聚烯烃铬系催化剂铝改性的应用研究进展
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摘要
自Phillips公司发明铬系催化剂以来,其一直是烯烃聚合领域的研究热点。本文综述了铬系催化剂在铝改性方面的研发现状、制备方法以及对乙烯聚合性能的影响。改性后的铬系催化剂聚合活性和氢调敏感性明显提高,生成聚合物的相对分子质量分布变宽,耐环境应力开裂性能改善,产品加工性能优异。
Since chrome catalyst invented by Phillips company,it has been a hot research topic in the field of olefin polymerization.The research status,preparation methods,properties of chromium catalyst modified by alumina and its effect o on the ethylene polymerization are described.After modified,the polymerization activity and hydrogen sensitivity of chromium catalyst was improved significantly.The polymer obtained from the catalyst has broader molecular weight distribution,better environmental stress cracking resistance and excellent processing properties.
Since chrome catalyst invented by Phillips company,it has been a hot research topic in the field of olefin polymerization.The research status,preparation methods,properties of chromium catalyst modified by alumina and its effect o on the ethylene polymerization are described.After modified,the polymerization activity and hydrogen sensitivity of chromium catalyst was improved significantly.The polymer obtained from the catalyst has broader molecular weight distribution,better environmental stress cracking resistance and excellent processing properties.
引文
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[16]ANTONIO Iannibello,SERGIO Marengo,PAOLO Tittarelli,et al.Spectroscopic study of the structure of chromium(Ⅵ),molybdenum(Ⅵ)and tungsten(Ⅵ)oxospecies anchored on aluminium oxide[J].J.Chem.Soc.Faraday Trans.1,1984,80(8):2209-2223.
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[18]HOLM V C F,CLARK A.Reduction studies on supported metal oxide catalysts[J].Journal of Catalysis,1968,11:305-316.
[19]FINCH J N.Reduction studies on supported chromic anhydride catalysts[J].Journal of Catalysis,1976,43(1/2/3):111-121.
[20]MCDANIEL Max P,SMITH Paul D,NORWOOD Donald D.Olefin polymers prepared by polymerization with treated alumina supported chromium:US5401820[P].1995-03-28.
[21]MCDANIEL Max P,COLLINS Kathy S,BENHAM Elizabeth A,et al.Method of preparing active chromium/alumina catalysts viatreatment with sulfate and polymer produced using chromium/alumina catalysts:JP2011006714[P].2011-01-13.
[22]MCDANIEL M P,JENSEN J D,JAYARATNE K,et al.Metallocene activation by solid acids[C]//Society of Plastics Engineers 2007Conference,Houston:TX,2007:25-28.
[23]MCDANIEL M P,BENHAM E A,MARTIN S J,et al.Compositions that can produce polymers:US6300271[P].2001-10-09.
[24]BALLARD D G H.Pi and sigma transition metal carbon compounds as catalysts for the polymerization of vinyl monomers and olefins[J].Advances in Catalysis,1973,23(1):263-325.
[25]SMITH P D,MCDANIEL M P.Ethylene polymerization catalysts from supported organotransition metal complexes:I.pentadienyl derivatives of Ti,V,and Cr[J].Journal of Polymer Science,Part A:Polymer Chemistry,1989,27(8):2695-2710.
[26]MCDANIEL Max P,COLLINS Kathy S,BENHAM Elizabeth A,et al.Polymers having low levels of long chain branching and methods of making the same:US7112643[P].2006-09-26.
[27]MCDANIEL M P,JOHNSON M M.A comparison of Cr/SiO2and Cr/AlPO4 polymerization catalysts.2.Chain transfer[J].Macromolecules,1987,20(4):773-778.
[28]DEBRAS Guy.Titanated chromium/silica-aluminophosphate catalyst:US6225253[P].2001-05-01.
[29]MCDANIEL Max P,BENHAM Elizabeth A,WOLFE Al R,et al.烯烃聚合物、制造方法和其应用:1745109[P].2006-03-08.
[30]DESLAURIERS P J.MCDANIEL M P,ROHLFLNG D C,et al..A comparative study of multimodal vs.Bimodal polyethylene pipe resins for PE-100applications[J].Polymer Engineer and Science,2005,45(9):1203-1213.
[31]PAUL J Des Lauriers,TSO Chung,YU Youlu,et al.Long-chain branching in PE from Cr/aluminophosphate catalysts[J].Applied Catalysis A:General,2010,388(1/2):102-112.
[2]任红,严婕,刘胜春.气相法铬系聚乙烯催化剂QCP-01的评价[J].塑料工业,1999,27(5):36-38.
[3]ERIC Schwerdtfeger,RICHARD Buck,MAX Mcdaniel.Reduction of Cr(Ⅵ)polymerization catalysts by non-olefinic hydrocarbons[J].Applied Catalysis A:General,2012,423/424:91-99.
[4]WECKHUYSEN B M,SCHOONHEYDT R A.Olefin polymerization over supported chromium oxide catalysts[J].Catalysis Today,1999,51(2):215-221.
[5]ROBERT Meyers.Handbook of Petrochemicals Production Processes[M].New York:McGraw-Hill Professional,2005.
[6]MCDANIEL M P.Controlling polymer properties with the Phillips chromium catalystsf[J].Industrial&Engineering Chemistry Research,1988,27(9):1559-1564.
[7]MARSDEN C E.Advances in supported chromium catalysts[J].Plastics.Rubber and Composites Processing and Applications,1994,21(4):193-200.
[8]REBENSTORF B.The active species of the chromium(Phillips type)catalysts for the polymerization of ethylene:a unifying approach[J].Journal of Polymer Science,Part A:Polymer Chemistry,1991,29(13):1949-1953.
[9]REBENSTORF B,SHENG T C.Influence of chromium concentration and addition of fluorine,titanium,or boron on the chromium species of the Phillips catalyst:a quantitative evaluation[J].Langmuir,1991,7(10):2160-2165.
[10]REKERS L J,KATZEN S J,KREKELER J H.Olefin polymerization catalyst:US3984351[P].1976.
[11]LEEMPUT J M A Van de.Chromium-based catalysts for the polymerization of l-alkenes:US4146695[P].1979.
[12]REKERS L J,KATZEN S J,KREKELER J H.Olefin polymerization catalyst:US4260706[P].1981.
[13]REKERS L J,FRENCH R J,MAYHEW H W.Production of polyolefins having improved ESCR:US4356294[P].1982.
[14]MOHAMED I Zaki,NASR E Fouad,GEOFFREY C Bond,et al.Temperature-programmed reduction of calcined chromia-coated alumina and silica catalysts:probing chromium(Ⅵ)-oxygen species[J].Thermochem.Acta,1996,285(1):167-179.
[15]BERT M Weckhuysen,ISRAEL E Wachs,ROBERT A Schoonheydt.Surface chemistry and spectroscopy of chromium in inorganic oxides[J].Chemical Reviews,1996,96(8):3327-3350.
[16]ANTONIO Iannibello,SERGIO Marengo,PAOLO Tittarelli,et al.Spectroscopic study of the structure of chromium(Ⅵ),molybdenum(Ⅵ)and tungsten(Ⅵ)oxospecies anchored on aluminium oxide[J].J.Chem.Soc.Faraday Trans.1,1984,80(8):2209-2223.
[17]MAX P McDaniel.Advances in Catalysis[M].Bruce C G,Helmut K,edit,Academic Press,2010:123-606.
[18]HOLM V C F,CLARK A.Reduction studies on supported metal oxide catalysts[J].Journal of Catalysis,1968,11:305-316.
[19]FINCH J N.Reduction studies on supported chromic anhydride catalysts[J].Journal of Catalysis,1976,43(1/2/3):111-121.
[20]MCDANIEL Max P,SMITH Paul D,NORWOOD Donald D.Olefin polymers prepared by polymerization with treated alumina supported chromium:US5401820[P].1995-03-28.
[21]MCDANIEL Max P,COLLINS Kathy S,BENHAM Elizabeth A,et al.Method of preparing active chromium/alumina catalysts viatreatment with sulfate and polymer produced using chromium/alumina catalysts:JP2011006714[P].2011-01-13.
[22]MCDANIEL M P,JENSEN J D,JAYARATNE K,et al.Metallocene activation by solid acids[C]//Society of Plastics Engineers 2007Conference,Houston:TX,2007:25-28.
[23]MCDANIEL M P,BENHAM E A,MARTIN S J,et al.Compositions that can produce polymers:US6300271[P].2001-10-09.
[24]BALLARD D G H.Pi and sigma transition metal carbon compounds as catalysts for the polymerization of vinyl monomers and olefins[J].Advances in Catalysis,1973,23(1):263-325.
[25]SMITH P D,MCDANIEL M P.Ethylene polymerization catalysts from supported organotransition metal complexes:I.pentadienyl derivatives of Ti,V,and Cr[J].Journal of Polymer Science,Part A:Polymer Chemistry,1989,27(8):2695-2710.
[26]MCDANIEL Max P,COLLINS Kathy S,BENHAM Elizabeth A,et al.Polymers having low levels of long chain branching and methods of making the same:US7112643[P].2006-09-26.
[27]MCDANIEL M P,JOHNSON M M.A comparison of Cr/SiO2and Cr/AlPO4 polymerization catalysts.2.Chain transfer[J].Macromolecules,1987,20(4):773-778.
[28]DEBRAS Guy.Titanated chromium/silica-aluminophosphate catalyst:US6225253[P].2001-05-01.
[29]MCDANIEL Max P,BENHAM Elizabeth A,WOLFE Al R,et al.烯烃聚合物、制造方法和其应用:1745109[P].2006-03-08.
[30]DESLAURIERS P J.MCDANIEL M P,ROHLFLNG D C,et al..A comparative study of multimodal vs.Bimodal polyethylene pipe resins for PE-100applications[J].Polymer Engineer and Science,2005,45(9):1203-1213.
[31]PAUL J Des Lauriers,TSO Chung,YU Youlu,et al.Long-chain branching in PE from Cr/aluminophosphate catalysts[J].Applied Catalysis A:General,2010,388(1/2):102-112.