高密度聚乙烯催化剂的制备研究
|
摘要
本文分别用己烷和工厂已有的200#作溶剂,加入异丙醇、大颗粒乙氧基镁和四氯化钛制备出适合Hostalen工艺的HDPE催化剂。己烷为溶剂得到的聚乙烯堆密度高,但催化剂活性较差；200#为溶剂制备的催化剂活性大于10000gPE·g-1Cat.,PE的堆密度达到了0.3g·cm-3以上,PE的粒径分布较窄,可以替代目前使用的HDPE催化剂。本催化剂具有引发期短、活性高、活性衰减缓慢、氢调性能好等特点,能够满足Hostalen乙烯工艺应用的要求。
在催化剂制备过程中,筛选出了由大颗粒乙氧基镁为前体制备Hostalen工艺HDPE催化剂的TiCl4与Mg(OEt)2摩尔比,保温温度,保温时间,添加组分,四氯化钛的滴加速度,反应温度,200#溶剂用量,搅拌速度的较优反应参数。在这些参数下,制备的催化剂聚合活性达到14100gPE·g-1Cat.,聚乙烯堆密度达到0.33g·cm-3。
通过红外光谱测定和组成测定估算确定本文制备的催化剂主要由Ti(OEt)Cl3和MgCl2构成,催化剂的活性组分是Ti(OEt)Cl3。证明了通过测定催化剂的Ti、EtO含量与形态,可以初步判断催化剂的催化性能。
本论文对大颗粒乙氧基镁前体制备方法进行了研究,探索了不同方法对制备的前体性能的影响,为制备大颗粒的乙氧基镁提供了有益资料。
This paper prepares a catalyst of high density polyethylene which is used in Hostalen process with hexane solvent and the200#solvent in industry,i-C3H7OH and Mg(OEt)2precursor. The PE has a high bulk density with hexane sol vent, but the actvity is low. The activity of catalyst with200#solvent is over10000gPE·g-1Cat..The bulk density of PE is also over0.3g·cm-3And the PE has a narrow particles distribution.So the catalyst can replace the catalyst of high density polyethylene used at present.The catalyst has a short induction period, high activity, slow attenuation,good hydrogen tonal and so on,which is suitable for the Hostalen process.
In the preparation of catalyst,we screen out the optimal parameters of catalyst of high density polyethylene which is prepared by the large particles Mg(OEt)2for the Hostalen process.The parameter includes the molar ratio of TiCl4and Mg(OEt)2,keeping temperature,keeping time,the dropping rate of TiCl4,the reaction temperature,the amount of200#,the stirring rate.In the parameters,the polymerized activity is14100gPE·g-1Cat. and the bulk density of polyethylene is0.33g·cm-3.
The content of catalyst preparation in this thesis is Ti(OEt)Cl3and MgCl2by the measuring of IR and components.The active content is Ti(OEt)Cl3.We can judge the catalytic character of catalyst through measuring the morphology and the content of Ti,EtO.
The paper has a research in the preparation of Mg(OEt)2precursor with large particles.And we explore the effect of precursor character with different preparing conditions,which provides a helpful information for the preparation of Mg(OEt)2with larger paricles.
在催化剂制备过程中,筛选出了由大颗粒乙氧基镁为前体制备Hostalen工艺HDPE催化剂的TiCl4与Mg(OEt)2摩尔比,保温温度,保温时间,添加组分,四氯化钛的滴加速度,反应温度,200#溶剂用量,搅拌速度的较优反应参数。在这些参数下,制备的催化剂聚合活性达到14100gPE·g-1Cat.,聚乙烯堆密度达到0.33g·cm-3。
通过红外光谱测定和组成测定估算确定本文制备的催化剂主要由Ti(OEt)Cl3和MgCl2构成,催化剂的活性组分是Ti(OEt)Cl3。证明了通过测定催化剂的Ti、EtO含量与形态,可以初步判断催化剂的催化性能。
本论文对大颗粒乙氧基镁前体制备方法进行了研究,探索了不同方法对制备的前体性能的影响,为制备大颗粒的乙氧基镁提供了有益资料。
This paper prepares a catalyst of high density polyethylene which is used in Hostalen process with hexane solvent and the200#solvent in industry,i-C3H7OH and Mg(OEt)2precursor. The PE has a high bulk density with hexane sol vent, but the actvity is low. The activity of catalyst with200#solvent is over10000gPE·g-1Cat..The bulk density of PE is also over0.3g·cm-3And the PE has a narrow particles distribution.So the catalyst can replace the catalyst of high density polyethylene used at present.The catalyst has a short induction period, high activity, slow attenuation,good hydrogen tonal and so on,which is suitable for the Hostalen process.
In the preparation of catalyst,we screen out the optimal parameters of catalyst of high density polyethylene which is prepared by the large particles Mg(OEt)2for the Hostalen process.The parameter includes the molar ratio of TiCl4and Mg(OEt)2,keeping temperature,keeping time,the dropping rate of TiCl4,the reaction temperature,the amount of200#,the stirring rate.In the parameters,the polymerized activity is14100gPE·g-1Cat. and the bulk density of polyethylene is0.33g·cm-3.
The content of catalyst preparation in this thesis is Ti(OEt)Cl3and MgCl2by the measuring of IR and components.The active content is Ti(OEt)Cl3.We can judge the catalytic character of catalyst through measuring the morphology and the content of Ti,EtO.
The paper has a research in the preparation of Mg(OEt)2precursor with large particles.And we explore the effect of precursor character with different preparing conditions,which provides a helpful information for the preparation of Mg(OEt)2with larger paricles.
引文
[1]郭华,初宇红,张晓凌,等.国内外聚乙烯生产现状及市场分析[J].弹性体,2009,19(2)：71-76.
[2]邓世强,房广信,何小龙HDPE工艺技术进展[J].合成树脂及塑料,2002,19(5)：48-53.
[3]邵鹏程,王雁玉,李渤,等.高密度聚乙烯的研究及应用.塑料制造,2011,4：98-100.
[4]Ziegler K, Holzkamp E, Martin H, et al.Das Mulheimer Normaldruck-Polyathylen-Verfahren [J]. Angewandte Chemie,1955,67:541-547.
[5]ALBIZZATI E, GIANNINI U, COLLINA G, et al. Polypropylene Handbook [M]. New York: Hanser Publishers,1996.
[6]MORINI G, BALBONTIN G, GULEVICH Y, et al. Components and catalysts for the polymerization of olefins:WO,00/63261Al[P].2000-10-26.
[7]肖士镜,余赋生.烯烃配位聚合催化剂及聚烯烃[M].北京：北京工业大学出版社,2002.
[8]HERMANS J, HENRIOULLE P. Process for the preparation of a Ziegler-Natta type catalyst:US,3769233A[P].1973-10-30.
[9]CHO H S, LEE W Y. Synthesis of inorganic MgCl2-alcohol adduct via recrystallization method and its application in supported organometallic catalysts for the polymerization of ethylene with hexene [J]. Journal of Molecular Catalysis A:Chemical,2003,191(2):155-165.
[10]AURIEMMA G T, CORRADINI P. Progress and development of catalytic olefin polymerization [M]. Tokyo:Technology and Education Publishers,2000.
[11]黄葆同,沈之荃.烯烃双烯烃配位聚合进展[M].北京：科学出版社,1998.
[12]洪定一主编.聚丙烯一原理、工艺与技术[M].北京：中国石化出版社,2002.
[13]HIMONT INCORPORATED. Components and catalysts for the polymerization of olefins:EP, 0361494A2[P].1990-04-04.
[14]HIMONT INCORPORATED. Diethers usable in the preparation of Ziegler-Natta catalysts:EP,0361493A1[P].1990-04-04.
[15]ALLIZZATI E, GIANNINI U, MORINI G. Recent advances in propylene polymerization with MgCl2 supported catalysts [J]. Macromolecular Symposia,1995,89:73-89.
[16]董春明.乙烯淤浆聚合催化剂的放大研究[D].大庆：东北石油大学,2011.
[17]杨泽Ti-Mg催化剂的活性及载体研究[D].杭州：浙江大学,2008.
[18]PAOLO P, LUCIANNO N. High yield catalysts in olefin polymerization. General outlook on theoretical aspects and industrial uses [J]. Angewandte Makromolekulare Chemie,1984,120(1):73-90.
[19]宋阳.内给电子体对TiCl4/MgCl2丙烯聚合催化剂性能影响研究[D].北京：北京化工大学,2006.
[20]Barbe P C, Cecchin G, Noristi L. The ctalytic system Ti-complex/MgCl2 [J]. Advances in Polymer Science,1987,81:1-81.
[21]肖士镜,余赋生.烯烃配位聚合催化剂及聚烯烃[M].北京：北京工业大学出版社,2002：17-18.
[22]DOI Y, MURATA M, YANO K, et al. Gas-Phase Polymerization of Propene with the Supported Ziegler Catalyst: TiCl4/MgCl2/C6H5COOC2H5/Al (C2H5)3 [J]. Industries & Engineering Chemistry Product Research and Development,1982,21(4):580-585.
[23]KAZUO S, TAKESHI S. Ziegler-Natta catalysts for olef in polymerization [J]. Progress in Polymer Science,1997,22(7):1503-1546.
[24]CHADWIEK J C. Ziegler-Natta Catalysts in:Encyclopedia of polymer science and technology [M]. NewYork:John Wiley & Sons Inc,2003.
[25]GIANNINI U, CASSATA A, LONG I P, et al. Process for the stereoregular polymerization of alpha-olefins:US,4336360A[P].1982-06-22.
[26]FORTE C M, COUTINJO M B F. Highly active magnesium chloride supported Ziegler-Natta catalysts with controlled morphology [J].Europen Polymer Journal,1996,32 (2): 223-231.
[27]PARADA A, RAJMANKIN T, CHIRINOS J. Study of the MgCl2 recrystallization conditions on Ziegler-Natta catalyst properties [J]. Polymer Bulletin,1999,43(2-3):231-238.
[28]CHUNG J S, CHOI J H, SONG I K, et al. Effect of ethanol treatment in the preparation of MgCl2 support for the propylene polymerization catalyst. Macromolecules 1995,28 (5):1717-1718.
[29]ASANUMA T, SHIOMURA T. Process for polymerization of alpha-olefins and catalysts therefore:US,4581426A[P].1986-04-08.
[30]BANZI V, BARBE P C, NORISTI L. Catalysts components and catalysts for the polymerization of olefins. US,4529716A[P].1985-07-16.
[31]NOTO V D, BRESADOLA S. New synthesis of a highly active δ-MgCl2 for MgCl2/TiCl4/AIEt3 catalytic systems [J]. Macromolocular Chemistry and Physics,1996,197(11):3827-2835.
[32]NOTO V D, FREFONESE D, MARIGO A, et al. High yield MgCl2-supported catalysts for propene Polymerization:effects of ethyl propionate as internal donor on the activity and stereospecificity [J]. Macromolecular Chemistry and Physics,1998,199 (4):633-640.
[33]毛炳权,杨菊秀,李珠兰,等.烯烃聚合用的球形催化剂组分、制备方法和应用及球形催化剂：中国,1036011C[P].1997-08-23.
[34]洪晓宇,景振华,张科,等.聚丙烯球形催化剂及其载体的制备：中国,1109067A[P].1995-09-27.
[35]荣峻峰,张巍,景振华,等.一种烯烃聚合催化剂载体的制备方法：中国,1264713A[P]. 2000-08-30.
[36]吉恩-克劳德·安德鲁·伯利,斯苔连诺斯·圣迪斯.烯烃聚合催化剂德预活化载体及其制备方法：中国,1036852C.1997-12-31.
[37]胡友良.烯烃聚合催化剂研究开发进展[J].石化技术与应用,2002,20(1)：1-6,12.
[38]化工百科全书[M].北京：化学工业出版,1995,9：309.
[39]Hohne G W H, Schawe J E K. The phase transition behaviour of linear polyethylenes at high pressure [J]. Thermochimica Acta,1997,296(1-3):1-10.
[40]KISSIN Y V, LIU X SPOLLICH D J, et al. Ziegler-Natta catalysts for propylene polymerization:Chemistry of reactions leading to the formations of active centers [J].Journal of Molecular Catalysis A:Chemical,2008,287(1-2):45-52.
[41]CHOI K Y. Control of molecular weight distribution of polyethylene in continuous stirred tank reactors with high activity soluble Ziegler-type catalysts [J]. Journal of Applied Polymer Science,1985,30(6):2707-2710.
[42]BRITOVSEK G J P, GIBSON V C, KIMBERLEY B S, et al. Novel olefin polymerization catalysts based on iron and cobalt [J]. Chemical Communications,1998, (7):849-850.
[43]BOOR J. Zuegler-Natta Catalysts and Polymerization [M].New York:Academic Press Inc,1979.
[44]HUTCHINSON R A, RAY W H. Polymerization of olefins heterogeneous catalysis. Ⅷ.Monomer sorption effects [J]. Journal of Applied Polymer Science,1990,41(1-2):51-81.
[45]SPITZ R, DURANEL L, GUYOT A. Copolymerization of propene and butadiene with MgCl2 supported titanium catalytic systems [J].Makromolrkulare Chemie,1993,194(9):2631-2639.
[46]CHOI K Y, RAY W H. Polymerization of olefins through heterogeneous catalysis.Ⅱ Kinetics of gas phase propylene polymerization with Ziegler-Natta catalysts [J]. Journal of Applied Polymer Science,1985,30(3):1065-1081.
[47]MCDANIEL M P. Supported chromium catalysts for ethylene polymerization [J].Advances in Catalysis,1985,33:47-98.
[48]REQUEJO F G, RAMALLO J M. The effect of the composition of heterogeneous polymerization catalyst on ethylene-1-butene copolymerization[J]. Catalysis Today,2008,132(1-4):879-885.
[49]WOLF C R, MADALENA M. Characterization of the nature of chemical species of heterogeneous Ziegler-Natta catalysts for the production of HDPE [J]. Catalysis Today,2005:107-108,451-457.
[50]戈峰,彗星.国外聚烯烃生产技术进展[M].上海：上海科学技术出版社,1982.
[51]谢佩.超低密度聚乙烯评述[J].石油化工,1995,24(10)：44.
[52]李省岐.聚乙烯工艺比较及进展[J].齐鲁石油化工,2000,28(4)：305-308.
[53]宁英男,范娟娟,毛国梁,等.釜式淤浆法生产高密度聚乙烯工艺及催化剂研究进展[J].化工进展,2010,29(2)：250-254.
[54]LUDWIG L B. The Ethylene Polymerization with Ziegler Catalysts:Fifty Years After the Discovery [J]. Angewandte Chemie International Edition,2003,42 (41):5010-5030.
[55]MONTECATINI EDISON S P A. Neue Polymerisations Katalysatoren, ihre Herstellung und Veiwendung:DE,2000585A1[P].1970-7-16.
[56]MISTSUI PETROCHEMICAL INDUSTRIES LTD. Process for polymerization or copolymerization of olefin and catalyst compositions Used Therefore:US, 4071674A[P].1978-1-31.
[57]MONTECATINI EDISON S P A. Katalysator komponenten und Katalysatoren Fuer Diepolym erisation von Alpha-Olefinen:DE,2933997A1[P].1980-3-6.
[58]HOECHST AG. Verfahren zur herstellung eines poly-1-olefins:DE,4017661A1[P]. 1991-12-5.
[59]HOECHST AG. Verfahren zur herstellung eines Poly-1-olefins:EP,0613909A1[P]. 1994-2-24.
[60]三井化学株式会社.固体钛催化剂组分、含该组分的乙烯聚合催化剂和乙烯聚合工艺：中国,1112373C[P].2003-6-25.
[61]郭子方.乙烯淤浆聚合Ziegler-Natta催化剂的研究进展[J].石油化工,2009,38(4)：451-455.
[62]MISTSUI PETROCHEMICAL INDUSTRIES LTD. Process for polymerization or copolymerization of olef in and catalyst compositions used therefore:US,4071674 [P]. 1978-1-31.
[63]郭子方,张敬梅,陈伟,等.新型高效淤浆工艺聚乙烯催化剂的制备及其催化性能[J].石油化工,2005,34(9)：840-843.
[64]杨红旭,郭子方,周俊领.高性能淤浆法聚乙烯催化剂的研究[J].石油化工,2007,36(11)：1119-1122.
[65]三星综合化学株式会社.用于烯烃均聚和共聚反应的改进的催化剂：中国,1374971A[P].2002-10-16.
[66]三星综合化学株式会社.乙烯均聚和共聚催化剂：中国,1373777A[P].2002-10-9.
[67]三星综合化学株式会社.一种用于乙烯均聚和共聚反应的催化剂：中国,1454217A[P].2003-11-5.
[68]三星综合化学株式会社.用于乙烯聚合和共聚的催化剂：中国,1471542A[P].2004-1-28.
[69]三星综合化学株式会社.乙烯的聚合与共聚用催化剂：中国,1527843A[P].2004-9-8.
[70]住友化学工业株式会社.制备。-烯烃聚合用固体催化剂组分和催化剂的方法以及制备a-烯烃聚合物的方法：中国,1311260A[P].2001-9-5.
[71]巴塞尔聚烯烃意大利有限公司.烯烃聚合用组分和催化剂：中国,1681853A[P].2005-10-12.
[72]三井石油化学工业株式会社.固体钛催化剂组分、含该组分的乙烯聚合催化剂和乙烯聚合工艺：中国,1140722A[P].1997-1-22.
[73]JOACHIM B, BERND D, RAINER F, et al. Process for thepreparation of a polyolefin and a catalyst for this process:US,4447587[P].1984-5-8.
[74]郭子方.乙烯淤浆聚合Ziegler-Natta催化剂的研究进展[J].石油化工,2009,38(4)：451-455.
[75]Basell公司新型HDPE催化剂工业化[N/OL].中国化工在线,2003,(3)：6.
[76]Basell公司推出新型HDPE催化剂[N].中国化工报,2003,20(1)：65.
[77]宁英男,范娟娟,毛国梁.釜式淤浆法生产高密度聚乙烯工艺及催化剂研究进展[J].化工进展,2010,29(2)：250-254.
[78]张勇,郭子方,周俊领.乙烯淤浆聚合BCE催化剂的工业应用[J].石油化工,2008,37(3)：281-285.
[79]张文平,胡建东,石勤智.BCH聚乙烯高效催化剂生产过程的工艺优化[J]石化技术,2001,8(4)：218-221.
[80]华庆民,刘兴旺,吴冠京,等.国产钛系BCH催化剂在淤浆法HDPE装置上的应用[J].石油炼制与化工,1995,26(25)：21-23.
[81]化学工业部北京化工研究院.用于乙烯聚合或共聚合的催化剂及其制备方法：中国,1180712A[P].1998-5-6.
[82]中国石油化工集团公司.用于乙烯聚合或共聚合催化剂及其制法：中国,1229092A[P].1999-9-22.
[83]中国石油化工集团公司北京化工研究院.烯烃聚合用高活性催化剂及其制备方法和该催化剂的应用：中国,1268521A[P].2000-10-4.
[84]中国石油化工集团公司,中国石油化工股份有限公司石油化工科学研究院.一种烯烃聚合催化剂载体的制备方法：中国,1128822C[P].2003-11-26.
[85]张巍,季宝云,张勇,等.NT-1催化剂在淤浆法HDPE生产中的工业试用[J].合成树脂与塑料,2006,23(5)：34-37.
[86]冯艳秋,郑国彤,王立成,等.XYH型淤浆法聚乙烯高效催化剂的开发[J].石化技术与应用,2002,20(5)：311-314.
[87]营口市向阳化工总厂.一种乙烯聚合反应用催化剂的制备方法：中国,1322764A[P].2001-11-21.
[88]郭子方,张敬梅,陈伟,等.新型高效淤浆工艺聚乙烯催化剂的制备及其催化性能[J].石油化工,2005,34(9)：840-843.
[89]中石油化工股份有限公司.一种用于乙烯聚合或共聚合的催化剂及其制备方法：中国,1552743A[P].2004-12-8.
[90]GUO Z F, CHEN W, ZHOU J L, et al. Novel high performance Ziegler-Natta catalyst for ethylene slurry polymerization [J]. Chinese Journal of Chemical Engineering,2009,17(3):530-534.
[91]姜明,闫成玉,李倩倩,等.聚乙烯高效催化剂JM-1的开发及工业应用[J].化工科技,2006,14(5)：11-15.
[92]JOACIM B, BERND D, RAINER F, et al. Process for the preparation of a polyolefin and a catalyst for this process:US,4447587A[P].1984-5-8.
[93]韩哲文.高分子科学教程[M].上海：华东理工大学出版社,2008.
[94]赵明阳,谢仪.TiCl4-Mg(OC2H5)2乙烯聚合催化剂制备及改性：Ⅲ.添加SiCl4对催化性能的影响及作用机理[J].石油化工,1987,16(34)：269-274.
[95]赵明阳,谢仪.TiCl4-Mg(OC2H5)2乙烯聚合催化剂制备及改性：Ⅱ.载体的形成及结构对催化剂性能的影响[J].石油化工,1987,16(34)：269-274.
[96]赵明阳,谢仪.TiCl4-Mg(OC2H5)2乙烯聚合催化剂制备及改性：Ⅰ.钛组分Ti(OEt)nCl4-n的形成和对催化性能的影响[J].石油化工,1987,16(3)：206-212.
[97]姜明,张元礼,高晓玉,等.Hoechst淤浆法高密度聚乙烯催化剂的开发及工业应用[J].石化技术与应用,2007,25(4)：327-331.
[98]SHOHJIROH T, KIYOKAZU K, SUSUMU I, et al. Particle growth of magnesium alkoxide as a carrier material for polypropylene polymerization catalyst [J].Applied Catalysis A:General,2008,350(2):197-206.
[2]邓世强,房广信,何小龙HDPE工艺技术进展[J].合成树脂及塑料,2002,19(5)：48-53.
[3]邵鹏程,王雁玉,李渤,等.高密度聚乙烯的研究及应用.塑料制造,2011,4：98-100.
[4]Ziegler K, Holzkamp E, Martin H, et al.Das Mulheimer Normaldruck-Polyathylen-Verfahren [J]. Angewandte Chemie,1955,67:541-547.
[5]ALBIZZATI E, GIANNINI U, COLLINA G, et al. Polypropylene Handbook [M]. New York: Hanser Publishers,1996.
[6]MORINI G, BALBONTIN G, GULEVICH Y, et al. Components and catalysts for the polymerization of olefins:WO,00/63261Al[P].2000-10-26.
[7]肖士镜,余赋生.烯烃配位聚合催化剂及聚烯烃[M].北京：北京工业大学出版社,2002.
[8]HERMANS J, HENRIOULLE P. Process for the preparation of a Ziegler-Natta type catalyst:US,3769233A[P].1973-10-30.
[9]CHO H S, LEE W Y. Synthesis of inorganic MgCl2-alcohol adduct via recrystallization method and its application in supported organometallic catalysts for the polymerization of ethylene with hexene [J]. Journal of Molecular Catalysis A:Chemical,2003,191(2):155-165.
[10]AURIEMMA G T, CORRADINI P. Progress and development of catalytic olefin polymerization [M]. Tokyo:Technology and Education Publishers,2000.
[11]黄葆同,沈之荃.烯烃双烯烃配位聚合进展[M].北京：科学出版社,1998.
[12]洪定一主编.聚丙烯一原理、工艺与技术[M].北京：中国石化出版社,2002.
[13]HIMONT INCORPORATED. Components and catalysts for the polymerization of olefins:EP, 0361494A2[P].1990-04-04.
[14]HIMONT INCORPORATED. Diethers usable in the preparation of Ziegler-Natta catalysts:EP,0361493A1[P].1990-04-04.
[15]ALLIZZATI E, GIANNINI U, MORINI G. Recent advances in propylene polymerization with MgCl2 supported catalysts [J]. Macromolecular Symposia,1995,89:73-89.
[16]董春明.乙烯淤浆聚合催化剂的放大研究[D].大庆：东北石油大学,2011.
[17]杨泽Ti-Mg催化剂的活性及载体研究[D].杭州：浙江大学,2008.
[18]PAOLO P, LUCIANNO N. High yield catalysts in olefin polymerization. General outlook on theoretical aspects and industrial uses [J]. Angewandte Makromolekulare Chemie,1984,120(1):73-90.
[19]宋阳.内给电子体对TiCl4/MgCl2丙烯聚合催化剂性能影响研究[D].北京：北京化工大学,2006.
[20]Barbe P C, Cecchin G, Noristi L. The ctalytic system Ti-complex/MgCl2 [J]. Advances in Polymer Science,1987,81:1-81.
[21]肖士镜,余赋生.烯烃配位聚合催化剂及聚烯烃[M].北京：北京工业大学出版社,2002：17-18.
[22]DOI Y, MURATA M, YANO K, et al. Gas-Phase Polymerization of Propene with the Supported Ziegler Catalyst: TiCl4/MgCl2/C6H5COOC2H5/Al (C2H5)3 [J]. Industries & Engineering Chemistry Product Research and Development,1982,21(4):580-585.
[23]KAZUO S, TAKESHI S. Ziegler-Natta catalysts for olef in polymerization [J]. Progress in Polymer Science,1997,22(7):1503-1546.
[24]CHADWIEK J C. Ziegler-Natta Catalysts in:Encyclopedia of polymer science and technology [M]. NewYork:John Wiley & Sons Inc,2003.
[25]GIANNINI U, CASSATA A, LONG I P, et al. Process for the stereoregular polymerization of alpha-olefins:US,4336360A[P].1982-06-22.
[26]FORTE C M, COUTINJO M B F. Highly active magnesium chloride supported Ziegler-Natta catalysts with controlled morphology [J].Europen Polymer Journal,1996,32 (2): 223-231.
[27]PARADA A, RAJMANKIN T, CHIRINOS J. Study of the MgCl2 recrystallization conditions on Ziegler-Natta catalyst properties [J]. Polymer Bulletin,1999,43(2-3):231-238.
[28]CHUNG J S, CHOI J H, SONG I K, et al. Effect of ethanol treatment in the preparation of MgCl2 support for the propylene polymerization catalyst. Macromolecules 1995,28 (5):1717-1718.
[29]ASANUMA T, SHIOMURA T. Process for polymerization of alpha-olefins and catalysts therefore:US,4581426A[P].1986-04-08.
[30]BANZI V, BARBE P C, NORISTI L. Catalysts components and catalysts for the polymerization of olefins. US,4529716A[P].1985-07-16.
[31]NOTO V D, BRESADOLA S. New synthesis of a highly active δ-MgCl2 for MgCl2/TiCl4/AIEt3 catalytic systems [J]. Macromolocular Chemistry and Physics,1996,197(11):3827-2835.
[32]NOTO V D, FREFONESE D, MARIGO A, et al. High yield MgCl2-supported catalysts for propene Polymerization:effects of ethyl propionate as internal donor on the activity and stereospecificity [J]. Macromolecular Chemistry and Physics,1998,199 (4):633-640.
[33]毛炳权,杨菊秀,李珠兰,等.烯烃聚合用的球形催化剂组分、制备方法和应用及球形催化剂：中国,1036011C[P].1997-08-23.
[34]洪晓宇,景振华,张科,等.聚丙烯球形催化剂及其载体的制备：中国,1109067A[P].1995-09-27.
[35]荣峻峰,张巍,景振华,等.一种烯烃聚合催化剂载体的制备方法：中国,1264713A[P]. 2000-08-30.
[36]吉恩-克劳德·安德鲁·伯利,斯苔连诺斯·圣迪斯.烯烃聚合催化剂德预活化载体及其制备方法：中国,1036852C.1997-12-31.
[37]胡友良.烯烃聚合催化剂研究开发进展[J].石化技术与应用,2002,20(1)：1-6,12.
[38]化工百科全书[M].北京：化学工业出版,1995,9：309.
[39]Hohne G W H, Schawe J E K. The phase transition behaviour of linear polyethylenes at high pressure [J]. Thermochimica Acta,1997,296(1-3):1-10.
[40]KISSIN Y V, LIU X SPOLLICH D J, et al. Ziegler-Natta catalysts for propylene polymerization:Chemistry of reactions leading to the formations of active centers [J].Journal of Molecular Catalysis A:Chemical,2008,287(1-2):45-52.
[41]CHOI K Y. Control of molecular weight distribution of polyethylene in continuous stirred tank reactors with high activity soluble Ziegler-type catalysts [J]. Journal of Applied Polymer Science,1985,30(6):2707-2710.
[42]BRITOVSEK G J P, GIBSON V C, KIMBERLEY B S, et al. Novel olefin polymerization catalysts based on iron and cobalt [J]. Chemical Communications,1998, (7):849-850.
[43]BOOR J. Zuegler-Natta Catalysts and Polymerization [M].New York:Academic Press Inc,1979.
[44]HUTCHINSON R A, RAY W H. Polymerization of olefins heterogeneous catalysis. Ⅷ.Monomer sorption effects [J]. Journal of Applied Polymer Science,1990,41(1-2):51-81.
[45]SPITZ R, DURANEL L, GUYOT A. Copolymerization of propene and butadiene with MgCl2 supported titanium catalytic systems [J].Makromolrkulare Chemie,1993,194(9):2631-2639.
[46]CHOI K Y, RAY W H. Polymerization of olefins through heterogeneous catalysis.Ⅱ Kinetics of gas phase propylene polymerization with Ziegler-Natta catalysts [J]. Journal of Applied Polymer Science,1985,30(3):1065-1081.
[47]MCDANIEL M P. Supported chromium catalysts for ethylene polymerization [J].Advances in Catalysis,1985,33:47-98.
[48]REQUEJO F G, RAMALLO J M. The effect of the composition of heterogeneous polymerization catalyst on ethylene-1-butene copolymerization[J]. Catalysis Today,2008,132(1-4):879-885.
[49]WOLF C R, MADALENA M. Characterization of the nature of chemical species of heterogeneous Ziegler-Natta catalysts for the production of HDPE [J]. Catalysis Today,2005:107-108,451-457.
[50]戈峰,彗星.国外聚烯烃生产技术进展[M].上海：上海科学技术出版社,1982.
[51]谢佩.超低密度聚乙烯评述[J].石油化工,1995,24(10)：44.
[52]李省岐.聚乙烯工艺比较及进展[J].齐鲁石油化工,2000,28(4)：305-308.
[53]宁英男,范娟娟,毛国梁,等.釜式淤浆法生产高密度聚乙烯工艺及催化剂研究进展[J].化工进展,2010,29(2)：250-254.
[54]LUDWIG L B. The Ethylene Polymerization with Ziegler Catalysts:Fifty Years After the Discovery [J]. Angewandte Chemie International Edition,2003,42 (41):5010-5030.
[55]MONTECATINI EDISON S P A. Neue Polymerisations Katalysatoren, ihre Herstellung und Veiwendung:DE,2000585A1[P].1970-7-16.
[56]MISTSUI PETROCHEMICAL INDUSTRIES LTD. Process for polymerization or copolymerization of olefin and catalyst compositions Used Therefore:US, 4071674A[P].1978-1-31.
[57]MONTECATINI EDISON S P A. Katalysator komponenten und Katalysatoren Fuer Diepolym erisation von Alpha-Olefinen:DE,2933997A1[P].1980-3-6.
[58]HOECHST AG. Verfahren zur herstellung eines poly-1-olefins:DE,4017661A1[P]. 1991-12-5.
[59]HOECHST AG. Verfahren zur herstellung eines Poly-1-olefins:EP,0613909A1[P]. 1994-2-24.
[60]三井化学株式会社.固体钛催化剂组分、含该组分的乙烯聚合催化剂和乙烯聚合工艺：中国,1112373C[P].2003-6-25.
[61]郭子方.乙烯淤浆聚合Ziegler-Natta催化剂的研究进展[J].石油化工,2009,38(4)：451-455.
[62]MISTSUI PETROCHEMICAL INDUSTRIES LTD. Process for polymerization or copolymerization of olef in and catalyst compositions used therefore:US,4071674 [P]. 1978-1-31.
[63]郭子方,张敬梅,陈伟,等.新型高效淤浆工艺聚乙烯催化剂的制备及其催化性能[J].石油化工,2005,34(9)：840-843.
[64]杨红旭,郭子方,周俊领.高性能淤浆法聚乙烯催化剂的研究[J].石油化工,2007,36(11)：1119-1122.
[65]三星综合化学株式会社.用于烯烃均聚和共聚反应的改进的催化剂：中国,1374971A[P].2002-10-16.
[66]三星综合化学株式会社.乙烯均聚和共聚催化剂：中国,1373777A[P].2002-10-9.
[67]三星综合化学株式会社.一种用于乙烯均聚和共聚反应的催化剂：中国,1454217A[P].2003-11-5.
[68]三星综合化学株式会社.用于乙烯聚合和共聚的催化剂：中国,1471542A[P].2004-1-28.
[69]三星综合化学株式会社.乙烯的聚合与共聚用催化剂：中国,1527843A[P].2004-9-8.
[70]住友化学工业株式会社.制备。-烯烃聚合用固体催化剂组分和催化剂的方法以及制备a-烯烃聚合物的方法：中国,1311260A[P].2001-9-5.
[71]巴塞尔聚烯烃意大利有限公司.烯烃聚合用组分和催化剂：中国,1681853A[P].2005-10-12.
[72]三井石油化学工业株式会社.固体钛催化剂组分、含该组分的乙烯聚合催化剂和乙烯聚合工艺：中国,1140722A[P].1997-1-22.
[73]JOACHIM B, BERND D, RAINER F, et al. Process for thepreparation of a polyolefin and a catalyst for this process:US,4447587[P].1984-5-8.
[74]郭子方.乙烯淤浆聚合Ziegler-Natta催化剂的研究进展[J].石油化工,2009,38(4)：451-455.
[75]Basell公司新型HDPE催化剂工业化[N/OL].中国化工在线,2003,(3)：6.
[76]Basell公司推出新型HDPE催化剂[N].中国化工报,2003,20(1)：65.
[77]宁英男,范娟娟,毛国梁.釜式淤浆法生产高密度聚乙烯工艺及催化剂研究进展[J].化工进展,2010,29(2)：250-254.
[78]张勇,郭子方,周俊领.乙烯淤浆聚合BCE催化剂的工业应用[J].石油化工,2008,37(3)：281-285.
[79]张文平,胡建东,石勤智.BCH聚乙烯高效催化剂生产过程的工艺优化[J]石化技术,2001,8(4)：218-221.
[80]华庆民,刘兴旺,吴冠京,等.国产钛系BCH催化剂在淤浆法HDPE装置上的应用[J].石油炼制与化工,1995,26(25)：21-23.
[81]化学工业部北京化工研究院.用于乙烯聚合或共聚合的催化剂及其制备方法：中国,1180712A[P].1998-5-6.
[82]中国石油化工集团公司.用于乙烯聚合或共聚合催化剂及其制法：中国,1229092A[P].1999-9-22.
[83]中国石油化工集团公司北京化工研究院.烯烃聚合用高活性催化剂及其制备方法和该催化剂的应用：中国,1268521A[P].2000-10-4.
[84]中国石油化工集团公司,中国石油化工股份有限公司石油化工科学研究院.一种烯烃聚合催化剂载体的制备方法：中国,1128822C[P].2003-11-26.
[85]张巍,季宝云,张勇,等.NT-1催化剂在淤浆法HDPE生产中的工业试用[J].合成树脂与塑料,2006,23(5)：34-37.
[86]冯艳秋,郑国彤,王立成,等.XYH型淤浆法聚乙烯高效催化剂的开发[J].石化技术与应用,2002,20(5)：311-314.
[87]营口市向阳化工总厂.一种乙烯聚合反应用催化剂的制备方法：中国,1322764A[P].2001-11-21.
[88]郭子方,张敬梅,陈伟,等.新型高效淤浆工艺聚乙烯催化剂的制备及其催化性能[J].石油化工,2005,34(9)：840-843.
[89]中石油化工股份有限公司.一种用于乙烯聚合或共聚合的催化剂及其制备方法：中国,1552743A[P].2004-12-8.
[90]GUO Z F, CHEN W, ZHOU J L, et al. Novel high performance Ziegler-Natta catalyst for ethylene slurry polymerization [J]. Chinese Journal of Chemical Engineering,2009,17(3):530-534.
[91]姜明,闫成玉,李倩倩,等.聚乙烯高效催化剂JM-1的开发及工业应用[J].化工科技,2006,14(5)：11-15.
[92]JOACIM B, BERND D, RAINER F, et al. Process for the preparation of a polyolefin and a catalyst for this process:US,4447587A[P].1984-5-8.
[93]韩哲文.高分子科学教程[M].上海：华东理工大学出版社,2008.
[94]赵明阳,谢仪.TiCl4-Mg(OC2H5)2乙烯聚合催化剂制备及改性：Ⅲ.添加SiCl4对催化性能的影响及作用机理[J].石油化工,1987,16(34)：269-274.
[95]赵明阳,谢仪.TiCl4-Mg(OC2H5)2乙烯聚合催化剂制备及改性：Ⅱ.载体的形成及结构对催化剂性能的影响[J].石油化工,1987,16(34)：269-274.
[96]赵明阳,谢仪.TiCl4-Mg(OC2H5)2乙烯聚合催化剂制备及改性：Ⅰ.钛组分Ti(OEt)nCl4-n的形成和对催化性能的影响[J].石油化工,1987,16(3)：206-212.
[97]姜明,张元礼,高晓玉,等.Hoechst淤浆法高密度聚乙烯催化剂的开发及工业应用[J].石化技术与应用,2007,25(4)：327-331.
[98]SHOHJIROH T, KIYOKAZU K, SUSUMU I, et al. Particle growth of magnesium alkoxide as a carrier material for polypropylene polymerization catalyst [J].Applied Catalysis A:General,2008,350(2):197-206.