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    Catalysts and methods of use thereof to produce vinyl terminated polymers
    1.
    发明授权
    Catalysts and methods of use thereof to produce vinyl terminated polymers 有权
    催化剂及其制备乙烯基封端聚合物的方法

    公开(公告)号：US08455597B2

    公开(公告)日：2013-06-04

    申请号：US13072280

    申请日：2011-03-25

    申请人： Donna J. Crowther ,  Patrick Brant ,  Carlos U. De Gracia ,  Jacqueline A. Lovell

    发明人： Donna J. Crowther ,  Patrick Brant ,  Carlos U. De Gracia ,  Jacqueline A. Lovell

    IPC分类号： C08F4/6592 ,  C08F4/643 ,  C08F110/06 ,  B01J31/22

    CPC分类号： C08F4/65912 ,  B01J31/12 ,  B01J31/14 ,  B01J31/2295 ,  B01J2531/48 ,  B01J2531/49 ,  C08F4/16 ,  C08F4/65908 ,  C08F4/6592 ,  C08F4/76 ,  C08F110/06 ,  C08F210/06 ,  Y10S526/943 ,  C08F210/16 ,  C08F2500/03 ,  C08F10/06 ,  C08F4/65927

    摘要： This invention relates to a homogenous process for making a vinyl terminated propylene polymer, wherein the process comprises: contacting, propylene, under polymerization conditions, with a catalyst system comprising an activator and at least one metallocene compound, where the metallocene compound is represented by the formula: where: M is hafnium or zirconium; each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system); each R1 is, independently, a C1 to C10 alkyl group; each R2 is, independently, a C1 to C10 alkyl group; each R3 is, independently, hydrogen; each R4, R5, and R6, is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group; T is a bridging group; each R7 is, independently, hydrogen, halogen, or a C1 to C20 hydrocarbyl, and two R7 can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system; and further provided that any of adjacent R4, R5, and R6 groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated.

    摘要翻译： 本发明涉及一种用于制备乙烯基封端的丙烯聚合物的均匀方法，其中该方法包括：在聚合条件下使丙烯与包含活化剂和至少一种金属茂化合物的催化剂体系接触，其中茂金属化合物由 式：其中：M是铪或锆; 每个X独立地选自具有1至20个碳原子的烃基，氢化物，酰胺，醇盐，硫化物，磷化物，卤化物，二烯，胺，膦，醚及其组合（两个X的 可形成稠环或环系的一部分）; 每个R 1独立地为C 1至C 10烷基; 每个R 2独立地为C 1至C 10烷基; 每个R 3独立地是氢; 每个R 4，R 5和R 6独立地是氢或取代或未取代的烃基，含杂原子或杂原子的基团; T是一个桥接组; 每个R 7独立地是氢，卤素或C 1至C 20烃基，并且两个R 7可以形成包括芳族，部分饱和或饱和的环状或稠环体系的环状结构; 并且进一步规定相邻的R 4，R 5和R 6基团中的任何一个可以形成稠合环或多中心稠环体系，其中所述环可以是芳族的，部分饱和的或饱和的。

    Heterogeneous in-reactor polymer blends
    2.
    发明授权
    Heterogeneous in-reactor polymer blends 有权
    不均匀的反应器内聚合物共混物

    公开(公告)号：US08106127B2

    公开(公告)日：2012-01-31

    申请号：US12638861

    申请日：2009-12-15

    申请人： Carlos U. De Gracia ,  Kevin R. Squire ,  Peijun Jiang ,  Armenag H. Dekmezian ,  Beverly J. Poole ,  Cesar A. Garcia-Franco

    发明人： Carlos U. De Gracia ,  Kevin R. Squire ,  Peijun Jiang ,  Armenag H. Dekmezian ,  Beverly J. Poole ,  Cesar A. Garcia-Franco

    IPC分类号： C08F8/00 ,  C08L23/04 ,  C08L23/10 ,  C08K5/00

    CPC分类号： C08L23/16 ,  C08L23/12 ,  C08L2314/06 ,  C08L2666/06

    摘要： An in-reactor polymer blend comprises (a) a propylene-containing first polymer; and (b) an ethylene-containing second polymer such that the polymer blend comprises between about 50 wt % and about 80 wt % units derived from ethylene and between about 50 wt % and about 20 wt % units derived from propylene. The blend is substantially free of dienes and the content of ethylene in the second polymer in the form of ethylene-ethylene-ethylene triads is at least 40%. The second polymer contains at least 0.1 branch having 8 or more carbon atoms per 10,000 carbons. In addition, the blend has a strain hardening index of at least 1.8, a shear thinning slope in the plot of log(dynamic viscosity) versus log(frequency) of less than −0.2 and exhibits at least two peaks when subjected to Differential Scanning Calorimetry (first melt) corresponding to a first melting point of at least 150° C. and a second melting point of at least 40° C. such that the difference between the first and second melting temperatures is at least 20° C.

    摘要翻译： 反应器内聚合物共混物包含（a）含丙烯的第一聚合物; 和（b）含乙烯的第二聚合物，使得聚合物共混物包含衍生自乙烯的约50重量％至约80重量％的单元和衍生自丙烯的约50重量％至约20重量％的单元。 共混物基本上不含二烯，乙烯 - 乙烯 - 乙烯三单元组形式的第二聚合物中的乙烯含量至少为40％。 第二聚合物含有至少0.1个分支，每10,000个碳原子具有8个或更多个碳原子。 此外，共混物的应变硬化指数为至少1.8，对数（动态粘度）对log（频率）的曲线图中的剪切变稀斜率小于-0.2，并且当进行差示扫描量热法时显示出至少两个峰 （第一熔体），其对应于至少150℃的第一熔点和至少40℃的第二熔点，使得第一和第二熔融温度之间的差异为至少20℃。

    Novel Catalysts And Methods Of Use Thereof To Produce Vinyl Terminated Polymers
    4.
    发明申请
    Novel Catalysts And Methods Of Use Thereof To Produce Vinyl Terminated Polymers 有权
    新型催化剂及其使用方法生产乙烯基封端的聚合物

    公开(公告)号：US20120245311A1

    公开(公告)日：2012-09-27

    申请号：US13072280

    申请日：2011-03-25

    申请人： Donna J. Crowther ,  Patrick Brant ,  Carlos U. De Gracia ,  Jacqueline A. Lovell

    发明人： Donna J. Crowther ,  Patrick Brant ,  Carlos U. De Gracia ,  Jacqueline A. Lovell

    IPC分类号： C08F4/16 ,  B01J31/14 ,  B01J31/12

    CPC分类号： C08F4/65912 ,  B01J31/12 ,  B01J31/14 ,  B01J31/2295 ,  B01J2531/48 ,  B01J2531/49 ,  C08F4/16 ,  C08F4/65908 ,  C08F4/6592 ,  C08F4/76 ,  C08F110/06 ,  C08F210/06 ,  Y10S526/943 ,  C08F210/16 ,  C08F2500/03 ,  C08F10/06 ,  C08F4/65927

    摘要： This invention relates to a homogenous process for making a vinyl terminated propylene polymer, wherein the process comprises: contacting, propylene, under polymerization conditions, with a catalyst system comprising an activator and at least one metallocene compound, where the metallocene compound is represented by the formula: where: M is hafnium or zirconium; each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system); each R1 is, independently, a C1 to C10 alkyl group; each R2 is, independently, a C1 to C10 alkyl group; each R3 is, independently, hydrogen; each R4, R5, and R6, is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group; T is a bridging group; each R7 is, independently, hydrogen, halogen, or a C1 to C20 hydrocarbyl, and two R7 can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system; and further provided that any of adjacent R4, R5, and R6 groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated.

    摘要翻译： 本发明涉及一种用于制备乙烯基封端的丙烯聚合物的均匀方法，其中该方法包括：在聚合条件下使丙烯与包含活化剂和至少一种金属茂化合物的催化剂体系接触，其中茂金属化合物由 式：其中：M是铪或锆; 每个X独立地选自具有1至20个碳原子的烃基，氢化物，酰胺，醇盐，硫化物，磷化物，卤化物，二烯，胺，膦，醚及其组合（两个X的 可形成稠环或环系的一部分）; 每个R 1独立地为C 1至C 10烷基; 每个R 2独立地为C 1至C 10烷基; 每个R 3独立地是氢; 每个R 4，R 5和R 6独立地是氢或取代或未取代的烃基，含杂原子或杂原子的基团; T是一个桥接组; 每个R 7独立地是氢，卤素或C 1至C 20烃基，并且两个R 7可以形成包括芳族，部分饱和或饱和的环状或稠环体系的环状结构; 并且进一步规定相邻的R 4，R 5和R 6基团中的任何一个可以形成稠合环或多中心稠环体系，其中所述环可以是芳族的，部分饱和的或饱和的。

    Heterogeneous In-Reactor Polymer Blends
    5.
    发明申请
    Heterogeneous In-Reactor Polymer Blends 有权
    非均相反应器聚合物共混物

    公开(公告)号：US20100152390A1

    公开(公告)日：2010-06-17

    申请号：US12638861

    申请日：2009-12-15

    申请人： Carlos U. De Gracia ,  Kevin R. Squire ,  Peijun Jiang ,  Armenag H. Dekmezian ,  Beverly J. Poole ,  Cesar A. Garcia-Franco

    发明人： Carlos U. De Gracia ,  Kevin R. Squire ,  Peijun Jiang ,  Armenag H. Dekmezian ,  Beverly J. Poole ,  Cesar A. Garcia-Franco

    IPC分类号： C08L23/06

    CPC分类号： C08L23/16 ,  C08L23/12 ,  C08L2314/06 ,  C08L2666/06

    摘要： An in-reactor polymer blend comprises (a) a propylene-containing first polymer; and (b) an ethylene-containing second polymer such that the polymer blend comprises between about 50 wt % and about 80 wt % units derived from ethylene and between about 50 wt % and about 20 wt % units derived from propylene. The blend is substantially free of dienes and the content of ethylene in the second polymer in the form of ethylene-ethylene-ethylene triads is at least 40%. The second polymer contains at least 0.1 branch having 8 or more carbon atoms per 10,000 carbons. In addition, the blend has a strain hardening index of at least 1.8, a shear thinning slope in the plot of log(dynamic viscosity) versus log(frequency) of less than −0.2 and exhibits at least two peaks when subjected to Differential Scanning Calorimetry (first melt) corresponding to a first melting point of at least 150° C. and a second melting point of at least 40° C. such that the difference between the first and second melting temperatures is at least 20° C.

    摘要翻译： 反应器内聚合物共混物包含（a）含丙烯的第一聚合物; 和（b）含乙烯的第二聚合物，使得聚合物共混物包含衍生自乙烯的约50重量％至约80重量％的单元和衍生自丙烯的约50重量％至约20重量％的单元。 共混物基本上不含二烯，乙烯 - 乙烯 - 乙烯三单元组形式的第二聚合物中的乙烯含量至少为40％。 第二聚合物含有至少0.1个分支，每10,000个碳原子具有8个或更多个碳原子。 此外，共混物的应变硬化指数为至少1.8，对数（动态粘度）对log（频率）的曲线图中的剪切变稀斜率小于-0.2，并且当进行差示扫描量热法时显示出至少两个峰 （第一熔体），其对应于至少150℃的第一熔点和至少40℃的第二熔点，使得第一和第二熔融温度之间的差异为至少20℃。

    Process to produce ethylene propylene copolymers
    6.
    发明授权
    Process to produce ethylene propylene copolymers 有权
    生产乙烯丙烯共聚物的方法

    公开(公告)号：US09382361B2

    公开(公告)日：2016-07-05

    申请号：US14640871

    申请日：2015-03-06

    申请人： Daniel Bilbao ,  Jeffrey L. Brinen ,  Carlos U. De Gracia ,  Henry Dong

    发明人： Daniel Bilbao ,  Jeffrey L. Brinen ,  Carlos U. De Gracia ,  Henry Dong

    IPC分类号： C08F210/18 ,  C08F4/643 ,  C08F4/653 ,  C08F4/6592 ,  C08F4/659

    CPC分类号： C08F210/18 ,  C08F4/65904 ,  C08F4/65908 ,  C08F4/6592 ,  C08F210/06 ,  C08F236/20 ,  C08F2500/25 ,  C08F2500/03 ,  C08F2500/17 ,  C08F4/65927

    摘要： This invention relates to a copolymer prepared using two or more non-coordinating anion activators comprising a first C2 to C12 alpha olefin (such as ethylene), a second C3 to C12 alpha olefin (such as propylene) different from the first alpha olefin, and diene (such as ethylidene norbornene and/or vinyl norbornene), where the polymer has: a) first alpha olefin (ethylene) content of 35 to 90 mol %; b) second alpha olefin (propylene) content of 9.8 to 64.8 mol %; c) diene content of 0.2 to 5 mol %; d) a branching index g′ave of 0.95 or more; e) a complex viscosity ratio (eta*(0.01 rad/s)/eta*(100 rad/s), at 125° C.) greater than 1.1*Y0, where Y0=Y1+{[(Y2−Y1)/(X2−X1)](X0−X1)}, where X0 is the wt % of a first non-coordinating anion activator, NCA1, used to prepare the copolymer (based upon weight of NCA1 and a second non-coordinating anion activator, NCA2, used to prepare the copolymer), X1=0, X2=100, Y1=complex viscosity ratio of polymer made with 100% NCA1 and 0% NCA2, Y2 is complex viscosity ratio of polymer made with 100% NCA2 and 0% NCA1, where NCA1 has an Mw lower than the Mw of NCA2; f) an Mw/Mn of 4.0 or less; g) a melting point of 30° C. or less; and h) a Composition Distribution Breadth Index of 50% or more.

    摘要翻译： 本发明涉及使用两种或多种非配位阴离子活化剂制备的共聚物，其包含第一C 2 -C 12α-烯烃（如乙烯），不同于第一α-烯烃的第二C 3 -C 12α-烯烃（如丙烯），以及 二烯（如亚乙基降冰片烯和/或乙烯基降冰片烯），其中聚合物具有：a）35-90％摩尔的第一α-烯烃（乙烯）含量; b）第二α-烯烃（丙烯）含量为9.8至64.8mol％; c）二烯含量为0.2-5mol％; d）支化指数g'ave为0.95以上; e）大于1.1 * Y0的复数粘度比（eta *（0.01rad / s）/ eta *（100rad / s）），其中Y0 = Y1 + {[（Y2-Y1）/（ X2-X1）]（X0-X1）}，其中X0是用于制备共聚物的第一非配位阴离子活化剂NCA1的重量％（基于NCA1的重量和第二非配位阴离子活化剂NCA2 ，用于制备共聚物），X1 = 0，X2 = 100，Y1 =用100％NCA1和0％NCA2制成的聚合物的复数粘度比，Y2是用100％NCA2和0％NCA1制成的聚合物的复数粘度比， 其中NCA1具有低于NCA2的Mw的Mw; f）Mw / Mn为4.0以下; g）熔点为30℃以下; 和h）组合物分布宽度指数为50％以上。

    Process to Produce Ethylene Propylene Copolymers
    7.
    发明申请
    Process to Produce Ethylene Propylene Copolymers 有权
    生产乙烯丙烯共聚物的工艺

    公开(公告)号：US20150307641A1

    公开(公告)日：2015-10-29

    申请号：US14640871

    申请日：2015-03-06

    申请人： Daniel Bilbao ,  Jeffrey L. Brinen ,  Carlos U. De Gracia ,  Henry Dong

    发明人： Daniel Bilbao ,  Jeffrey L. Brinen ,  Carlos U. De Gracia ,  Henry Dong

    IPC分类号： C08F210/18

    CPC分类号： C08F210/18 ,  C08F4/65904 ,  C08F4/65908 ,  C08F4/6592 ,  C08F210/06 ,  C08F236/20 ,  C08F2500/25 ,  C08F2500/03 ,  C08F2500/17 ,  C08F4/65927

    摘要： This invention relates to a copolymer prepared using two or more non-coordinating anion activators comprising a first C2 to C12 alpha olefin (such as ethylene), a second C3 to C12 alpha olefin (such as propylene) different from the first alpha olefin, and diene (such as ethylidene norbornene and/or vinyl norbornene), where the polymer has: a) first alpha olefin (ethylene) content of 35 to 90 mol %; b) second alpha olefin (propylene) content of 9.8 to 64.8 mol %; c) diene content of 0.2 to 5 mol %; d) a branching index g′ave of 0.95 or more; e) a complex viscosity ratio (eta*(0.01 rad/s)/eta*(100 rad/s), at 125° C.) greater than 1.1*Y0, where Y0=Y1+{[(Y2−Y1)/(X2−X1)](X0−X1)}, where X0 is the wt % of a first non-coordinating anion activator, NCA1, used to prepare the copolymer (based upon weight of NCA1 and a second non-coordinating anion activator, NCA2, used to prepare the copolymer), X1=0, X2=100, Y1=complex viscosity ratio of polymer made with 100% NCA1 and 0% NCA2, Y2 is complex viscosity ratio of polymer made with 100% NCA2 and 0% NCA1, where NCA1 has an Mw lower than the Mw of NCA2; f) an Mw/Mn of 4.0 or less; g) a melting point of 30° C. or less; and h) a Composition Distribution Breadth Index of 50% or more.

    摘要翻译： 本发明涉及使用两种或多种非配位阴离子活化剂制备的共聚物，其包含第一C 2 -C 12α-烯烃（如乙烯），不同于第一α-烯烃的第二C 3 -C 12α-烯烃（如丙烯），以及 二烯（如亚乙基降冰片烯和/或乙烯基降冰片烯），其中聚合物具有：a）35-90％摩尔的第一α-烯烃（乙烯）含量; b）第二α-烯烃（丙烯）含量为9.8至64.8mol％; c）二烯含量为0.2-5mol％; d）支化指数g'ave为0.95以上; e）大于1.1 * Y0的复数粘度比（eta *（0.01rad / s）/ eta *（100rad / s）），其中Y0 = Y1 + {[（Y2-Y1）/（ X2-X1）]（X0-X1）}，其中X0是用于制备共聚物的第一非配位阴离子活化剂NCA1的重量％（基于NCA1的重量和第二非配位阴离子活化剂NCA2 ，用于制备共聚物），X1 = 0，X2 = 100，Y1 =用100％NCA1和0％NCA2制成的聚合物的复数粘度比，Y2是用100％NCA2和0％NCA1制成的聚合物的复数粘度比， 其中NCA1具有低于NCA2的Mw的Mw; f）Mw / Mn为4.0以下; g）熔点为30℃以下; 和h）组合物分布宽度指数为50％以上。