CA2256668C - Elastomers and process for their manufacture - Google Patents

Elastomers and process for their manufacture Download PDF

Info

Publication number
CA2256668C
CA2256668C CA002256668A CA2256668A CA2256668C CA 2256668 C CA2256668 C CA 2256668C CA 002256668 A CA002256668 A CA 002256668A CA 2256668 A CA2256668 A CA 2256668A CA 2256668 C CA2256668 C CA 2256668C
Authority
CA
Canada
Prior art keywords
silanetitanium
dimethyl
rls
reactor
butylamido
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CA002256668A
Other languages
French (fr)
Other versions
CA2256668A1 (en
Inventor
Brian W.S. Kolthammer
Robert S. Cardwell
Deepak R. Parikh
Morris S. Edmondson
Stanley W. Smith
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of CA2256668A1 publication Critical patent/CA2256668A1/en
Application granted granted Critical
Publication of CA2256668C publication Critical patent/CA2256668C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A process for polymerizing ethylene .alpha.-olefin and optionally diene monomers is disclosed. The process comprises the steps of contacting: (1) ethylene, (2) at least one C3-C20 aliphatic .alpha.-olefin, (3) optionally, at least one C4-C20 diene, (4) a catalyst, the catalyst comprising (a) a metallocene complex, and (b) an activator, and (5) a solven t. The process can be conducted in a single or multiple reactors, and if in multiple reactors, then the reactors can be configured in series o r parallel. Solvent is removed from the polymer stream in an anhydrous, first stage solvent recovery operation such that the solids concentration of the product stream is increased by at least 100 percent. Additional solvent is removed in an anhydrous, second stage solvent recovery operation from the product of the first stage solvent recovery operation such that the solids concentration of the product stream is in excess of 65 weight percent.

Description

ELASTOMERS AND PROCESS FOR THEIR MANUFACTURE
This invention relates to elastomers. In one aspect, this invention relates to ethylene-propylene (EP) and ethylene-propylenediene monomer (EPDM) elastomers while in another aspect, this invention relates to a process for their manufacture. In yet another aspect, this invention relates to elastomers made by a process in which the catalyst is a metallocene complex, more particularly to a class of Group 4 metal complexes.
Metallocene complexes and methods for their preparation are disclosed in US-A-5,470,993 (published also as EP-A-705,269 and W095/00526); USSN 545,403, filed July 3, 1990 (published also as EP-A-416,815); USSN 547,718, filed July 3, 1990 (published also as EP-A-468,651); USSN 702,475, filed May 20, 1991 (published also as EP-A-514,828);
USSN 876,268, filed May 1, 1992, (published also as EP-A-520,732) and USSN 8,003, filed January 21, 1993 (published also as W093/19104), as well as US-A-5,055,438, US-A-5,057,475, US-A-5,096,867, US-A-5,064,802, US-A-5,132,380.
The term "elastomer" was first defined in 1940 to mean synthetic thermosetting high polymers having properties similar to those of vulcanized natural rubber, that is, having the ability to be stretched to at least twice their original length and to retract very rapidly to approximately their original length when released. Representative of these "high polymers" were styrene-butadiene copolymer, polychloroprene, nitrite butyl rubber and ethylene-propylene terpolymers (also known as EPDM rubbers). The term "elastomer" was later extended to include uncrosslinked thermoplastic polyolefins, TPO's.
ASTM D 1566 defines various physical properties, and the test methods for measuring these properties, of rubbers. USP 5,001,205 (Hoel) provides an overview of the known elastomers comprising ethylene copolymerized with an a-olefin. As Hoel describes, commercially viable eiastomers have various minimum properties, such as a Mooney viscosity no less than 10, a weight average molecular weight (Mw) no less than 110,000, a glass transition temperature below -40°C, and a degree of crystallinity no greater than 25 percent. USP 5,001,205 discloses a process for polymerizing high molecular weight elastomers using liquid phase polmerization in the presence of a metallocene/alumoxane (specifically, a bis(cyclopentadienyl) alumoxane) catalyst.
We have now discovered a process for the manufacture of ethylenepropylene and ethylene/a-olefin/diene monomer polymers. In one embodiment, the process is characterized by the following steps:
A. contacting in a first reactor ( 1 ) ethylene, (2) at least one C3-C20 aliphatic a-olefin, (3) optionally, at least one C4-C20 dime, (4) a catalyst, the catalyst comprising (a) a metallocene complex, and (b) at least one activator, and (S) a solvent, the first reactor operated such that a first product is produced at a solids concentration of from I to 15 weight percent, based on the weight of the reaction mass in the first reactor;
B. contacting in a second reactor ( 1 ) ethylene, (2) at least one C3-C2p aliphatic a-olefin, (3) optionally, at least one C4-C20 dime, (4) a catalyst, the catalyst comprising (a) a metallocene complex, and (b) at least one activator, (5) a solvent, and (6) a product stream from the first reactor, the second reactor operated such that a second product is produced at a solids concentration of from 2 to 30 weight percent, based on the weight of the reaction mass in the second reactor;
C. removing a product stream from the second reactor;
D. removing solvent from the product stream of the second reactor in an anhydrous, first stage solvent recovery operation such that the solids concentration of the product stream is increased by at least 100 percent; and E. removing additional solvent in an anhydrous, second stage solvent recovery operation from the product of first stage solvent recovery operation such that the solids concentration of the product stream is in excess of 65 weight percent.
In another embodiment of this invention, the process is characterized by additional anhydrous solvent recovery operations in which the solids concentration of the final product is increased to greater than 99 weight percent. Preferably, the product of the first reactor has a weight average molecular weight greater than that of the product of the second reactor.
In yet another embodiment, the process is characterized by the following steps:
A. contacting in a first reactor ( 1 ) ethylene, (2) at least one C3-C2p aliphatic a-olefin, (3) optionally, at least one C4-C2p dime, (4) a catalyst, the catalyst comprising (a) a metallocene complex, and (b) at least one activator, and (5) a solvent, the first reactor operated such that a first product is produced at a solids concentration of from 1 to 30 weight percent, based on the weight of the reaction mass in the first reactor;
B. contacting in a second reactor ( 1 ) ethylene, (2) at least one C3-C20 aliphatic a-olefin, (3) optionally, at least one C4-C20 diene, (4) a catalyst, the catalyst comprising (a) a metallocene complex, (b) at least one activator, and (5) a solvent, 3p the second reactor operated such that a second product is produced at a solids concentration of from 1 to 30 weight percent, based on the weight of the reaction mass in the second reactor;
C. recovering a product stream from each of the first and second reactors, and then blending these individual product streams into a combined product stream;
D. removing solvent from the combined product stream in an anhydrous, first stage solvent recovery operation such that the solids concentration of the combined product stream is increased by at least 100 percent; and E. removing additional solvent in an anhydrous, second stage solvent recovery operation from the combined product stream such that the solids concentration of the combined product stream is in excess of 65 weight percent.
In another embodiment of this invention, the process is further characterized by additional anhydrous solvent recovery operations in which the solids concentration of the final product is increased to greater than 99 weight percent. Preferably, the product of one reactor has a weight average molecular weight greater than that of the product of the other reactor.
According to one aspect of the present invention, there is provided a process for the manufacture of an ethylene/a-olefin or an ethylene/a-olefin/diene monomer elastomer having a density of from 0.850 g/cm3 to 0.895 g/cm3 and comprising a high molecular weight fraction and a low molecular weight fraction, the process comprising the steps of: A. contacting in a first reactor (1) ethylene, (2) at least one C3-C2o aliphatic a-olefin, (3) optionally at least one C4-CZO dime, (4) an activated catalyst comprising a Group 4 metal metallocene complex, and (5) a solvent, the first reactor operated such that the high molecular weight fraction of the elastomer is produced at a solids concentration of from 1 to 15 weight percent, based on the weight of the reaction mass in the first reactor; B.
contacting in a second reactor (1) ethylene, (2) at least one C3-C2o aliphatic a-olefin, (3) optionally at least one Cq-CZp diene, (4) an activated catalyst comprising a Group 4 metal metallocene complex, and (5) a solvent, and (6) the high molecular weight fraction of the elastomer from the first reactor, the second reactor operated such that the low molecular weight fraction of the elastomer is produced at a solids concentration of from 2 to 30 weight percent, based on the weight of the reaction mass in the first reactor; C.
removing an elastomeric product stream from the second reactor; D, removing solvent from the elastomeric product stream of the second reactor in an anhydrous, first stage solvent recovery operation such that the solids concentration of the elastomeric product stream is increased by at least 100 percent; and E. removing additional solvent in an anhydrous, second stage solvent recovery operation from the elastomeric product of the first stage solvent recovery operation such that the solids concentration of the elastomeric product stream is in excess of 65 weight percent.
According to another aspect of the present invention, there is provided a process for the manufacture of an ethylene/a-olefin or an ethylene/a-olefin/diene monomer elastomer having a density of from 0.850 g/cm3 to 0.895 g/cm3 and comprising a high molecular weight fraction and a low molecular weight fraction, the process comprising the steps of: A. contacting in a first reactor (1) ethylene, (2) at least one C3-C2o aliphatic a-olefin, (3) optionally at least one C4-C2o dime, (4) an activated catalyst comprising a Group 4 metal metallocene complex, and (5) a solvent, the first reactor operated such that the high molecular weight fraction of the elastomer is produced at a solids concentration of from 1 to 30 weight percent, based on the weight of the reaction mass in the first reactor;
B. contacting in a second reactor (1) ethylene, (2) at least -3a one C3-CZO aliphatic a-olefin, (3) optionally at least one C4-C2o dime, (4) an activated catalyst comprising a Group 4 metal metallocene complex, and (5) a solvent, the second reactor operated such that the low molecular weight fraction of the elastomer is produced at a solids concentration of from 1 to 30 weight percent, based on the weight of the reaction mass in the second reactor; C. recovering an elastomeric product stream from each of the first and second reactors, and then blending these individual product streams into a combined elastomeric product stream; D. removing solvent from the elastomeric product stream of the second reactor in an anhydrous, first stage solvent recovery operation such that the solids concentration of the elastomeric product stream is increased by at least 100 percent; and E. removing additional solvent in an anhydrous, second stage solvent recovery operation from the elastomeric product of the first stage solvent recovery operation such that the solids concentration of the elastomeric product stream is in excess of 65 weight percent.
Figure 1 is a diagramatic representation of the two principal zones of the polymerization process of this invention.
Figure 2 is a diagramatic representation of a single reactor embodiment of Zone I of Figure 1.
Figure 3 is a diagramatic representation of an in-series dual reactor configuration of Zone I of Figure 1.
Figure 4 is a diagramatic representation of an in-parallel dual reactor configuration of zone I of Figure 1.
Figure 5 is a diagramatic representation of four possible three-reactor configurations of Zone I of Figure 1.
-3b-Figure 6 is a diagramatic representation of one embodiment of Zone 11 of Figure 1.
The elastomers made according to the new process disclosed herein are interpolpners of ethylene (CH2=CH2) with at least one comonomer selected from the group consisting of aliphatic C3-CZp alpha-olefins, conjugated dienes, and nonconjugated dienes. The term interpolymer includes copolymers, such as ethylene propylene (EP) copolymers, and terpolymers, such as EPDM, but is not intended to limit the elastomers made to only one or two monomers copolymerized with ethylene.
Examples of the aliphatic C3-C2p a-olefins include propene, I-butene, 4-methyl-I-pentene, 1-hexene, I-octene, I-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, I-octadecene and 1-eicosene. The a-olefin can also contain a cyclic structure such as cyclohexane ar cyclopentane. resulting in an a-olefin such as 3-cyclohexyl-1-propene (allylcyclohexane) and vinyl-cyclohexane. Although not a-olefins in the classical sense of the term, certain cyclical olefins such as norbornene and related olefins can be used in place of some or all of the a-olefins.
Examples of nonconjugated dienes include aliphatic dienes such as l,4pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-I,5-hexadiene, 1,6-heptadiene, 6-methyl-1,5-heptadienc, I,6-octadiene, I,7-octadiene, 7-methyl- 1,6-octadiene, 1,13-tetradecadiene, and 1,19-eicosadiene;
cyclic dienes such as -3c-1,4-cyclohexadiene, bicyclo[2.2.1]hept-2,5-diene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, bicyclo[2.2.2]oct-2,5-diene, 4v.inylcyclohex-1-ene, bicyclo[2.2.2]oct-2,6-diene, 1,7,7-trimethylbicyclo-[2.2.1]hept-2,5-diene, dicyclopentadiene, methyltetrahydroindene, 5-allylbicyclo[2.2.1]hept-2-ene, and 1,5-cyclooctadiene; aromatic dimes such as 1,4-diallylbenzene, 4-allyl- 1H-indene; and trienes such as 2,3-diisopropenyl idiene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2propenyl-2,5-norbornadiene, 1,3,7-octatriene, and 1,4,9-decatriene; with 5ethylidene-2-norbornene being a preferred nonconjugated diene.
Examples of conjugated dimes include butadiene, isoprene, 2,3dimethylbutadiene-1,3, 1,2-dimethylbutadiene-1,3, 1,4-dimethylbutadiene-1,3, lethylbutadiene- 1,3, 2-phenylbutadiene-1,3, hexadiene- 1,3, 4-methylpentadiene- 1,3, 1,3-pentadiene (CH3CH=CH-CH=CH2;
commonly called piperylene), 3-methyll,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, and 3-ethyl-1,3-pentadiene; with 1,3-pentadiene being a preferred conjugated dime.
Copolymers of ethylene and one aliphatic C3-C2p a-olefin or one dime (either conjugated or nonconjugated) can be prepared using the process of this invention. Interpolymers of ethylene, at least one aliphatic C3-C2p a-olefin, and/or at least one dime (either conjugated or nonconjugated) can also be made by using this process. Exemplary copolymers include ethylene/propylene and ethylene/1-octene. Exemplary terpolymers include ethylene/propylene/I-octene, ethylene/propylene/ 5-ethylidene-2-norbornene, ethylene/1-octene/5-ethylidene-2-norbornene, ethylene/propylene/1,3-pentadiene, and ethylene/1-octene/1,3-pentadiene. Exemplary tetrapolymers include ethylene/propylene/1-octene/diene (ENB) and ethylene/propylene/mixed dienes, such as ethylene/propylene/5-ethylidene-2-norbornene/piperylene. In addition, the elastomers made using the process of this invention can include minor amounts, for instance, 0.05 - 0.5 percent by weight, of long chal n branch enhancers, such as 2,5-norbornadiene {which is bicyclo[2,2,1]hepta-2,5-dime), diallylbenzene, 1,7-octadiene (H2C=CH(CH2)4CH=CH2), and 1,9-decadiene (H2C=CH(CH2)6CH=CH2).
At a general minimum, the elastomers made by the process of this invention comprise at least 30, preferably at least 40 and more preferably at least 50 weight percent ethylene; at least 15, preferably at least 20 and more preferably at least 25 weight percent of at least one a-olefin; and if present, preferably at least 0.1 and more preferably at least 0.5 weight percent of at least one conjugated or nonconjugated diene. At a general maximum, the elastomers made by the process of this invention comprise not more than 85, preferably not more than 80 and more preferably not more than 75 weight percent ethylene; not more than 70, preferably not more than 60 and more preferably not more than 55 weight percent of at least one a-olefin; and not more than 20, preferably not more than 15 and more preferably not more than 12 weight percent of at least one of a conjugated or nonconjugated diene. All weight percentages are based on weight of the elastomer which can be determined using any conventional method.
The polydispersity {molecular weight distribution or Mw/Mn) of the interpolymer elastomers generally ranges from 1.5, preferably from 1.8, and especially from 2.0 to 15, preferably to 10, and especially to 6.
Measurement of the polydispersity index is done according to the following technique: The polymers are analyzed by gel permeation chromatography (GPC) on a Waters 150°C
high temperature chromatographic unit equipped with three linear mixed bed columns (Polymer Laboratories (10 micron particle size)), operating at a system temperature of 140°C. The solvent is 1,2,4-trichlorobenzene, from which about 0.5 percent by weight solutions of the samples are prepared for injection. The flow rate is 1.0 milliliter/minute and the injection size is 100 microliters.
The molecular weight determination is deduced by using narrow molecular weight distribution polystyrene standards (from Polymer Laboratories) in conjunction with their elutsion volumes. The equivalent polyethylene molecular weights are determined by using appropriate I S Mark-Houwink coefficients for polyethylene and polystyrene (as described by Williams and Ward in Journal of Polymer Science, Polymer Letters, Vol. 6, (621 ) 1968) to derive the equation:
Mpolyethylene = {a) (Mpolystyrene)b In this equation, a = 0.4316 and b = 1Ø Weight average molecular weight, Mw, is calculated in the usual manner according to the formula:
Mvv ~(wi)(Mi) where wi and Mi are the weight fraction and molecular weight respectively of the ith fraction eluting from the GPC column. Generally the Mw of the interpolymer elastomers ranges from 10,000, preferably from 20,000, more preferably from 40,000, and especially from 60,000 to 1,000,000, preferably to 800,000, more preferably to 600,000, and especially to 500,000.
The elastomers made by the process of this invention cover a range of viscosities, depending upon the molecular weight of the elastomer and optional post polymerization rheological modification. In general, the viscosity of elastomers is characterized by Mooney viscosity which is measured according to ASTM D 1646-89, using a shear rheometer at 125°C.
The Mooney viscosity for the elastomers generally ranges from a minimum of 1, preferably 5, more preferably 10, and especially 15 to a maximum of 150, preferably 125, more preferably 100, and especially 80.
The density of the elastomers is measured according to ASTM D-792, and these densities range from 0.850 grams/cubic centimeter (g/cm3), preferably from 0.853 g/cm3, and especially from 0.855 g/cm3, to 0.895 g/cm3, preferably to 0.885 g/cm3, and especially to 0.875 g/cm3.
Exemplary catalysts used in the process of this invention are metallocene complexes, and these catalysts and methods for their preparation are disclosed in USSN
545,403, filed July 3, 1990 (EP-A-416,815); USSN 702,475, filed May 20, 1991 (EP-A-514,828); as well as US-A-5,470,993; 5,374,696; 5,231,106; 5,055,438; 5,057,475; 5,096,867;
5,064,802; 5,132,380;
5,321,106; 5,470,993; 5,486,632.
In USSN 720,041, filed June 24, 1991, (EP-A-514,828) certain borane derivatives of the foregoing metallocene complex catalysts are disclosed and a method for their preparation taught and claimed. In US-A-5,453,410, combinations of cationic metallocene complex catalysts with an alumoxane are disclosed as suitable olefin polymerization catalysts.
Preferred for use herein are catalyst compositions comprising:
al ) a metal complex corresponding to the formula: ZLMXpX'q. that has been or subsequently is rendered catalytically active by combination with an activating cocatalyst or by use of an activating technique, wherein M is a metal of Group 4 of the Periodic Table of the Elements having an oxidation state of +2, +3 or +4, bound in an r15 bonding mode to L;
L is a cyclopentadienyl-, indenyl-, tetrahydroindenyl-, fluorenyl-, tetrahydrofluorenyl-, or octabydrofluorenyl- group covalently substituted with at least a divalent moiety, Z. and L further may be substituted with from 1 to 8 substituents independently selected from the group consisting of hydrocarbyl, halo, halohydrocarbyl, hydrocarbyloxy, dibydrocarbylamine, dihydrocarbylphosphino or silyl groups containing up to 20 nonhydrogen atoms;
Z is a divalent moiety bound to both L and M via 6-bonds, said Z comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally, also comprising nitrogen, phosphorus, sulfur or oxygen;
X is an anionic or dianionic ligand group having up to 60 atoms exclusive of the class of ligands that are cyclic, delocalized, ~-bound ligand groups;
X' independently each occurrence is a neutral Lewis base ligating compound, having up to 20 atoms;
p is 0, 1 or 2, and is two less than the formal oxidation state of M, with the proviso that when X is a dianionic ligand group, p is 1; and q is 0, 1 or 2; said metal complex being rendered catalytically active by combination with an activating cocatalyst or use of an activating technique; or a catalyst composition comprising a cationic complex a2) corresponding to the formula (ZLM*X*p*)*A-, wherein: M* is a metal of Group 4 of the Periodic Table of the Elements having an oxidation state of +3 or +4, bound in an r15 bonding mode to L;
L is a cyclopentadienyl-, indenyl-, tetrahydroindenyl-, fluorenyl-, tetrahydrofluorenyl-, or octahydrofluorenyl- group covalently substituted with at least a divalent moiety, Z. and L further may be substituted with from 1 to 8 substituents independently selected from the group consisting of hydrocarbyl, halo, halohydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, dihydrocarbylphosphino or silyl groups contalning up to 20 nonhydrogen atoms;
Z is a divalent moiety bound to both L and M* via 6-bonds, said Z comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also optionally comprising nitrogen, phosphorus, sulfur or oxygen;
X* is an anionic ligand group having up to 60 atoms exclusive of the class of ligands that are cyclic, delocalized, ~c-bound ligand groups;
p* is 0 or 1, and is three less than the formal oxidation state of M; and A* is an inert, noncoordinating anion.
All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1989.
Also, any references to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
Zwitterionic complexes result from activation of a Group 4 metal dime complex, that is, complexes in the form of a metallocyclopentene wherein the metal is in the +4 formal oxidation state, by the use of a Lewis acid activating cocatalyst, especially tris(perfluoroaryl)borane compounds.
These zwitterionic complexes are believed to correspond to the formula:
L-M* -X**-A-M is a Group 4 metal in the +4 formal oxidation state;
L and Z are as previously defined;
X** is the divalent remnant of the conjugated dime, X', formed by ring opening at one of the carbon to metal bonds of a metallocyclopentene; and A- is the moiety derived from the activating cocatalyst.
As used herein, the recitation "noncoordinating, compatible anion" means an anion which either does not coordinate to component al) or which is only weakly coordinated therewith remalning sufficiently labile to be displayed by a neutral Lewis base. A non-coordinating, compatible anion specifically refers to a compatible anion which when functioning as a charge balancing anion in the catalyst system of this invention, does not transfer an anionic substituent or fragment thereof to said cation thereby forming a neutral four coordinate metallocene and a neutral metal byproduct.
"Compatible anions" are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerizations.
Preferred X' groups are phosphines, especially trimethylphosphine, triethylphosphine, triphenylphosphine and bis(1,2-dimethylphosphino)ethane; P(OR)3, wherein R is as previously defined; ethers, especially tetrahydrofuran; amines, especially pyridine, bipyridine, tetramethylethylenediamine (TMEDA), and triethylamine; olefins, and conjugated dienes having from 4 to 40 carbon atoms. Complexes including the latter X' groups include those wherein the metal is in the +2 formal oxidation state.
Preferred metal complexes al) used according to the present invention are complexes corresponding to the formula:
R R R
R O R R O
or ~ M-X
P
R O ~X .X~q R R ~X~P
R P
wherein:
R independently each occurrence is a group selected from hydrogen, hydrocarbyl, halohydrocarbyl, silyl, germyl and mixtures thereof, said group containing up to 20 nonhydrogen atoms;
M is titanium, zirconium or hafnium;
Z is a divalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen, said moiety having up to 60 nonhydrogen atoms;
X and X' are as previously defined;
p is 0, 1 or2; and qis0orl;
with the proviso that;
when p is 2, q is 0, M is in the +4 formal oxidation state, and X is an anionic ligandselected from the group consisting of halide, hydrocarbyl, hydrocarbyloxy, di(hydrocarbyl)arnido, di(hydrocarbyl)phosphido, hydrocarbylsulfido, and silyl groups, as well as halo-, di(hydrocarbyl)amino-, hydrocarbyloxy- and di(hydrocarbyl)phoshino-substituted derivatives thereof, said X group having up to 20 nonhydrogen atoms, when p is 1, q is 0, M is in the +3 formal oxidation state, and X is a stabilizing anionic ligand group selected from the group consisting of allyl, 2-(N,N-dimethylaminomethyl)phenyl, and 2-(N,N-dimethyl)aminobenzyl, or M is in the +4 formal oxidation state, and X is a divalent derivative of a conjugated diene, M and X
together forming a metallocyclopentene group, and when p is 0, q is 1, M is in the +2 formal oxidation state, and X' is a neutral, conjugated or nonconjugated dime, optionally substituted with one or more hydrocarbyl groups, said X' having up to 40 carbon atoms and forming a ~-complex with M.
More preferred coordination complexes al) used according to the present invention are complexes corresponding to the formula:
_g_ R R R
R ~ R or R *~
y Z*_ C~--, M_Xp R O M- ~~ R R \X~p R
wherein R independently each occurrence is hydrogen or C 1 _6 alkyl;
M is titanium; Y is-O-, -S-, -NR*-, -PR*-;
Z* is SiR*2, CR*2, SiR*2SiR*2, CR*2CR*2, CR*=CR*, CR*2SiR*2, or GeR*2;
R* each occurrence is independently hydrogen, or a member selected from hydrocarbyl, hydrocarbyioxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, and R* having up to 20 nonhydrogen atoms, and optionally, two R* groups from Z
(when R* is not hydrogen), or an R* group from Z and an R* group from Y form a ring system;
p is 0, 1 or 2;
q is 0 or 1;
with the proviso that:
when p is 2, q is 0, M is in the +4 formal oxidation state, and X is independently each occurrence methyl or benzyl, when p is 1, q is 0, M is in the +3 formal oxidation state, and X is 2- (N,N-dimethyl)aminobenzyl); or M is in the +4 formal oxidation state and X is l,4butadienyl, and when p is 0, q is 1, M is in the +2 formal oxidation state, and X' is 1,4-dipenyl-1,3-butadiene or 1,3-pentadiene. The latter diene is illustrative of unsymetrical dime groups that result in production of metal complexes that are actually mixtures of the respective geometrical isomers.
The complexes can be prepared by use of well known synthetic techniques. A
preferred process for preparing the metal complexes is disclosed in US-A-5,491,246 (published also as W096/34001 ). The reactions are conducted in a suitable noninterfering solvent at a temperature from -100 to 300 °C, preferably from -78 to 100 °C, most preferably from 0 to 50°C. A reducing agent may be used to cause the metal M to be reduced from a higher to a lower oxidation state. Examples of suitable reducing agents are alkali metals, alkaline earth metals, aluminum and zinc, alloys of alkali metals or alkaline earth metals such as sodium/mercury amalgam and sodium/potassium alloy, sodium naphthalenide, potassium graphite, lithium alkyls, lithium or potassium alkadienyls, and Grignard reagents.
Suitable reaction media for the formation of the complexes include aliphatic and aromatic hydrocarbons, ethers, and cyclic ethers, particularly branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof;
cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, and xylene, C1-4 dialkyl ethers, C1-4 dialkyl ether derivatives of (poly)alkylene glycols, and tetrahydrofuran. Mixtures of the foregoing are also suitable.
Suitable activating cocatalysts useful in combination with component al) are those compounds capable of abstraction of an X substituent from al) to form an inert, noninterfering counter ion, or that form a zwitterionic derivative of al). Suitable activating cocatalysts for use herein include perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluorophenyl)borane;
nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium- or sulfonium- salts of compatible, noncoordinating anions, and ferritenium salts of compatible, noncoordinating anions. Suitable activating techniques include the use of bulk electrolysis (explained in more detal l hereinafter). A combination of the foregoing activating cocatalysts and techniques may be employed as well. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes in the following references: EP-A-277,003, US-A-5,153,157, US-A-5,064,802, EP-A-468,651 (equivalent to USSN 07/547,718), EP-A-520,732 (equivalent to USSN 07/876,268), and EP-A-520,732 (equivalent to USSN 07/884,966 filed May 1, 1992). More particularly, suitable ion forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion, A-.
Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined.
Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitrites.
Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are well known, particularly such compounds containing a single boron atom in the anion portion, and are available commercially.
Preferably such cocatalysts may be represented by the following general formula:
(L*-H)d* (A)d_ wherein:
L* is a neutral Lewis base;
(L*-H)+ is a Bronsted acid;

Ad- is a noncoordinating, compatible anion having a charge of d-, and d is an integer from 1-3.
More preferably Ad- corresponds to the formula: [M'Q4]-;
wherein:
M' is boron or aluminum in the formal +3 formal oxidation state; and Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl, halosubstitutedhydrocarbyloxy, and halosubstituted silylhydrocarbyl radicals (including perhalogenated hydrocarbylperhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide. Examples of suitable hydrocarbyloxide Q groups are disclosed in USP 5,296,433.
In a more preferred embodiment, d is 1, that is, the counter ion has a single negative charge and is A-. Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula:
(L*-H)+(BQ4) wherein:
L* is as previously defined;
B is boron in a formal oxidation state of 3; and Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.
Most preferably, Q is at each occurrence a fluorinated aryl group, especially, a pentafluorophenyl group.
Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are trisubstituted ammonium salts such as: trimethylammonium tetrakis(pentafluorophenyl) borate, triethylammonium tetrakis(pentafluorophenyl) borate, tripropylammonium tetrakis(pentafluorophenyl) borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate, N,N-dimethyIanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate, N,N-d imethylanilinium benzyltris(pentafluorophenyl)borate, N,N-dimethylaniiinium tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl} borate, N,N-dimethylanilinium tetrakis(4-(triisopropysilyl)-2,3,5,6-tetrafluorophenyl) borate, N,N-dimethylanilinium pentafluorophenoxytris(pentafluorphenyl) borate, N,N-diethylaniiinium tetrakis(pentafluorphenyl) borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate, trimethyiammonium tetrakis (2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophcnyl) borate, tri(n-butyl)ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl(t-butyl)ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N,N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N,N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, and N,N-dimenhyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate; disubstituted ammonium salts such as: di-(i-propyl) ammonium tetrakis(pentafluorophenyl) borate, and dicyclohexylammonium tetrakis(pentafluorophenyl) borate;
trisubstituted phosphonium salts such as: triphenylphosphonium tetrakis(pentafluorophenyl) borate, trio-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, and tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate; disubstituted oxonium salts such as:
diphenyloxonium tetrakis(pentafluorophenyl) borate, di(o-tolyl)oxonium tetrakis(pentafluororphenyl) borate, and di(2,6-dimethylphenyl oxonium tetrakis (pentafluorophenyl) borate;
disubstituted sulfonium salts such as:
diphenylsulfonium tetrakis(pentafluorophenyl) borate, di(o-tolyl)sulfoniumtetrakis(pentafluorophenyl) borate, and bis(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl) borate.
Preferred (L*-H)+ cations are N,N-dimethylanilinium and tributylammonium.
Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula:
(Oxc+)d(Ad-)e wherein:
Oxe+ is a cationic oxidizing agent having a charge of a+;
a is an integer from 1 to 3; and Ad- and d are as previously defined.
Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag+ or Pb+2. Preferred embodiments of Ad- are those anions previously defined with respect to the Bronsted acid contalning activating cocatalysts, especially tetrakis(pentafluorophenyl)borate.
Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula:
~+ A-wherein:
~+ is a C 1 _2p carbenium ion; and A- is as previously defined. A preferred carbenium ion is the trityl cation, that is, triphenylmethylium.

A further suitable ion forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula:
R"' 3 Si *A-wherein:
R"' is C1_10 hydrocarbyl, and A- is as previously defined.
Preferred silylium salt activating cocatalysts are trimethylsilylium tetrakispentafluorophenylborate, triethylsilylium tetrakispentafluorophenylborate and ether substituted adducts thereof. Silylium salts have been previously generically disclosed in J. Chem Soc. Chem.
Comm.. 1993, 383-384, as well as Lambert, J.B., et al, Organometallics, 1994, 13, 2430-2443. The use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is claimed in US-A-5,625,087.
Certain complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and may be used according to the present invention. Such cocatalysts are disclosed in USP 5,296,433.
The technique of bulk electrolysis involves the electrochemical oxidation of the metal complex under electrolysis conditions in the presence of a supporting electrolyte comprising a noncoordinating, inert anion. In the technique, solvents, supporting electrolytes and electrolytic potentials for the electrolysis are used such that electrolysis byproducts that would render the metal complex catalytically inactive are not substantially formed during the reaction. More particularly, suitable solvents are materials that are (i) liquids under the conditions of the electrolysis (generally temperatures from 0 to 100°C), (ii) capable of dissolving the supporting electrolyte, and (iii) inert.
"Inert solvents" are those that are not reduced or oxidized under the reaction conditions employed for the electrolysis. It is generally possible in view of the desired electrolysis reaction to choose a solvent and a supporting electrolyte that are unaffected by the electrical potential used for the desired electrolysis. Preferred solvents include diduorobenzene (all isomers), dimethoxyethane {DME), and mixtures thereof.
The electrolysis may be conducted in a standard electrolytic cell contalning an anode and cathode (also referred to as the working electrode auld counterelectrode respectively). Suitable materials of construction for the cell are glass, plastic, ceramic and glass-coated metal. The electrodes are prepared from inert conductive materials, by which are meant conductive materials that are unaffected by the reaction mixture or reaction conditions. Platinum or palladium are preferred inert conductive materials. Normally an ion permeable membrane such as a fine glass grit separates the cell into separate compartments, the working electrode compartment and counterelectrode compartment.
The working electrode is immersed in a reaction medium comprising the metal complex to be activated, solvent, supporting electrolyte, and any other materials desired for moderating the electrolysis or stabilizing the resulting complex. The counterelectrode is immersed in a mixture of the solvent and supporting electrolyte. The desired voltage may be determined by theoretical calculations or experimentally by sweeping the cell using a reference electrode such as silver electrode immersed in the cell electrolyte. The background cell current, the current draw in the absence of the desired electrolysis, is also determined. The electrolysis is completed when the current drops from the desired level to the background level. In this manner, complete conversion of the initial metal complex can be easily detected.
Suitable supporting electrolytes are salts comprising a cation and a compatible, noncoordinating anion, A-. Preferred supporting electrolytes are salts corresponding to the formula G+A-;
wherein:
G+ is a cation which is nonreactive towards the starting and resulting complex, and A-is as previously defined.
Examples of cations, G+, include tetrahydrocarbyl substituted ammonium or phosphonium cations having up to 40 nonhydrogen atoms. Preferred cations are the tetra(n-butylammonium)- and tetraethylammonium- cations.
During activation of the complexes of the present invention by bulk electrolysis the cation of the supporting electrolyte passes to the counterelectrode and A-migrates to the working electrode to become the anion of the resulting oxidized product. Either the solvent or the cation of the supporting electrolyte is reduced at the counterelectrode in equal molar quantity with the amount of oxidized metal complex formed at the working electrode. Preferred supporting electrolytes are tetrahydrocarbylammonium salts of tetrakis(perfluoroaryl) borates having from 1 to 10 carbons in each hydrocarbyl or perfluoroaryl group, especially tetra(n-butylammonium)tetrakis{pentafiuorophenyl) borate.
A further recently discovered electrochemical technique for generation of activating cocatalysts is the electrolysis of a disilane compound in the presence of a source of a noncoordinating compatible anion. All of the foregoing techniques are more fully disclosed and claimed in US-A-5,372,682 (published also as EP-656,075 and W095/00683}. In as much as the activation technique ultimately produces a cationic metal complex, the amount of such resulting complex formed during the process can be readily determined by measuring the quantity of energy used to form the activated complex in the process.
Alumoxanes, especially methylalumoxane or triisobutylaluminum modified methylalumoxane are also suitable activators and may be used for activating the present metal complexes.
A most preferred activating cocatalyst is trispentafluorophenylborane.

The molar ratio of metal complex: activating cocatalyst employed preferably ranges from 1:1000 to 2:1, more preferably from 1:5 to 1.5:1, most preferably from 1:2 to 1:1.
Highly preferred metal complexes are:
tetramethylcyclopentadienyl complexes:
(n-butylamido)dimethyl(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (n-butylamido)dimethyl(r15-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)dimethyl(r15-tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)dimethyl(rls-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (n-butylamido)dimethyl(rls-tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl, (t-butyiamido)dimethyl(rl5-tetramethylcyclopentadienyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido)dimethyl(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (t-butylamido)dimethyl(rls-tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (t-butylamido)dimethyl(rls-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (t-butylamido)dimethyl(rls-tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)dimethyl(r15-tetramethylcyclopentadienyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (cyclododecylamido)dimethyl(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethyl(r15-tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)dimethyl(rls-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (cyclododecylamido)dimethyl(r15-tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)dimethyl(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (2,4,6-trimethylanilido)dimethyl(rls-tetramethyicyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)dimethyl(rls-tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)dimethyl(r15-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)dimethyl(rls-tetramethylcyclopentadienyl)silanetitaniurn (IV) dibenzyl, (1-adamantylamido)dimethyl(r)5-tetramethylcyclopentadienyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (1-adamantylamido)dimethyl(r)5-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)dimethyl(115-tetramethylcyclopentadienyl)silanetitanium (III) 2-{N,N-dimethylamino)benzyl, (1-adamantyiamido)dimethyl(115-tetramethylcyclopentadienyl)silanetitanium {IV) dimethyl, (1-adamantylamido)dimethyl(115-tetramethyicyclopentadienyI)silanetitanium (IV) dibenzyl, (t-butylamido)dimethyl(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido)dimethyl(r15-tetramethylcyclopentadienyl)silanetitanium {II) 1,3-pentadiene, (t-butylamido)dimethyl(115-tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (t-butylamido)dimethyl(115-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (t-butylamido)dimethyl(115-tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl, (n-butylamido)diisopropoxy(115-tetramethylcyclopentadienyl)silanetitanium {II) 1,4-diphenyl-1,3-butadiene, (n-butylamido)diisopropoxy(115-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)diisopropoxy(115-tetramethylcyclopentadienyl)silanetitanium (III} 2-(N,N-dimethylamino)benzyl, (n-butylamido)diisopropoxy(115-tettamethylcyclopentadienyl)silanetitaniurn (IV) dimethyl, (n-butylamido)diisopropoxy(115-tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)diisopropoxy{715-tetramethylcyclopentadieny!)-silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (cyclododecylamido)diisopropoxy(115-tetramethylcyciopentadienyl)-silanetitanium (II) 1,3-pentadiene, (cyclododecyiamido)diisopropoxy(115-tetramethylcyclopentadienyl)-silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyciododecylamido)diisopropoxy(t15-tetramethylcyclopentadienyl)-silanetitanium (IV) dimethyl, (cyclododecylamido)diisopropoxy(11S-tetramethylcyclopentadienyl)-silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)diisopropoxy(115-2-methyl-indenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (2,4,6-trimethylanilido)diisopropoxy(115-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)diisopropoxy(115-2-methylin-denyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)diisopropoxy(115-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)diisopropoxy(115-tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)diisopropoxy(115-tetramethylcyclopentadienyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (I-adamantylamido)diisopropoxy(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)diisopropoxy(r15-tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)diisopropoxy(rls-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (1-adamantylamido)diisopropoxy(rls-tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl, (n-butylamido)dimethoxy(rls-tetramethylcyclopentadieny()silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (n-butylamido)dimethoxy(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)dimethoxy(rls-tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)dimethoxy(rls-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (n-butylamido)dimethoxy(~S-tetramethyicyclopentadienyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)dimethoxy(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (cyclododecylamido)dimethoxy(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethoxy(rl5-tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)dimethoxy(rls-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (cyclododecylamido)dimethoxy(r15-tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)dimethoxy(r15-tetramethylcyclopentadienyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (2,4,6-trimethylanilido)dimethoxy(rl5-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)dimethoxy(rls-tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)dimethoxy(r15-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)dimethoxy(r15-tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl' (I-adamantylamido)dimethoxy(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (1-adamantylamido)dimethoxy(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (I-adamantylamido)dimethoxy(rls-tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)dimethoxy(r15-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (I-adamantylamido)dimethoxy(r15-tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl, (n-butylamido)ethoxymethyl(rls-tetrametllylcyclopentadienyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (n-butylamido)ethoxymethyl(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)ethoxymethyl(rls-tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)ethoxymethyl(rls-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (n-butylamido)ethoxymethyl(rls-tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)ethoxymethyl(r15-tetramethylcyclopentadienyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (cyclododecylamido)ethoxymethyl(r15-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)ethoxymethyl(rls-tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)ethoxymethyl(rls-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (cyclododecylamido)ethoxymethyl(r15-tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)ethoxymethyl(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (2,4,6-trimethylanilido)ethoxymethyl(r15-tetramethylcyclopentadienyl)silanetitanium (II) IS 1,3-pentadiene, (2,4,6-trimethylanilido)ethoxymethyl(r15-tetrametllylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)ethoxymethyl(rl5tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)ethoxymethyl(rl5tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)ethoxymethyl(rls-tetramethylcyclopentadienyl)silanetitanium) (II) 1,4-Biphenyl-1,3-butadiene, (I-adamantylamido)ethoxymethyl(rls-tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)ethoxymethyl(rls-tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)ethoxymethyl(rls-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl, (1-adamantylarnido)ethoxymethyl(rI5-tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl, 2-methylindenyi complexes:
(t-butylamido)dimethyl(>?S-2-methylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (t-butylamido)dimethyl(rls-2-methylindenyl)silanetitanium (II) I,3-pentadiene, (t-butylamido)dimethyl(rIS-2-methylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (t-butylamido)dimethyl(r15-2-methylindenyl)silanetitanium (IV) dimethyl, (t-butylamido)dimethyl(tIS-2-methylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)dimethyl(r15-2-methylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (n-butylamido)dimethyl(r15-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)dimethyl(r15-2-methylindenyl)silanetitanium (III) 2-(N,N-dimethylarnino)benzyl, (n-butylamido)dimethyl(rls-2-methylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)dimethyl(rls-2-methylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)dimethyl(r15-2-methylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (cyclododecylamido)dimethyl(rls-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethyl(rls-2-methylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)dimethyl(rls-2-methylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)dimethyl(~5-2-methylindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)dimethyl(rls-2-methylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (2,4,6-trimethylanilido)dimethyl(rls-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)dimethyl(rls-2-methylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)dimethyl(rls-2-methylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)dimethyl(rls-2-methylindenyl)silanetitanium (IV) dibenzyl, (I-adamantylamido)dimethyl(rls-2-methylindenyl)silanetitanium (II) 1,4-diphenyll,3-butadiene, (I-adamantylamido)dimethyl(~5-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)dimethyl(rls-2-methylindenyl)silanetitanium (III) 2-(N,N-dimethyiamino)benzyl, (1-adamantylamido)dimethyl(rls-2-methylindenyl)silanetitanium (1V) dimethyl, (1-adamantylamido)dimethyl(rls-2-methylindenyl)silanetitanium (IV) dibenzyl, (t-butylamido)dimethyl(rls-2-methylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido)dimethyl(r15-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (t-butylamido)dimethyl(rls-2-methylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (t-butylamido)dimethyl(rls-2-methylindenyl)silanetitanium (IV) dimethyl, (t-butylamido)dimethyl(rls-2-methylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)diisopropoxy(rls-2-methylindenyl)silanetitanium (II) 1,4-diphenyl 1,3-butadiene, (n-butylamido)diisopropoxy(rls-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)diisopropoxy(r15-2-methylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (n-butylamido)diisopropoxy(r15-2-methylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)diisopropoxy(rls-2-methylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)diisopropoxy(rls-2-methylindenyl)silanetitanium (II) 1,4 diphenyl-1,3-butadiene, (cyclododecylamido)diisopropoxy(r15-2-methylindenyl)-silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)diisopropoxy(rls-2-methyiindenyl)-silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)diisopropoxy(rls-2-methylindenyl)-silanetitanium (IV)dimethyl, (cyclododecylamido)diisopropoxy(r15-2-methylindenyl)-silanetitanium (IV)dibenzyl, (2,4,6-trimethylanilido)diisopropoxy(t~s-2-methyl-indenyl)silanetitanium (II) 1,4-diphenyl- I ,3-butadiene, (2,4,6-trimethylanilido)diisopropoxy(rls-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)diisopropoxy(r15-2-methylindenyl)silanetitanium (III) (N,N-dimethylamino)benzyl, (2,4,6-trimethyanilido)diisopropoxy(rls-2-methylindenyl)silanetitanium (IV)dimethyl, (2,4,6-trimethylanilido)diisopropoxy{rls-2-methylindenyl)silanetitanium (IV)dibenzyl, (1-adamantylamido)diisopropoxy(rls-2-methylindenyl)silanetitanium (II) l,4diphenyl-1,3-butadiene, (I-adamantylamido)diisopropoxy(r15-2-methylindenyl)silanetitanium (II) 1,3 pentadiene, (I-adamantylamido)diisopropoxy(r15-2-methylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (I-adamantylamido)diisopropoxy(rls-2-methylindenyl)silanetitanium (IV)dimethyl, (I-adamantylamido)diisopropoxy(rls-2-methylindenyl)silanetitanium (IV)dibenzyl, (n-butylamido)dimethoxy(rls-2-methylindenyl)silanetitanium (II) 1,4-dipheny11,3-butadiene, (n-butylamido)dimethoxy(~5-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)dimethoxy(r15-2-methylindenyl)silanetitanium (I1I) 2-(N,N
dimethylamino)benzyl, (n-butylamido)dimethoxy(rls-2-methylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)dimethoxy(r15-2-methylindenyl)silanetitaniurn (IV} dibenzyl, (cyclododecylamido)dimethoxy(~5-2-methylindenyl)silanetitanium(II) l,4diphenyl-1,3-butadiene, (cyclododecylamido)dimethoxy(rls-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethoxy(rls-2-methylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)dimethoxy(r15-2-methylindenyl}silanetitanium (IV) dimethyl, (cyclododecylamido)dimethoxy(rls-2-methylindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)dimethoxy(rls-2-methylindenyl)silanetitanium (II) 1,4 diphenyl-1,3-butadiene, (2,4,6-trimethylanilido)dimethoxy(rls-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)dimethoxy(rls-2-methylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (2,4,6-trimethylanilido)dimethoxy(r15-2-methylindenyl)silanetitanium (IV)dimethyl, (2,4,6-trimethylanilido)dimethoxy(115-2-methylindenyl)silanetitanium (IV)dibenzyl, (I-adamantylamido)dimethoxy(rls-2-methylindenyl(silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (1-adamantylamido)dimethoxy(rls-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (I-adamantylamido)dimethoxy(r15-2-methylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (I-adamantylamido)dimethoxy(r15-2-methylindenyl)silanetitanium (IV) dimethyl, (1-adamantylamido)dimethoxy(rls-2-methylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)ethoxymethyl(r15-2-methylindenyl)silanetitanium (II) 1,4-Biphenyl 1,3-butadiene, (n-butylamido)ethoxymethyl(rls-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)ethoxymethyl(rls-2-methylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)ethoxymethyl(rls-2-methylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)ethoxymethyl(rls-2-methylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)ethoxymethyl(~5-2-methylindenyl)silanetitanium (III) 1,4-Biphenyl-1,3-butadiene, (cyclododecylamido)ethoxymethyl(rls-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)ethoxymethyl(r15-2-methylindenyl)silanetitanium (III) 2-{N,N-dimethylamino)benzyl, (cyclododecylamido)ethoxymethyl(r15-2-methylindenyl)silanetitanium (IV)dimethyl, (cyclododecylamido)ethoxymethyl(r15-2-methylindenyl)silanetitanium (IV)dibenzyl, {2,4,6-trimethylanilido)ethoxymethyl(rls-2-methyiindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (2,4,6-trimethylanilido)ethoxymethyl(rls-2-methylindenyl)silanetitanium (IIl 1,3-pentadiene, (2,4,6-trimethylanilido)ethoxymethyl(rls-2-methylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)ethoxymethyl(r)S-2-methylindenyl)silanetitanium (IV)dimethyl, (2,4,6-trimethylanilido)ethoxymethyl(r15-2-methylindenyl)silanetitanium (IV)dibenzyl, (1-adamantylamido)ethoxymethyl(rls-2-methylindenyl)siianetitanium (II) l,4diphenyl-1,3-butadiene, (1-adamantylamido)ethoxymethyl(rI5-2-methylindenyl)silanetitanium (II) 1,3-pentadiene, (I-adamantylamido)ethoxymethyl(r15-2-methylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)ethoxymethyl(r15-2-methylindenyl)silanetitanium (IV) dimethyl, (1-adamantylamido)ethoxymethylr155-2-methylindenyl)silanetitanium (IV) dibenzyl, 2,3-dimethylinden,~l complexes:
(t-butylamido)dimethyl(r15-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyll,3-butadiene, (t-butylamido)dimethyl(~5-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (t-butylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (t-butylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (IV) dimethyl, (t-butylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)dimethyl(~5-2,3-dimethylindenyl)-silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (n-butylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)dimethyl(rls-2,3-dimethylindenyl)-silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (n-butylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)dimethyl(rl5-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl, i0 (cyclododecylamido)dimethyl(r15-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (cyclododecylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, 15 (cyclododecylamido)dimethyl(r!5-2,3-dimethylindenyl)silanetitanium (IV)dimethyl, (cyclododecylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (IV)dibenzyl, (2,4,6-trimethylanilido)dimethyl(~5-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (2,4,6-trimethylanilido)dimethyl(r15-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, 20 (2,4,6-trimethylanilido)dimethyl(~5-2,3-dimethylindenyl)silanetitanium (III) 2 (N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)dimethyl{r15-2,3-dimethylindenyl)silanetitanium (IV)dimethyl, (2,4,6-trimethylanilido)dimethyl(r15-2,3-dimethylindenyl)silanetitanium (IV)dibenzyl, (1-adamantylamido)dimethyl(~5-2,3-dimethylindenyl)silanetitanium (II) l,4diphenyl-1,3-butadiene, 25 (1-adamantylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (1-adamantylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (IV)dimethyl, (1-adamantylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (IV)dibenzyl, 30 (t-butylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyl I,3-butadiene, (t-butylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (t-butylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (t-butylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (IV) dimethyl, 35 (t-butylamido)dimethyl(rls-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)diisopropoxy(r15-2,3-dimethylindenyl)silanetitanium (II) l,4diphenyl-1,3-butadiene, (n-butylamido)diisopropoxy(rls-2,3-dimethylindenyl)-silanetitanium (II) 1,3-pentadiene, (n-butylamido)diisopropoxy(rls-2,3-dimethylindenyl)-silanetitanium (III) 2-(N,N-dimethylamino)benzyl (n-butylamido)diisopropoxy(rls-2,3-dimethylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)diisopropoxy(rls-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)diisopropoxy(r)5-2,3-dimethylindenyl)-silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (cyclododecyiamido)diisopropoxy(rls-2,3-dimethylindenyl)-silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)diisopropoxy(rls-2,3-dimethylindenyl)-silanetitanium (III) (N,N-dimethylamino)benzyl, (cyclododecylamido)diisopropoxy(rls-2,3-dimethylindenyl)-silanetitanium (IV) dimethyl, (cyclododecylamido)diisopropoxy(rls-2,3-dimethylindenyl)-silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)diisopropoxy(r15-2,3-dimethyl-indenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (2,4,6-trimethylanilido)diisopropoxy(rls-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)diisopropoxy(r15-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)diisopropoxy(r15-2,3-dimethylindenyl)siianetitanium (IV) dimethyl, (2,4,6-trimethyianilido)diisopropoxy(rls-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)diisopropoxy(r)5-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (1-adamantylamido)diisopropoxy(r15-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)diisopropoxy(r15-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)diisopropoxy(~5-2,3-dimethylindenyl)silanetitanium (IV) dimethyl, (1-adamantylamido)diisopropoxy(rls-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)dimethoxy(rls-2,3-dimethylindenyl)silanetitanium (1i) 1,4-dipheny11,3-butadiene, (n-butylamido)dimethoxy(rls-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)dimethoxy(r)5-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)dimethoxy(rls-2,3-dimethylindenyl)silanetitanium {IV) dimethyl, (n-butylamido)dimethoxy(rls-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)dimethoxy(r15-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyl- I ,3-butadiene, (cyclododecylamido)dimethoxy(r15-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethoxy(rls-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)dimethoxy(r15-2,3-dimethylindenyl)silanetitanium (IV)dimethyl, (cyclododecylamido)dimethoxy(rls-2,3-dimethylindenyl)silanetitanium (IV)dibenzyl, (2,4,6-trimethylanilido)dimethoxy(r15-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (2,4,6-trimethylanilido)dimethoxy(~5-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)dimethoxy(r15-2,3-dimethylindenyl)silanetitanium (III) (N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)dimethoxy(rls-2,3-dimethylindenyl)silanetitanium (IV)dimethyl, (2,4,6-trimethylanilido)dimethoxy(rls-2,3-dimethylindenyl)silanetitanium (IV)dibenzyl, (1-adamantylamido)dimethoxy(r15-2,3-diemethylindenyl)silanetitanium (II) 1,4 diphenyl-l,3-butadiene, (I-adamantylamido)dimethoxy(~5-2,3-dimethylindenyl)silanetitanium(II) 1,3-pentadiene, (i-adamantylamido)dimethoxy(rls-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)dimethoxy(r15-2,3-dimethylindenyl)silanetitanium (IV)dimethyl, (1-adamantylamido)dimethoxy(r~s-2,3-dimethylindenyl)silanetitanium (IV)dibenzyl, (n-butylamido)ethoxymethyl{rls-2,3-dimethylindenyl)-silanetitanium (II) l,4diphenyl-1,3-butadiene, (n-butylamido)ethoxymethyl(rls-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido}ethoxymethyl(rls-2,3-dimethylindenyl)silanetitanium (iII) 2-(N,N
dimethylamino)benzyl, (n-butylamido)ethoxymethyl(~5-2,3-dimethylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)ethoxymethyl(r15-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)ethoxymethyl(rls-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (cyclododecylamido)ethoxymethyl(rls-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)ethoxymethyl(rls-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido}ethoxymethy!(r15-2,3-dimethylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)ethoxymethyl(r15-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)ethoxymethyl(rls-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (2,4,6-trimethylanilido)ethoxymethyl(rls-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)ethoxymethyl(r15-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)ethoxymethyl(rls-2,3-dimethylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)ethoxymethyl(rls-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl, (I-adamantylamido)ethoxymethyl(rls-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (I-adamantylamido)ethoxymethyl(rls-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene, (I-adamantylamido)ethoxymethyl(r15-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)ethoxymethyl(rls-2,3-dimethylindenyl)silanetitanium (IV)dimethyl, (I-adamantylamido)ethoxymethyl(r15-2,3-dimethylindenyl)silanetitanium (IV)dibenzyl, 3-methylindenyl complexes:
(t-butylamido)dimethyl(rls-3-methylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (t-butylamido)dimethyl(rls-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (t-butyiamido)dimethyl(rls-3-methylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (t-butylamido)dimethyl(rI5-3-methylindenyl)silanetitanium (IV) dimethyl, (t-butylamido)dimethyl(rls-3-methylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido}dimethyl(rls-3-methylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (n-butylamido)dimethyl(rls-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)dimethyl(tls-3-methylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (n-butylamido)dimethyl(rls-3-methylindenyl)silanetitanium (IV) dimethyl, {n-butylamido)dimethyl(r15-3-methylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)dimethyl(115-3-methylindenyl)silanetitanium (II) 1,4 Biphenyl-1,3-butadiene, (cyclododecyiamido)dimethyl(r15-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethyl(rls-3-methylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (cyclododecylamido)dimethyl(r15-3-methylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)dimethyl(rls-3-methylindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)dimethyl(r15-3-methylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (2,4,6-trimethylanilido)dimethyl(rls-3-methylylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)dimethyl(r15-3-methylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (2,4,6-trimethylanilido)dimethyl(rls-3-methylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)dimethyl(rls-3-methylindenyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)dimethyl(rls-3-methylindenyl)silanetitanium (II) 1,4-diphenyl 1,3-butadiene, (1-adamantylamido)dimethyl{r15-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)dimethyl(rls-3-methylindenyl)silanetitanium (III) 2-(N,N
dimethylamino}benzyl, {1-adamantylamido)dimethyl(r15-3-methylindenyl)silanetitanium (IV) dimethyl, (1-adamantylamido)dimethyl(rls-3-methylindenyl)silanetitanium (IV) dibenzyl, (t-butylamido)dimethyl(rls-3-methylindenyl}silanetitanium (II) 1,4-diphenyl-l,3butadiene, {t-butylamido)dimethyl(r15-3-methylindenyl)silanetitaniurn (II) 1,3-pentadiene, (t-butylamido)dimethyl(r)5-3-methylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (t-butylamido)dimethyl(~5-3-methylindenyl)silanetitanium (IV) dimethyl, (t-butylamido)dimethyl(rls-3-methylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)diisopropoxy(rls-3-methylindenyl)silanetitanium (II) 1,4-diphenyl 1,3-butadiene, (n-butylamido)diisopropoxy(rls-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)diisopropoxy(rls-3-methylindenyl)silanetitanium (II) 2-(N,N-dimethylamino)benzyl, (n-butylamido)diisopropoxy(rls-3-methylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)diisopropoxy(~5-3-methylylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)diisopropoxy(rls-3-methylindenyl)-silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (cyclododecylamido)diisopropoxy(r15-3-methylindenyl)-silanetitanium (III) 1,3-pentadiene, (cyclododecylamido)diisopropoxy(rls-3-methylindenyl)-silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)diisopropoxy(rls-3-methylindenyl)-silanetitanium (IV) dimethyl, (cyclododecylamido)diisopropoxy(r15-3-methylindenyl)-silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)diisopropoxy(r15-3-methylindenyl)silanetitanium (II) 1 diphenyl-1,3-butadiene, (2,4,6-trimethylanilido)diisopropoxy(rls-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)diisopropoxy(rls-3-methylindenyl}silanetitanium (III) (N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)diisopropoxy(rls-3-methylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)diisopropoxy(rls-3-methylindenyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)diisopropoxy(r15-3-methylindenyl)silanetitanium (II) l,4diphenyl-1,3-butadiene, (1-adamantylamido)diisopropoxy(r15-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (1-adarnantyiamido)diisopropoxy(~5-3-methylindenyl)silanetitanium (III} 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)diisopropoxy(r15-3-methylindenyl)silanetitanium (IV) dimethyl, (1-adamantylamido)diisopropoxy(r15-3-methylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)dimethoxy(rls-3-methylindenyl)silanetitanium (II) 1,4-Biphenyl 1,3-butadiene, (n-butylamido)dimethoxy(r)5-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)dimethoxy(rls-3-methylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)dimethoxy(r15-3-methylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)dimethoxy(rls-3-methylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)dimethoxy(r15-3-methylindenyl)silanetitanium (II) l,4diphenyl-1,3-butadiene, (cyclododecylamido)dimethoxy(rls-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethoxy(rls-3-methylindenyl)silanetitanium (1II) 2-(N,N
dimethylamino)benzyl, (cyclododecylamido)dimethoxy(rls-3-methylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)dimethoxy(rls-3-methylindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)dimethoxy(r15-3-methylindenyl)silanetitanium (II) 1,4-diphenyl-I ,3-butadiene, (2,4,6-trimethylanilido)dimethoxy(rls-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)dimethoxy(r15-3-methylindenyl)silanetitanium {III} 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethyianilido)dimethoxy(rls-3-methylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)dimethoxy(r~5-3-methylindenyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)dimethoxy(rls-3-methylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (1-adamantylamido)dimethoxy(r15-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)dimethoxy(rls-3-methylindenyl)silanetitanium {III) 2-(N,N
dimethylamino)benzyl, (1-adamantylamido)dimethoxy(r15-3-methylindenyl)silanetitanium (IV) dimethyl, (1-adamantytamido)dimethoxy(~5-3-methylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)ethoxymethyl(r15-3-methylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (n-butylamido)ethoxymethyl(r15-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)ethoxymethyl(rls-3-methylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (n-butylamido)ethoxymethyl(rls-3-methylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)ethoxymethyl(rls-3-methylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)ethoxymethyl(r15-3-methylindenyl)silanetitanium (II) 1,4-diphenyl- I ,3-butadiene, (cyclododecylamido)ethoxymethyl(~5-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)ethoxymethyl(r15-3-methylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)ethoxymethyl(r!5-3-methylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)ethoxymethyl(>75-3-methylindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)ethoxymethyl(r15-3-methylindenyl)silanetitanium (II) 1,4-diphenyl-I,3-butadiene, (2,4,6-trimethylanilido)ethoxymethyl(r15-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)ethoxymethyl(r153-methylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)ethoxymethyl(rls-3-methylindenyl)silanetitanium (IV)dimethyl, (2,4,6-trimethylanilido)ethoxymethyl(r15-3-methylindenyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)ethoxymethyl(r15-3-methylindenyl)silanetitanium (I1) l,4diphenyl-1,3-butadiene, (1-adamantylamido)ethoxymethyl(r!5-3-methylindenyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)ethoxymethyl(rls-3-methylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (1-adamantylamido)ethoxymethyl(rls-3-methylindenyl)silanetitanium (1V) dimethyl, (1-adamantylamido)ethoxymethyi(rls-3-methylindenyl)silanetitanium (IV) dibenzyl, 2-meth-3-ethylindenyl complexes:
(t-butylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido)dimethyl(r!5-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene, (t-butylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (t-butylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (t-butylamido)dimethyl(~5-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido}dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium, (II) I,4diphenyl-1,3-butadiene, _28_ (n-butylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)dimethyl(rls-2-methyl-3-ethylindenyl)-silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (cyclododecylamido)dimethyl(~5-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (IlI) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)dimethyl(r)5-2-methyl-3-ethylindenyl)siianetitanium (IV) dimethyl, (cyclododecylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)dimethyl(r15-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (2,4,6-trimethylanilido)dimethyl(r15-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)dimethyl(~5-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)dimethyl(~5-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium {IV) dibenzyl, (1-adamantylamido)dimethyl(r15-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (1-adamantylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)dimethyl(115-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (1-adamantylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl, (t-butylamido)dimethyl(rls-2-methyl-3-ethylindenyl)-silanetitanium (II) l,4diphenyl-1,3-butadiene, (t-butylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene, (t-butylamido)dimethyl(rls-2-methyl-3-ethylindenyl)-silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (t-butylamido)dimethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (t-butylamido)dimethyl(r!5-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)diisopropoxy(~5-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (n-butylamido)diisopropoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)diisopropoxy(r15-2-methy(-3-ethylindenyl}silanetitanium (1II) 2-(N,N-dimethylamino)benzyl, (n-butylamido)diisopropoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (n-butylarnido)diisopropoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)diisopropoxy(rl5-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (cyclododecylamido)diisopropoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)diisopropoxy(r15-2-methyl-3-ethylindenyl)-silanetitanium, (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)diisopropoxy(rls-2-methyl-3-ethylindenyl)-silanetitanium (IV) dimethyl, (cyclododecylamido)diisopropoxy(rls-2-methyl-3-ethylindenyl)-silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)diisopropoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (2,4,6-trimethylanilido)diisopropoxy(r15-2-methyl-3-ethyiindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)diisopropoxy{r15-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)diisopropoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)diisopropoxy(r15-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl' (1-adamantylamido)diisopropoxy(r15-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (1-adamantylamido)diisopropoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)diisopropoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (I-adamantylamido)diisopropoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (1-adamantylamido)diisopropoxy(rl5-2-methyl-3-ethyIindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)dimethoxy(~S-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (n-butylamido)dimethoxy(r15-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)dimethoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (n-butylamido)dimethoxy(r15-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)dimethoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)dimethoxy(r15-2-methyl-3-ethyl-indenyl)silanetitanium (II) I,4-Biphenyl-1,3-butadiene, (cyclododecylamido)dimethoxy(rls-2-methyl-3-ethyiindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethoxy(r15-2-methyl-3-ethylindenyl)silanetitanium (III) (N,N-dimethylamino)benzyl, (cyclododecylamido)dimethoxy(r15-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)dimethoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)dimethoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-diphenyl- I ,3-butadiene, (2,4,6-trimethylanilido)dimethoxy(r15-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)dimethoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)dimethoxy(~5-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)dimethoxy(rls-2-methyl-3-ethlylindenyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)dimethoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (1-adamantylamido)dimethoxy(~5-2-methyl-3-ethylindenyl)siianetitanium (II) 1,3-pentadiene, (I-adamantylamido)dimethoxy(r15-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)dimethoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (1V) dimethyl, (I-adamantylamido)dimethoxy(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)ethoxymethyl(r15-2-methyl-3-ethylindenyl)sifanetitanium (II) 1,4-Biphenyl-1,3-butadiene, {n-butylamido)ethoxymethyl(~5-2-methyl-3-ethylindenyl)silanetitanium {II) 1,3-pentadiene, (n-butylamido)ethoxymethyl(r15-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)ethoxymethyl(r)5-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)ethoxymethyl(r15-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)ethoxymethyl(rls-2-methyl-3-ethyl-indenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (cyclododecylamido)ethoxymethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (II) I ,3-pentadiene, (cyclododecylamido)ethoxymethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)ethoxymethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)ethoxymethyl(r)5-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl, S (2,4,6-trimethylanilido)ethoxymethyl(r)5-2-methyl-3-ethylindenyl)silanetitanium (II) I ,4-diphenyl- I,3-butadiene, (2,4,6-trimethylanilido}ethoxymethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)ethoxymethyl(r15- 2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)ethoxymethyl(r)5-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)ethoxymethyl(r)5-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)ethoxymethyl(r)5-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (1-adamantylamido)ethoxymethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (II) IS 1,3-pentadiene, (I-adamantylamido)ethoxymethyl(r15-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)ethoxymethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl, (1-adamantylamido)ethoxymethyl(rls-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl, 2,3,4,6-tetramethylindenyl complexes (t-butylamido)dimethyl(r)5-2,3,4,6-tetramethylindenyl)silanetitaniumJ (II) l,4diphenyl-1,3-butadiene, 2S (t-butylamido)dimethyl(r15-2,3,4,6-tetramethylindenyl)silanetitaniurn (III) 1,3-pentadiene, (t-butylamido)dimethyl(r15-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N
dimethylamino)benzyl, (t-butylamido)dimethyI(r15-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (t-butylamido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)dimethyl(r)5-2,3,4,6-tetramethylindenyl)silanetitanium (II) l,4diphenyl-1,3-butadiene, (n-butylamido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II} 1,3-pentadiene, (n-butylamido)dimethyl(r)5-2,3,4,6-tetramethylindenyl)-silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylarnido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, 3S (n-butylamido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)dimethyl(rI5-2,3,4,6-tetramethylindenyl}silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (cyclododecylamido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethyl(~5-2,3,4,6-tetramethylindenyl)silanetitaniurn (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylaniiido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (2,4,6-trimethylanilido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)dimethyl(r15-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)dimethyl(r15-2,3,4,6-tetiamethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (1-adamantylamido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (III) (N,N-dimethylamino)benzyl, (1-adamantylamido)dimethyl(r15-2,3,4,6-tetramethylindenyl)siianetitanium (IV) dimethyl, (1-adamantylamido)dimethyl(rl5-2,3,4,6-tetrarnethylindenyl)silanetitanium (IV) dibenzyl, (t-butylamido)dimethyl(rl5-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (t-butylamido)dimethyl(~5-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene, (t-butylamido)dimethyl(r15-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (t-butylamido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (t-butylamido)dimethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)diisopropoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (n-butylamido)diisopropoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)diisopropoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (III) (N,N-dimethylamino)benzyl, (n-butylamido)diisopropoxy(rl5-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)diisopropoxy(r15-2,3,4,6-tetramethylindenyl)silanetitanium (1V) dibenzyl, (cyclododecylamido)diisopropoxy(r)5-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (cyclododecylamido)diisopropoxy(rl 5-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)diisopropoxy(rls-2,3,4,6-tetramethyiindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)diisopropoxy(rl5-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)diisopropoxy(r15-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)diisopropoxy(r)5-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (2,4,6-trimethylanilido)diisopropoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)diisopropoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)diisopropoxy(r15-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)diisopropoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl (I-adamantylamido)diisopropoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (1-adamantylamido)diisopropoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene, (I-adamantylamido)diisopropoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)diisopropoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (I-adamantylamido)diisopropoxy(r)5-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)dimethoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (n-butylamido)dimethoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)dimethoxy(r15-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)dimethoxy(r)5-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)dimethoxy(r15-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)dimethoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (cyclododecylamido)dimethoxy{r15-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethoxy(r15-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecyiamido)dimethoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)dimethoxy(r15-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)dimethoxy(r15-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (2,4,6-trimethylanilido)dimethoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)dimethoxy(rl5-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)dimethoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium {IV) dimethyl, (2,4,6-trimethylanilido)dimethoxy(r15-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)dimethoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-Biphenyl- I ,3-butadiene, (I-adamantylamido)dimethoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene, (I-adamantylamido)dimethoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyi, (I-adamantylamido)dimethoxy(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (1-adamantylamido)dimethoxy(r15-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)ethoxymethyl(~5-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (n-butylamido)ethoxymethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium(II) 1,3-pentadiene, (n-butylamido}ethoxymethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)ethoxymethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)ethoxymethyl(~5-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)ethoxymethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (cyclododecylamido)ethoxymethyl(r15-2,3,4,6-tetramethylindenyl)si fanetitanium (II) 1,3-pentadiene, (cyclododecylamido)ethoxymethyl(r15-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)ethoxymethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)ethoxymethyl(rls -2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)ethoxymethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (2,4,6-trimethylanilido)ethoxymethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)ethoxymethyl(r15-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)ethoxymethyl(r15-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)ethoxymethyl(r15-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl, ( 1-adamantylamido)ethoxymethyl(rl5-2,3,4,6-tetramethylindenyl)sitanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (I-adamantylamido)ethoxymethyl(rls-2,3,4,6-tetramethyindenyl)silanetitanium (II) 1,3-pentadiene, (I-adamantylamido)ethoxymethyl(r15-2,3,4,6-tetramethyiindeny!)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)ethoxymethyl(rls-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl, and (1-adamantylamido)ethoxymethyl(r15-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl 2,3.4.6,7pentamethylinden l~hlexes:
(t-butylamido)dimethyl(r15-2,3,4,6,7-pentamethyiindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (t-butylamido)dimethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene, (t-butylamido)dimethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (t-butylamido)dimethyl(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (1V) dimethyl, (t-butylamido)dimethyl(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)dimethyl(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (n-butylamido)dimethyl(rls-2,3,4,6,7-pentamethylindenyi)silanetitanium (II) 1,3-pentadiene, (n-butylamido)dimethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)dimethyl(r15-2,3,4,6,?-pentamethylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)dimethyl (rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl, (cyclododecyiamido)dimethyl(rIS-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,4-Biphenyl- I ,3-butadiene, (cyclododecylamido)dimethyl(rls-2,3,4,6,7-pentamethylindenyl)si(anetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethyl(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)dimethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)dimethyl(rls-2,3,4,6,7-pentamethylindenyi)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)dimethyl(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (2,4,6-trimethylanilido)dimethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)dimethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium {III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)dimethyl(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)dimethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)dimethyl(~5-2,3,4,6,7-pentamethylindenyl)siianetitanium (II) 1,4-Biphenyl-1,3-butadiene, (I-adamantylamido)dimethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (1I) 1,3-pentadiene, (1-adamantylamido)dimethyl(r)5-2,3,4,6,7-pentamethylindenyl)siianetitanium (III) 2-(N,N-dimethylamino)benzyl, (I-adamantylamido)dimethyl(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (I-adamantylamido)dimethyl(rIS-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl, (t-butylamido)dimethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (t-butylamido)dimethyl(r)5-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene, (t-butylamido)dimethyl(rIS-2,3,4,6,7-pentamethyiindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (t-butylamido)dimethyl{r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (t-butylamido)dimethyl(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)diisopropoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (n-butylamido)diisopropoxy(115-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)diisopropoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)diisopropoxy(~5-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)diisopropoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)diisopropoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium {II) 1,4-Biphenyl-I,3-butadiene, (cyclododecylamido)diisopropoxy(r)5-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)diisopropoxy(rl5-2,3,4,6,7-pentamethyiindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)diisopropoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)diisopropoxy(rls-2,3,4,6,7-pentamethyIindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)diisopropoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (2,4,6-trimethylanilido)diisopropoxy(rls-2,3,4,6,7-pentamethylindenyt)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)diisopropoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)diisopropoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)diisopropoxy(r)5-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)diisopropoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) I,4-Biphenyl-I,3-butadiene, (I-adamantylamido)diisopropoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)diisopropoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (I-adamantylamido)diisopropoxy(~5-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (1-adamantylamido)diisopropoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)dimethoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (n-butylamido)dimethoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)dimethoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)dimethoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)dimethoxy(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium {IV) dibenzyl, (cyclododecylamido)dimethoxy(r15-2,3,4,6,7-pentamethyiindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (cyclododecylamido)dimethoxy(rls-2,3,4,6,?-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)dimethoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)dimethoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)dimethoxy(r15-2,3,4,6,7-pentamethytindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)dimethoxy(r15-2,3,4,6,7-pentamethytindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (2,4,6-trimethylanilido)dimethoxy(r15-2,3,4,6,7-pentamethylindenyt)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)dimethoxy(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)dimethoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)dimethoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)dimethoxy(rl5-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (I-adamantylamido)dimethoxy(~5-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)dimethoxy(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)dimethoxy(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (I-adamantylamido)dimethoxy(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl, (n-butylamido)ethoxymethyl(rl5-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (n-butylamido)ethoxymethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene, (n-butylamido)ethoxymethyl(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (n-butylamido)ethoxymethyt(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (n-butylamido)ethoxymethyl(r)S-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl, (cyclododecylamido)ethoxymethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,4-Biphenyl-1,3-butadiene, (cyclododecylamido)ethoxymethyl(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene, (cyclododecylamido)ethoxymethyl(r15-2,3,4,6,7-pentamethytindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (cyclododecylamido)ethoxymethyl(r15-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (cyclododecylamido)ethoxymethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl, (2,4,6-trimethylanilido)ethoxymethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (2,4,6-trimethylanilido)ethoxymethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene, (2,4,6-trimethylanilido)ethoxymethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (2,4,6-trimethylanilido)ethoxymethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, (2,4,6-trimethylanilido)ethoxymethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl, (1-adamantylamido)ethoxymethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (1-adamantylamido)ethoxymethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene, (1-adamantylamido)ethoxymethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl, (1-adamantylamido)ethoxymethyl(rls-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl, and (1-adamantylamido)ethoxymethyl(rl5-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl.
In general, the polymerization according to the present invention may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky Sinn type polymerization reactions, that is, temperatures from 0 to 250°C and pressures from atmospheric to 1000 atmospheres ( 100 MPa). Suspension, solution, slurry, gas phase or other polymerization process conditions may be employed if desired, however, solution polymerization process conditions, especially continuous solution polymerization process conditions, are preferred. A support may be employed but preferably the catalysts are used in a homogeneous manner, that is, they are dissolved in the solvent. Of course, the active catalyst system can form in sitr~ if the catalyst and its cocatalyst components are added directly to the polymerization process and a suitable solvent or diluent (such as hexane or iso-octane) including condensed monomer, are also used. Preferably the active catalyst is formed separately in a suitable solvent, such as in a slip stream, prior to adding it fo the polymerization mixture.
As previously mentioned, the present catalyst system is particularly useful in the preparation of EP and EPDM copolymers in high yield and productivity. The process employed may be either a solution or slurry process both of which are previously known in the art. Kaminsky, J.
Pol~Sci., Vol. 23, pp. 2151-64 (1985) reported the use of a soluble bis(cyclopentadienyl) zirconium dimethyl-alumoxane catalyst system for solution polymerization of EP and EPDM
elastomers. USP
5,229,478 disclosed a slurry polymerization process utilizing similar bis(cyclopentadienyl) zirconium based catalyst systems.

In general terms, it is desirable to produce such EP and EPDM elastomers under conditions of increased reactivity of the dime monomer component. The reason for this was explained in USP 5,229,478 in the following manner, which still remains true despite the advances attained in such reference. A major factor affecting production costs and hence the utility of an EPDM is the dime monomer cost. The dime is a more expensive monomer material than ethylene or propylene. Further, reactivity of dime monomers with previously known metallocene catalysts is lower than that of ethylene and propylene. Consequently, to achieve the requisite degree of dime incorporation to produce an EPDM with an acceptably fast cure rate, it has been necessary to use a dime monomer concentration which, expressed as a percentage of the total concentration of monomers present, is in substantial excess compared to the percentage of diene desired to be incorporated into the final EPDM product. Since substantial amounts of unreacted dime monomer must be recovered from the polymerization reactor effluent for recycle, the cost of production is increased unnecessarily.
Further adding to the cost of producing an EPDM is the fact that, generally, the IS exposure of an olefin polymerization catalyst to a dime, especially the high concentrations of dime monomer required to produce the requisite level of dime incorporation in the final EPDM product, often reduces the rate or activity at which the catalyst will cause polymerization of ethylene and propylene monomers to proceed. Correspondingly, lower throughputs and longer reaction times have been required, compared to the production of an ethylene-propylene copolymer elastomer or other a.-olefin copolymer elastomer.
Advantageously, a metallocene catalyst, especially a monocyclopentadienyl or -indenyl metallocene, is chosen that allows for increased dime reactivity which results in the preparation of EPDM polymers in high yield. For example, the monocyclopentadienyl and indenyl metallocene catalysts described previously, perform well in this respect.
Additionally, these catalyst systems achieve the economical production of fast curing EPDM polymers with dime contents of up to 20 weight percent or higher.
As a further illustration of the solution polymerization embodiment of this invention, reference is made to the figures. Optional aspects of the embodiments described in the figures are depicted with a dashed line.
In Figure 1, the process is illustrated as comprising two principal zones or steps, that is, ( 1 ) polymer formation and (2) polymer recovery, and solvent and unreacted monomer recovery and recycle or disposal. In the first zone, the process reagents are admixed in proper proportion and under appropriate conditions to form the desired polymer while in the second zone, the desired polymer is separated from unreacted monomer and solvent. The polymer is recovered for storage and/or use, the solvent is recycled, and the unreacted monomers are either recycled or disposed (the choice being dependent upon various factors such as monomer concentration, and monomer price).

Figure 2 illustrates a single reactor embodiment of Zone I of Figure 1. In this embodiment, the process reagents, that is, ethylene, one or more a-olefins, optionally one or more dienes, solvent, catalyst and optionally a molecular weight regulator (such as hydrogen), are fed to a single reaction vessel of any suitable design, such as stirred tank or loop.
The process reagents are S contacted within the reaction vessel under appropriate conditions to form the desired polymer, and then the output of the reactor is transferred to Zone II. All of the output can be transferred at one time to Zone II (as in the case of a single pass or other batch reactor), or it can be in the form of a bleed stream which forms only a part, typically a minor part, of the reaction mass (as in the case of a continuous process reactor in which an output stream is bled from the reactor at the same rate at which reagents are added to malntaln the polymerization at steady-state conditions).
Recovered solvent and unreacted monomers from Zone II can be recycled back to Zone I.
Figure 3 illustrates a preferred embodiment of Zone I of Figure I in which two reactors are configured and operated in series, that is, the output of one reactor is fed to the second reactor. The reactors can be the same or different but preferably, each is the same and each is a loop reactor. The reactors can be operated in like or different modes, but preferably the first reactor is operated in such a manner that the formation of the high molecular weight fraction of the desired polymer is promoted while the second reactor (that is, the reactor that receives as a feed the output from the first reactor) is operated in such a manner that the formation of the low molecular weight fraction of the desired polymer is promoted.
The temperature difference between the first and second reactor influences the molecular weight distribution (MWD) of the final product, such that the greater the temperature difference, the broader the MWD. While the operating temperature of each reactor will depend upon a host of factors, such as the a-olefin(s), the diene(s) (if any), the catalyst, the solvent, equipment and equipment design, pressure, flow rate and turbulence, the relative amounts of the reagents, and desired product properties, a typical operating temperature for the first reactor is between 65 and 90°C, and a typical operating temperature for the second reactor is between 85 and 120°C. The residence time of the reactants in the individual reactors will also depend upon these factors, but a typical residence time for the reactants in each reactor is between 2 and 90 minutes.
Ethylene, a-olefin, dime (if any), solvent and, optionally, hydrogen are blended by any convenient means in desired proportion, and then the blend is introduced into the first reactor, that is, the reactor whose output is used as a feed for the other or second reactor. Catalyst is typically introduced into the first reactor apart from the other reagents. Preferably, the first and second reactors are operated on a continuous basis such that as output from the first reactor is withdrawn as feed for the second reactor, additional reagents are added to the first reactor to malntaln the reaction mass in a steady-state, that is, a relatively constant and proportional concentration of ethylene, a-olefin, dime (if any), solvent, catalyst and molecular weight regulator (if any).

The first and second reactors are in fluid communication with one another, typically connected by one or more conduits. These conduits are typically equipped with one or more mixers (to promote a homogeneous blending of the reaction mass).
As with the first reactor, ethylene, a-olefin, diene (if any), solvent and, optionally, hydrogen are blended by any convenient means in desired proportion, and then the blend is introduced into the second reactor, that is, the reactor that receives as a feed the output from the other or first reactor. Likewise, catalyst (the same as or different from the catalyst used in the first reactor) is typically introduced into the second reactor apart from the other reagents.
The output from the first reactor typically contains from 1 to 30 weight percent solids (that is, polymer), and it either can be fed to the second reactor apart from the other reagents, or it can first be blended with one or more of the other reagents prior to its introduction into the second reactor. The output from the second reactor typically contains between 8 to 30 weight percent solids, and it is transferred to Zone II in which the desired polymer product is separated from the solvent and unreacted monomers, and the latter (that is, solvent and unreacted monomers) are individually either recycled to Zone I or disposed in a safe and environmentally acceptable manner.
Figure 4 illustrates a preferred embodiment of Zone I of Figure 1 in which two reactors are configured and operated in parallel, that is, neither reactor produces a feed for the other reactor. Here too, the reactors can be the same or different, but preferably each is the same as the other and each is a loop reactor. The reactors can be operated in like or different modes, but preferably one reactor is operated in such a manner that the formation of the high molecular weight fraction of the desired polymer is promoted while the other reactor is operated in such a manner that the formation of the low molecular weight fraction of the desired polymer is promoted. Preferably each reactor is operated in a steady-state mode with an operating temperature and reagent residence time similar to that of the reactors configured and operated in series.
Mixers, pumps and other such equipment are employed as desired.
The output from each reactor typically coma 1 ns between about 1 and about 30 weight percent solids. While the output from the individual reactors can be routed separately to Zone II, typically the output from each reactor is mixed with the other prior to routing to Zone II.
Figure 5 illustrates four possible configurations for embodiments of this invention comprising three reactors. Configuration A depicts three reactors in series with the output from the first reactor serving as a feed for the second reactor, and the output from the second reactor serving as a feed for the third reactor. Configuration B depicts three reactors in parallel in which none of the reactors use as a feed the output from one of the other reactors.
Configuration C depicts three reactors in which the two reactors are in series, and the two in series are in parallel with the third.
Configuration D depicts three reactors in which two are in parallel, and the two in parallel are in series with the third. Similar configurations can be drawn for embodiments comprising four or more reactors.
Figure 6 illustrates one embodiment of Zone II of this invention. Reaction product, that is the ultimate EP or EPDM product comprising both the high and low molecular weight fractions, is removed from Zone I (which ends at the points) at which reaction product is no longer routed to another reactor) to a first stage solvent recovery system. The reaction product is typically between 8 and 30 weight percent solids, and comprises EP or EPDM copolymer, solvent, unreacted comonomers, catalyst and catalyst residue, and residual amounts of hydrogen. Recovery of the copolymer requires its separation from these other components and according to the process of this invention, this is accomplished without the use of steam stripping, that is, essentially under anhydrous conditions (although minor amounts of water may be present in the reaction product from other sources, for instance, as a deactivator for the borane component of the catalyst).
The reaction product or product stream from Zone I is typically at a temperature between 90 and 120°C (the operating temperature of the second reactor in a two reactor configuration) and for embodiments in which a flash devolatilizer is the equipment of the first stage solvent recovery zone, the temperature of this stream is preferably ral sed to between 210 and 250°C by routing the stream through a series of heat exchangers. In the devolatilizer the product stream is subjected to a sudden pressure drop of at least 50 percent which results in a majority of the solvent and unreacted monomers to flash off for eventual separation, recycle and purification or disposal. The remaining portion of the product stream, that is, the condensed or polymer-coma I ning phase, is discharged, typically through a gear pump which is operated under a positive pressure (for instance, from 5 to 100 psig (35 to 700 kPa)), into the second stage solvent recovery zone, which is, for instance, a vacuum extruder or other vacuum vessel, or a thetrna) dryer. At this point, the solids content of the product stream has increased over 100 percent, for instance, to between 20 and 80 weight percent.
The second stage recovery zone is operated under conditions in which the solids content of the product stream is increased to over 99 weight percent before it is transferred in a molten state to the polymer isolation zone. This zone can comprise any equipment in which the polymer product is finished for use, storage and/or shipping, for instance, a pelletizer or baler.
In another embodiment of this invention, the process comprises more than two anhydrous solvent recovery operations in which the solids concentration of the final product is greater than 99 weight percent. For example, two flash vessels can be used in combination with a vacuum extruder or thermal dryer or three flash vessels can be operated in series with at least one vessel operated under vacuum conditions.
In other embodiments of this invention, the first stage solvent recovery zone can comprise a thermal dryer or vacuum extruder and the second stage solvent recovery zone can comprise a flash devolatilizer. Alternatively, the first and second stage solvent recovery zones can comprise a flash devolatilizer or a vacuum extruder or a thermal dryer.
In yet other embodiments of this invention, additives, modifiers and other materials can be blended with the EP or EPDM product. Certain of these materials, such as antioxidants, can be added directly to one or more of the reactors or to the product as it passes from one reactor to another.
Typically, however, materials are not added to the product stream until after it is discharged from the last reactor through which it will pass. For example, prior to entering the heat exchangers, the product stream can be admixed with such materials as processing alds, for instance, calcium stearate, catalyst deactivators, for instance, minor amounts of water (which deactivates any remalning boron cocatalyst), antioxidants, for instance, Irganox~ 1076 (a hindered phenol manufactured and sold by Ciba-Geigy Corporation), and a peroxide to promote crosslinking (which in turn promotes an increase in Mooney viscosity).
Preferred EP or EPDM products are made with a metallocene catalyst that is free of aluminum (the presence of which has a detrimental effect on certain of the product physical properties, such as color). Moreover, due to the high efficiency of these aluminum-free catalysts, less is required and since less is required, less catalyst residue is present in the final product. In fact so little catalyst residue is present in the final product that the process of these embodiments does not require a catalyst residue removal or treatment step as is required in conventional processes.
The EP and EPDM
products made by the process of this invention are also substantially free of color bodies.
Fabricated articles made from EP and/or EPDM made by the process of this invention may be prepared using any conventional polyolefin processing technique. Useful articles include films (such as, cast, blown and extrusion coated), fibers (such as, staple fibers, spunbond fibers or melt blown fiber systems as disclosed in USP 4,340,563, USP 4,663,220, USP
4,668,566, or USP
4,322,027, and gel spun fiber systems as disclosed in USP 4,413,110), both woven and nonwoven fabrics (such as, spunlaced fabrics disclosed in USP 3,485,706) or structures made from such fibers (including, blends of these fibers with other fibers, such as polyethyleneterephthalat (PET) or cotton) and molded articles (such as those made using an injection molding process, a blow molding process or a rotomolding process). The new polymers described herein are also useful for wire and cable coating operations, as well as in sheet extrusion for vacuum forming operations.
Examples The polymer products of Examples 1-4 were produced in a solution polymerization process using two continuously stirred reactors operated in series. The catalyst used in these examples was formed in situ and consisted of a monocyclopentadienyl metallocene complex with titanium in the plus 4 oxidation state, trispentafluorophenyl borane activator, and modified methyl aluminoxane (MMAO) scavenger. The polymer products of Examples 1-4 were each stabilized with 1250 ppm calcium stearate, 1000 ppm IrganoxTM 1076, and 1600 ppm PEPQTM. IrganoxT"' 1076 is a hindered phenol stabilizer, that is, octadecyl-3, 5-ditertiarybutyl- 4-hydroxyhydrocinnamate, and PEPQT"' is a phosphonite stabilizer, that is, tetrakis(2,4-ditertiarybutylphenol)4,4'-biphenylene diphosphonite.
Irganox is a trademark of and is made by Ciba-Geigy Corporation. PEPQ is a trademark of and is made by Sandoz. These additives were added to the second reactor exit stream.
Ethylene was introduced into a mixture of Isopar E (a mixture of Cg-C 10 saturated hydrocarbons made by Exxon), propylene and 5-ethylidene-2-norbornene (ENB) forming a reactor feed stream. This stream was continuously injected into the first reactor. A
similar reactor feed stream was prepared for the second reactor except hydrogen was mixed with the ethylene prior to combining the ethylene with the diluent and comonomers. The reactor feed stream compositions for reactors one and two are reported in Tables 2 and 3, respectively. The polymerization reactions of Examples I-4 were performed under steady state conditions, that is, with a constant reactant concentration and continual input of solvent, monomers, and catalyst, and withdrawal of unreacted monomers, solvent and polymer. For these polymerizations, the first reactor pressure was held at 550 psig (3.8 MPa), and the second reactor pressure was held at 525 psig (3.6 MPa).
After polymerization, the reactor exit stream was introduced into a flash vessel in which the solids concentration was increased by at least 100 percent. A
portion of the unreacted monomers, that is, the ENB, ethylene and propylene, and the unused diluent were then collected and disposed, and the product exit stream from the flash vessel was then transferred to a devolatilizing extruder. The remaining unreacted monomers and unused diluent were removed and discarded, and the resulting polymer was strand chopped into pellets after being cooled in a water bath. Table 1 describes the overall process conditions:
Table 1 Overall process conditions Example 1 2 3 4 Total ethylene conversion, percent77.0 72.9 52.7 78.1 Propylene in polyethylene, mole 17.72 19.88 32.78 38.28 percent Propylene in polyethylene, wt. 23.24 25.89 40.66 45.85 percent Total propylene conversion, percent43.1 43.9 27.4 52.4 Propylene/Total monomer ratio 0.32 0.34 0.52 0.52 ENB in polyethylene, mole percent0.98 0.93 0.81 1.08 ENB in polyethylene, wt. percent 5.69 5.35 4.43 5.74 Total ENB conversion, percent 27.66 25.53 14.31 31.27 ENB/Total monomer ratio 0.12 0.12 0.11 0.11 Solvent+ENB+Propylene/ethylene 9.45 12.10 13.13 19.83 ratio Catalyst efficiency, million kg 0.994 1.409 2.059 0.283 polymer/kg Ti Table 2 1 st reactor process conditions Example 1 2 3 4 Percent of total polymer* from 1 22.9 30.7 34.1 20.3 st reactor, percent Ethylene conversion* 1st reactor, 48.7 48.7 36.3 36.3 percent Propylene in polyethylene *, mole 15.24 15.24 32.06 32.06 percent Propylene in polyethylene*, wt. percent20.20 20.20 39.87 39.87 Propylene conversion* 1 st reactor, 23.7 23.3 19.8 19.7 percent Propylene/Total monomer feed ratio 0.31 0.32 0.51 0.51 ENB in polyethylene*, mole percent 0.99 0.99 0.81 0.81 ENB in polyethylene*, wt. percent 5.80 5.80 4.46 4.46 ENB conversion* 1st reactor, percent16.88 16.49 11.26 11.26 ENB/Total monomer ratio_ 0.13 0.13 0.10 0.10 Solvent+ENB+propylene/ethylene ratio11.26 I 1.0314.53 14.54 Hydrogen concentration, mole percent0 0 0 0 Solids, wt. percent 5.37 5.47 4.20 4.20 Feed temp., C 9.9 I 0.9 7.1 7.3 Reactor temp., C 82.7 81.6 69.7 69.2 Exit temp., C 105.0 99.0 89.0 85.9 Catalyst efficiency, million kg polymer/kg2.105 3.231 3.192 2.124 Ti ~ ~ I I 1 *Calculated value Table 3 Second reactor process conditions Example 1 2 3 4 Ethylene conversion* 2d reactor, 71.8 64.3 42.2 73.1 percent Propylene in polyethylene*, mole 18.47 21.98 33.16 39.95 percent Propylene in polyethylene*, wt. percent24.14 28.41 41.07 47.37 Propylene conversion* 2d reactor, 37.8 37.3 20.1 47.5 percent Propylene/Total monomer fresh feed 0.33 0.36 0.53 0.53 ratio Propylene/Total monomer overall ratio0.34 0.37 0.54 0.54 ENB in polyethylene*, mole percent 0.97 0.90 0.80 1.15 ENB in polyethylene*, wt. percent 5.65 5.16 4.42 6.07 ENB conversion* 2d reactor, percent 22.67 18.62 9.88 27.70 ENB/Total monomer fresh ratio 0.12 0.11 0.12 0.12 ENB/Total monomer overall ratio 0.13 0.13 0.12 0.12 Solvent+ENB+Propylene/ethylene fresh8.36 13.16 11.72 25.18 feed ratio Solvent+ENB+Propylene/ethylene overall11.70 15.98 16.04 24.27 ratio Hydrogen concentration, mole percent0.081 0 0 0 Solids, wt. percent 10.45 8.23 6.90 7.80 Feed temp., C 14.3 14.2 13.8 7.8 Reactor temp., C l 15.0104.1 95.3 91.6 Catalyst efficiency, million kg polymer/kg0.859 1.127 1.739 0.231 Ti *Calculated value Table 4 Feed rates Example I 2 3 4 Ethylene 1 st reactor, kg/hr (pph**)0.684 0.667 0.685 0.685 (1.50) (1.47) (1.51)(1.51) Propylene 1st reactor, kg/hr (pph) 0.381 0.381 0.903 0.903 (0.84) (0.84) (1.99)(1.99) ENB 1 st reactor, kg/hr (pph) 0.154 0.154 0.177 0.177 (0.34) (0.34) (0.39)(0.39) Isopar E I st reactor, kg/hr (pph) 6.305 6.278 8.437 8.215 (13.90)(13.84)(18.60)(18.11) Hydrogen 1 st reactor, sccm * * 0 0 0 0 *

Polyethylene rate*, kg/hr (pph) 0.454 0.454 0.454 0.454 (I.0) (1.0) (1.0) (1.0) Ethylene 2d reactor, kg/hr (pph) I .129 0.680 0.676 0.676 (2.49) (1.50) {1.49)(1.49) Propylene 2d reactor, kg/hr {pph) 0.676 0.463 1.04 1.02 ( 1.49)( 1.02)(2.29)(2.25) ENB 2d reactor, kg/hr (pph) 0.25 0.15 0.23 0.23 (0.55) (0.32) (0.50)(0.50) Isopar E 2d reactor, kg/hr (pph) 8.1 8.15 6.369 14.96 S 1 I ( 14.04)(32.97) ( 17.97)( 17.97) Hydrogen 2d reactor, sccm 9.97 0 0 0 Polyethylene rate*, kg/hr (pph) 1.5 1 0.86 1.8 (3.3) (2.2) (1.9) (3.9) Additive flow, kg/hr (pph) 0.54 0.41 0.36 0.36 (1.2) (0.9) (0.8) (0.8) Catalyst 1 st reactor, ml/min 4.92 3.13 3.23 4.85 Borane cocatalyst I st reactor, 5.43 3.46 2.69 4.08 ml/min MMAO 1 st reactor, ml/min 8.98 5.73 4.32 6.56 1 st reactor borane/Ti molar ratio 4.9 5.0 3.4 3.5 1 st reactor MMAO/Ti molar ratio 7.9 7.9 l 1.7 11.9 Catalyst 2d reactor, ml/min 4.96 2.4 2.79 10.71 Borane cocatalyst 2d reactor, ml/min3.70 1.64 4.17 9.24 MMAO 2d reactor, ml/min 7.00 3.50 3.90 4.90 2d reactor borane/Ti molar ratio 3.0 3.0 3.0 3.5 2d reactor MMAO/Ti molar ratio I 3.0 3.0 3.0 3.0 ~

"~Lalculated value **pph = pounds per hour ***sccm = standard cubic centimeters per minute

Claims (19)

CLAIMS:
1. A process for the manufacture of an ethylene/.alpha.-olefin or an ethylene/.alpha.-olefin/diene monomer elastomer having a density of from 0.850 g/cm3 to 0.895 g/cm3 and comprising a high molecular weight fraction and a low molecular weight fraction, the process comprising the steps of:
A. contacting in a first reactor (1) ethylene, (2) at least one C3-C20 aliphatic .alpha.-olefin, (3) optionally at least one C4-C20 diene, (4) an activated catalyst comprising a Group 4 metal metallocene complex, and (5) a solvent, the first reactor operated such that the high molecular weight fraction of the elastomer is produced at a solids concentration of from 1 to 15 weight percent, based on the weight of the reaction mass in the first reactor;
B. contacting in a second reactor (1) ethylene, (2) at least one C3-C20 aliphatic .alpha.-olefin, (3) optionally at least one C9-C20 diene, (4) an activated catalyst comprising a Group 4 metal metallocene complex, and (5) a solvent, and (6) the high molecular weight fraction of the elastomer from the first reactor, the second reactor operated such that the low molecular weight fraction of the elastomer is produced at a solids concentration of from 2 to 30 weight percent, based on the weight of the reaction mass in the first reactor;
C. removing an elastomeric product stream from the second reactor;
D. removing solvent from the elastomeric product stream of the second reactor in an anhydrous, first stage solvent recovery operation such that the solids concentration of the elastomeric product stream is increased by at least 100 percent; and E. removing additional solvent in an anhydrous, second stage solvent recovery operation from the elastomeric product of the first stage solvent recovery operation such that the solids concentration of the elastomeric product stream is in excess of 65 weight percent.
2. A process for the manufacture of an ethylene/.alpha.-olefin or an ethylene/.alpha.-olefin/diene monomer elastomer having a density of from 0.850 g/cm3 to 0.895 g/cm3 and comprising a high molecular weight fraction and a low molecular weight fraction, the process comprising the steps of:
A. contacting in a first reactor (1) ethylene, (2) at least one C3-C20 aliphatic .alpha.-olefin, (3) optionally at least one C4-C20 diene, (4) an activated catalyst comprising a Group 4 metal metallocene complex, and (5) a solvent, the first reactor operated such that the high molecular weight fraction of the elastomer is produced at a solids concentration of from 1 to 30 weight percent, based on the weight of the reaction mass in the first reactor;
B. contacting in a second reactor (1) ethylene, (2) at least one C3-C20 aliphatic .alpha.-olefin, (3) optionally at least one C4-C20 diene, (4) an activated catalyst comprising a Group 4 metal metallocene complex, and (5) a solvent, the second reactor operated such that the low molecular weight fraction of the elastomer is produced at a solids concentration of from 1 to 30 weight percent, based on the weight of the reaction mass in the second reactor;
-49a-C. recovering an elastomeric product stream from each of the first and second reactors, and then blending these individual product streams into a combined elastomeric product stream;
D, removing solvent from the elastomeric product stream of the second reactor in an anhydrous, first stage solvent recovery operation such that the solids concentration of the elastomeric product stream is increased by at least 100 percent; and E. removing additional solvent in an anhydrous, second stage solvent recovery operation from the elastomeric product of the first stage solvent recovery operation such that the solids concentration of the elastomeric product stream is in excess of 65 weight percent.
3. The process of Claim 1 in which the elastomer has (a) a polydispersity of between 1.5 to 15, and (b) a weight average molecular weight of between 10,000 and 1,000,000.
4. The process of Claim 3 in which the elastomer has a Mooney viscosity of between 1 and 150.
5. The process of Claim 3 in which the elastomer comprises, based on the weight of the elastomer, at least 30 weight percent ethylene, at least 15 weight percent of a C3-C20 aliphatic .alpha.-olefin, and at least 0.1 weight percent of at least one C4-C20 diene.
6. The process of Claim 5 in which the elastomer comprises, based on the weight of the polymer, less than 85 weight percent ethylene, and less than 20 weight percent of at least one C4-C20 diene.
7. The process of Claim 6 in which the C3-C20 aliphatic .alpha.-olefin is at least one of propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetra-decene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-cyclohexyl-1-propene, and vinyl cyclohexane, and the C4-C20 diene is at least one of butadiene, isoprene, piperylene, 1,4-pentadiene, 1,4-hexadiene, 1.5-hexadiene, 2-methyl-1,5-hexadiene, 1,6-octadiene, 1,7-octadiene, 7-methyl-1,6-octadiene, 2,5-norbornadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, and 5-vinyl-2-norbornene.
8. The process of Claim 7 in which the C3-C20 aliphatic .alpha.-olefin is propene and the C4-C20 diene is at least one of 5-ethylidene-2-norbornene and piperylene.
9. The process of Claim 7 in which the metallocene complex of both the first and second reactor catalysts corresponds to the formula:
ZLMX p X'q in which M is a metal of Group 4 of the Periodic Table of the Elements having an oxidation state of +2, +3 or +4 bound in an .eta.5 bonding mode to L;
L is a cyclopentadienyl-, indenyl-, tetrahydroindenyl-, fluorenyl-, tetrahydrofluorenyl-, or octahydrofluorenyl-group covalently substituted with at least a divalent moiety, Z, and L further may be substituted with from 1 to 8 substituents independently selected from the group consisting of hydrocarbyl, halo, halohydrocarbyl, hydrocarbyloxy, dihydrocarbylamine, dihydrocarbylphosphino or silyl groups containing up to 20 nonhydrogen atoms;
Z is a divalent moiety bound to both L and M via .sigma.-bonds, said Z
comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally, also comprising nitrogen, phosphorus, sulfur or oxygen;
X is an anionic or dianionic ligand group having up to 60 atoms exclusive of the class of ligands that are cyclic, delocalized, .pi.-bound ligand groups;
X' independently each occurrence is a neutral Lewis base ligating compound having up to 20 atoms;
-50a-p is 0, 1 or 2, and is two less than the formal oxidation state of M, with the proviso that when X is a dianionic ligand group, p is 1; and q is 0, 1 or 2.
10. The process of Claim 9 in which M is titanium, zirconium or hafnium, and L
is cyclopentadienyl or indenyl.
11. The process of Claim 10 in which the metallocene complex is activated with a perfluorinated tri(aryl)boron compound.
12. The process of Claim 11 in which the perfluorinated tri(aryl)boron compound is tris(pentafluorophenyl)borane.
13. The process of Claim 10 in which the metallocene complex is activated by an activating technique.
14. The process of Claim 13 in which the activating technique is bulk electrolysis.
15. The process of Claim 7 in which the activated catalyst of both the first and second reactor corresponds to the formula:
(ZLM*X*.RHO..cndot.)-A-in which M* is a metal of Group 4 of the Periodic Table of the Elements having an oxidation state of at least one of +2 and +3, bound in an .eta.5 bonding mode to L;
L is a cyclopentadienyl-, indenyl-, tetrahydroindenyl-, fluorenyl-, tetrahydrofluorenyl-, or octahydrofluorenyl-group covalently substituted with at least a divalent moiety, Z, and L further may be substituted with from 1 to 8 substituents independently selected from the group consisting of hydrocarbyl, halo, halohydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, dihydrocarbylphosphino or silyl groups containing up to 20 nonhydrogen atoms;
Z is a divalent moiety bound to both L and M* via .sigma.-bonds, said Z
comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also optionally comprising nitrogen, phosphorus, sulfur or oxygen;
-50b-X* is an anionic ligand group having up to 60 atoms exclusive of the class of ligands that are cyclic, delocalized, .pi.-bound ligand groups;
p* is 0 or 1, and is three less than the formal oxidation state of M; and A- is an inert, noncoordinating anion.
16. The process of Claim 15 in which M is titanium, zirconium or hafnium, L is cyclopentadienyl or indenyl, and A- is derived from a cocatalyst corresponding to the formula (L*-H)d- (A)d-in which L* is a neutral Lewis base;
(L*-H)- is a Bronsted acid;
(A)d- is a noncordinating, compatible anion having a charge of d-, and d is an integer of 1-3.
17. The process of Claim 16 in which the catalyst of the first reactor is the same as the catalyst of the second reactor.
18. The process of Claim 16 in which the catalyst of the first reactor is different than the catalyst of the second reactor.
19. The process of Claim 9 in which the first reactor is operated at a temperature between 65 and 90 C, and the second reactor is operated at a temperature between 85 and 120 C.
-50c-
CA002256668A 1996-07-12 1997-07-09 Elastomers and process for their manufacture Expired - Lifetime CA2256668C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US08/679,538 1996-07-12
US08/679,538 US6545088B1 (en) 1991-12-30 1996-07-12 Metallocene-catalyzed process for the manufacture of EP and EPDM polymers
PCT/US1997/012294 WO1998002471A1 (en) 1996-07-12 1997-07-09 Elastomers and process for their manufacture

Publications (2)

Publication Number Publication Date
CA2256668A1 CA2256668A1 (en) 1998-01-22
CA2256668C true CA2256668C (en) 2006-08-22

Family

ID=24727319

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002256668A Expired - Lifetime CA2256668C (en) 1996-07-12 1997-07-09 Elastomers and process for their manufacture

Country Status (19)

Country Link
US (1) US6545088B1 (en)
EP (1) EP0910593B1 (en)
JP (1) JP2000514857A (en)
KR (1) KR100496101B1 (en)
CN (1) CN1098289C (en)
AT (1) ATE200680T1 (en)
AU (1) AU718342B2 (en)
BR (1) BR9710347A (en)
CA (1) CA2256668C (en)
CZ (1) CZ9499A3 (en)
DE (1) DE69704617T2 (en)
ES (1) ES2156001T3 (en)
HU (1) HUP9904354A3 (en)
NO (1) NO990095L (en)
NZ (1) NZ332880A (en)
PL (1) PL331038A1 (en)
TR (1) TR199900050T2 (en)
TW (1) TW341576B (en)
WO (1) WO1998002471A1 (en)

Families Citing this family (180)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4418107B2 (en) 1998-03-04 2010-02-17 エクソンモービル・ケミカル・パテンツ・インク Products and methods for producing polyolefin polymer dispersions
US6319998B1 (en) 1998-03-04 2001-11-20 Exxon Mobil Chemical Patents Inc. Method for making polymer blends by using series reactors
JP4275857B2 (en) * 1998-03-04 2009-06-10 エクソンモービル・ケミカル・パテンツ・インク Method for enhancing diene conversion in EPDM type polymerization
JP5276757B2 (en) * 1998-11-02 2013-08-28 ダウ グローバル テクノロジーズ エルエルシー Shear thinning ethylene / α-olefin interpolymers and methods for their production
US6369176B1 (en) * 1999-08-19 2002-04-09 Dupont Dow Elastomers Llc Process for preparing in a single reactor polymer blends having a broad molecular weight distribution
JP4566305B2 (en) * 1999-08-31 2010-10-20 日本ポリプロ株式会社 Method for purifying a solvent containing a component derived from a metallocene compound
US6838540B2 (en) 2000-01-26 2005-01-04 Mitsui Chemicals, Inc. Olefin polymer and production processes thereof
DE60122572T2 (en) 2000-10-25 2007-10-04 Exxonmobil Chemical Patents Inc., Baytown METHOD AND DEVICE FOR CONTINUOUS SOLUTION POLYMERIZATION
WO2002046251A2 (en) * 2000-12-04 2002-06-13 Exxonmobil Chemical Patents Inc. Ethylene copolymer compositions suitable for viscosity index improvers and lubricant compositions
AU2002227427A1 (en) * 2000-12-20 2002-07-01 Exxonmobil Chemical Patents Inc Olefin polymerization process to produce branched polymer compositions
US7022766B2 (en) 2001-05-31 2006-04-04 Mitsui Chemicals, Inc. Olefin block copolymer, viscosity index improver for lubricating oils and lubricating oil composition
SG120869A1 (en) * 2001-05-31 2006-04-26 Mitsui Chemicals Inc Olefin block copolymer, viscosity index improver for lubricating oils and lubricating oil composition
WO2003050148A1 (en) 2001-12-12 2003-06-19 Exxonmobil Chemical Patents Inc. Compositions suitable for elastomeric membranes
WO2003066725A2 (en) 2002-02-08 2003-08-14 Exxonmobil Chemical Patents Inc. Multimodal ethylene, alpha-olefin and diene polymers, processes for making and devices comprising such compositions
US6806336B2 (en) 2002-06-19 2004-10-19 Exxonmobil Chemical Patents Inc. Process for polymerizing ethylene, higher alpha-olefin comonomer and dienes, especially vinyl norbornene; polymers made using such processes; and articles made from such polymers
US7294681B2 (en) 2002-10-15 2007-11-13 Exxonmobil Chemical Patents Inc. Mutliple catalyst system for olefin polymerization and polymers produced therefrom
EP1586591A4 (en) * 2003-01-23 2006-06-14 Mitsui Chemicals Inc PROCESS FOR PRODUCING ETHYLENE/a-OLEFIN/UNCONJUGATED POLYENE COPOLYMER AND ETHYLENE/a-OLEFIN/UNCONJUGATED POLYENE COPOLYME R
WO2004111123A1 (en) * 2003-06-10 2004-12-23 Dow Global Technologies Inc. Film layers made from ethylene polymer blends
ES2337936T3 (en) 2003-08-19 2010-04-30 Dow Global Technologies Inc. SUITABLE INTERPOLIMEROS FOR USE IN THERMOPLASTIC TAILS AND PROCESSES TO PREPARE THEM.
US7084319B2 (en) 2003-12-05 2006-08-01 Exxonmobil Chemical Patents Inc. Catalyst fluidization in oxygenate to olefin reaction systems
RU2375381C2 (en) 2004-03-17 2009-12-10 Дау Глобал Текнолоджиз Инк. Catalyst composition, containing shuttle agent, for formation of multi-block-copolymer of higher olefin
JP5159302B2 (en) 2004-03-17 2013-03-06 ダウ グローバル テクノロジーズ エルエルシー Catalyst composition comprising a shuttling agent for forming an ethylene copolymer
BRPI0508173B1 (en) 2004-03-17 2016-03-15 Dow Global Technologies Inc multiblock copolymers, polymer, copolymer, a functional derivative, homogeneous polymer blend, process for preparing a propylene-containing multiblock copolymer and process for preparing a 4-methyl-1-pentene multiblock copolymer
GB0420396D0 (en) 2004-09-14 2004-10-13 Bp Chem Int Ltd Polyolefins
ATE517944T1 (en) * 2004-10-13 2011-08-15 Exxonmobil Chem Patents Inc ELASTOMERIC REACTOR BLEND COMPOSITIONS
KR100586922B1 (en) 2004-11-18 2006-06-08 금호폴리켐 주식회사 Preparation Method of EPDM Elastomer and Method of Controlling Productivity of The EPDM
TW200630449A (en) * 2004-12-21 2006-09-01 Dow Global Technologies Inc Polypropylene-based adhesive compositions
EP1674490A1 (en) * 2004-12-23 2006-06-28 Borealis Technology Oy Copolymer
EP1846498B1 (en) * 2005-01-31 2013-08-14 ExxonMobil Chemical Patents Inc. Polymer blends and pellets and methods of producing same
CN101142246B (en) 2005-03-17 2011-05-25 陶氏环球技术公司 Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation
CA2600318A1 (en) 2005-03-17 2006-09-28 Dow Global Technologies Inc. Catalyst composition comprising shuttling agent for regio-irregular multi-block copolymer formation
CN101321853A (en) 2005-03-17 2008-12-10 陶氏环球技术公司 Viscosity index improver for lubricant compositions
US9410009B2 (en) 2005-03-17 2016-08-09 Dow Global Technologies Llc Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation
WO2006138052A1 (en) 2005-06-13 2006-12-28 Exxonmobil Chemical Patents Inc. Thermoplastic blend compositions
RU2008114492A (en) * 2005-09-15 2009-10-20 Дау Глобал Текнолоджиз Инк. (Us) CONTROL OF THE STRUCTURE AND MOLECULAR MASS DISTRIBUTION OF POLYMERS BY MEANS OF TRANSFERRING BASED ON THE PRINCIPLE OF THE AGENT SHUTTLE WITH A LOT OF CENTERS
AR058449A1 (en) 2005-09-15 2008-02-06 Dow Global Technologies Inc CATALYTIC OLEFINE BLOCK COPOLYMERS VIA A POLYMERIZABLE TRANSFER AGENT
ATE542836T1 (en) * 2006-03-30 2012-02-15 Total Petrochemicals Res Feluy METHOD FOR PRODUCING ETHYLENE POLYMERS USING A SERIES OF REACTORS ARRANGE IN Sequence
EP2004776A1 (en) 2006-03-31 2008-12-24 ExxonMobil Chemical Patents Inc. Product recovery in gas-solids reactors
US7744746B2 (en) 2006-03-31 2010-06-29 Exxonmobil Research And Engineering Company FCC catalyst stripper configuration
US9120888B2 (en) 2006-06-15 2015-09-01 Dow Global Technologies Llc Functionalized olefin interpolymers, compositions and articles prepared therefrom and methods for making the same
US8785531B2 (en) * 2006-07-06 2014-07-22 Dow Global Technologies Llc Dispersions of olefin block copolymers
JP5535630B2 (en) * 2006-09-11 2014-07-02 ダウ グローバル テクノロジーズ エルエルシー Polyolefin dispersion technology used for resin-coated sand
US8476326B2 (en) * 2006-09-22 2013-07-02 Dow Global Technologies Llc Fibrillated polyolefin foam
PT2109641T (en) * 2007-01-17 2017-05-25 Agrofresh Inc Delivery of ethylene blocking and/or promoting agents
BRPI0812687A2 (en) 2007-07-16 2014-12-23 Dow Global Technologies Inc "COMPOSITION, FUNCTIONALIZED PROPILENE-BASED POLYMER ARTICLE"
CA2598957C (en) 2007-08-27 2014-07-15 Nova Chemicals Corporation Process for high temperature solution polymerization
CA2598960C (en) 2007-08-27 2015-04-07 Nova Chemicals Corporation High temperature process for solution polymerization
US8431096B2 (en) 2007-08-27 2013-04-30 Nova Chemicals (International) S.A Process for high temperature solution polymerization
US20100279032A1 (en) * 2007-09-24 2010-11-04 Dow Global Technologies Inc. Synthetic turf with shock absorption layer
EP2197942A2 (en) 2007-09-28 2010-06-23 Dow Global Technologies Inc. Dispersions of higher crystallinity olefins
BRPI0816589B1 (en) * 2007-10-25 2018-07-31 Dow Global Technologies Inc Method to form an article
US7910679B2 (en) * 2007-12-20 2011-03-22 Exxonmobil Research And Engineering Company Bulk homogeneous polymerization process for ethylene propylene copolymers
KR101254384B1 (en) * 2007-12-28 2013-04-15 다우 글로벌 테크놀로지스 엘엘씨 Pe-based crosslinked elastomeric foam with high filler loadings for making shockpads and articles used in footwear and flooring applications
FR2934599B1 (en) * 2008-07-29 2012-12-21 Arkema France MANUFACTURE OF POLYETHYLENE FROM RENEWABLE MATERIALS, POLYETHYLENE OBTAINED AND USES
DE102008039218A1 (en) 2008-08-22 2010-02-25 Woco Industrietechnik Gmbh Vulcanizable rubber compounds and elastomer molded parts obtainable from these rubber compounds
WO2010036642A1 (en) * 2008-09-23 2010-04-01 Dow Global Technologies Inc. Radically functionalized olefin-based polymer with reduced molecular weight change and method
US8969481B2 (en) 2008-12-18 2015-03-03 Exxonmobil Chemical Patent Inc. Peroxide cured TPV
WO2010111869A1 (en) 2009-03-31 2010-10-07 Dow Global Technologies Inc. Film made from heterogeneous ethylene/alpha-olefin interpolymer
US8722817B2 (en) * 2009-06-05 2014-05-13 Dow Global Technologies Llc Process to make long chain branched (LCB), block, or interconnected copolymers of ethylene
MX2011012938A (en) 2009-06-05 2012-01-27 Dow Global Technologies Llc Process to make long chain branched (lcb), block, or interconnected copolymers of ethylene.
US20110003940A1 (en) 2009-07-01 2011-01-06 Dow Global Technologies Inc. Ethylene-based polymer compositions for use as a blend component in shrinkage film applications
US8173232B2 (en) 2009-07-01 2012-05-08 Dow Global Technologies Llc Stretch hood films
US20120129417A1 (en) 2009-07-01 2012-05-24 Dow Global Technologies Llc Ethylenic polymer and its use
US8389086B2 (en) 2009-07-01 2013-03-05 Dow Global Technologies Llc Composition for stretch hood, method of producing the same, and articles made therefrom
KR101262305B1 (en) 2009-07-01 2013-05-08 주식회사 엘지화학 Process for preparation of elastomeric polymer using transition catalyst
US8629214B2 (en) 2009-07-01 2014-01-14 Dow Global Technologies Llc. Ethylene-based polymer compositions for use as a blend component in shrinkage film applications
CN102481770B (en) 2009-07-01 2016-12-21 陶氏环球技术有限责任公司 Polyvinyls and application thereof
KR101741857B1 (en) 2009-07-15 2017-05-30 다우 글로벌 테크놀로지스 엘엘씨 Polymer compositions, methods of making the same, and articles prepared from the same
BR112012001948B1 (en) 2009-07-29 2019-08-20 Dow Global Technologies Llc Chain transfer agent, process for polymerizing at least one addition polymerizable monomer, multi-block copolymer and catalyst composition
JP5766702B2 (en) 2009-09-14 2015-08-19 ダウ グローバル テクノロジーズ エルエルシー Polymers containing units derived from ethylene and poly (alkoxide)
EP2478025B1 (en) 2009-09-14 2018-12-05 Dow Global Technologies LLC Polymers comprising units derived from ethylene and siloxane
US8987385B2 (en) 2009-09-14 2015-03-24 Dow Global Technologies Llc Interconnected copolymers of ethylene in combination with one other polyalkene
US9546446B2 (en) 2009-10-23 2017-01-17 Toyo Boseki Kabushiki Kaisha Highly functional polyethylene fibers, woven or knit fabric, and cut-resistant glove
CN101734996B (en) * 2009-12-29 2012-12-19 岳阳昌德化工实业有限公司 Method for recycling and utilizing waste liquor containing 4-vinyl cyclohexene
US20110172354A1 (en) * 2010-01-04 2011-07-14 Dow Global Technologies Inc. Ethylene-based polymer compositions for use in fiber applications
US8653196B2 (en) 2010-01-11 2014-02-18 Dow Global Technologies, Llc Method for preparing polyethylene with high melt strength
WO2011087729A2 (en) 2010-01-14 2011-07-21 Exxonmobil Chemical Patents Inc. Processes and apparatus for polymer finishing and packaging
US8425847B2 (en) 2010-01-14 2013-04-23 Exxonmobil Chemical Patents Inc. Processes and apparatus for continuous solution polymerization
KR101414298B1 (en) 2010-01-14 2014-07-02 엑손모빌 케미칼 패턴츠 인코포레이티드 Processes and apparatus for continuous solution polymerization
US8372924B2 (en) 2010-01-14 2013-02-12 Exxonmobil Chemical Patents Inc. Processes and apparatus for continuous solution polymerization
MX2012008189A (en) 2010-01-14 2013-02-27 List Holding Ag A vacuum devolatilizer.
JP5858935B2 (en) 2010-03-02 2016-02-10 ダウ グローバル テクノロジーズ エルエルシー Ethylene polymer composition
WO2011153540A1 (en) 2010-06-04 2011-12-08 Dow Global Technologies Llc Electronic device module comprising film of homogeneous polyolefin copolymer and adhesive property enhancing graft polymer
CN102918069A (en) 2010-06-04 2013-02-06 陶氏环球技术有限公司 Electronic device module comprising film of homogeneous polyolefin copolymer and grafted silane
MX355375B (en) 2010-06-14 2018-04-17 Dow Global Tech Llc Star Ethylene-based polymer compositions for use as a blend component in shrinkage film applications.
JP2013533623A (en) 2010-06-24 2013-08-22 ダウ グローバル テクノロジーズ エルエルシー Electronic device module comprising ethylene long chain branched (LCB), block, or interconnected copolymer, and optionally silane
EP2591060B1 (en) 2010-07-09 2016-12-21 Luna Innovations Incorporated Coating systems capable of forming ambiently cured highly durable hydrophobic coatings on substrates
US8907034B2 (en) 2010-09-30 2014-12-09 Dow Global Technologies Llc Comb architecture olefin block copolymers
US9150681B2 (en) 2010-10-29 2015-10-06 Dow Global Technologies Llc Ethylene-based polymers and processes for the same
US20120116034A1 (en) * 2010-11-08 2012-05-10 Dow Global Technologies, Inc. Solution polymerization process and procatalyst carrier systems useful therein
US8877880B2 (en) 2010-11-17 2014-11-04 Exxonmobil Chemical Patents Inc. Method for controlling polyolefin properties
SG190985A1 (en) 2010-12-03 2013-07-31 Dow Global Technologies Llc Processes to prepare ethylene-based polymer compositions
CA2724943A1 (en) 2010-12-10 2012-06-10 Nova Chemicals Corporation Catalyst activation in a dual reactor process
KR101845119B1 (en) 2010-12-17 2018-04-03 다우 글로벌 테크놀로지스 엘엘씨 Ethylene-based polymers and processess to make the same
KR101871533B1 (en) 2010-12-30 2018-06-26 다우 글로벌 테크놀로지스 엘엘씨 Compositions, methods of making the same, and articles prepared from the same
JP5985625B2 (en) 2011-06-30 2016-09-06 ダウ グローバル テクノロジーズ エルエルシー Multilayer polyolefin-based film having a layer comprising a crystalline block copolymer composite or block copolymer composite resin
JP5986630B2 (en) 2011-07-05 2016-09-06 ダウ グローバル テクノロジーズ エルエルシー Ethylene-based polymer and method for producing the same
WO2013040519A2 (en) * 2011-09-14 2013-03-21 Materia, Inc. Improved electrolytic cell covers comprising a resin composition polymerized with a group 8 olefin metathesis catalyst
CN103906817B (en) 2011-09-30 2017-04-19 陶氏环球技术有限责任公司 Controlled peel laminate adhesive films
IN2014CN04444A (en) 2011-12-20 2015-09-04 Dow Global Technologies Llc
MX360854B (en) 2011-12-22 2018-11-20 Dow Global Technologies Llc Ethylene-based polymers with improved melt strength and processes for the same.
US8552117B1 (en) 2012-06-13 2013-10-08 Teknor Apex Company Sealing elements and sealing element compositions
CN104583304B (en) 2012-06-29 2017-06-16 陶氏环球技术有限责任公司 For the ethylene/alpha-olefin/unconjugated polyene based composition and use thereof in packaging of TPV
US9255168B2 (en) * 2012-08-16 2016-02-09 Exxonmobil Chemical Patents Inc. Highly branched compositions and processes for the production thereof
US8796408B2 (en) 2012-08-31 2014-08-05 Exxonmobil Chemical Patents Inc. Plants and processes for forming polymers
CN104822713B (en) 2012-09-28 2018-05-18 陶氏环球技术有限公司 Polyvinyl and its manufacturing method
EP2900703B1 (en) 2012-09-28 2018-10-17 Dow Global Technologies LLC Ethylene-based polymers and processes to make the same
KR101391692B1 (en) 2012-11-14 2014-05-07 주식회사 엘지화학 Elastic terpolymer and preparation method thereof
KR102215305B1 (en) 2012-11-30 2021-02-16 다우 글로벌 테크놀로지스 엘엘씨 Ethylene/alpha-olefin/nonconjugated polyene based compositions and foams formed from the same
CN104812783B (en) 2012-11-30 2021-07-16 陶氏环球技术有限责任公司 Ethylene/alpha-olefin/polyene based compositions
KR102182399B1 (en) 2012-12-28 2020-11-24 다우 글로벌 테크놀로지스 엘엘씨 Ethylene-based polymers and processes to make the same
KR20140144076A (en) 2013-06-10 2014-12-18 주식회사 엘지화학 Preparation method of elastic terpolymer
WO2014209084A1 (en) 2013-06-28 2014-12-31 주식회사 엘지화학 Trinary elastic copolymer comprising diene and method for preparing same
KR101585204B1 (en) 2013-06-28 2016-01-13 주식회사 엘지화학 Elastic diene terpolymer and preparation method thereof
KR101585206B1 (en) 2013-07-22 2016-01-13 주식회사 엘지화학 Elastic diene terpolymer and preparation method thereof
EP2883889A4 (en) 2013-06-28 2016-06-01 Lg Chemical Ltd Trinary elastic copolymer comprising diene and method for preparing same
IN2015DN02232A (en) 2013-06-28 2015-08-21 Lg Chemical Ltd
WO2015100302A1 (en) 2013-12-26 2015-07-02 Dow Global Technologies Llc Ethylene-based polymers formed using asymmetrical polyenes
KR102284307B1 (en) 2013-12-26 2021-08-04 다우 글로벌 테크놀로지스 엘엘씨 Processes to improve reactor stability for the preparation of ethylene-based polymers using asymmetrical polyenes
CN105829362B (en) 2013-12-26 2019-06-07 陶氏环球技术有限责任公司 The method for forming the polymer based on ethylene using asymmetric polyenoid
KR101791810B1 (en) 2014-03-21 2017-10-30 엑손모빌 케미칼 패턴츠 인코포레이티드 Process to produce ethylene propylene copolymers
KR101655392B1 (en) 2014-04-21 2016-09-07 주식회사 엘지화학 Elastic diene terpolymer and preparation method thereof
KR101660480B1 (en) 2014-04-25 2016-09-27 주식회사 엘지화학 Elastic diene terpolymer and preparation method thereof
JP6628744B2 (en) 2014-06-24 2020-01-15 ダウ グローバル テクノロジーズ エルエルシー Polyolefin photovoltaic backsheet with stabilized polypropylene layer
CN106463556B (en) 2014-06-24 2020-04-21 陶氏环球技术有限责任公司 Photovoltaic modules comprising organoclays
US20170152377A1 (en) 2014-06-26 2017-06-01 Dow Global Technologies Llc Breathable films and articles incorporating same
EP3161023A1 (en) 2014-06-27 2017-05-03 Dow Global Technologies LLC Ethylene-based polymers comprising units derived from carbon monoxide and a rheology modifying agent
BR112016029789A2 (en) 2014-06-30 2017-08-22 Dow Global Technologies Llc multilayer film with strips
EP3227370B1 (en) 2014-12-01 2019-11-20 Dow Global Technologies LLC Polymer compositions, shrink films, and methods of making thereof
EP3237467A1 (en) 2014-12-23 2017-11-01 Dow Global Technologies LLC Ethylene-based interpolymers and composition comprising the same
JP6718453B2 (en) 2014-12-29 2020-07-08 ダウ グローバル テクノロジーズ エルエルシー Method for forming oil-containing ethylene-based polymer
JP6752794B2 (en) 2014-12-29 2020-09-09 ダウ グローバル テクノロジーズ エルエルシー Methods for Forming Ethylene / Alpha-Olefin Interpolymers
CN107108791A (en) 2014-12-30 2017-08-29 陶氏环球技术有限责任公司 Control polymerize the method for the yield and quality for the polymer based on ethene to be formed by high-pressure free radical
BR112017020525B1 (en) 2015-03-31 2022-07-19 Dow Global Technologies Llc PROCESS FOR FORMING A POLYMER COMPOSITION
WO2016176821A1 (en) 2015-05-05 2016-11-10 Dow Global Technologies Llc Functionalized, halogenated olefin-based adhesive, articles containing and process for using thereof
FR3037586A1 (en) 2015-06-17 2016-12-23 Michelin & Cie PROCESS FOR CONTINUOUS POLYMERIZATION OF DIENE ELASTOMER
EP3310853B1 (en) 2015-06-17 2022-03-30 Dow Global Technologies LLC Process for making crosslinked cable insulation using high melt strength ethylene-based polymer made in a tubular reactor and optionally modified with a branching agent
EP3310818B1 (en) 2015-06-22 2020-01-22 Dow Global Technologies LLC Process for making ethylene-based polymers using carbon-carbon free radical initiators
KR102575869B1 (en) 2015-06-24 2023-09-08 다우 글로벌 테크놀로지스 엘엘씨 Method for producing ethylene-based polymers with improved melt-strength
US10400046B2 (en) 2015-06-25 2019-09-03 Joseph J. Matsko Portable powered paint system
WO2017040088A1 (en) 2015-09-02 2017-03-09 Dow Global Technologies Llc Flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation
US10490319B2 (en) 2015-09-02 2019-11-26 Dow Global Technologies Llc Flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation
WO2017048448A1 (en) 2015-09-14 2017-03-23 Exxonmobil Chemical Patents Inc. Process for making branched epdm and epdm therefrom
JP6936795B2 (en) 2015-10-29 2021-09-22 ダウ グローバル テクノロジーズ エルエルシー Crosslinkable polymer compositions for flexible crosslinked cable insulators, and methods for making flexible crosslinked cable insulators.
EP3168238A1 (en) 2015-11-10 2017-05-17 Dow Global Technologies LLC Ethylene-based polymers formed by high pressure free radical polymerizations
EP3168237A1 (en) 2015-11-10 2017-05-17 Dow Global Technologies LLC High pressure, free radical polymerizations to produce ethylene-based polymers
EP3168239A1 (en) 2015-11-10 2017-05-17 Dow Global Technologies LLC High pressure free radical polymerizations
AU2016383056B2 (en) 2015-12-29 2020-11-19 Dow Global Technologies Llc Highly grafted ethylene-based polymers, highly grafted ethylene-based polymer compositions, and processes for forming the same
CN108602997B (en) 2016-02-23 2021-10-15 陶氏环球技术有限责任公司 Ethylene-based polymers and methods of making the same
BR112018070841A2 (en) 2016-04-29 2019-02-05 Dow Global Technologies Llc compositions comprising ethylene carbon monoxide copolymers
WO2017206009A1 (en) 2016-05-30 2017-12-07 Dow Global Technologies Llc Ethylene/alpha-olefin/diene interpolymers compositions
WO2017206008A1 (en) 2016-05-30 2017-12-07 Dow Global Technologies Llc Ethylene/alpha-olefin/diene interpolymer
CN107474194B (en) * 2016-06-08 2022-03-18 中国石油化工股份有限公司 Method for preparing high molecular polymer material
US11098144B2 (en) 2016-06-30 2021-08-24 Dow Global Technologies Llc Ethylene/alpha-olefin/polyene interpolymers and compositions containing the same
BR112018077402B1 (en) 2016-06-30 2023-04-25 Dow Global Technologies Llc COMPOSITIONS BASED ON ETHYLENE/ALPHA-OLEFIN/POLYENE
WO2018111638A1 (en) 2016-12-16 2018-06-21 Dow Global Technologies Llc Ethylene/ alpha-olefin interpolymer compositions
US11098183B2 (en) 2017-02-28 2021-08-24 Dow Global Technologies Llc Ethylene-based polymers with good processability for use in multilayer films
KR102551637B1 (en) 2017-06-02 2023-07-06 다우 글로벌 테크놀로지스 엘엘씨 Ethylene polymers and their preparation
EP3672811A1 (en) 2017-08-24 2020-07-01 Dow Global Technologies LLC Ethylene/c5-c10 alpha-olefin/ polyene interpolymers
CN111278871B (en) 2017-10-31 2023-09-19 陶氏环球技术有限责任公司 ethylene/CO copolymers and methods of making the same
EP3480220A1 (en) 2017-11-06 2019-05-08 Borealis AG Combined sequential parallel reactor configuration
KR101918484B1 (en) 2017-11-15 2019-01-31 금호폴리켐 주식회사 Catalyst compositions for preparing elastomeric copolymers and preparation method for elastomeric copolymers containing ethylene and α-olefin, or ethylene, α-olefin and non-conjugated diene using the same
US11041034B2 (en) 2018-02-09 2021-06-22 Exxonmobil Chemical Patents Inc. Ethylene-a-olefin-diene elastomers and methods of making them
CN111868166A (en) 2018-02-14 2020-10-30 陶氏环球技术有限责任公司 Ethylene/alpha-olefin interpolymer compositions having improved long term heat aging properties
EP3752559B1 (en) 2018-02-14 2023-08-30 Dow Global Technologies LLC Ethylene/alpha-olefin interpolymer compositions with improved continuous high temperature resistance
EP3752554B1 (en) 2018-02-14 2023-05-31 Dow Global Technologies LLC Ethylene/alpha-olefin interpolymer compositions with improved continuous high temperature resistance
US11873377B2 (en) 2018-06-15 2024-01-16 Dow Global Technologies Llc Blown films comprising bimodal ethylene-based polymers having high molecular weight high density fractions
CN112399976A (en) 2018-06-15 2021-02-23 陶氏环球技术有限责任公司 Process for producing ethylene-based bimodal polymers having a high molecular weight high density fraction
CN112368327B (en) 2018-06-15 2023-10-10 陶氏环球技术有限责任公司 Cast film comprising an ethylene-based bimodal polymer having a high molecular weight high density fraction
EP3807329A1 (en) 2018-06-15 2021-04-21 Dow Global Technologies Llc Bimodal ethylene-based polymers having high molecular weight high density fractions
WO2020006104A1 (en) 2018-06-28 2020-01-02 Dow Global Technologies Llc Ethylene-based polymers with improved melt strength and thermal stability
SG11202107057WA (en) 2018-12-28 2021-07-29 Dow Global Technologies Llc Curable compositions comprising unsaturated polyolefins
SG11202107051UA (en) 2018-12-28 2021-07-29 Dow Global Technologies Llc Telechelic polyolefins and processes for preparing the same
KR20210121029A (en) 2018-12-28 2021-10-07 다우 글로벌 테크놀로지스 엘엘씨 Curable composition comprising telechelic polyolefin
JP7463378B2 (en) 2018-12-28 2024-04-08 ダウ グローバル テクノロジーズ エルエルシー CURABLE COMPOSITION COMPRISING UNSATURATED POLYOLEFIN - Patent application
KR20220016881A (en) 2019-05-31 2022-02-10 다우 글로벌 테크놀로지스 엘엘씨 Low Density Polyethylene with Improved Processability
WO2021061577A1 (en) 2019-09-24 2021-04-01 Dow Global Technologies Llc Ethylene/alpha-olefin/polyene interpolymer compositions
BR112022005357A2 (en) 2019-09-24 2022-06-14 Dow Global Technologies Llc Composition and article
US20230151195A1 (en) 2020-04-06 2023-05-18 Dow Global Technologies Llc Enhanced melt strength low-density polyethylene for use in films or blends
CA3195320A1 (en) 2020-10-14 2022-04-21 Akanksha GARG Polyethylene compositions suitable for use in cast stretch films

Family Cites Families (84)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3485706A (en) 1968-01-18 1969-12-23 Du Pont Textile-like patterned nonwoven fabrics and their production
US4200722A (en) 1971-09-24 1980-04-29 Stamicarbon, B.V. Rubber-like copolymers of ethylene, at least one other α-alkene and one or more polyenes possessing increased building tack
US4184027A (en) 1971-10-26 1980-01-15 Monsanto Company Recycle control system for continuous polymerization
US4102761A (en) 1974-01-03 1978-07-25 The Firestone Tire & Rubber Company Radiation cure of synthetic rubbers
JPS5111882A (en) 1974-07-20 1976-01-30 Sumitomo Chemical Co Mihannotanryotaio jokyosuruhoho
FR2297713A1 (en) 1975-01-17 1976-08-13 Telecommunications Sa INTRODUCTION PROCEDURE
FR2322883A1 (en) 1975-09-02 1977-04-01 Michelin & Cie ELASTOMERS OF THE E P T TYPE, AND ARTICLES CONTAINING SUCH ELASTOMERS
JPS52141888A (en) 1976-05-21 1977-11-26 Nippon I P Rubber Kk Ethyleneepropylene copolymers rubber
US4075287A (en) 1976-10-27 1978-02-21 Phillips Petroleum Company Separation process
DE2735355A1 (en) 1977-08-05 1979-02-15 Basf Ag PROCESS FOR PREPARING HOMOPOLYMERIZED AND COPOLYMERIZED PRODUCTS OF ETHYLENE
US4182810A (en) 1978-04-21 1980-01-08 Phillips Petroleum Company Prevention of fouling in polymerization reactors
JPS6030326B2 (en) 1978-08-17 1985-07-16 三井化学株式会社 Manufacturing method of ethylene copolymer rubber
US4340563A (en) 1980-05-05 1982-07-20 Kimberly-Clark Corporation Method for forming nonwoven webs
US4413110A (en) 1981-04-30 1983-11-01 Allied Corporation High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore
JPS587402A (en) 1981-07-07 1983-01-17 Mitsui Petrochem Ind Ltd Polymerization process
US4792595A (en) 1983-06-15 1988-12-20 Exxon Research & Engineering Co. Narrow MWD alpha-olefin copolymers
US4663220A (en) 1985-07-30 1987-05-05 Kimberly-Clark Corporation Polyolefin-containing extrudable compositions and methods for their formation into elastomeric products including microfibers
US4722971A (en) 1985-08-02 1988-02-02 Exxon Chemical Patents Inc. Easy processing ethylene propylene elastomers
US4668566A (en) 1985-10-07 1987-05-26 Kimberly-Clark Corporation Multilayer nonwoven fabric made with poly-propylene and polyethylene
US4701432A (en) 1985-11-15 1987-10-20 Exxon Chemical Patents Inc. Supported polymerization catalyst
US5084534A (en) 1987-06-04 1992-01-28 Exxon Chemical Patents, Inc. High pressure, high temperature polymerization of ethylene
DE3853487T2 (en) 1987-01-19 1995-07-27 Sumitomo Chemical Co Elastic copolymers of ethylene, propylene and a non-conjugated diene and the use thereof.
US5153157A (en) 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5241025A (en) 1987-01-30 1993-08-31 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5096867A (en) 1990-06-04 1992-03-17 Exxon Chemical Patents Inc. Monocyclopentadienyl transition metal olefin polymerization catalysts
US5055438A (en) 1989-09-13 1991-10-08 Exxon Chemical Patents, Inc. Olefin polymerization catalysts
PL276385A1 (en) 1987-01-30 1989-07-24 Exxon Chemical Patents Inc Method for polymerization of olefines,diolefins and acetylene unsaturated compounds
US5408017A (en) 1987-01-30 1995-04-18 Exxon Chemical Patents Inc. High temperature polymerization process using ionic catalysts to produce polyolefins
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5264405A (en) 1989-09-13 1993-11-23 Exxon Chemical Patents Inc. Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin-copolymer production catalysts
US4804794A (en) 1987-07-13 1989-02-14 Exxon Chemical Patents Inc. Viscosity modifier polymers
JP2573613B2 (en) 1987-08-14 1997-01-22 三菱化学株式会社 Ethylene polymerization method
US5147949A (en) 1988-03-29 1992-09-15 Exxon Chemical Patents Inc. Polymerization process using a silica gel supported metallocene-alumoxane catalyst
US5231106A (en) 1988-05-18 1993-07-27 Novo Nordisk A/S Azacyclic carboxylic acid derivatives and their preparation and use
CA1327673C (en) 1988-06-16 1994-03-08 Sigmund Floyd Process for production of high molecular weight epdm elastomers using a metallocene-alumoxane catalyst system
US5229478A (en) 1988-06-16 1993-07-20 Exxon Chemical Patents Inc. Process for production of high molecular weight EPDM elastomers using a metallocene-alumoxane catalyst system
US5001205A (en) 1988-06-16 1991-03-19 Exxon Chemical Patents Inc. Process for production of a high molecular weight ethylene α-olefin elastomer with a metallocene alumoxane catalyst
CA2034759C (en) 1988-08-01 2003-06-03 Won R. Song Novel ethylene alpha-olefin polymer substituted mono- and dicarboxylic acid dispersant additives
US5229022A (en) 1988-08-01 1993-07-20 Exxon Chemical Patents Inc. Ethylene alpha-olefin polymer substituted mono- and dicarboxylic acid dispersant additives (PT-920)
ATE154060T1 (en) * 1988-09-30 1997-06-15 Exxon Chemical Patents Inc LINEAR ETHYLENE COPOLYMER BLENDS OF COPOLYMERS WITH NARROW MOLECULAR WEIGHT AND COMPOSITION DISTRIBUTIONS
US5017665A (en) 1989-07-25 1991-05-21 Exxon Chemical Patents Inc. Supported catalyst for 1-olefin and 1,4-diolefin copolymerization
NZ235032A (en) * 1989-08-31 1993-04-28 Dow Chemical Co Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component
US5057475A (en) 1989-09-13 1991-10-15 Exxon Chemical Patents Inc. Mono-Cp heteroatom containing group IVB transition metal complexes with MAO: supported catalyst for olefin polymerization
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
JP2807502B2 (en) 1989-10-05 1998-10-08 三井化学株式会社 Ethylene-propylene-diene rubber, elastomer composition and vulcanized rubber thereof
FR2654108B1 (en) 1989-11-08 1993-08-20 Norsolor Sa NOVEL POLYOLEFIN RUBBERS AND THEIR PREPARATION METHOD.
US5519091A (en) 1990-02-13 1996-05-21 Mitsui Petrochemical Industries, Ltd. Method for the preparation of ethylene polymer compositions
US5149318A (en) 1990-03-14 1992-09-22 Minnesota Mining And Manufacturing Company Quick-changeover blood handling apparatus
MY107639A (en) 1990-04-18 1996-05-30 Mitsui Chemicals Incorporated Process for the preparation of an ethylene copolymer and an olefin polymer, and catalyst for olefin polymeri -zation
US5272236A (en) 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
JP2545006B2 (en) 1990-07-03 1996-10-16 ザ ダウ ケミカル カンパニー Addition polymerization catalyst
US5189192A (en) 1991-01-16 1993-02-23 The Dow Chemical Company Process for preparing addition polymerization catalysts via metal center oxidation
CA2060019A1 (en) 1991-03-04 1992-09-05 Phil Marvin Stricklen Process for producing polyolefins having a bimodal molecular weight distribution
JP2894858B2 (en) 1991-04-05 1999-05-24 三井化学株式会社 Ethylene / α-olefin / diene rubber and use thereof
JP3275211B2 (en) 1991-05-20 2002-04-15 ザ ダウ ケミカル カンパニー Method for producing addition polymerization catalyst
US5721185A (en) 1991-06-24 1998-02-24 The Dow Chemical Company Homogeneous olefin polymerization catalyst by abstraction with lewis acids
US5278272A (en) 1991-10-15 1994-01-11 The Dow Chemical Company Elastic substantialy linear olefin polymers
GB9125934D0 (en) 1991-12-05 1992-02-05 Exxon Chemical Patents Inc Process for polymerising olefinic feeds under pressure
WO1993013143A1 (en) 1991-12-30 1993-07-08 The Dow Chemical Company Ethylene interpolymer polymerizations
KR100262023B1 (en) 1992-01-06 2000-07-15 그레이스 스티븐 에스. Improved catalyst composition
KR950014847B1 (en) 1992-01-23 1995-12-16 미쓰이세끼유 가가꾸고오교오 가부시끼가이샤 Process for preparation of ethylene copolymer
US5374696A (en) 1992-03-26 1994-12-20 The Dow Chemical Company Addition polymerization process using stabilized reduced metal catalysts
US5296433A (en) 1992-04-14 1994-03-22 Minnesota Mining And Manufacturing Company Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom
BE1005795A3 (en) * 1992-05-13 1994-02-01 Solvay Olefin polymerization process and (co) polymer blocks derivatives at least olefine.
US5240894A (en) 1992-05-18 1993-08-31 Exxon Chemical Patents Inc. Method for making and using a supported metallocene catalyst system
US5434115A (en) 1992-05-22 1995-07-18 Tosoh Corporation Process for producing olefin polymer
EP0646140B1 (en) 1992-06-15 1998-12-30 Exxon Chemical Patents Inc. High temperature polymerization process using ionic catalysts to produce polyolefins
WO1993025591A1 (en) 1992-06-18 1993-12-23 Spherilene S.R.L. Process for preparing an ethylenic polymer
WO1994000500A1 (en) 1992-06-26 1994-01-06 Exxon Chemical Patents Inc. Solution phase polymerization process utilizing metallocene catalyst with production of olefin polymers
NL9201970A (en) 1992-11-11 1994-06-01 Dsm Nv Indenyl compounds and catalyst components for the polymerization of olefins.
CA2103380C (en) * 1992-11-19 2002-07-02 Mitsui Chemicals, Inc. Ethylene/.alpha.-olefin copolymer composition, graft modified ethylene/.alpha.-olefin copolymer composition, ethylene copolymer composition, and multi-stage olefin polymerization process
ZA94612B (en) 1993-01-29 1995-07-28 Dow Chemical Co Ethylene interpolymerization
US6313240B1 (en) 1993-02-22 2001-11-06 Tosoh Corporation Process for producing ethylene/α-olefin copolymer
US5372682A (en) 1993-06-24 1994-12-13 The Dow Chemical Company Electrochemical preparation of addition polymerization catalysts
ES2096475T3 (en) 1993-06-24 1997-03-01 Dow Chemical Co COMPLEXES OF TITANIUM (II) OR ZIRCONIUM (II) AND POLYMERIZATION CATALYSTS BY ADDITION OBTAINED FROM THEM.
US5470993A (en) 1993-06-24 1995-11-28 The Dow Chemical Company Titanium(II) or zirconium(II) complexes and addition polymerization catalysts therefrom
WO1995016716A1 (en) 1993-12-14 1995-06-22 Exxon Chemical Patents Inc. Process for producing elastomers with an indenyl metallocene catalyst system
BR9500663A (en) 1994-02-17 1995-10-31 Union Carbide Chem Plastic Catalyst composition process for preparing a catalyst composition and process for the production of ethylene homopolymers or copolymers
US5486632A (en) 1994-06-28 1996-01-23 The Dow Chemical Company Group 4 metal diene complexes and addition polymerization catalysts therefrom
DE4432798A1 (en) 1994-09-15 1996-03-21 Basf Ag Highly flexible propylene-ethylene copolymers
US5677382A (en) 1994-12-19 1997-10-14 Japan Synthetic Rubber Co., Ltd. Ethylene-α-olefin-non-conjugated diene copolymer rubber composition
TW383314B (en) 1994-12-20 2000-03-01 Mitsui Petrochemical Ind Ethylene-alpha-olefin-nonconjugated polyene random copolymer, rubber composition, and process for preparing the random copolymer
US5696213A (en) 1995-04-21 1997-12-09 Exxon Chemical Patents Inc. Ethylene-α-olefin-diolefin elastomers solution polymerization process
EP0743066A3 (en) 1995-05-16 1998-09-30 Mitsui Pharmaceuticals, Inc. Wound-healing agent

Also Published As

Publication number Publication date
US6545088B1 (en) 2003-04-08
CN1223670A (en) 1999-07-21
NO990095D0 (en) 1999-01-11
HUP9904354A3 (en) 2000-05-29
KR20000023740A (en) 2000-04-25
ES2156001T3 (en) 2001-06-01
DE69704617D1 (en) 2001-05-23
NZ332880A (en) 2000-07-28
CZ9499A3 (en) 1999-03-17
PL331038A1 (en) 1999-06-21
CN1098289C (en) 2003-01-08
JP2000514857A (en) 2000-11-07
DE69704617T2 (en) 2001-08-02
EP0910593B1 (en) 2001-04-18
AU3727997A (en) 1998-02-09
AU718342B2 (en) 2000-04-13
TR199900050T2 (en) 1999-03-22
ATE200680T1 (en) 2001-05-15
NO990095L (en) 1999-01-12
WO1998002471A1 (en) 1998-01-22
KR100496101B1 (en) 2005-06-17
BR9710347A (en) 1999-08-17
EP0910593A1 (en) 1999-04-28
HUP9904354A2 (en) 2000-04-28
TW341576B (en) 1998-10-01
CA2256668A1 (en) 1998-01-22

Similar Documents

Publication Publication Date Title
CA2256668C (en) Elastomers and process for their manufacture
US6420507B1 (en) Olefin polymers prepared with substituted indenyl containing metal complexes
JP6165685B2 (en) Process for producing polymer blends with a broad molecular weight distribution in a single reactor
EP0863924B1 (en) Mono-olefin/polyene interpolymers, method of preparation, compositions containing the same, and articles made thereof
JP5323150B2 (en) High melt strength polymer and method for producing the same
AU686670B2 (en) Gas phase polymerization of olefins
US6017842A (en) Olefin polymerization catalyst composition comprising group 13 compound
US6074977A (en) Olefin addition polymerization catalyst composition
AU742617B2 (en) Olefin polymers prepared with substituted indenyl containing metal complexes
CA2237914C (en) Mono-olefin/polyene interpolymers, method of preparation, compositions containing the same, and articles made thereof
CA2171103C (en) Gas phase polymerization of olefins
US6630545B2 (en) Polymerization process
CZ375899A3 (en) Olefin polymers being prepared with metal complexes containing substituted indenyl

Legal Events

Date Code Title Description
EEER Examination request
MKEX Expiry

Effective date: 20170710