公开(公告)号：US06566450B2

公开(公告)日：2003-05-20

申请号：US10037934

申请日：2002-01-04

申请人： Guy Debras ,  Abbas Razavi ,  Jacques Michel

发明人： Guy Debras ,  Abbas Razavi ,  Jacques Michel

IPC分类号： C08L2300

CPC分类号： C08F210/16 ,  C08F4/65916 ,  C08F110/02 ,  C08L23/06 ,  C08L23/0815 ,  C08L2205/02 ,  C08L2205/025 ,  C08L2308/00 ,  C08L2314/02 ,  C08L2314/04 ,  C08L2314/06 ,  C08F4/65925 ,  C08F4/65927 ,  C08F2/001 ,  C08L2666/04 ,  C08F210/14 ,  C08F2500/01 ,  C08F2500/02 ,  C08F2500/13 ,  C08F2500/07 ,  C08F2500/12 ,  C08F2500/05 ,  C08F2500/08 ,  C08F4/24

摘要： A process for the preparation of polyethylene resins having a multimodal molecular weight distribution which comprises: (i) contacting ethylene monomer and a comonomer comprising an alpha-olefin having from 3 to 10 carbon atoms with a first catalyst system in a first reactor under first polymerization conditions to produce a first polyethylene having a first molecular weight, an HLMI of not more than 0.5 g/10 min and a first density of not more than 0.925 g/ml and the first catalyst system comprising (a) a metallocene catalyst comprising a bis tetrahydroindenyl compound of the general formula (IndH4)2R″MQ2 in which each Ind is the same or different and is indenyl or substituted indenyl, R″ is a bridge which comprises a C1-C20 alkylene radical, a dialkyl germanium or silicon or siloxane, or an alkyl phosphine or amine radical, which bridge is substituted or unsubstituted, M is a Group IVB transition metal or vanadium and each Q is hydrocarbyl having 1 to 20 carbon atoms or halogen; and (b) a cocatalyst which activates the catalyst component; (ii) providing a second polyethylene having a second lower molecular weight and second higher density than the first polyethylene, the second polyethylene having been produced using a catalyst other than the bis tetrahydroindenyl compound; and (iii) mixing together the first and second polyethylenes to form a polyethylene resin having a multimodal molecular weight distribution.

摘要翻译： 一种用于制备具有多峰分子量分布的聚乙烯树脂的方法，其包括：（i）在第一聚合反应器中，将第一催化剂体系中的乙烯单体和包含具有3-10个碳原子的α-烯烃的共聚单体与第一催化剂体系接触 制备具有第一分子量，HLMI不大于0.5g / 10min和第一密度不大于0.925g / ml的第一聚乙烯的第一催化剂体系，所述第一催化剂体系包含（a）茂金属催化剂，其包含双 四氢茚基化合物，其中每个Ind相同或不同，并且是茚基或取代的茚基，R“是包含C 1 -C 20亚烷基，二烷基锗或硅的桥，或 硅烷或烷基膦或胺基，该桥是取代或未取代的，M为ⅣB族过渡金属或钒，Q为具有1至20个碳原子的烃基或卤素; 和（b）活化催化剂组分的助催化剂;（ii）提供具有比第一聚乙烯低的第二较低分子量和第二高密度的第二聚乙烯，所述第二聚乙烯使用不同于所述双四氢茚基化合物的催化剂制备; 和（iii）将第一和第二聚乙烯混合在一起以形成具有多峰分子量分布的聚乙烯树脂。

公开(公告)号：US06380311B1

公开(公告)日：2002-04-30

申请号：US09424430

申请日：2000-02-07

申请人： Abbas Razavi ,  Guy Debras

发明人： Abbas Razavi ,  Guy Debras

IPC分类号： C08L2300

CPC分类号： C08F297/08 ,  C08F4/65912 ,  C08F4/65916 ,  C08F10/02 ,  C08F110/02 ,  C08F210/16 ,  C08L23/0815 ,  C08L2205/02 ,  C08L2308/00 ,  C08L2314/06 ,  C08F2/001 ,  C08F4/65927 ,  C08L2666/04 ,  C08F2500/12 ,  C08F2500/07 ,  C08F210/14

摘要： A process for the preparation of polyolefins having a bi- or multimodal molecular weight distribution, the process comprising the steps of: (i) contacting an olefin monomer and a first co-reactant with a catalyst system in a first reaction zone under first polymerization conditions to produce a product comprising a first polyolefin having a first molecular weight distribution; and (ii) contacting an olefin monomer and a second co-reactant with a catalyst system in a second reaction zone under second polymerization conditions to produce a product comprising a second polyolefin having a second molecular weight distribution different from the first molecular weight distribution; wherein the first and second polyolefins are mixed together, wherein one of the co-reactants is hydrogen and the other is a comonomer selected from butene, methylpentene, hexene or octene, and wherein each catalyst system comprises (a) a metallocene catalyst component comprising a bis tetrahydroindenly compound of the general formula (IndH4)2R″MQ2 in which each Ind is the same or different and is indenyl or substituted indenyl, R″ is a bridge which comprises a C1-C4 alkylene radical, a dialkly mernamium or silicon or siloxane, or an alkyl phosphine or amine radical, which bridge is substitued or unsubstituted, M is a Group IV metal or vanadium and each Q is hydrocarbyl having 1 to 20 carbon atoms or halogen; and (b) a cocatalyst which activates the catalyst component.

摘要翻译： 一种制备具有双峰或多峰分子量分布的聚烯烃的方法，所述方法包括以下步骤：（i）在第一聚合条件下在第一反应区中使烯烃单体和第一共反应物与催化剂体系接触 以产生包含具有第一分子量分布的第一聚烯烃的产品; 和（ii）在第二聚合条件下在第二反应区中使烯烃单体和第二共反应物与第二反应区接触以产生包含具有不同于第一分子量分布的第二分子量分布的第二聚烯烃的产物; 其中所述第一和第二聚烯烃混合在一起，其中所述共反应物之一是氢，另一个是选自丁烯，甲基戊烯，己烯或辛烯的共聚单体，并且其中每个催化剂体系包含（a）茂金属催化剂组分， （IndH4）2R''MQ2的双四氢茚基化合物，其中每个Ind相同或不同，并且是茚基或取代的茚基，R“是包含C 1 -C 4亚烷基，双键或三聚氰基的桥 或硅烷，或烷基膦或胺基，所述桥被取代或未被取代，M是第Ⅳ族金属或钒，并且每个Q是具有1至20个碳原子的烃基或卤素; 和（b）活化催化剂组分的助催化剂。

公开(公告)号：US06346575B1

公开(公告)日：2002-02-12

申请号：US09405369

申请日：1999-09-24

申请人： Guy Debras ,  Abbas Razavi ,  Jacques Michel

发明人： Guy Debras ,  Abbas Razavi ,  Jacques Michel

IPC分类号： C08L2300

CPC分类号： C08F210/16 ,  C08F4/65916 ,  C08F110/02 ,  C08L23/06 ,  C08L23/0815 ,  C08L2205/02 ,  C08L2205/025 ,  C08L2308/00 ,  C08L2314/02 ,  C08L2314/04 ,  C08L2314/06 ,  C08F4/65925 ,  C08F4/65927 ,  C08F2/001 ,  C08L2666/04 ,  C08F210/14 ,  C08F2500/01 ,  C08F2500/02 ,  C08F2500/13 ,  C08F2500/07 ,  C08F2500/12 ,  C08F2500/05 ,  C08F2500/08 ,  C08F4/24

摘要： A process for the preparation of polyethylene resins having a multimodal molecular weight distribution which comprises: (i) contacting ethylene monomer and a comonomer comprising an alpha-olefin having from 3 to 10 carbon atoms with a first catalyst system in a first reactor under first polymerisation conditions to produce a first polyethylene having a first molecular weight, an HLMI of not more than 0.5 g/10 min and a first density of not more than 0.925 g/ml and the first catalyst system comprising (a) a metallocene catalyst comprising a bis tetrahydroindenyl compound of the general formula (IndH4)2R″MQ2 in which each Ind is the same or different and is indenyl or substituted indenyl, R″ is a bridge which comprises a C1-C20 alkylene radical, a dialkyl germanium or silicon or siloxane, or an alkyl phosphine or amine radical, which bridge is substituted or unsubstituted, M is a Group IVB transition metal or vanadium and each Q is hydrocarbyl having 1 to 20 carbon atoms or halogen; and (b) a cocatalyst which activates the catalyst component; (ii) providing a second polyethylene having a second lower molecular weight and second higher density than the first polyethylene, the second polyethylene having been produced using a catalyst other than the bis tetrahydroindenyl compound; and (iii) mixing together the first and second polyethylenes to form a polyethylene resin having a multimodal molecular weight distribution.

摘要翻译： 一种制备具有多峰分子量分布的聚乙烯树脂的方法，其包括：（i）在第一聚合反应器的第一反应器中使乙烯单体和包含具有3-10个碳原子的α-烯烃的共聚单体与第一催化剂体系接触 制备具有第一分子量，HLMI不大于0.5g / 10min和第一密度不大于0.925g / ml的第一聚乙烯的第一催化剂体系，所述第一催化剂体系包含（a）茂金属催化剂，其包含双 四氢茚基化合物，其中每个Ind相同或不同，并且是茚基或取代的茚基，R“是包含C 1 -C 20亚烷基，二烷基锗或硅的桥，或 硅烷或烷基膦或胺基，该桥是取代或未取代的，M为ⅣB族过渡金属或钒，Q为具有1至20个碳原子的烃基或卤素; 和（b）活化催化剂组分的助催化剂;（ii）提供具有比第一聚乙烯低的第二较低分子量和第二高密度的第二聚乙烯，所述第二聚乙烯使用不同于所述双四氢茚基化合物的催化剂制备; 和（iii）将第一和第二聚乙烯混合在一起以形成具有多峰分子量分布的聚乙烯树脂。

公开(公告)号：US06218472B1

公开(公告)日：2001-04-17

申请号：US09404773

申请日：1999-09-24

申请人： Guy Debras ,  Abbas Razavi ,  Jacques Michel

发明人： Guy Debras ,  Abbas Razavi ,  Jacques Michel

IPC分类号： G08F2300

CPC分类号： C08L23/0815 ,  C08F110/02 ,  C08F210/16 ,  C08L2205/02 ,  C08L2314/02 ,  C08L2314/06 ,  C08L2666/04 ,  C08F2500/07 ,  C08F2500/12 ,  C08F210/14 ,  C08F2500/05

摘要： A process for the preparation of polyethylene resins having a multimodal molecular weight distribution which comprises: (i) contacting ethylene monomer and a comonomer comprising an alpha-olefin having from 3 to 10 carbon atoms with a first catalyst system in a first reactor under first polymerization conditions in a slurry process to produce a first polyethylene having a first molecular weight an HLMI of not more than 0.5 g/10 min and a first density of not more than 0.925 g/ml and the first catalyst system comprising (a) a first metallocene catalyst of general formula R″(CpRm)(Cp′R′n)MQ2, wherein Cp is a cyclopentadienyl moiety, Cp′ is a substituted or unsubstituted fluorenyl ring; each R is independently hydrogen or hydrocarbyl having 1 to 20 carbon atoms in which 0≦m≦4; each R′ is independently hydrocarbyl having 1 to 20 carbon atoms in which 0≦n≦8, R″ is a bridge which comprises a C1-C20alkylene radical, a dialkyl germanium or silicon or siloxane, or an alkyl phosphine or amine radical, which bridge is substituted or unsubstituted, M is a Group IVB transition metal or vanadium and each Q is hydrocarbyl having 1 to 20 carbon atoms or halogen, the metallocene catalyst a centroid-M-centroid angle in the range 105° to 125°; and (b) a cocatalyst which activates the catalyst component; (ii) providing a second polyethylene having a second lower molecular weight and higher density than the first polyethylene; and (iii) mixing together the first and second polyethylenes to form a polyethylene resin having a multimodal molecular weight distribution.

摘要翻译： 一种用于制备具有多峰分子量分布的聚乙烯树脂的方法，其包括：（i）在第一聚合反应器中，将第一催化剂体系中的乙烯单体和包含具有3-10个碳原子的α-烯烃的共聚单体与第一催化剂体系接触 制备浆料方法中的条件以产生具有不大于0.5g / 10min的HLMI的第一分子量和不大于0.925g / ml的第一密度的第一分子量的第一聚乙烯，并且所述第一催化剂体系包含（a）第一茂金属 通式R“（CpRm）（Cp'R'n）MQ2的催化剂，其中Cp是环戊二烯基部分，Cp'是取代或未取代的芴基环; 每个R独立地是氢或具有1至20个碳原子的烃基，其中0≤m≤4; 每个R'独立地是具有1至20个碳原子的烃基，其中0 <= n <8，R“是包含C 1 -C 20亚烷基，二烷基锗或硅或硅氧烷或烷基膦或胺的桥 自由基，该桥是取代或未取代的，M是ⅣB族过渡金属或钒，Q是具有1至20个碳原子的烃基或卤素，茂金属催化剂在105°至125°范围内的重心M-心形角 ; 和（b）活化催化剂组分的助催化剂;（ii）提供具有比第一聚乙烯更低的第二分子量和更高密度的第二聚乙烯; 和（iii）将第一和第二聚乙烯混合在一起以形成具有多峰分子量分布的聚乙烯树脂。

公开(公告)号：US06218330B1

公开(公告)日：2001-04-17

申请号：US09296034

申请日：1999-04-21

申请人： Abbas Razavi ,  Guy Debras

发明人： Abbas Razavi ,  Guy Debras

IPC分类号： B01J3100

CPC分类号： B01J31/143 ,  B01J31/2295 ,  B01J2531/48 ,  B01J2531/49 ,  C08F4/65912 ,  C08F4/65927 ,  C08F10/00 ,  C08F110/02 ,  C08F110/06 ,  C08F210/16 ,  Y10S526/943 ,  C08F4/65916 ,  C08F2500/12 ,  C08F2500/18 ,  C08F210/14

摘要： A process for the preparation of supported metallocene-alumoxane catalysts comprising the steps of: a) reacting a metallocene with an alumoxane at a temperature comprised between 15 and 50° C., b) recovering a mixture comprising an alkylmetallocenium cation and an anionic alumoxane oligomer, c) reacting said mixture with a support, and d) recovering a supported metallocene-alumoxane catalyst as a dry solid, the reaction with the support being carried out at a temperature comprised between 85° C. and 110° C., preferably between 90 and 130° C., and their use for the polymerization or copolymerization of olefins.

摘要翻译： 一种制备负载型茂金属 - 铝氧烷催化剂的方法，包括以下步骤：a）在15-50℃的温度下使茂金属与铝氧烷反应，b）回收包含烷基金属茂阳离子和阴离子铝氧烷低聚物 c）使所述混合物与载体反应，和d）回收作为干固体的负载型茂金属 - 铝氧烷催化剂，与载体的反应在85℃至110℃之间，优选在90℃ 和130℃，以及它们用于烯烃聚合或共聚的用途。

公开(公告)号：US06479589B2

公开(公告)日：2002-11-12

申请号：US10037504

申请日：2002-01-04

申请人： Guy Debras ,  Abbas Razavi ,  Jacques Michel

发明人： Guy Debras ,  Abbas Razavi ,  Jacques Michel

IPC分类号： C08L2300

CPC分类号： C08F210/16 ,  C08F4/65916 ,  C08F110/02 ,  C08L23/06 ,  C08L23/0815 ,  C08L2205/02 ,  C08L2205/025 ,  C08L2308/00 ,  C08L2314/02 ,  C08L2314/04 ,  C08L2314/06 ,  C08F4/65925 ,  C08F4/65927 ,  C08F2/001 ,  C08L2666/04 ,  C08F210/14 ,  C08F2500/01 ,  C08F2500/02 ,  C08F2500/13 ,  C08F2500/07 ,  C08F2500/12 ,  C08F2500/05 ,  C08F2500/08 ,  C08F4/24

摘要： A process for preparing polyethylene, including contacting ethylene monomer and an alpha-olefin comonomer to produce a first polyethylene (HLMI of ≦0.5 g/10 min, density ≦0.925 g/ml). The a catalyst system is a bis tetrahydroindenyl formula (IndH4)2R″MQ2 wherein each Ind is the same or different and is indenyl or substituted indenyl, R″ is a bridge which comprises a C1-C20 alkylene radical, a dialkyl germanium or silicon or siloxane, or an alkyl phosphine or amine radical, which bridge is substituted or unsubstituted, M is a Group IVB transition metal or vanadium and each Q is hydrocarbyl having 1 to 20 carbon atoms or halogen. The polyethylene resin having multimodal molecular weight distribution is formed by mixing the first polyethylene with a second polyethylene (produced with a different catalyst and with a lower molecular weight and higher density than the first polyethylene).

摘要翻译： 一种制备聚乙烯的方法，包括使乙烯单体和α-烯烃共聚单体接触以制备第一种聚乙烯（HLMI <= 0.5g / 10min，密度<= 0.925g / ml）。 该催化剂体系是双四氢茚基配基（IndH4）2R''MQ2，其中每个Ind相同或不同，并且是茚基或取代的茚基，R“是包含C 1 -C 20亚烷基，二烷基锗或 硅或硅氧烷，或烷基膦或胺基，该桥是取代或未取代的，M为ⅣB族过渡金属或钒，Q为具有1至20个碳原子的烃基或卤素。 具有多峰分子量分布的聚乙烯树脂通过将第一聚乙烯与第二聚乙烯（用不同的催化剂制得，分子量低于第一聚乙烯的密度较低）混合形成。

公开(公告)号：US08940815B2

公开(公告)日：2015-01-27

申请号：US12674704

申请日：2008-08-25

申请人： Guy Debras ,  Romain Luijkx

发明人： Guy Debras ,  Romain Luijkx

IPC分类号： B82Y30/00 ,  C08J3/22 ,  C08K3/04 ,  C08L23/02 ,  C08L67/04 ,  H01B1/24 ,  C08J5/00 ,  C09K5/14 ,  C08K7/24 ,  C08L23/10 ,  H01B3/44

CPC分类号： C09K5/14 ,  B82Y30/00 ,  C08J3/226 ,  C08J5/005 ,  C08J2323/02 ,  C08J2367/04 ,  C08J2467/00 ,  C08K7/06 ,  C08K7/24 ,  C08K2201/011 ,  C08L23/02 ,  C08L23/10 ,  C08L67/04 ,  C08L2203/12 ,  C08L2314/06 ,  C08L2666/18 ,  H01B1/24 ,  H01B3/441 ,  Y10S977/742 ,  C08L67/00

摘要： A resin composition comprising a polyolefin, carbon nanotubes and poly(hydroxy carboxylic acid). The invention also covers a process for preparing a resin composition comprising a polyolefin, carbon nanotubes and poly(hydroxy carboxylic acid) by (i) blending a poly(hydroxy carboxylic acid) with carbon nanotubes to form a composite (ii) blending the composite with a polyolefin. The use of poly(hydroxy carboxylic acids) as a compatibilizer to blend carbon nanotubes into polyolefins is also claimed.

摘要翻译： 一种树脂组合物，其包含聚烯烃，碳纳米管和聚（羟基羧酸）。 本发明还涉及通过（i）将聚（羟基羧酸）与碳纳米管共混以形成复合材料（ii）将该复合物与 聚烯烃 还要求使用聚（羟基羧酸）作为增容剂将碳纳米管混合成聚烯烃。

公开(公告)号：US06489428B1

公开(公告)日：2002-12-03

申请号：US09712462

申请日：2000-11-14

申请人： Guy Debras ,  Jean-Pierre Dath

发明人： Guy Debras ,  Jean-Pierre Dath

IPC分类号： C08F11002

CPC分类号： C08F10/00 ,  C08F210/16 ,  Y02P20/52 ,  C08F210/14 ,  C08F2500/07 ,  C08F2500/12 ,  C08F2500/17 ,  C08F2500/04 ,  C08F2500/13 ,  C08F4/025 ,  C08F4/22 ,  C08F4/69146

摘要： The present invention relates to a supported chromium-based catalyst titanated under specific conditions and used for the homopolymerisation or the copolymerisation of ethylene. The polyethylene obtained with this catalyst has high shear resirance and environmental stress crack resistance, and can be used for manufacturing films with improved tear properties.

摘要翻译： 本发明涉及在特定条件下钛酸化并用于乙烯的均聚或共聚的负载型铬基催化剂。 用该催化剂得到的聚乙烯具有高剪切抗拉性和耐环境应力开裂性，可用于制造具有改进的撕裂性能的膜。

公开(公告)号：US06245869B1

公开(公告)日：2001-06-12

申请号：US09344193

申请日：1999-06-24

申请人： Guy Debras ,  Philippe Bodart

发明人： Guy Debras ,  Philippe Bodart

IPC分类号： C08F424

CPC分类号： C08F210/16 ,  C08F4/69 ,  C08F210/14 ,  C08F2500/12 ,  C08F2500/19 ,  C08F2500/04

摘要： A process for producing medium density polyethylene by copolymerizing ethylene and an alpha-olefinic comonomer comprising from 3 to 10 carbon atoms in the presence of a chromium-based catalyst having a support comprising silica and titania, the catalyst being fluorinated and having been chemically reduced by carbon monoxide, and in the presence of a co-catalyst selected from at least one of an aluminum alkyl and a zinc alkyl to produce a polyethylene copolymer having a density of from 0.930 to 0.945 g/cc and a dispersion index (D) of from 9 to 13.

摘要翻译： 一种通过在含有二氧化硅和二氧化钛的载体的铬基催化剂存在下共聚乙烯和含有3-10个碳原子的α-烯烃共聚单体来生产中密度聚乙烯的方法，该催化剂被氟化并且被化学还原 一氧化碳，并且在选自烷基铝和烷基锌中的至少一种的助催化剂存在下，制备密度为0.930至0.945g / cc的聚乙烯共聚物和分散指数（D）为 9至13。

公开(公告)号：US06245866B1

公开(公告)日：2001-06-12

申请号：US09484481

申请日：2000-01-18

申请人： Guy Debras

发明人： Guy Debras

IPC分类号： C08F200

CPC分类号： C08F210/16 ,  B01J8/24 ,  B01J19/242 ,  B01J19/2435 ,  Y10S526/901 ,  Y10S526/904 ,  C08F4/22 ,  C08F4/69

摘要： A process of producing polyethylene, the process comprising copolymerizing ethylene and an alpha-olefinic comonomer comprising from 3 to 8 carbon atoms in the presence of a chromium-based catalyst in a main polymerization reactor and, in a gas-phase preliminary reactor upstream of the main polymerization reactor, chemically treating the chromium-based catalyst with at least one treatment agent prior to introduction of the catalyst into the main polymerization reactor and releasing from the preliminary reactor waste gases produced during the chemical treatment. An apparatus for producing polyethylene, the apparatus comprising a main reactor having an inlet for receiving gaseous olefin monomer and an outlet for outputting polyethylene, and a preliminary reactor connected to a second inlet of the main reactor, the preliminary reactor being arranged to be operable in the gas phase and having at least one respective inlet for receiving a solid catalyst and at least one treatment agent and a respective outlet for releasing waste gases from the preliminary reactor.

摘要翻译： 一种生产聚乙烯的方法，该方法包括在主聚合反应器中的铬基催化剂存在下，在乙烯和含有3-8个碳原子的α-烯烃共聚单体之间共聚，在气相预备反应器 主要聚合反应器，在将催化剂引入主聚合反应器之前用至少一种处理剂对铬基催化剂进行化学处理，并从预处理反应器中释放在化学处理期间产生的废气。 一种用于生产聚乙烯的设备，该设备包括具有用于接收气态烯烃单体的入口和用于输出聚乙烯的出口的主反应器，以及连接到主反应器的第二入口的预反应器，该预反应器被设置为可操作 气相，并具有用于接收固体催化剂的至少一个相应的入口和至少一个处理剂和用于从预备反应器释放废气的相应出口。