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1. 发明授权

US06995109B2 Method of making a bimetallic catalyst with higher activity 失效
标题翻译：制备活性较高的双金属催化剂的方法
公开(公告)号：US06995109B2
公开(公告)日：2006-02-07
申请号：US10492444
申请日：2002-10-03
申请人： Robert I. Mink , Thomas E. Nowlin , Kenneth G. Schurzky , Pradeep P. Shirodkar , Robert L. Santana
发明人： Robert I. Mink , Thomas E. Nowlin , Kenneth G. Schurzky , Pradeep P. Shirodkar , Robert L. Santana
IPC分类号： B01J31/00 , B01J37/00 , C08F4/02 , C08F4/60
CPC分类号： C08F10/02 , C08F4/65904 , C08F4/65912 , C08F4/65925 , C08F4/6546 , C08F4/65916 , C08F4/025
摘要： Methods of preparing bimetallic catalysts are disclosed. The methods include the steps of providing a supported non-metallocene catalyst, contacting a slurry of the supported non-metallocene catalyst in a non-polar hydrocarbon with a solution of a metallocene compound and an alumoxane, and drying the contact product to obtain a supported bimetallic catalyst. The supported non-metallocene catalyst is prepared by dehydrating a particulate support material at a temperature of greater than 600° C., preparing a slurry of the dehydrated support in a non-polar hydrocarbon, contacting the slurry with an organomagnesium compound and an alcohol, contacting the resulting slurry with a non-metallocene compound of a Group 4 or Group 5 transition metal, and drying the contact product to obtain a supported non-metallocene catalyst as a free-flowing powder. The bimetallic catalysts show increased activity relative to catalysts prepared using support materials dehydrated at lower temperatures.
摘要翻译：公开了制备双金属催化剂的方法。所述方法包括提供负载的非金属茂催化剂的步骤，使非极性烃中负载的非金属茂催化剂的浆液与茂金属化合物和铝氧烷的溶液接触，并干燥该接触产物以获得负载的双金属催化剂。负载的非金属茂催化剂是通过在大于600℃的温度下脱水颗粒载体材料制备的，将脱水载体的浆料制备在非极性烃中，使该浆料与有机镁化合物和醇接触，使所得浆料与第4族或第5族过渡金属的非茂金属化合物接触，并干燥该接触产物，得到作为自由流动粉末的负载型非茂金属催化剂。相对于使用在较低温度下脱水的载体材料制备的催化剂，双金属催化剂显示出增加的活性。

2. 发明授权

US06420298B1 Metallocene catalyst compositions, processes for making polyolefin resins using such catalyst compositions, and products produced thereby 失效
标题翻译：茂金属催化剂组合物，使用这种催化剂组合物制备聚烯烃树脂的方法，以及由此制备的产品
公开(公告)号：US06420298B1
公开(公告)日：2002-07-16
申请号：US09387186
申请日：1999-08-31
申请人： Robert I. Mink , Thomas E. Nowlin , Sandra D. Schregenberger , Kenneth G. Schurzky , Pradeep P. Shirodkar
发明人： Robert I. Mink , Thomas E. Nowlin , Sandra D. Schregenberger , Kenneth G. Schurzky , Pradeep P. Shirodkar
IPC分类号： B01J3100
CPC分类号： C08F10/00 , C08F4/65912 , C08F4/65925 , C08F110/02 , Y10S526/943 , C08F2500/07 , C08F2500/12 , C08F2500/20 , C08F2500/26 , C08F4/65904 , C08F4/6546
摘要： A catalyst composition for the polymerization of one or more 1-olefins (e.g., ethylene) comprises a transition metal catalyst precursor and a cocatalyst, the transition metal catalyst precursor comprising a contact product of an unsubstituted metallocene compound and an aluminum alkyl compound in a hydrocarbon solvent solution. In another embodiment, the transition metal catalyst precursor is bimetallic and contains a non-metallocene transition metal catalyst component. When a bimetallic catalyst precursor is used, the resin product exhibits improved properties, and has a bimodal molecular weight distribution, long chain branching (LCB), and good bubble stability.
摘要翻译：用于聚合一种或多种1-烯烃（例如乙烯）的催化剂组合物包括过渡金属催化剂前体和助催化剂，所述过渡金属催化剂前体包含未取代的茂金属化合物与烷基铝化合物在烃中的接触产物溶剂溶液。在另一个实施方案中，过渡金属催化剂前体是双金属的并且含有非金属茂过渡金属催化剂组分。当使用双金属催化剂前体时，树脂产物具有改进的性能，并且具有双峰分子量分布，长链支化（LCB）和良好的气泡稳定性。

3. 发明授权

US4849389A Catalyst composition for polymerizing alpha-olefin polymers of narrow molecular weight distribution 失效
标题翻译：用于聚合窄分子量分布的α-烯烃聚合物的催化剂组合物
公开(公告)号：US4849389A
公开(公告)日：1989-07-18
申请号：US143989
申请日：1988-01-14
申请人： Thomas E. Nowlin , Kenneth G. Schurzky
发明人： Thomas E. Nowlin , Kenneth G. Schurzky
IPC分类号： C08F4/658 , C08F4/60 , C08F4/62 , C08F4/64 , C08F10/00
CPC分类号： C08F10/00
摘要： A supported alpha-olefin polymerization catalyst composition is synthesized by reacting (1) a slurry of a solid catalyst carrier in a non-polar solvent, e.g., hexane, with a dialkyl organomagnesium composition; (2) contacting the slurry of step (1) with a hydroxyl group-containing compound, e.g., an alcohol; (3) contacting the slurry of step (2) with at least one transition metal compound; (4) removing the non-polar solvent to obtain a dry-flowing powder; and, (5) activating the powder with trimethylaluminum. The resulting catalyst composition is extremely active in polymerizing C.sub.2 -C.sub.10 alpha-olefins and exhibits very good higher (C.sub.3 -C.sub.10) alpha-olefin incorporation properties.

4. 发明授权

US5093443A Alpha-olefins polymerization with chlorinated alcohol-containing catalyst composition 失效
标题翻译：用含氯化醇的催化剂组合物进行α-烯烃聚合
公开(公告)号：US5093443A
公开(公告)日：1992-03-03
申请号：US540961
申请日：1990-06-20
申请人： Thomas E. Nowlin , Kenneth G. Schurzky
发明人： Thomas E. Nowlin , Kenneth G. Schurzky
IPC分类号： C08F10/00
CPC分类号： C08F10/00
摘要： A supported alpha-olefin polymerization catalyst composition is synthesized by reacting (1) a slurry of a solid catalyst carrier in a non-polar solvent, e.g., hexane, with a dialkyl organomagnesium composition; (2) contacting the slurry of step (1) with a chlorinated alcohol; (3) contacting the slurry of step (2) with at least one transition metal compound; (4) removing the non-polar solvent to obtain a dry-flowing powder; and, (5) activating the powder with an activator. The resulting catalyst composition has high polymerization activity in the polymirazation of C.sub.2 -C.sub.10 alpha-olefins and exhibits very good higher (C.sub.3 -C.sub.10) alpha-olefin incorporation properties in the copolymerization of ethylene with the higher alpha-olefins.
摘要翻译：通过使（1）固体催化剂载体在非极性溶剂如己烷中的浆料与二烷基有机镁组合物反应来合成负载的α-烯烃聚合催化剂组合物; （2）使步骤（1）的浆料与氯化醇接触; （3）使步骤（2）的浆料与至少一种过渡金属化合物接触; （4）除去非极性溶剂得到干流粉末; 和（5）用活化剂活化粉末。所得催化剂组合物在C2-C10α-烯烃的聚酰胺化中具有高聚合活性，并且在乙烯与较高级α-烯烃的共聚合中表现出非常好的较高（C 3 -C 10）α-烯烃结合性能。

5. 发明授权

US4954470A Chlorinated alcohol-containing catalyst composition for polymerizing alpha-olefins 失效
标题翻译：用于聚合α-烯烃的含氯化醇的催化剂组合物
公开(公告)号：US4954470A
公开(公告)日：1990-09-04
申请号：US287214
申请日：1988-12-21
申请人： Thomas E. Nowlin , Kenneth G. Schurzky
发明人： Thomas E. Nowlin , Kenneth G. Schurzky
IPC分类号： C08F10/00
CPC分类号： C08F10/00
摘要： A supported alpha-olefin polymerization catalyst composition is synthesized by reacting (1) a slurry of a solid catalyst carrier in a non-polar solvent, e.g., hexane, with a dialkyl organomagnesium composition; (2) contacting the slurry of step (1) with a chlorinated alcohol; (3) contacting the slurry of step (2) with at least one transition metal compound; (4) removing the non-polar solvent to obtain a dry-flowing powder; and, (5) activating the powder with an activator. The resulting catalyst composition has high polymerization activity in the polymerization of C.sub.2 -C.sub.10 alpha-olefins and exhibits very good higher (C.sub.3 -C.sub.10) alpha-olefin incorporation properties in the copolymerization of ethylene with the higher alpha-olefins.
摘要翻译：通过使（1）固体催化剂载体在非极性溶剂如己烷中的浆料与二烷基有机镁组合物反应来合成负载的α-烯烃聚合催化剂组合物; （2）使步骤（1）的浆料与氯化醇接触; （3）使步骤（2）的浆料与至少一种过渡金属化合物接触; （4）除去非极性溶剂得到干流粉末; 和（5）用活化剂活化粉末。所得催化剂组合物在C2-C10α-烯烃的聚合中具有高聚合活性，并且在乙烯与较高级α-烯烃的共聚合中表现出非常好的较高（C 3 -C 10）α-烯烃结合性能。

6. 发明授权

US06410474B1 Process for controlling the MWD of a broad/bimodal resin in a single reactor 失效
标题翻译：在单个反应器中控制宽/双峰树脂的MWD的方法
公开(公告)号：US06410474B1
公开(公告)日：2002-06-25
申请号：US08814526
申请日：1997-03-10
申请人： Thomas E. Nowlin , Sandra D. Schregenberger , Pradeep P. Shirodkar , Grace O. Tsien
发明人： Thomas E. Nowlin , Sandra D. Schregenberger , Pradeep P. Shirodkar , Grace O. Tsien
IPC分类号： B01J3100
CPC分类号： B01J31/2295 , B01J31/122 , B01J31/128 , B01J31/143 , B01J31/1616 , B01J2531/46 , B01J2531/48 , B01J2531/49 , C08F4/65904 , C08F4/65912 , C08F4/65916 , C08F10/00 , Y02P20/588 , Y10S526/943
摘要： A make-up catalyst of at least one metallic component of a bimetallic catalyst component is used in conjunction with a bimetallic catalyst to control the proportion of weight fractions in broad or bimodal molecular weight distribution olefin resin product. The bimetallic catalyst which is formed with at least one metallocene of a transition metal, produces broad or bimodal molecular weight distribution polyolefin resin whose composition depends on the ratio of the concentration of the two catalyst components producing the HMW/LMW components. The make-up catalyst consisting of a single metal component is added in proportion necessary to make-up the deficiencies in the amount of the HMW/LMW component. The type of make-up catalyst added depends on whether increase of the HMW or LMW component produced by the bimetallic catalyst is sought.
摘要翻译：将双金属催化剂组分的至少一种金属组分的补充催化剂与双金属催化剂结合使用，以控制宽双模分子量分布烯烃树脂产物中重量分数的比例。由至少一种过渡金属茂金属形成的双金属催化剂产生广泛或双峰分子量分布聚烯烃树脂，其组成取决于产生HMW / LMW组分的两种催化剂组分的浓度比。由单一金属组分组成的补充催化剂以必要的比例加入以弥补HMW / LMW组分的量的不足。添加的补充催化剂的种类取决于是否寻求由双金属催化剂产生的HMW或LMW组分的增加。

7. 发明授权

US5939348A Catalyst for the manufacture of polythylene with a narrow molecular weight distribution 失效
标题翻译：用于制造具有窄分子量分布的聚乙烯的催化剂
公开(公告)号：US5939348A
公开(公告)日：1999-08-17
申请号：US779260
申请日：1996-12-12
申请人： Robert I. Mink , Thomas E. Nowlin
发明人： Robert I. Mink , Thomas E. Nowlin
IPC分类号： B01J31/12 , B01J31/14 , C08F4/44 , C08F4/654 , C08F10/00 , C08F4/656 , C08F10/02
CPC分类号： B01J31/128 , B01J31/122 , B01J31/143 , C08F10/00
摘要： An ethylene-alpha-olefin copolymerization catalyst is prepared by impregnating a porous support, such as silica, with a contact mixture of an organomagnesium compound such as dialkyl magnesium and a silane compound which is free of hydroxyl groups, such as tetraethyl orthosilicate. A transition metal component such as 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：通过用诸如二烷基镁的有机镁化合物和不含羟基的硅烷化合物如原硅酸四乙酯的接触混合物浸渍多孔载体如二氧化硅来制备乙烯-α-烯烃共聚催化剂。然后将过渡金属组分如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。

8. 发明授权

US5539076A Bimodal molecular weight distribution polyolefins 失效
标题翻译：双峰分子量分布聚烯烃
公开(公告)号：US5539076A
公开(公告)日：1996-07-23
申请号：US391373
申请日：1995-02-15
申请人： Thomas E. Nowlin , Sandra D. Schregenberger , Pradeep P. Shirodkar , Grace O. Tsien
发明人： Thomas E. Nowlin , Sandra D. Schregenberger , Pradeep P. Shirodkar , Grace O. Tsien
IPC分类号： C08J5/18 , B29C49/00 , C08F4/643 , C08F4/6592 , C08F10/02 , C08F210/16 , C08L23/04 , C08F210/02
CPC分类号： C08F10/02 , B29C47/0883 , C08L23/04 , B29C47/0021 , C08F210/16
摘要： Resins which are in situ catalytically produced blends of broad bimodal molecular weight distribution ethylene resin are produced. The resins of the invention are characterized by a blend of low molecular weight component and high molecular weight component with HMW component weight fraction which is greater than 0 (zero). Generally, the LMW/HMW weight fraction can be controlled within a very broad range. The resin has a molecular weight distribution, which is characterized as MFR or Mw/Mn. The bimodal molecular weight resins can be processed into films on existing equipment, and exhibit good processability in blown film production and provide film product of excellent FQR. The resin of the invention exhibits reduced tendency towards die-lip buildup and smoking in on-line operations.
摘要翻译：产生原位催化产生宽双峰分子量分布乙烯树脂的共混物的树脂。本发明的树脂的特征在于具有大于0（零）的HMW组分重量分数的低分子量组分和高分子量组分的共混物。通常，LMW / HMW重量分数可以在非常宽的范围内控制。树脂具有MFR或Mw / Mn的分子量分布。双峰分子量树脂可以在现有设备上加工成膜，并且在吹塑薄膜生产中表现出良好的加工性能，并提供优异的FQR薄膜产品。本发明的树脂在在线操作中表现出减少乳汁积聚和吸烟的倾向。

9. 发明授权

US5470812A High activity polyethylene catalysts prepared with alkoxysilane reagents 失效
标题翻译：用烷氧基硅烷试剂制备的高活性聚乙烯催化剂
公开(公告)号：US5470812A
公开(公告)日：1995-11-28
申请号：US151666
申请日：1993-11-15
申请人： Robert I. Mink , Thomas E. Nowlin
发明人： Robert I. Mink , Thomas E. Nowlin
IPC分类号： C08F4/658 , B01J31/02 , B01J31/12 , B01J31/14 , C08F4/614 , C08F4/618 , C08F10/02 , C08F210/00 , C08F210/16
CPC分类号： B01J31/14 , B01J31/0274 , B01J31/122 , B01J31/128 , B01J31/143 , B01J31/38 , C08F10/02 , C08F210/16 , Y02P20/52
摘要： An ethylene copolymerization catalyst is prepared by impregnating a porous support, such as silica, with an organomagnesium compound such as a magnesium alkyl and contacting the magnesium-containing support with a silane compound which is free of hydroxyl groups, such as a tetraalkyl orthosilicate, e.g. tetraethyl orthosilicate (TEOS). A transition metal component such as 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 which is effective for the production of ethylene copolymers.
摘要翻译：通过用诸如烷基镁的有机镁化合物浸渍多孔载体如二氧化硅制备乙烯共聚催化剂，并使含镁载体与不含羟基的硅烷化合物接触，例如原硅酸四烷基酯，例如四烷基硅酸盐。原硅酸四乙酯（TEOS）。然后将过渡金属组分如四氯化钛以与镁和硅烷组分的特定比例引入载体中。该催化剂前体与三烷基铝化合物的活化导致对生产乙烯共聚物有效的催化剂。

10. 发明授权

US5034483A Process for preparing high density, broad molecular weight distribution alpha-olefin polymers 失效
标题翻译：制备高密度，宽分子量分布的α-烯烃聚合物的方法
公开(公告)号：US5034483A
公开(公告)日：1991-07-23
申请号：US520160
申请日：1990-05-07
申请人： Nemesio D. Miro , Thomas E. Nowlin
发明人： Nemesio D. Miro , Thomas E. Nowlin
IPC分类号： C08F10/00
CPC分类号： C08F10/00
摘要： Broad molecular weight distribution, and high molecular weight olefin polymers, are prepared by polymerizing at least one olefin in the presence of a vanadium--and a titanium-containing catalyst composition. A catalyst precursor is synthesized by contacting a solid, porous carrier sequentially with a metal or a compound of a metal of Group IIB of the Periodic Chart of the Elements, e.g., a zinc compound, a halogen-containing aluminum compound, a vanadium compound and a titanium compound. The precursor is then combined with a suitable co-catalyst and a halogenating agent to produce the catalyst composition used to polymerize olefins.
摘要翻译：通过在钒和含钛催化剂组合物的存在下聚合至少一种烯烃制备宽分子量分布和高分子量烯烃聚合物。通过使固体多孔载体与元素周期表IIB族金属的金属或化合物顺序接触来合成催化剂前体，例如锌化合物，含卤素的铝化合物，钒化合物和钛化合物。然后将前体与合适的助催化剂和卤化剂组合以产生用于聚合烯烃的催化剂组合物。

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