1000-6613.2017-0462

摘要/Abstract

摘要： 综述了聚烯烃类弹性体的国内外发展现状与研究进展，介绍了二元乙丙胶（EPM）、三元乙丙胶（EPDM）、茂金属三元乙丙胶（mEPDM）等乙丙弹性体，及乙烯/α-烯烃无规共聚物弹性体（POE）和嵌段共聚物弹性体（OBC）等的主要生产商、产品商标、牌号及性能特点，以及合成工艺与催化剂体系的发展。指出POE、OBC类热塑性弹性体不仅具有聚烯烃类弹性体卓越的力学性能，而且成型加工简便、可回收使用，发展迅速。茂金属催化剂具有活性高、对α-烯烃共聚能力强和单一活性中心的优点。我国目前尚不能进行mEPDM、POE、OBC等性能更为优异、利润更为丰厚的聚烯烃弹性体和热塑性弹性体的生产。要进行这些产品的自主开发，必须加强对耐高温茂金属催化剂和烯烃高温溶液共聚工艺的研究。

关键词: 聚合物, 生产, 合成, 弹性体, 聚合, 催化剂

Abstract: In this review,state-of-the-art technology of polyolefin-based elastomer manufacture,including major producers and product trademarks,grades and properties were summarized. Research and developments on production process and catalyst system for the ethylene-propylene binary and ternary rubbers(EPM,EPDM,mEPDM),the poly(ethylene-co-α-olefin) elastomer(POE)and the poly(ethylene-block-α-olefin) elastomer(OBC)were also introduced. It has been pointed out that the thermoplastic elastomer,such as POE and OBC,and the polyolefin plastomer not only had excellent mechanical and physical properties of polyolefin-based elastomer,but also was easy molding and processing,and can be recycled and reused. And the metallocene catalyst had the advantages of high activity,good ability to catalyze copolymerization with α-olefin,and single active site. In order to independently develop the polyolefin-based elastomer,the thermoplastic elastomer and plastomer with more excellent performance and more profitable,such as mEPDM,POE and OBC et al,the researches on the metallocene catalyst with high temperature adaptability and the high temperature solution polymerization process must be strengthened.

Key words: polymer, production, synthesis, elastomer, polymerization, catalyst

中图分类号:

李伯耿, 张明轩, 刘伟峰, 王文俊. 聚烯烃类弹性体——现状与进展[J]. 化工进展, 2017, 36(09): 3135-3144.

LI Bo-Geng, ZHANG Mingxuan, LIU Weifeng, WANG Wenjun. State-of-the-art and research progress of polyolefin-based elastomer[J]. Chemical Industry and Engineering Progress, 2017, 36(09): 3135-3144.

参考文献

[1] 卢颖,彭宗林,梁红梅,等. 丙烯-乙烯共聚物Vistamaxx的结构性能表征[J]. 弹性体,2007,17(4):9-12. LU Y, PENG Z L,LIANG H M,et al. Structure and properties characterization for a novel propylene-ethylene copolymer Vistamaxx[J]. China Elastomerics, 2007,17(4):9-12.
[2] LOVISI H,TAVARES M B I,DA SILVA N M,et al. Influence of comonomer content and short branch length on the physical properties of metallocene propylene copolymers[J]. Polymer,2001,42(24):9791-9799.
[3] 蔡小平,陈文启,关颖,等. 乙丙橡胶及聚烯烃类热塑性弹性体[M]. 北京:中国石化出版社,2011:1-4. CAI X P,CHEN W Q,GUAN Y,et al. Ethylene-propylene rubber and polyolefin thermoplastic elastomers[M]. Beijing:China Petrochemical Press,2011:1-4.
[4] 张涛,邹云峰,车浩,等. 乙丙橡胶生产工艺与技术[J]. 化工进展,2016,35(8):2317-2322. ZHANG T,ZOU Y F,CHE H,et al.[J]. Chemical Industry and Engineering Progress,2016,35(8):2317-2322.
[5] HERWIG J,KAMINSKY W. Halogen-free soluble Ziegler catalysts with methylalummoxan as catalyst[J]. Polymer Bulletin,1983,9(8):464-469.
[6] KAMINSKY W,MIRI M. Ethylene propylene diene terpolymers produced with a homogeneous and highly active zirconium catalyst[J]. J. Polym. Sci. A:Polym. Chem.,1985,23(8):2151-2164.
[7] KAMINSKY W,SCHLOBOHM M. Elastomers by atactic linkage of α-olefins using soluble Ziegler catalysts[J]. Macromol. Symp.,1986,4(1):103-118.
[8] CHIEN J C W,HE D. Olefin copolymerization with metallocene catalysts. I. Comparison of catalysts[J]. J. Polym. Sci. A:Polym. Chem.,1991,29(11):1583-1593.
[9] STEVENS J C,NEITHAMER D R. Metal complex compounds:US5064802[P]. 1991-11-12.
[10] 胡建军,陈伟,刘东兵,等. 限制几何构型催化剂研究及应用进展[J]. 石油化工,2004,33(s1):525-527. HU J J,CHEN W,LIU D B,et al. Constrained geometry catalyst and their applications[J]. Petrochemical Technology,2004,33(s1):525-527.
[11] BRAUNSCHWEIG H,BREITLING F. Constrained geometry complexes-synthesis and applications[J]. Coordin. Chem. Rev.,2006,250(21-22):2691-2720.
[12] FLOYD S,LYNN H E. Process for producing elastomers with an indenyl metallocene catalyst system:WO9516716[P]. 1995-06-22.
[13] SCHIFFINO R S. High temperature solution polymerization process using substituted unbridged matallocene catalyst:US5625016[P]. 1997-04-29.
[14] Mitsui announces EPDM plant[J]. Europ. Rubber J.,1998,180(10):9.
[15] IJPEIJ E,ARTS H,VAN DOREMAELE G,et al. Polymerization catalyst comprising an amidine ligand:US7956140[P]. 2011-06-07.
[16] WINDMULLER P,VAN DORREMELE G. Process for the production of a polymer comprising monomeric units of ethylene,an α-olefin and vinyl norbornene:US8124707[P]. 2012-02-28.
[17] Dow Chemical Company. NORDEL^TM EPDM product selection guide[EB/OL].[2017-03-04]. http://www.dow.com/elastomers/products/nordel.htm.
[18] Lanxess Company. Keltan Brochure[EB/OL].[2017-03-04]. http://keltan.com/en/the-power-of-keltan/premium-quality/brochures/#c123157.
[19] Exxon Mobile Corporation. Product datasheets for Vistalon^TM EPDM rubber[EB/OL].[2017-03-04]. http://www.exxonmobilchemical.com.cn/Chem-English/brands/vistalon-ethylene-propylene-diene-EPDM-rubber-grades-and-datasheets.aspx?QM=40:3994%7C1493&RBFLT=86044:5&PG=1&PGSIZE=20&CULTURE=zh-CN&S=&USERID=1422171&I=74710&UNIT=1&C=_Default&SORT=&ln=productsservices.
[20] DATTA S,KRESGE E N. Easy processing ethylene propylene elastomers:US4722971[P]. 1988-02-02.
[21] JACOB S,JOURDAIN E P. Adavancements in EPDM sponge compound processing using EPDM bimodal polymers[J]. Rubber Chem. Techn.,2011,84(4):527-542.
[22] MADDOX P J,MCNALLY J P,PRATT D. Polymerization process:US6410659[P]. 2002-06-25.
[23] RAVISHANKAR P S. Process for polymerizing ethylene,higher alpha-olefin comonomer and dienes,especially vinyl norbornene; polymers made using such processes; and articles made from such polymers:US 6806336[P]. 2004-10-19.
[24] 梁诚. 新型乙丙橡胶生产与应用进展[J]. 新型化工材料,2005,3(2):1-4. LIANG C. Progress in production and application of new ethylene-propylene elastomer[J]. New Chemical Materials,2005,3(2):1-4.
[25] KAMINSKY W,WEINGARTEN U. Quarter polymerization of ethene/propene/hexene/ethylidenenorbornene and ethylene/propylene/octene/ethylidenenorbornene with[Me₂C(3-MeCp)(Flu)]ZrCl₂/MAO[J]. Polym. Bull.,2001,45(6):451-456.
[26] WAYNE T R,LEE J T. Roof sheeting:WO9955750A1[P]. 1999-11-04.
[27] RAVISHANKAR P S. Ethylene,higher alpha-olefin comonomor and diene,especially vinyl norbornene and polymers made using such process:US7135533[P]. 2006-11-14.
[28] KAO C I,CAMP G A,COMBS R B,et al. Olefin solution polymerization:WO9736942A1[P]. 1997-10-09.
[29] Dow Chemical Company. ENGAGETM polyolefin elastomers product selection guide[EB/OL].[2017-03-04]. http://www.dow.com/elastomers/products/engage.htm.
[30] Mitsui Elastomers LTD. Applications of TAFMER^TM DF & A[EB/OL].[2017-03-04]. http://www.mitsuichem.com/special/tafmer/products/series.htm#dfa.
[31] LG Chem. Producr info[EB/OL].[2017-03-04]. http://www.lgchem.com/global/ncc-po/poe-poly-olefin-elastomer/product-detail-PDBBC000.
[32] 王文俊,刘伟峰,李伯耿,等. 一种乙烯和α-烯烃共聚物的溶液聚合制备方法:103880999A[P]. 2014-06-25. WANG W J,LIU W F,LI B G,et al. Solution polymerization preparation method of ethylene-alpha-olefin copolymer:103880999A[P]. 2014-06-25.
[33] 李伯耿,王文俊,刘伟峰,等. 一种乙烯和α-烯烃共聚物的制备方法:103936909A[P]. 2014-07-23. LI B G,WANG W J,LIU W F,et al. Preparation method of ethylene/alpha-olefin copolymer:103936909A[P]. 2014-07-23.
[34] ARRIOLA D J,CARNAHAN E M,CHEUNG Y W,et al. Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation:US8198374[P]. 2012-06-12.
[35] ARRIOLA D J,CARNAHAN E M,HUSTAD P D,et al. Catalytic production of olefin block copolymers via chain shuttling polymerization[J]. Science,2006,312(5774):714-719.
[36] CHUM P S,SWOGGER K W. Olefin polymer technologies-history and recent progress at The Dow Chemical Company[J]. Prog. Polym. Sci.,2008,33(8):797-819.
[37] HUSTAD P D. Frontiers in olefin polymerization:reinventing the World's most common synthetic polymers[J]. Science,2009,325(5941):704-707.
[38] STEVENS J C,VANDERLENDE D D. Isotactic propylene copolymers,their preparation and use:US6960635[P]. 2005-11-01.
[39] Dow Chemical Company. INFUSE olefin block copolymers product selection guide[EB/OL].[2017-03-04]. http://www.dow.com/elastomers/products/infuse.htm.
[40] 赵旭涛,刘大华,等. 合成橡胶工业手册[M]. 2版. 北京:化学工业出版社,2006:588-593. ZHAO X T,LIU D H,et al. A comprehensive handbook of synthetic rubber technology[M]. 2nd ed. Beijing:Chemical Industry Press,2006:588-593.
[41] 陈焕君. 乙丙橡胶新牌号开发及工业化研究[D]. 上海:上海师范大学,2016. CHEN H J. Development and industrialization of new grades of ethylene propylene rubber[D]. Shanghai:Shanghai Normal University,2016.
[42] 蔡小平,陈文启,关颖,等. 乙丙橡胶及聚烯烃类热塑性弹性体[M]. 北京:中国石化出版社,2011:125-127. CAI X P,CHEN W Q,GUAN Y,et al. Ethylene-propylene rubber and polyolefin thermoplastic elastomers[M]. Beijing:China Petrochemical Press,2011:125-127.
[43] RIX F C. Bridged metallocenes for olefin copolymerization:WO0024793[P]. 2000-05-04.
[44] 里克斯F C. 烯烃共聚合用的桥连茂金属:1138796C[P]. 2004-02-18. RIX F C. Bridge metallocenes for olefine copolymerization:1138796C[P]. 2004-02-18.
[45] LEE C H,LEE E J,JUNG S,et al. Transition metal complexes,catalyst compositions containing the same,and olefin polymerization using the catalyst compositions:US7538239[P]. 2009-05-26.
[46] NABIKA M,MIYATAKE T. Transition metal compound,catalyst for addition polymerization,and process for producing addition polymer:US6548686[P]. 2003-04-15.
[47] SENDA T,HANAOKA H,NAKAHARA S. et al. Rational design of silicon-bridged fluorenyl-phenoxy group 4 metal complexes as catalysts for producing high molecular weight copolymers of ethylene and 1-hexene at elevated temperature[J]. Macromolecules,2010,43(5):2299-2306.
[48] 刘伟峰. 乙烯/辛烯溶液共聚及其聚合物链结构的调控[D]. 杭州:浙江大学,2014. LIU W F. Tailoring ethylene/1-octene copolymers in a solution copolymerization process[D]. Hangzhou:Zhejiang University,2014.
[49] FIGUEROA R,FROESE R,HE Y,et al. Synthesis of imino-enamido hafnium and zirconium complexes:a new family of olefin polymerization catalysts with ultrahigh-molecular-weight capabilities[J]. Organometallics,2011,30(6):1695-1709.
[50] 王红英,郑刚,刘长城,等. 一种烯烃共聚物及其制备方法:102464751[P]. 2012-05-23. WANG H Y,ZHENG G,LIU C C,et al. Olefin copolymer and preparation method thereof:102464751[P]. 2012-05-23.
[51] DESHPANDE K,DIXIT R S. Olefin-based polymers and dispersion polymerizations:WO088235[P]. 2012-06-28.
[52] DESHPANDE K,STEPHENSON S K,DIXI R S. Polymerization process and raman analysis for olefin-based polymers:WO2012088217[P]. 2012-06-28.
[53] DESHPANDE K,DIXIT R S,JAIN P. Ethylene-based polymers prepared by dispersion polymerization:WO2013096418[P]. 2013-06-27.
[54] 刘兵. MOFs负载的乙烯齐聚/聚合催化剂的制备与表征[D]. 杭州:浙江大学,2016. LIU B. Preparation and performance of catalysts supported by MOFs for ethylene oligomerization/polymerization[D]. Hangzhou:Zhejiang University,2016.
[55] ZHANG J,LI B-G,FAN H,et al. Synthesis of ethylene-1-hexene copolymers from ethylene stock by tandem action of bis(2-dodecylsulfanyl-ethyl) amine-CrCl₃ and Et(Ind)(2)ZrCl₂[J]. J. Polym. Sc.i A,Polym. Chem.,2007,45(16):3562-3569.
[56] ZHANG J,FAN H,LI B-G,et al. Modeling and kinetics of tandem polymerization of ethylene catalyzed by bis(2-dodecylsulfanyl-ethyl) amine-CrCl₃ and Et(Ind)(2)ZrCl₂[J]. Chem. Eng. Sci.,2008,63(8):2057-2065.
[57] GUO S,FAN H,BU Z,et al. High temperature high pressure tandem polymerization of ethylene for synthesis of ethylene-1-hexene copolymers from single reactor with SNS-Cr and CGC-Ti catalyst[J]. Macromol. React. Eng.,2015,9(1):32-39.
[58] GUO S,FAN H,BU Z,et al. Tandem action of SNS-Cr and CGC-Ti in preparation of ethylene-1-hexene copolymers from ethylene feedstock[J]. Macromol. Chem. Phys.,2014,215(17):1661-1667.
[59] 吕玉相. 国外乙丙橡胶合成新技术进展[J]. 弹性体,2003,13(1):47-52. LV Y X. Advances on synthetic technology of EPDM[J]. China Elastomerics,2003,13(1):47-52.
[60] 李留忠,达建文. 气相法工艺生产三元乙丙橡胶新技术[J]. 化工科技,2000,8(2):50-53. LI L Z,DA J W. New EPDM synthesizing technology using gas-phase process[J]. Science & Technology in Chemical Industry,2000,8(2):50-53.
[61] 杜娟,王积悦,孙凯英. 限制几何构型催化剂气相法生产EPDM的性能[J]. 橡胶参考资料,2004,34(4):35-47. DU J,WANG J Y,SUN K Y. The performance of EPDM which produced by gas phase method using the constrained geometry catalyst[J]. Xiangjiao Cankaoziliao,2004,34(4):35-47.