开发异丁烯下游高附加值产品聚异丁烯的新技术可以促进相关产业的可持续发展,缓解国内异丁烯上游产品甲基叔丁基醚行业产能过剩的压力。综述了不同分子量聚异丁烯的理化特性,并介绍聚异丁烯的技术研究进展、工业化产品的牌号、产品的特性,以及不同分子量的聚异丁烯在化工各个专业领域中的应用。指出国内聚异丁烯产业存在的主要问题,并对聚异丁烯未来发展方向进行展望。
As the upstream product of isobutene,the production of domestic methyl t-butyl ether (MTBE) is over capacitated.Thus,it is necessary to develop new techniques for high value-added polyisobutylene (PIB),a downstream product of isobutylene,which can promote the sustainable development of related industries and alleviate the pressure of overcapacity of MTBE.The physicochemical properties of various molecular weight PIB were reviewed.The technical research progress of PIB,the grades of industrialized products,the characteristics of products,and the applications of PIB with different molecular weights in various specialized fields of chemical industry were introduced.The main problems of domestic polyisobutylene industry were pointed out,and the future development directions of polyisobutylene were discussed.
[1] Boyd R H,Pant P V K.Molecular packing and diffusion in polyisobutylene[J].Macromolecules,1991,24(23):6325-6331.
[2] Kunal K,Paluch M,Roland C M,et al.Polyisobutylene:a most unusual polymer[J].Journal of Polymer Science Part B:Polymer Physics,2008,46(13):1390-1399.
[3] Zigmond J,Gray A,Moore J.2019 IEEE 21st electronics packaging technology conference (EPTC),Singapore,2019[C].Singapore:IEEE,2019.
[4] Zhao M,Chen H,Yuan J,et al.The study of ionic and entanglements self-healing behavior of zinc dimethacrylate enhanced natural rubber and natural rubber/butyl rubber composite[J].Journal of Applied Polymer Science,2022,139(17):52048.
[5] Gauthier M.Arborescent polymers and other dendrigraft polymers:a journey into structural diversity[J].Journal of Polymer Science Part A:Polymer Chemistry,2007,45(17):3803-3810.
[6] Kali G,Vavra S,László K,et al.Thermally responsive amphiphilic conetworks and gels based on poly (N-isopropylacrylamide) and polyisobutylene[J].Macromolecules,2013,46(13):5337-5344.
[7] Kostjuk S V,Yeong H Y,Voit B.Cationic polymerization of isobutylene at room temperature[J].Journal of Polymer Science Part A:Polymer Chemistry,2013,51(3):471-486.
[8] Vasilenko I V,Berezianko I A,Shiman D I,et al.New catalysts for the synthesis of highly reactive polyisobutylene:chloroaluminate imidazole-based ionic liquids in the presence of diisopropyl ether[J].Polymer Chemistry,2016,7(36):5615-5619.
[9] 王凤荣,高萌,张超,等.高活性聚异丁烯催化剂的研究进展[J].炼油与化工,2019,30(2):3-4.
[10] 齐泮仑,西晓丽,顾爱萍,等.高活性聚异丁烯的合成[J].石油炼制与化工,2006,37(3):19-23.
[11] 韩秀山.高活性低相对分子质量聚异丁烯[J].化学推进剂与高分子材料,2001(2):21-24.
[12] 彭学成,崔立强,孙峰,等.低分子量聚异丁烯的开发及应用[J].合成树脂及塑料,2003,20(2):67-70.
[13] Shiman D I,Vasilenko I V,Kostjuk S V.Cationic polymerization of isobutylene by AlCl3/ether complexes in non-polar solvents:effect of ether structure on the selectivity of b-H elimination[J].Polymer,2013,54:2235-2242.
[14] Vasilenko I V,Shiman D I,Kostjuk S V.Highly reactive polyisobutylenes via AlCl3OBu2-coinitiated cationic polymerization of isobutylene:effect of solvent polarity,temperature,and initiator[J].Journal of Polymer Science Part A:Polymer Chemistry,2012,50(4):750-758.
[15] Liu Q,Wu Y X,Zhang Y,et al.A cost-effective process for highly reactive polyisobutylenes via cationic polymerization coinitiated by AlCl3[J].Polymer,2010,51(25):5960-5969.
[16] 吴一弦,刘刚.高反应活性聚异丁烯的制备方法:中国,100572403[P].2009-12-23.
[17] 任纪文,赵朕,于兆鹏,等.高活性聚异丁烯的合成与结构表征[J].高分子通报,2022,8:61-69.
[18] 吴康达.官能化聚异丁烯及其异丁烯基聚氨酯的合成与性能研究[D].北京:北京石油化工学院,2020.
[19] Simison K L,Stokes C D,Harrison J J,et al.End-quenching of quasilivingcarbocationic isobutylene polymerization with hindered bases:quantitative formation of exo-olefin-terminated polyisobutylene[J].Macromolecules, 2006,39(7):2481-2487.
[20] Ummadisetty S,Morgan D L,Stokes C D,et al.Synthesis of exo-olefin terminated polyisobutylene by sulfide/base quenching of living polyisobutylene[J].Macromolecules,2011,44:7901-7910.
[21] Morgan D L,Martinez-Castro N,Storey R F.End-quenching of TiCl4-catalyzed quasiliving polyisobutylene with alkoxybenzenes for direct chain end functionalization[J].Macromolecules,2010,43(21):8724-8740.
[22] Li X,Wu Y,Zhang J,et al.Synthesis of highly reactive polyisobutylenes via cationic polymerization in ionic liquids:characteristics and mechanism[J].Polymer Chemistry,2019,10(2):201-208.
[23] Kostyuk A V,Ignatenko V Y,Antonov S V,et al.Effect of surface contamination on the durability and strength of stainless steel-polyisobutylene pressure-sensitive adhesive bonds[J].International Journal of Adhesion and Adhesives,2019,95:102434.
[24] 张文学,贾军纪,黄安平,等.高活性聚异丁烯的生产状况及最新合成方法[J].石油化工,2014,43(2):226-232.
[25] 李慧芳,贾军纪,黄安平,等.聚异丁烯的性能及应用[J].广东化工,2014,41(8):84-84.
[26] 赵在庆.燃料乙醇来了,MTBE的出路[J].中国石油和化工经济分析,2018(2):53-56.
[27] Thomas R M,Sparks W J,Frolich P K,et al.Preparation and structure of high molecular weight polybutenes[J].Journal of the American Chemical Society,1940,62(2):276-280.
[28] Qiu Y,Wu Y,Gu X,et al.Cationic polymerization of isobutylene with H2O/TiCl4 initiating system in the presence of electron pair donors[J].European Polymer Journal,2005,41(2):349-358.
[29] Kaszas G,Puskas J E,Chen C C,et al.Electron pair donors in carbocationic polymerization[J].Polymer Bulletin,1988,20(5):413-419.
[30] Matyjaszewski K,Sigwalt P.Unified approach to living and non-living cationic polymerization of alkenes[J].Polymer International,1994,35(1):1-26.
[31] Hadjikyriacou S,Acar M,Faust R.Living and controlled polymerization of isobutylene with alkylaluminum halides as coinitiators[J].Macromolecules,2004,37(20):7543-7547.
[32] Li Y,Wu Y,Xu X,et al.Electron-pair-donor reaction order in the cationic polymerization of isobutylene coinitiated by AlCl3[J].Journal of Polymer Science Part A:Polymer Chemistry,2007,45(14):3053-3061.
[33] 陈颖,伍一波,郭文莉,等.2,6-二叔丁基吡啶在异丁烯活性正离子聚合中的作用研究[J].化学试剂,2013,35(11):967-970.
[34] Vasilenko I V,Nikishev P A,Shiman D I,et al.Cationic polymerization of isobutylene in toluene:toward well-defined exo-olefin terminated medium molecular weight polyisobutylenes under mild conditions[J].Polymer Chemistry,2017,8(8):1417-1425.
[35] Guerrero A,Kulbaba K,Bochmann M.“Highly reactive” poly (isobutene)s via room temperature polymerization with a new zinc-based initiator system[J].Macromolecules,2007,40(12):4124-4126.
[36] Jin Y,Dong K,Xu L,et al.Facile synthesis of medium molecular weight polyisobutylene with remarkable efficiency employing the complexed BF3·EtOH/TiCl4·H2O initiating system[J].European Polymer Journal,2019,120:109204.
[37] 骆广生,王凯,王佩坚,等.微反应器内聚合物合成研究进展[J].化工学报,2014,65(7):2563-2573.
[38] Zhu S,Lu Y,Wang K,et al.Flow synthesis of medium molecular weight polyisobutylene coinitiated by AlCl3[J].European Polymer Journal,2016,80:219-226.
[39] 王兴亚.高分子量聚异丁烯的合成[J].兰化科技,1995,13(3):157-160.
[40] Li Y,Wu Y,Liang L,et al.Cationic polymerization of isobutylene coinitiated by AlCl3 in the presence of ethyl benzoate[J].Chinese Journal of Polymer Science,2010,28(1):55-62.
[41] Huang Q,He P,Wang J,et al.Synthesis of high molecular weight polyisobutylene via cationic polymerization at elevated temperatures[J].Chinese Journal of Polymer Science,2013,31(8):1139-1147.
[42] Jin Y,Chen L,Guo X,et al.A complexed initiating system alcl3·phenetole/TiCl4·H2O with dominant synergistic effect for efficient synthesis of high molecular weight polyisobutylene[J].Polymers,2019,11(12):2121.
[43] Bochmann M.Highly electrophilic organometallics for carbocationic polymerizations:from anion engineering to new polymer materials[J].Accounts of Chemical Research,2010,43(9):1267-1278.
[44] Saßmannshausen J.Cationic and dicationiczirconocene compounds as initiators of carbocationic isobutene polymerisation[J].Dalton Transactions,2009(41):9026-9032.
[45] Kumar K R,Hall C,Penciu A,et al.Isobutene polymerization initiated by[CP*TiMe2]+ in the presence of a series of novel,weakly coordinating counteranions[J].Journal of Polymer Science Part A:Polymer Chemistry,2002,40(19):3302-3311.
[46] Csihony S,Janssen N,Mühlbach K.Controlling heat transfer for the manufacturing of high molecular weight polyisobutylene via formation of micelles[J].Chinese Journal of Polymer Science,2019,37(9):898-902.
[47] 何宇航,刘晴捷,吕阳成.微反应器内丁基橡胶溶液法制备体系的反应特性研究[J].化工学报,2021,72(2):1001-1008.
[48] 陈亮.合成中,高分子量聚异丁烯的高效AlCl3/含氧化合物催化体系的研究[D].上海:华东理工大学,2017.
基金资助
国家自然科学基金面上项目(52073033);中国石油天然气股份有限公司兰州化工研究中心资助项目(KYWX-21-014)