公开(公告)号：US06194520B1

公开(公告)日：2001-02-27

申请号：US08083864

申请日：1993-06-28

申请人： Subrahmanyam Cheruvu ,  Thomas E. Nowlin ,  S. Christine Ong ,  Giyarpuram N. Prasad ,  Paul P. Tong

发明人： Subrahmanyam Cheruvu ,  Thomas E. Nowlin ,  S. Christine Ong ,  Giyarpuram N. Prasad ,  Paul P. Tong

IPC分类号： C08L2308

CPC分类号： C08L23/06 ,  B01J8/26 ,  B01J2219/0004 ,  C08F210/16 ,  C08F297/083 ,  C08L23/0815 ,  C08L2308/00 ,  C08L2314/02 ,  C08L2666/04 ,  C08F210/14 ,  C08F2500/12 ,  C08F2500/05 ,  C08F2500/26 ,  C08F2500/01 ,  C08F2500/18 ,  C08F2500/02

摘要： A class of relatively high molecular weight, high density ethylene polymer blends is disclosed capable of being blow molded with excellent processability into articles, e.g., bottles, of superior mechanical and other properties, such blends having a density of at least about 0.930 g/cc, a flow index (I21) of at least about 2 g/10 min., a melt flow ratio (MFR) of at least about 60, and a polydispersity index of at least about 8, the polymers of said blend consisting essentially of at least about 0.3 weight fraction of a relatively high molecular weight (HMW) component having a density of at least about 0.900 g/cc, a flow index or high load melt index (I21) of at least about 0.2 g/10 min., and a flow ratio (FR) at least about 10, and a relatively low molecular weight (LMW) component having a density of at least about 0.930 g/cc and a melt index (I2) no greater than about 1000 g/10 min.

摘要翻译： 公开了一类相对高分子量的高密度乙烯聚合物共混物，其能够以优异的加工性吹塑成具有优异的机械性能和其它性能的制品例如瓶，这种共混物的密度为至少约0.930g / cc ，至少约2g / 10min的流动指数（I 21），至少约60的熔体流动比（MFR）和至多约8的多分散指数，所述共混物的聚合物基本上由 至少约0.3重量份的密度为至少约0.900g / cc，流动指数或高负载熔体指数（I21）为至少约0.2g / 10min的相对高分子量（HMW）组分，以及 至少约10的流动比（FR）和至少约0.930g / cc的密度和不大于约1000g / 10min的熔体指数（I 2）的相对低分子量（LMW）组分。

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。

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。

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。

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。

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。

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。

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。

公开(公告)号：US5561091A

公开(公告)日：1996-10-01

申请号：US432879

申请日：1995-05-02

申请人： Robert I. Mink ,  Thomas E. Nowlin

发明人： Robert I. Mink ,  Thomas E. Nowlin

IPC分类号： C08F4/658 ,  C08F210/00 ,  C08F210/02 ,  C08F210/16 ,  C08F4/656

CPC分类号： C08F210/16 ,  Y02P20/52

摘要： A catalyst composition for producing linear low density polyethylene with relatively narrower molecular weight distributions is described. The catalyst is formed by treating silica having reactive OH groups with a dialkylmagnesium in a solvent for said dialkylmagnesium; then adding to said magnesium-containing support a mixture of ROH and SiCl.sub.4 to form an intermediate which is subsequently treated with a transition metal to form a transition metal-containing intermediate, the catalyst precursor. The catalyst precursor is activated with a trialkylaluminum compound.

摘要翻译： 描述了一种生产具有相对较窄分子量分布的线性低密度聚乙烯的催化剂组合物。 通过在二烷基镁的溶剂中用二烷基镁处理具有反应性OH基团的二氧化硅形成催化剂; 然后向所述含镁载体中加入ROH和SiCl 4的混合物以形成中间体，随后用过渡金属处理以形成含过渡金属的中间体催化剂前体。 催化剂前体用三烷基铝化合物活化。

公开(公告)号：US5336652A

公开(公告)日：1994-08-09

申请号：US788386

申请日：1991-11-06

申请人： Robert I. Mink ,  Thomas E. Nowlin

发明人： Robert I. Mink ,  Thomas E. Nowlin

IPC分类号： B01J31/02 ,  B01J31/12 ,  B01J31/14 ,  C08F4/614 ,  C08F4/618 ,  C08F10/02 ,  C08F210/16

CPC分类号： C08F10/02 ,  B01J31/0274 ,  B01J31/122 ,  B01J31/128 ,  B01J31/143 ,  B01J31/38 ,  C08F210/16 ,  Y02P20/52

摘要： There is disclosed a highly active catalyst composition for polymerizing alpha-olefins prepared by treating a support with an organomagnesium composition and contacting the thus formed solid support, containing magnesium, with a silane compound of the empirical formulaR.sup.1.sub.x SiR.sup.2.sub.ywherein Si is silicon atom; x is 1, 2, 3, or 4 and y is 0, 1, 2, or 3, provided that x+y is 4; R.sup.1 is R.sub.w --O-- wherein O is oxygen and R.sub.w is hydrocarbyl of 1 to 10 carbon atoms; and R.sup.2 is halogen or hydrocarbyl of 1 to 10 carbon atoms, or hydrogenand a transition metal compound, e.g., a tetravalent titanium compound. This catalyst is particularly useful for the production of linear low density polyethylene polymers. Also disclosed are methods of preparing polymers with the catalyst composition and the resulting polymers.

摘要翻译： 公开了一种用于聚合α-烯烃的高活性催化剂组合物，其通过用有机镁组合物处理载体并使如此形成的含镁的固体载体与经验式R 1 x Si R 2y的硅烷化合物接触而制备，其中Si是硅原子; x为1,2,3或4，y为0,1,2或3，条件是x + y为4; R1是Rw-O-，其中O是氧，Rw是1到10个碳原子的烃基; 并且R 2是卤素或具有1至10个碳原子的烃基，或氢和过渡金属化合物，例如四价钛化合物。 该催化剂特别可用于生产线性低密度聚乙烯聚合物。 还公开了使用催化剂组合物和所得聚合物制备聚合物的方法。