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1.发明授权One pot preparation of bimetallic catalysts for ethylene 1-olefin copolymerization 失效乙烯1-烯烃共聚双金属催化剂的一锅制备公开(公告)号：US06740617B2
公开(公告)日：2004-05-25
申请号：US10161537
申请日：2002-06-03
申请人： Robert I. Mink , Yury V. Kissin , Thomas E. Nowlin , Pradeep P. Shirodkar , Grace O. Tsien , Sandra D. Schregenberger
发明人： Robert I. Mink , Yury V. Kissin , Thomas E. Nowlin , Pradeep P. Shirodkar , Grace O. Tsien , Sandra D. Schregenberger
IPC分类号： B01J3116
CPC分类号： C08F10/00 , C08F4/65904 , C08F4/65912 , C08F4/65916 , C08F4/65925 , C08F210/16 , Y10S526/943 , C08F210/14 , C08F2500/12
摘要： A process of forming a bimetallic catalyst composition comprising a cocatalyst (a trialkylaluminum compound) and a catalyst precursor. The precursor comprises at least two transition metals; a metallocene complex is a source of one of said two transition metals. The precursor is produced in a single-pot process by contacting a porous carrier, in sequence, with a dialkylmagnesium compound, an aliphatic alcohol, a non-metallocene transition metal compound, a contact product of a metallocene complex and a trialkyl-aluminum compound, and methylalumoxane.
摘要翻译： 一种形成包含助催化剂（三烷基铝化合物）和催化剂前体的双金属催化剂组合物的方法。 前体包含至少两种过渡金属; 茂金属络合物是所述两种过渡金属之一的来源。 通过使多孔载体顺序地与二烷基镁化合物，脂族醇，非金属茂过渡金属化合物，茂金属络合物和三烷基铝化合物的接触产物接触，在单釜法中制备前体， 和甲基铝氧烷。
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公开(公告)号：US06713425B2
公开(公告)日：2004-03-30
申请号：US10161534
申请日：2002-06-03
申请人： Robert I. Mink , Yury V. Kissin , Thomas E. Nowlin , Pradeep P. Shirodkar , Grace O. Tsien , Sandra D. Schregenberger
发明人： Robert I. Mink , Yury V. Kissin , Thomas E. Nowlin , Pradeep P. Shirodkar , Grace O. Tsien , Sandra D. Schregenberger
IPC分类号： B01J3100
CPC分类号： C08F10/00 , C08F4/65904 , C08F4/65912 , C08F4/65916 , C08F4/65925 , C08F210/16 , Y10S526/943 , C08F210/14 , C08F2500/12
摘要： A process of forming a bimetallic catalyst composition comprising a cocatalyst (a trialkylaluminum compound) and a catalyst precursor. The precursor comprises at least two transition metals; a metallocene complex is a source of one of said two transition metals. The precursor is produced in a single-pot process by contacting a porous carrier, in sequence, with a dialkylmagnesium compound, an aliphatic alcohol, a non-metallocene transition metal compound, a contact product of a metallocene complex and a trialkyl-aluminum compound, and methylalumoxane.
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3.发明授权Bimetallic catalyst for ethylene polymerization reactions with uniform component distribution 失效用于乙烯聚合反应的双金属催化剂具有均匀的组分分布公开(公告)号：US06486089B1
公开(公告)日：2002-11-26
申请号：US08555816
申请日：1995-11-09
申请人： Yury V. Kissin , Robert I. Mink , Thomas E. Nowlin , Pradeep P. Shirodkar , Sandra D. Schregenberger , Grace O. Tsien
发明人： Yury V. Kissin , Robert I. Mink , Thomas E. Nowlin , Pradeep P. Shirodkar , Sandra D. Schregenberger , Grace O. Tsien
IPC分类号： C08F402
CPC分类号： B01J31/1616 , B01J31/122 , B01J31/143 , B01J31/2295 , B01J37/0203 , B01J37/0205 , B01J2531/48 , C08F4/61904 , C08F4/61912 , C08F4/61916 , C08F10/00 , Y10S526/943
摘要： The invention relates to a process for uniformly dispersing a transition metal metallocene complex on a carrier comprising (1) providing silica which is porous and has a particle size of 1 to 250 microns, having pores which have an average diameter of 50 to 500 Angstroms and having a pore volume of 0.5 to 5.0 cc/g; (2) slurrying the silica in an aliphatic solvent having a boiling point less than 110° C.; (3) providing a volume of a solution comprising metallocene and alumoxane wherein the volume of solution is less than that required to form a slurry of the silica, wherein the concentration of alumoxane, expressed as Al weight percent, is 5 to 20; (4) contacting the silica slurry (2) with said volume of said solution (3) and allowing the solution to impregnate the pores of silica and, to disperse the metallocene in and on the carrier; (5) evaporating the solvents from the contacted and impregnated silica to recover dry free-flowing catalyst particles.
摘要翻译： 本发明涉及一种将过渡金属茂金属络合物均匀分散在载体上的方法，包括（1）提供多孔的，具有1至250微米的粒径的二氧化硅，具有平均直径为50至500埃的孔， 孔体积为0.5-5.0cc / g;（2）将二氧化硅在沸点小于110℃的脂族溶剂中制浆;（3）提供体积的包含茂金属和铝氧烷的溶液，其中体积为 溶液小于形成二氧化硅浆料所需的溶液，其中铝氧烷的浓度以Al重量百分比表示为5至20; （4）使二氧化硅浆料（2）与所述体积的所述溶液（3）接触，并使所述溶液浸渍二氧化硅的孔隙，并将所述茂金属分散在所述载体上和载体上; （5）从接触和浸渍的二氧化硅蒸发溶剂以回收干燥的自由流动的催化剂颗粒。
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4.发明授权Bimetallic catalyst for ethylene polymerization reactions with uniform component distribution 失效用于乙烯聚合反应的双金属催化剂具有均匀的组分分布公开(公告)号：US06855654B2
公开(公告)日：2005-02-15
申请号：US10244930
申请日：2002-09-16
申请人： Yury V. Kissin , Robert I. Mink , Thomas E. Nowlin , Pradeep P. Shirodkar , Sandra D. Schregenberger , Grace O. Tsien
发明人： Yury V. Kissin , Robert I. Mink , Thomas E. Nowlin , Pradeep P. Shirodkar , Sandra D. Schregenberger , Grace O. Tsien
IPC分类号： B01J31/12 , B01J31/14 , B01J31/16 , B01J31/22 , B01J37/02 , C08F4/02 , C08F4/50 , C08F4/619 , C08F4/622 , C08F4/623 , C08F4/64 , C08F4/642 , C08F10/00 , C08F4/44
CPC分类号： B01J31/1616 , B01J31/122 , B01J31/143 , B01J31/2295 , B01J37/0203 , B01J37/0205 , B01J2531/48 , C08F4/61904 , C08F4/61912 , C08F4/61916 , C08F10/00 , Y10S526/943
摘要： The invention relates to a process for uniformly dispersing a transition metal metallocene complex on a carrier comprising (1) providing silica which is porous and has a particle size of 1 to 250 microns, having pores which have an average diameter of 50 to 500 Angstroms and having a pore volume of 0.5 to 5.0 cc/g; (2) slurrying the silica in an aliphatic solvent having a boiling point less than 110° C.; (3) providing a volume of a solution comprising the metallocene complex, alumoxane of formulas R—(Al(R)—O—)x—AlR2 for oligomeric linear alumoxanes and (—Al(R)—O—)y for cyclic alumoxanes wherein x is 1-40, y is 3-40, and R is a C1-C8 alkyl group in an aromatic and a solvent wherein the volume of solution is less than that required to form a slurry of the silica, wherein the concentration of alumoxane, expressed as Al weight percent, is 5 to 20; (4) contacting the silica slurry (2) with said volume of said solution (3) and allowing the solution to impregnate the pores of silica and, to disperse the metallocene in and on the carrier; (5)evaporating the solvents from the contacted and impregnated silica to recover dry free-flowing catalyst particles.
摘要翻译： 本发明涉及一种将过渡金属茂金属络合物均匀分散在载体上的方法，包括（1）提供多孔的，具有1至250微米的粒径的二氧化硅，具有平均直径为50至500埃的孔， 孔体积为0.5-5.0cc / g;（2）将二氧化硅在沸点低于110℃的脂肪族溶剂中制浆;（3）提供体积的包含金属茂配合物的溶液，式 低聚线型铝氧烷的R-（Al（R）-O-）x-AlR2和环状铝氧烷的（-Al（R）-O-）y，其中x为1-40，y为3-40，R为 芳族和溶剂中的C 1 -C 8烷基，其中溶液的体积小于形成二氧化硅浆料所需的体积，其中铝氧烷的浓度以Al重量百分比表示为5至20;（4）接触 二氧化硅浆料（2）与所述溶液（3）的体积一起并使溶液浸渍二氧化硅的孔隙， 在载体上和载体上存在金属茂;（5）从接触和浸渍的二氧化硅中蒸发溶剂以回收干燥的自由流动的催化剂颗粒。
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5.发明授权High activity polyethylene catalysts which produce bimodal or trimodal product molecular weight distributions 失效产生双峰或三峰产物分子量分布的高活性聚乙烯催化剂
公开(公告)号：US5693583A
公开(公告)日：1997-12-02
申请号：US799086
申请日：1997-02-11
摘要： A catalyst composition for copolymerizing ethylene and alpha-olefins is prepared by treating a silica carrier, in a non-polar hydrocarbon solvent, with a dialkyl magnesium compound, a halogen-containing compound and titanium tetrachloride, to form a catalyst precursor and activating the precursor with dimethylaluminum chloride. Also disclosed is a process for copolymerizing ethylene and alpha-olefins in the presence of the catalyst of the invention. The polymer products have multimodal molecular weight distributions unlike unimodal molecular weight distributions of polymers prepared with similar catalyst precursors but activated with different alkylaluminum activators, e.g., triethylaluminum or trimethylaluminum.
摘要翻译： 通过用二烷基镁化合物，含卤素化合物和四氯化钛处理非极性烃溶剂中的二氧化硅载体来制备用于共聚乙烯和α-烯烃的催化剂组合物，以形成催化剂前体并活化前体 与二甲基氯化铝。 还公开了在本发明的催化剂存在下共聚乙烯和α-烯烃的方法。 聚合物产物具有多峰分子量分布，不同于用类似的催化剂前体制备的聚合物的单峰分子量分布，但是用不同的烷基铝活化剂例如三乙基铝或三甲基铝活化。
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6.发明授权One pot preparation of bimetallic catalysts for ethylene 1-olefin copolymerization 失效乙烯1-烯烃共聚双金属催化剂的一锅制备公开(公告)号：US06417130B1
公开(公告)日：2002-07-09
申请号：US08621566
申请日：1996-03-25
申请人： Robert I. Mink , Yury V. Kissin , Thomas E. Nowlin , Pradeep P. Shirodkar , Grace O. Tsien , Sandra D. Schregenberger
发明人： Robert I. Mink , Yury V. Kissin , Thomas E. Nowlin , Pradeep P. Shirodkar , Grace O. Tsien , Sandra D. Schregenberger
IPC分类号： B01J3100
CPC分类号： C08F10/00 , C08F4/65904 , C08F4/65912 , C08F4/65916 , C08F4/65925 , C08F210/16 , Y10S526/943 , C08F210/14 , C08F2500/12
摘要： A process of forming a bimetallic catalyst composition comprising a cocatalyst (a trialkylaluminum compound) and a catalyst precursor. The precursor comprises at least two transition metals; a metallocene complex is a source of one of said two transition metals. The precursor is produced in a single-pot process by contacting a porous carrier, in sequence, with a dialkylmagnesium compound, an aliphatic alcohol, a non-metallocene transition metal compound, a contact product of a metallocene complex and a trialkylaluminum compound, and methylalumoxane.
摘要翻译： 一种形成包含助催化剂（三烷基铝化合物）和催化剂前体的双金属催化剂组合物的方法。 前体包含至少两种过渡金属; 茂金属络合物是所述两种过渡金属之一的来源。 通过使多孔载体依次与二烷基镁化合物，脂族醇，非茂金属过渡金属化合物，茂金属络合物和三烷基铝化合物的接触产物和甲基铝氧烷接触而在单釜法中制备前体 。
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7.发明授权Bimetallic catalysts for ethylene polymerization reactions activated with paraffin-soluble alkylalumoxanes 失效用石蜡溶解的烷基铝氧烷活化的乙烯聚合反应的双金属催化剂
公开(公告)号：US06001766A
公开(公告)日：1999-12-14
申请号：US998146
申请日：1997-12-24
申请人： Yury V. Kissin , Robert I. Mink , Thomas E. Nowlin
发明人： Yury V. Kissin , Robert I. Mink , Thomas E. Nowlin
IPC分类号： B01J31/14 , B01J31/22 , C08F4/02 , C08F4/60 , C08F4/658 , C08F4/659 , C08F4/6592 , C08F10/02 , C08F210/16 , B01J31/00 , B01J37/00
CPC分类号： B01J31/143 , B01J31/2295 , C08F10/02 , B01J2531/46 , B01J2531/48 , B01J2531/49 , C08F210/16 , C08F4/65912 , C08F4/65925 , Y10S526/943
摘要： Catalyst compositions for homopolymerization and copolymerization of ethylene which comprise two transition metal compounds, one of them a cyclopentadienyl complex of a transition metal and another a non-metallocene derivative of a transition metal are described. The catalysts are activated by alkylalumoxanes that are soluble in non-aromatic hydrocarbons. Bimetallic catalysts of this invention are suitable for the manufacture of ethylene homopolymers and copolymers with broad bimodal molecular weight distributions. The alkyl alumoxanes have at least one [AR(R)--O--] repeating group in which R is an alkyl group of at least two carbon atoms.
摘要翻译： 描述了包含两种过渡金属化合物的乙烯均聚和共聚的催化剂组合物，其中一种是过渡金属的环戊二烯基络合物和另一种过渡金属的非茂金属衍生物。 催化剂由可溶于非芳族烃的烷基铝氧烷活化。 本发明的双金属催化剂适用于制备具有宽双峰分子量分布的乙烯均聚物和共聚物。 烷基铝氧烷具有至少一个[AR（R）-O-]重复基团，其中R是至少两个碳原子的烷基。
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8.发明授权Process for forming a catalyst precursor for copolymerizing ethylene and an alpha-olefin of 3 to 10 carbon atoms 失效形成用于共聚乙烯和3至10个碳原子的α-烯烃的催化剂前体的方法
公开(公告)号：US5994256A
公开(公告)日：1999-11-30
申请号：US9621
申请日：1998-01-21
IPC分类号： B01J31/12 , B01J31/14 , C08F4/44 , C08F4/654 , C08F10/00 , B01J31/00 , B01J37/00 , C08F4/02 , C08F4/60
CPC分类号： B01J31/128 , B01J31/122 , B01J31/143 , C08F10/00
摘要： A process is described for forming a catalyst precursor, for copolymerizing ethylene and an alpha-olefin of 3 to 10 carbon atoms, by preparing a contact mixture of an inert solvent, dibutylmagnesium and tetraalkyl orthosilicate which is free of precipitate and adding silica to the contact mixture to form a slurry to form a supported catalyst precursor. Titanium tetrachloride is then incorporated into the support in a specific ratio to the magnesium and silane components. Activation of this catalyst precursor with a trialkylaluminum compound results in a catalyst system which is effective for the production of ethylene copolymers.
摘要翻译： 描述了通过制备不含沉淀物的惰性溶剂，二丁基镁和原硅酸四烷基酯与接触剂二氧化硅的接触混合物来形成用于共聚乙烯和3-10个碳原子的α-烯烃的催化剂前体的方法 混合物以形成浆料以形成负载型催化剂前体。 然后将四氯化钛以与镁和硅烷组分的特定比例引入载体中。 这种催化剂前体与三烷基铝化合物的活化导致催化剂体系对生产乙烯共聚物是有效的。
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公开(公告)号：US5514634A
公开(公告)日：1996-05-07
申请号：US257997
申请日：1994-06-10
IPC分类号： C08F4/658 , B01J31/02 , B01J31/12 , B01J31/14 , C08F4/656 , C08F10/02 , C08F210/00 , C08F210/02 , C08F210/16 , B01J31/00 , B01J37/00
CPC分类号： B01J31/0274 , B01J31/0204 , B01J31/0275 , B01J31/122 , B01J31/128 , B01J31/14 , B01J31/143 , C08F10/02 , C08F210/16
摘要： An ethylene polymerization catalyst is prepared by impregnating a porous support, such as silica, with an organomagnesium compound such as a dialkylmagnesium compound, contacting the magnesium-containing support with a silane compound which is free of hydroxyl groups, such as tetraalkoxysilanes, e.g. tetraethyl orthosilicate, and incorporating a transition metal component, such as titanium tetrachloride, in a specific ratio to the magnesium and silane components. Activation of this catalyst precursor with dimethylaluminum chloride as a cocatalyst results in a catalyst system which is effective for the production of ethylene copolymers with multimodal molecular weight distributions.
摘要翻译： 通过用有机镁化合物如二烷基镁化合物浸渍多孔载体如二氧化硅来制备乙烯聚合催化剂，使含镁载体与不含羟基的硅烷化合物接触，例如四烷氧基硅烷，例如四烷氧基硅烷。 原硅酸四乙酯，并以与镁和硅烷组分成比例的比例掺入过渡金属组分如四氯化钛。 用二甲基氯化铝作为助催化剂活化该催化剂前体，得到对于生产具有多峰分子量分布的乙烯共聚物有效的催化剂体系。
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公开(公告)号：US5258345A
公开(公告)日：1993-11-02
申请号：US979694
申请日：1992-11-20
申请人： Yury V. Kissin , Robert I. Mink , Thomas E. Nowlin
发明人： Yury V. Kissin , Robert I. Mink , Thomas E. Nowlin
IPC分类号： C08F4/658 , C08F4/656 , C08F10/02 , C08F210/16
摘要： The invention relates to catalysts which produce linear low density polyethylene with a bimodal molecular weight distribution, particularly those containing a high molecular weight fraction. The catalysts are formed by contacting a carrier with an organomagnesium compound to incorporate magnesium into the carrier, and subsequently contacting the carrier containing the incorporated magnesium with a silicon compound and subsequently with a transition metal source; the transition metal containing intermediate is again treated with an organomagesium compound to form a catalyst precursor, and the catalyst precursor is activated with dimethylaluminum chloride.
摘要翻译： 本发明涉及产生具有双峰分子量分布的线性低密度聚乙烯的催化剂，特别是含有高分子量分数的那些。 催化剂通过使载体与有机镁化合物接触而形成，以将镁引入载体中，随后使含有掺入的镁的载体与硅化合物接触，随后与过渡金属源接触; 再次用有机铵化合物处理含过渡金属的中间体，形成催化剂前体，催化剂前体用氯化二甲基铝活化。
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