茂金属催化剂在合成树脂生产中的应用
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摘要
综述了茂金属催化剂的发展历史及负载型茂金属催化剂的研究进展,并分析了其在聚乙烯、聚丙烯、聚苯乙烯、环状烯烃共聚物、合成润滑油添加剂等领域的应用。随着对有机载体性能、负载方法等研究的深入,将推进负载型茂金属催化剂用于高附加值聚烯烃的工业开发。茂金属线型低密度聚乙烯的力学性能优于普通线型低密度聚乙烯,产品质量可与乙烯-1-辛烯共聚物媲美。用茂金属催化剂可实现聚丙烯合金的可控聚合。国内应着力开发负载型茂金属催化剂,降低采用茂金属催化剂生产的聚烯烃成本。
The development history of metallocene catalyst and the research progress of supported metallocene catalyst were summarized. The applications of metallocene catalyst to polyethylene,polypropylene, polystyrene, cyclic olefin copolymer and synthetic lubricant additive, etc. were analyzed. The application of metallocene catalyst to the industrial development of high value-added polyolefin would be accelerated with further researches on organic carrier properties and supported methods. The mechanical properties of linear low density polyethylene which was prepared with metallocene catalyst were better than those of normal linear low density polyethylene. And the product quality was comparable with ethylene-1-octene copolymer. The controlled polymerization of polypropylene alloys was realized by means of metallocene catalyst. The research and development in China should be focused on the supported metallocene catalyst to reduce the production cost of metallocene olefins.
The development history of metallocene catalyst and the research progress of supported metallocene catalyst were summarized. The applications of metallocene catalyst to polyethylene,polypropylene, polystyrene, cyclic olefin copolymer and synthetic lubricant additive, etc. were analyzed. The application of metallocene catalyst to the industrial development of high value-added polyolefin would be accelerated with further researches on organic carrier properties and supported methods. The mechanical properties of linear low density polyethylene which was prepared with metallocene catalyst were better than those of normal linear low density polyethylene. And the product quality was comparable with ethylene-1-octene copolymer. The controlled polymerization of polypropylene alloys was realized by means of metallocene catalyst. The research and development in China should be focused on the supported metallocene catalyst to reduce the production cost of metallocene olefins.
引文
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[25]黄葆同,陈伟.茂金属催化剂及其烯烃聚合物[M].北京:化学工业出版社,2000:231-238.
[26]戴东鹏,王燕萍,王依民,等.茂金属环烯烃共聚物结构性能表征及其纤维的研制[J].合成纤维工业,2011,34(4):34-36.
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[28]温丽芳,杨敏,罗爽,等.氧桥连双核茂钛催化剂催化苯乙烯的聚合[J].高分子材料科学与工程,2011,27(7):9-12.
[29]江洪波,毋少庚.桥联茂金属催化1-癸烯聚合及其产物结构与性能[J].化工进展,2015,34(4):1088-1092.
[2]Coates G W.Precise control of polyolefin stereochemistry using single-site metal catalysts[J].Chem Rev,2000,100(4):1223-1252.
[3]De Rosa C,Auriemma F.Structure of syndiotactic propylene-ethylene copolymers:effect of the presence of ethylene units on the structural transitions during plastic deformation and annealing of syndiotactic polypropylene[J].Polymer,2006,47(6):2179-2188.
[4]张洪波,刘丽,柏影.茂金属催化剂及聚合物的进展[J].化工技术经济,2004,22(9):24-25.
[5]Heurtefeu B,Bouilhac C,Cloutet E,et al.Polymer support of"single-site"catalysts for heterogeneous olefin polymerization[J].Progress in Polymer Science,2011,36(1):89-126.
[6]王海琛.树枝状亚胺水杨醛镍配合物的合成及催化性能研究[D].大庆:东北石油大学,2013.
[7]朱博超,王雄,胡杰,等.负载型茂金属烯烃聚合催化剂有机载体研究进展[J].高分子通报,2014(2):46-53.
[8]肖娴,傅智盛,范志强.烯烃聚合用茂金属催化剂负载化机理的研究进展[J].合成树脂及塑料,2015,32(1):76-79.
[9]黄付玲,高宇新,郭桂悦,等.聚苯乙烯载体负载茂金属催化剂的合成及表征[J].塑料工业,2009,37(12):13-15.
[10]亢宇,张明森,谢伦嘉,等.空心球状介孔硅基材料负载茂金属催化剂及催化乙烯聚合的研究[J].石油化工,2012,41(1):27-32.
[11]Ma Zhi,Sun Wenhua,Zhu Ning,et al.Preparation of Silicasupported late transition metal catalyst and ethylene polymerization[J].Polym Int,2002,51(4):349-352.
[12]谢光勇,雷禄,郭宏磊,等.SBA-15负载二氯二茂锆催化剂的制备及催化乙烯聚合反应[J].中南民族大学学报:自然科学版,2011,30(2):6-9.
[13]崇雅丽,韦少义,张鹏,等.LHQ-12负载型茂金属催化剂乙烯淤浆聚合[J].石化技术与应用,2013,31(1):189-192.
[14]Saeid Ahmadjo,Hassan Arabi,Mehdi Nekoomanesh.Indirect synthesis of bis(2-Phlnd)ZrCl_2 metallocene catalyst,kinetic study and modeling of ethylene polymerization[J].Chemical Engineering&Technology,2011,34(2):249-256.
[15]Choi Y,Soares J B P.Ethylene slurry polymerization using nickel diimine catalysts covalently-attached onto MgCl_2-based supports[J].Polymer,2010,51(11):2271-2276.
[16]Sedov I V,Matkovskiy P E,Russiyan L N.Ethylene polymerization initiated by metallocene catalysts(C_5H_5)_4Mt-MAO(Mt=Ti,Zr)in the presence of organometallic modifiers[J].Polymer Science,Series B:rapid Communications Reviews,2010,52(1/2):63-66.
[17]李延亮,唐岩,李丽,等.茂金属线型低密度聚乙烯的结构表征[J].合成树脂及塑料,2013,30(6):35-39
[18]庞红伟.茂金属催化剂产品性能及应用[J].炼油与化工,2006(4):29-31.
[19]王霞,何华琴,屠德民,等.茂金属聚乙烯改性低密度聚乙烯介电性能与机械强度[J].电工技术学报,2007,22(5):29-34.
[20]吕书军,刘国辉,白潇,等.线性茂金属聚乙烯树脂18X10D的开发及应用[J].石油科技论坛,2011(5):63-65.
[21]王者民,王涛.茂金属催化剂在Unipol工艺HDPE装置的工业化应用[J].齐鲁石油化工,2014,42(3):204-205.
[22]董诚,牛慧,董金勇.三乙基铝调控的Ziegler-Natta/茂金属复合催化剂制备聚丙烯催化合金[J].高分子学报,2014(8):1143-1152.
[23]蒋羽中,朱美芳,张瑜,等.齐格勒纳塔等规聚丙烯和茂金属等规聚丙烯共混物结晶热力学研究[J].东北大学学报:自然科学版,2002,28(2):129-131.
[24]孟令柱,毛静,张宇,等.茂金属催化丙烯间规聚合的研究进展[J].高分子通报,2012(4):77-82.
[25]黄葆同,陈伟.茂金属催化剂及其烯烃聚合物[M].北京:化学工业出版社,2000:231-238.
[26]戴东鹏,王燕萍,王依民,等.茂金属环烯烃共聚物结构性能表征及其纤维的研制[J].合成纤维工业,2011,34(4):34-36.
[27]杨帆,吕振波,赵瑛祁.茂金属催化剂及烯烃齐聚物研究进展[J].当代化工,2014,43(6):973-974.
[28]温丽芳,杨敏,罗爽,等.氧桥连双核茂钛催化剂催化苯乙烯的聚合[J].高分子材料科学与工程,2011,27(7):9-12.
[29]江洪波,毋少庚.桥联茂金属催化1-癸烯聚合及其产物结构与性能[J].化工进展,2015,34(4):1088-1092.