WO1993014132A1 - Improved catalyst composition - Google Patents
Improved catalyst composition Download PDFInfo
- Publication number
- WO1993014132A1 WO1993014132A1 PCT/US1992/010360 US9210360W WO9314132A1 WO 1993014132 A1 WO1993014132 A1 WO 1993014132A1 US 9210360 W US9210360 W US 9210360W WO 9314132 A1 WO9314132 A1 WO 9314132A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- groups
- group
- formula
- alkyl
- alkoxy
- Prior art date
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
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
-
- 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
Definitions
- This invention relates to compositions of matter which are useful as addition polymerization catalysts, to a method for preparing these catalysts and to a method of using these catalysts. More particularly, this invention relates to catalyst compositions useful as olefin polymerization catalysts and to a method for polymerizing olefin monomers using the same.
- adjuvants such as trialkyl boron and trialkyiaiuminum compounds to remove catalyst poisons from biscyclopentadrenyl containing olefin polymerization catalysts.
- adjuvants have proven to be ineffective in combating the inhibition of cationic catalysts, especially cationic, constrained geometry catalysts, and when used in the polymerization of olefin monomers especially, actually may interfere with the desired catalytic process.
- a catalyst composition comprising in combination: a cationic complex of the formula: CpMYX n + 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 ⁇ 5 bonding mode to Cp; n is zero or one, depending on the oxidation state of M;
- Cp is a cyciopentadienyl-, indenyl-, tetrahydroindenyl-, fluorenyl-, or octahydrof luorenyl- group covalently substituted with at least a divalent moiety, R", said divalent moiety, R", having from 1 to 50 atoms and being covalently bonded to Y, Cp further may be substituted with from 1 to 4 alkyl, halogen, aryl, haloalkyl, alkoxy, aryfoxy or silyl groups containing up to 20 non-hydrogen atoms;
- Y is a divalent substituent selected from groups of the formula -NR-, -PR-, -O-or- S-, wherein R is C, 20 hydrocarbyl, and Y together with R", Cp and M forms a metallocycle;
- X if any, is a monovalent substituent selected from the group consisting of hydride, halo, alkyl, aryl, silyl, germyl, aryloxy, alkoxy, amide, siioxy, and phosphine groups, and combinations thereof, said groups or combination having up to 20 non-hydrogen atoms; and
- A- is an inert, noncoordinating anion, and an alumoxane; the molar ratio of alumoxane to cationic complex being from 0.1 : 1 to 50: 1.
- catalyst compositions in a preferred embodiment comprise the reaction product of: a) an organometallic complex of the formula: CpMYX n R, 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 ⁇ 5 bonding mode to Cp; n is zero or one, depending on the oxidation state of M; R is hydride or C 1 20 hydrocarbyl;
- Cp is a cyclopentadienyl-, indenyl-, tetrahydroindenyl-, fluorenyl-, or octahydrofluorenyl- group covalently substituted with at least a divalent moiety, R", said divalent moiety, R", having from 1 to 50 atoms and being covalently bonded to Y, Cp further may be substituted with from 1 to 4 alkyl, halogen, aryl, haloalkyl, alkoxy, aryloxy or silyl groups containing up to 20 non-hydrogen atoms; and
- Y is a divalent substituent selected from groups of the formula -NR-, -PR-, -O- or - S-, wherein R is C. 20 hydrocarbyl, and Y together with R", Cp and M forms a metallocycle; and
- X if any, is a monovalent substituent selected from: hydride, halo, alkyl, aryl, silyl, germyl, aryloxy, alkoxy, amide, siioxy, phosphine groups, and mixtures thereof, said groups having up to 20 non-hydrogen atoms; b) an active compound or complex, B', capable of converting the organometallic complex a) into a cationic complex of the formula: CpMYX n +A'-, where Cp, M, Y, X and n are as previously defined, and A' ' is the anion resulting from the combination of B' and R which is abstracted from complex a) or A' ' is the counterion from complex B'; and c) an alumoxane; the molar ratio of components b):a) being from 0.1 : 1 to 50: 1 , and the molar ratio of components c): a) being from 1 : 1 to
- compositions are usefully employed in the polymerization of addition polymerizable monomers, especially C 2 _ 2Q ⁇ -olefins, including mixtures thereof, to prepare polymers for molding, film, sheet, extrusion foaming and other applications.
- compositions of the present invention may be thought of as forming a mixture of a cationic species having a charge limited structure corresponding to the formula: CpMYX n +A-, and the alumoxane, c).
- Suitable aiumoxanes preferably include C. alkyiaiumoxanes, especially methylalumoxane- Both cyclic and linear aiumoxanes as well as mixtures thereof are suitable.
- Aiumoxanes are well known in the art and methods fortheir preparation are illustrated by US- A4,542,199, 4,544,762, 5,015,749, and 5,041,585.
- Particularly preferred aiumoxanes are so called modified aiumoxanes, that are completely soluble in alkane solvents, especially heptane, and include very little, if any, trialkyiaiuminum contaminant.
- a technique for preparing such a modified alumoxane has been disclosed in US-A 5,041,584. The teachings of the foregoing United States patents are incorporated herein in their entireties by reference thereto.
- Active compounds, B', useful as component b) are those compounds capable of abstraction of the R substituent f rom a) to form an inert, noninterfering counter ion.
- a preferred active compound istris(perfluorophenyI)boron. This compound results in the formation of an anionic species, A'-, that is RB(C g F 5 ) 3 " , where R is hydride or C,_ 20 hydrocarbyl.
- Examples of complexes useful as component b) include salts of a Bronsted acid and a noncoordinating, compatible anion. More particularly the non-coordinating, compatible anion may comprise a single coordination complex comprising a charge-bearing metal or metalloid core, which anion is both bulky and non-nucleophilic.
- the recitation "metalloid”, as used herein, includes non-metals such as boron, phosphorus and the like which exhibit semi- metallic characteristics-
- noncoordinating, compatible anion means an anion which either does not coordinate to component a) or which is only weakly coordinated therewith remaining sufficiently labile to be displaced 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 complexes useful as component b) are ferrocenium salts or silver salts of tetrakis(perfluorophenyl)borate. These components result in the formation of the anionic species, B(C 6 F 5 ) 4 ". which is A-. It should be noted that alkyiaiumoxanes are not satisfactory for use as component b).
- Component a) is preferably a cyclopentadienyl group containing complex of a Group 4 metal.
- the preferred X group if any, is an alkyl, aryl, silyl, germyl, aryloxy, or alkoxy group having up to 20 non-hydrogen atoms.
- additional neutral Lewis base compounds may also be associated with the metal complex by coordinate covalent or other weaker bonding forces. Such compounds include ethers, phosphines, amines, etc. However, the presence of such neutral coordinating ligands is not preferred.
- Cp is depicted by the formula:
- R' each occurrence is independently selected from the group consisting of hydrogen, alkyl and silyl groups of up to 4 non-hydrogen atoms;
- R" is -BR- or -ER 2 - wherein E is a member of Group 14 of the Periodic Table of the 0 Elements, and R is as previously defined.
- R"-Y- is
- E independently each occurrence is carbon, silicon, or germanium; p is an integer from 1 to 4.
- R is as previously defined. 0
- Preferred cationic complexes formed by contacting components a) and b) correspond to the formula:
- M is zirconium ortitanium
- Cp is a cyclopentadienyl group substituted with R" or such a cyclopentadienyl group further substituted with up to four C, _ 4 alkyl groups;
- R" is C 1 _ 4 dfalkylsilanediyl especially dimethylsilanediyl;
- Y is C-, 4 alkylamido
- X is C 1 4 alkyl, benzyl or 2-dimethylaminobenzyl; n is one; and
- A- is RB(C 6 F 5 ) 3 " or. B(C 6 F 5 ) 4 " , where R is as previously defined.
- the preferred ratio of components b):a) is 0.95:1 to 10: 1, more preferably 1 : 1 to 5:1-
- the preferred ratio of component c):a) is 2:1 to 100:1, most preferably 3:1 to 10: 1-
- the catalyst composition can be prepared by combining the components in a suitable solvent or diluent at a temperature within the range from -100 to 300°C, preferably 25 to 75°C.
- suitable solvents or diluents include any of the compounds known in the prior art to be useful as solvents or diluents in the polymerization of olefins, diolefins and acetylenically unsaturated monomers.
- Suitable compounds include, but are not necessarily limited to, straightand branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof; cyclic and alicydic hydrocarbons such cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene and mixtures thereof.
- straightand branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof
- cyclic and alicydic hydrocarbons such cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof and aromatic and alkyl-
- Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, cydopentene, 1-hexane, 3-methyl-1- pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, styrene, and mixtures thereof- Mixtures of two of more of the foregoing solvents mayalso be used if desired.
- liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, cydopentene, 1-hexane, 3-methyl-1- pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, styrene, and mixtures thereof- Mixtures of two of more of the foregoing solvents mayalso be used if desired.
- the catalyst compositions are used in addition polymerizations using conditions well known in the prior art- It will, of course, be appreciated that the catalyst composition will form in situ if the components thereof are added directly to the polymerization process. However, it is preferred to form the catalyst in a separate step in a suitable solvent priorto adding the same to the polymerization reactor-
- the respective components may be combined in any order of addition to form the catalyst composition of the invention.
- the catalysts and components are sensitive to both moisture and oxygen and should be handled and transferred in an inert atmosphere such as nitrogen, argon or helium.
- the catalyst is used to polymerize C 2 20 ⁇ -olefins and mixtures thereof, particularly ethylene or propylene, most preferably ethylene, at a temperature within the range from 0 c Cto 220°C, preferably 25 C C to 160°C and at a pressure within the range from atmospheric to 6,900 kPa (1000 psig) preferably 100 kPa to 4,800 kPa (15 to 700 psig).
- the catalyst is used either to homopolymerize ethylene or to copolymerize ethylene with a lower ⁇ -olefin having from 3 to 8 carbon atoms (including styrene) thereby yielding a copolymer.
- the monomers will be maintained at polymerization conditions for a time from 1 to 60 minutes.
- the catalyst will be used at a concentration from 10 "7 to 10 "1 moles per mole of monomer.
- a solvent for the reactants and/or the polymer may be used if desired.
- a cationic complex solution of 10 mL total volume was prepared by adding 6.0 mL of mixed alkane solvent (IsoparTM E, available from Exxon Chemical Inc.), 2.0 mL of the Ti reagent solution and 2.0 mL of a 0.010 M solution of tris(perfluorophenyl)boron in toluene to a 250 ml glass bottle. The solution was mixed for a few minutes and transferred by syringe to a catalyst injection cylinder on the polymerization reactor.
- IsoparTM E mixed alkane solvent
- a stirred, one-gallon (3.79L) autoclave reactor was charge with two liters of Isopar*" E containing varying amounts of methylalumoxane (MAO) solution and 150 mL of octene-1 which had been partially purified by passing over a molecular sieve bed before heating to reaction temperature.
- the reactor was charged with ethylene sufficient to bring the total pressure to 450 psig (3.1 MPa).
- An amount of the cationic complex solution as described under catalyst preparation was injected into the reactor.
- the reactor temperature and pressure were maintained constant at the desired final pressure and temperature by continually feeding ethylene during the polymerization run and cooling the reactor as necessary- The rate and duration of the reaction were monitored by measuring the demand flow of ethylene to the reactor for each polymerization.
- Ethyl ene/1-octene copolymer yield (reported as g PE) was calculated based on mass flow of ethylene to the reactor during the run. Results as a function of MAO content are contained in
- Example 4 The polymerization of Examples 1-3 was repeated excepting that the 1-octene employed is not purified prior to use in the reactor. Results are contained in Table 2.
- Example 7 the titanium complex was (t-butylamido)dimethyl(tetramethyl- ⁇ 5 -cyclopenta- dienyl)silanetitanium dibenzyl, prepared by a method analogous to that of Example 1.
- Example 8 the titanium complex was (t-butylamido)dimethyl(tetrahydro- fluoreny silanetitanium dimethyl, also prepared by a method analogous to that of Example 1. All reactions were conducted at 120°C excepting Examples 13 and 14 that were conducted at 140°C and 160°C respectively.
- Moles of octene were 1.0 excepting for run 1 1, when 0-5 moles were used-
- the 1 -octene feed was highly purified by first contacting with a molecular sieve bed followed by contacting with an alumina based deoxygenating agent (Q-5, available from Engelhard Corporation). All polymers were recovered, devolatilized and dried to determine yield. Polymer properties were tested by standard techniques- Results are contained in Table 4-
- a I 2 is measured according to ASTM D-1238 and indicates melt flow properties. Higher values of ⁇ 2 indicate greater melt flow.
- I ⁇ p is measured according to ASTM D-1238.
- c Methylalumoxane having molecular weight 1200 available from Schering A.G. in toluene.
- d Methylaluminoxane was modified methylalumoxane, prepared according to USP 5,041,584, available from Texas Al yls.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP51243193A JP3275078B2 (en) | 1992-01-06 | 1992-12-01 | Olefin polymerization method |
CA002105555A CA2105555C (en) | 1992-01-06 | 1992-12-01 | Improved catalyst composition |
KR1019930702664A KR100262023B1 (en) | 1992-01-06 | 1992-12-01 | Improved catalyst composition |
US08/108,693 US5453410A (en) | 1992-01-06 | 1992-12-01 | Catalyst composition |
EP92925471A EP0574561B1 (en) | 1992-01-06 | 1992-12-01 | Improved catalyst composition |
DE69224287T DE69224287T2 (en) | 1992-01-06 | 1992-12-01 | Catalyst composition |
FI933861A FI114641B (en) | 1992-01-06 | 1993-09-03 | Improved catalyst composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US81720292A | 1992-01-06 | 1992-01-06 | |
US07/817,202 | 1992-01-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993014132A1 true WO1993014132A1 (en) | 1993-07-22 |
Family
ID=25222564
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1992/010360 WO1993014132A1 (en) | 1992-01-06 | 1992-12-01 | Improved catalyst composition |
Country Status (10)
Country | Link |
---|---|
US (1) | US5453410A (en) |
EP (2) | EP0574561B1 (en) |
JP (1) | JP3275078B2 (en) |
KR (1) | KR100262023B1 (en) |
CA (1) | CA2105555C (en) |
DE (2) | DE69232297T2 (en) |
ES (2) | ES2165562T3 (en) |
FI (1) | FI114641B (en) |
TW (1) | TW211018B (en) |
WO (1) | WO1993014132A1 (en) |
Cited By (69)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994007927A1 (en) * | 1992-10-05 | 1994-04-14 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity and its use in polymerization process |
WO1995007941A1 (en) * | 1993-09-17 | 1995-03-23 | Exxon Chemical Patents Inc. | Olefin polymerisation process |
BE1007614A3 (en) * | 1993-10-11 | 1995-08-22 | Dsm Nv | Process for the polymerization of an olefin in the presence of a catalyst formed from HALOGEENMETALLOCEEN. |
EP0705849A1 (en) * | 1993-06-15 | 1996-04-10 | Idemitsu Kosan Company Limited | Process for producing olefin polymer and catalyst for olefin polymerization |
EP0708117A1 (en) * | 1994-10-03 | 1996-04-24 | Sumitomo Chemical Company Limited | Process for producing copolymer rubber |
US5801113A (en) * | 1990-06-22 | 1998-09-01 | Exxon Chemical Patents, Inc. | Polymerization catalyst systems, their production and use |
US5811379A (en) * | 1996-06-17 | 1998-09-22 | Exxon Chemical Patents Inc. | Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof (PT-1267) |
US6066603A (en) * | 1996-06-17 | 2000-05-23 | Exxon Chemical Patents Inc. | Polar monomer containing copolymers derived from olefins useful as lubricant and useful as lubricant and fuel oil additivies process for preparation of such copolymers and additives and use thereof |
US6147174A (en) * | 1998-07-16 | 2000-11-14 | Univation Technologies, Llc | Aluminum based lewis acid cocatalysts for olefin polymerization |
US6172015B1 (en) | 1997-07-21 | 2001-01-09 | Exxon Chemical Patents, Inc | Polar monomer containing copolymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such copolymers and additives and use thereof |
US6211312B1 (en) | 1998-06-12 | 2001-04-03 | Univation Technologies | Olefin polymerization process using activated lewis acid-base complexes |
US6294625B1 (en) | 1990-03-20 | 2001-09-25 | Exxonmobil Chemical Patents Inc. | Catalyst system of enhanced productivity and its use in polymerization process |
US6355819B1 (en) | 1997-04-14 | 2002-03-12 | Borealis Technology Oy | Substituted metallocene compounds for olefin polymerization catalyst systems, their intermediates and methods for preparing them |
US6403773B1 (en) | 1998-09-30 | 2002-06-11 | Exxon Mobil Chemical Patents Inc. | Cationic group 3 catalyst system |
US6476164B1 (en) | 1999-10-22 | 2002-11-05 | Exxonmobil Chemical Patents Inc. | Carbenium cationic complexes suitable for polymerization catalysts |
US6475946B1 (en) | 1999-10-22 | 2002-11-05 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalysis with aryl substituted carbenium cationic complexes |
US6486088B1 (en) | 1998-10-23 | 2002-11-26 | Exxonmobil Chemical Patents Inc. | High activity carbenium-activated polymerization catalysts |
US6489480B2 (en) | 1999-12-09 | 2002-12-03 | Exxonmobil Chemical Patents Inc. | Group-15 cationic compounds for olefin polymerization catalysts |
WO2003000740A2 (en) | 2001-06-20 | 2003-01-03 | Exxonmobil Chemical Patents Inc. | Polyolefins made by catalyst comprising a noncoordinating anion and articles comprising them |
US6562920B2 (en) | 1999-12-20 | 2003-05-13 | Exxonmobil Chemical Patents Inc. | Processes for the preparation polyolefin resins using supported ionic catalysts |
US6627723B2 (en) | 1999-12-22 | 2003-09-30 | Exxonmobil Chemical Patents Inc. | Adhesive alpha-olefin inter-polymers |
US6809168B2 (en) | 1999-12-10 | 2004-10-26 | Exxonmobil Chemical Patents Inc. | Articles formed from propylene diene copolymers |
US6809209B2 (en) | 2000-04-07 | 2004-10-26 | Exxonmobil Chemical Patents Inc. | Nitrogen-containing group-13 anionic compounds for olefin polymerization |
US6822057B2 (en) | 1999-12-09 | 2004-11-23 | Exxon Mobil Chemical Patents Inc. | Olefin polymerization catalysts derived from Group-15 cationic compounds and processes using them |
WO2005118605A1 (en) | 2004-05-26 | 2005-12-15 | Exxonmobil Chemical Patents, Inc. | Transition metal compounds for olefin polymerization and oligomerization |
US6977287B2 (en) | 1999-12-10 | 2005-12-20 | Exxonmobil Chemical Patents Inc. | Propylene diene copolymers |
US7005491B2 (en) | 1999-12-10 | 2006-02-28 | Exxonmobil Chemical Patents Inc. | Propylene diene copolymerized polymers |
US7067603B1 (en) | 1999-12-22 | 2006-06-27 | Exxonmobil Chemical Patents Inc. | Adhesive alpha-olefin inter-polymers |
US7153571B2 (en) | 2002-07-31 | 2006-12-26 | Exxonmobil Chemical Patents Inc. | Silane crosslinkable polyethylene |
US7220801B2 (en) | 2001-06-22 | 2007-05-22 | Exxonmobil Chemical Patents Inc. | Metallocene-produced very low density polyethylenes or linear low density polyethylenes as impact modifiers |
WO2007070041A1 (en) | 2005-12-14 | 2007-06-21 | Exxonmobil Chemical Patents Inc. | Halogen substituted metallocene compounds for olefin polymerization |
US7235607B2 (en) | 2002-09-05 | 2007-06-26 | Exxonmobil Chemical Patents Inc. | Shrink film |
WO2007136497A3 (en) * | 2006-05-17 | 2008-01-31 | Dow Global Technologies Inc | High temperature solution polymerization process |
US7601409B2 (en) | 2002-09-05 | 2009-10-13 | Exxonmobil Chemical Patents Inc. | Stretch film |
EP2112173A1 (en) | 2008-04-16 | 2009-10-28 | ExxonMobil Chemical Patents Inc. | Catalyst compounds and use thereof |
US7951873B2 (en) | 2006-05-05 | 2011-05-31 | Exxonmobil Chemical Patents Inc. | Linear low density polymer blends and articles made therefrom |
WO2011079042A2 (en) | 2009-12-24 | 2011-06-30 | Exxonmobil Chemical Patents Inc. | Process for producing novel synthetic basestocks |
WO2011087695A2 (en) | 2009-12-23 | 2011-07-21 | Invista Technologies S.A R.L. | Polyolefin elastic fiber |
WO2011087731A1 (en) | 2010-01-14 | 2011-07-21 | Exxonmobil Chemical Patents Inc. | Processes and apparatus for continuous solution polymerization |
WO2011087693A2 (en) | 2009-12-23 | 2011-07-21 | Invista Technologies S.A R.1. | Elastic fiber containing an anti-tack additive |
WO2011087729A2 (en) | 2010-01-14 | 2011-07-21 | Exxonmobil Chemical Patents Inc. | Processes and apparatus for polymer finishing and packaging |
WO2011087728A2 (en) | 2010-01-14 | 2011-07-21 | Exxonmobil Chemical Patents Inc. | Processes and apparatus for continuous solution polymerization |
WO2011087692A2 (en) | 2009-12-23 | 2011-07-21 | Invista Technologies S.A R.L. | Stretch articles including polyolefin elastic fiber |
EP2368896A1 (en) | 2010-03-01 | 2011-09-28 | ExxonMobil Chemical Patents Inc. | Mono-indenyl transition metal compounds and polymerization therewith |
WO2015073157A1 (en) | 2013-11-15 | 2015-05-21 | Exxonmobil Chemical Patents Inc. | Process to produce polymers from pyridyldiamido transition metal complexes and use thereof |
WO2015073132A1 (en) | 2013-10-31 | 2015-05-21 | Exxonmobil Chemical Patents Inc. | Process and apparatus for continuous solution polymerization |
WO2016171810A1 (en) | 2015-04-20 | 2016-10-27 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and processes for use thereof |
WO2016171809A1 (en) | 2015-04-20 | 2016-10-27 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and processes for use thereof |
WO2018022263A1 (en) | 2016-07-29 | 2018-02-01 | Exxonmobil Chemical Patents Inc. | Polymerization processes using high molecular weight polyhydric quenching agents |
WO2018044395A1 (en) | 2016-08-31 | 2018-03-08 | Exxonmobil Chemical Patents Inc. | Spiral heat exchanger as a preheater in polymer devolatilization processes |
US10041190B2 (en) | 2009-12-23 | 2018-08-07 | Invista North America S.A.R.L. | Fabric including polyolefin elastic fiber |
WO2018151903A1 (en) | 2017-02-20 | 2018-08-23 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and processes for use thereof |
WO2019027605A1 (en) | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | Films made from polyethylene compositions and processes for making the same |
WO2019027585A1 (en) | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | Mixed catalysts with unbridged hafnocenes with -ch2-sime3 moieties |
WO2019027587A1 (en) | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions and films prepared therefrom |
WO2019108327A1 (en) | 2017-12-01 | 2019-06-06 | Exxonmobil Chemical Patents Inc. | Films comprising polyethylene composition |
WO2019108977A1 (en) | 2017-12-01 | 2019-06-06 | Exxonmobil Chemical Patents Inc. | Catalyst systems and polymerization processes for using the same |
WO2019162760A1 (en) | 2018-02-05 | 2019-08-29 | Exxonmobil Chemical Patents Inc. A Corporation Of State Of Delaware | Enhanced processability of lldpe by addition of ultra-high molecular weight high density polyethylene |
WO2019173605A1 (en) | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Ethylene-propylene branched copolymers as viscosity modifiers with enhanced fuel economy |
WO2019173598A1 (en) | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Ethylene-propylene linear copolymers as viscosity modifiers |
WO2019246069A1 (en) | 2018-06-19 | 2019-12-26 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions and films prepared therefrom |
WO2020060745A1 (en) | 2018-09-19 | 2020-03-26 | Exxonmobil Chemical Patents Inc. | Devolatilization processes |
WO2020167399A1 (en) | 2019-02-11 | 2020-08-20 | Exxonmobil Chemical Patents Inc. | Biphasic polymerization processes and ethylene-based polyolefins therefrom |
WO2021041406A1 (en) | 2019-08-27 | 2021-03-04 | Chevron Oronite Company Llc | Ethylene copolymers and use as viscosity modifiers |
WO2021126443A2 (en) | 2019-12-17 | 2021-06-24 | Exxonmobil Chemical Patents Inc. | Solution polymerization process for making high-density polyethylene long-chain branching |
WO2021222280A2 (en) | 2020-05-01 | 2021-11-04 | Exxonmobil Chemical Patents Inc. | Linear low density polyethylene for film applications |
WO2021222016A2 (en) | 2020-05-01 | 2021-11-04 | Exxonmobil Chemical Patents Inc. | Linear low density polyethylene for film applications |
WO2022076216A1 (en) | 2020-10-08 | 2022-04-14 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and processes for use thereof |
WO2023097161A1 (en) | 2021-11-23 | 2023-06-01 | Exxonmobil Chemical Patents Inc. | Plants and processes for forming polymers |
Families Citing this family (201)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6025448A (en) | 1989-08-31 | 2000-02-15 | The Dow Chemical Company | Gas phase polymerization of olefins |
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 |
US6538080B1 (en) | 1990-07-03 | 2003-03-25 | Bp Chemicals Limited | Gas phase polymerization of olefins |
US6545088B1 (en) | 1991-12-30 | 2003-04-08 | Dow Global Technologies Inc. | Metallocene-catalyzed process for the manufacture of EP and EPDM polymers |
DE69322082T2 (en) * | 1992-04-20 | 1999-06-17 | Exxon Chemical Patents Inc | COPOLYMERS OF ETHYLENE WITH BRANCHED OLEFINS |
PL175108B1 (en) * | 1993-01-29 | 1998-11-30 | Dow Chemical Co | Ethylene interpolymerisation |
JP2736938B2 (en) * | 1993-06-24 | 1998-04-08 | ザ ダウ ケミカル カンパニー | Titanium (II) or zirconium (II) complex and addition polymerization catalyst comprising the same |
ES2164774T3 (en) * | 1994-08-03 | 2002-03-01 | Exxonmobil Chem Patents Inc | IONIC CATALITIC COMPOSITION SUPPORTED. |
US6143686A (en) * | 1994-08-03 | 2000-11-07 | Exxon Chemical Patents, Inc. | Supported ionic catalyst compositions |
US5643847A (en) * | 1994-08-03 | 1997-07-01 | Exxon Chemical Patents Inc. | Supported ionic catalyst composition |
US7153909B2 (en) * | 1994-11-17 | 2006-12-26 | Dow Global Technologies Inc. | High density ethylene homopolymers and blend compositions |
US6506866B2 (en) * | 1994-11-17 | 2003-01-14 | Dow Global Technologies Inc. | Ethylene copolymer compositions |
US5962714A (en) * | 1995-10-02 | 1999-10-05 | Mccullough; Laughlin Gerard | Monocyclopentadienyl transition metal catalyst and olefin polymerization process |
ID16442A (en) | 1996-01-22 | 1997-10-02 | Dow Chemical Co | WEIGHT POLYMER ETHYLENE ULTRA LOW MOLECULES |
US6225426B1 (en) * | 1996-04-10 | 2001-05-01 | Uniroyal Chemical Company, Inc. | Process for producing polyolefin elastomer employing a metallocene catalyst |
JPH09309926A (en) * | 1996-05-17 | 1997-12-02 | Dow Chem Co:The | Production of ethylene copolymer |
CA2261174C (en) * | 1996-07-23 | 2005-11-29 | The Dow Chemical Company | Olefin polymerization catalyst composition comprising group 13 compound |
US5849823A (en) * | 1996-09-04 | 1998-12-15 | The Dow Chemical Company | Homogeneously branched ethylene α-olefin interpolymer compositions for use in gasket applications |
US6271322B1 (en) | 1996-10-02 | 2001-08-07 | Mccullough Laughlin Gerard | Monocyclopentadienyl transition metal catalyst and olefin polymerization process |
PL188107B1 (en) * | 1996-11-15 | 2004-12-31 | Montell Technology Company Bv | Heterocyclic metalocenes and polymerisation catalysts |
US6812289B2 (en) | 1996-12-12 | 2004-11-02 | Dow Global Technologies Inc. | Cast stretch film of interpolymer compositions |
JP2001509185A (en) | 1997-01-08 | 2001-07-10 | ハーキュリーズ・インコーポレーテッド | Solid acids as catalysts for the production of hydrocarbon resins |
US6228794B1 (en) | 1997-03-14 | 2001-05-08 | University Of Iowa Research Foundation | Cationic group 13 complexes incorporating bidentate ligands as polymerization catalysts |
US5777120A (en) * | 1997-03-14 | 1998-07-07 | University Of Iowa Research Foundation | Cationic aluminum alkyl complexes incorporating amidinate ligands as polymerization catalysts |
AR012582A1 (en) | 1997-04-14 | 2000-11-08 | Dow Global Technologies Inc | POLYMERIC COMPOSITIONS OF IMPROVED ELONGATION AND ADHESIVE FORMULATIONS OF HOT MELTING INCLUDING SUCH COMPOSITION |
US6228795B1 (en) | 1997-06-05 | 2001-05-08 | Exxon Chemical Patents, Inc. | Polymeric supported catalysts |
JP2001512770A (en) | 1997-08-08 | 2001-08-28 | ザ ダウ ケミカル カンパニー | Sheet material suitable for use as floor, wall or ceiling covering, method for producing the same, and intermediate |
KR100556319B1 (en) | 1997-08-15 | 2006-03-03 | 다우 글로벌 테크놀로지스 인크. | Films produced from substantially linear homogeneous olefin polymer compositions |
DE69807708T2 (en) | 1997-08-27 | 2003-01-02 | Dow Chemical Co | ELASTOMERS WITH IMPROVED PROCESSABILITY |
US6696379B1 (en) | 1997-09-19 | 2004-02-24 | The Dow Chemical Company | Supported modified alumoxane catalyst activator |
DE19757524A1 (en) | 1997-12-23 | 1999-06-24 | Bayer Ag | Transition metal complex compound having half sandwich structure and donor-acceptor groups |
WO1999046435A1 (en) | 1998-03-11 | 1999-09-16 | The Dow Chemical Company | Fibers made from alpha-olefin/vinyl or vinylidene aromatic and/or hindered cycloaliphatic or aliphatic vinyl or vinylidene interpolymers |
AR018359A1 (en) * | 1998-05-18 | 2001-11-14 | Dow Global Technologies Inc | HEAT RESISTANT ARTICLE, CONFIGURED, IRRADIATED AND RETICULATED, FREE FROM A SILANAN RETICULATION AGENT |
US6245868B1 (en) | 1998-05-29 | 2001-06-12 | Univation Technologies | Catalyst delivery method, a catalyst feeder and their use in a polymerization process |
BR9911836A (en) | 1998-06-12 | 2001-10-16 | Avery Dennison Corp | Multilayer thermoplastic film, method for signal cutting and electronic delineation film |
US6437090B1 (en) * | 1998-06-17 | 2002-08-20 | Kabushiki Kaisha Toshiba | Curing catalyst, resin composition, resin-sealed semiconductor device and coating material |
US6329312B1 (en) | 1998-06-19 | 2001-12-11 | Phillips Petroleum Company | Metallocycle metallocenes and their use |
DE69902548T2 (en) | 1998-08-11 | 2003-04-10 | Dow Chemical Co | catalyst activator |
JP4435420B2 (en) | 1998-08-17 | 2010-03-17 | ダウ グローバル テクノロジーズ インコーポレーテッド | Three-coordinate aluminum catalyst activator composition |
AU3551499A (en) | 1998-08-18 | 2000-03-14 | Dow Chemical Company, The | Metalloid salt catalyst/activators |
CA2338472C (en) | 1998-09-16 | 2008-02-12 | The Dow Chemical Company | Functionalized catalyst supports and supported catalyst systems |
CA2338445C (en) | 1998-09-16 | 2009-12-08 | The Dow Chemical Company | Dinuclear fluoroaryl aluminum alkyl complexes |
US6521793B1 (en) | 1998-10-08 | 2003-02-18 | Symyx Technologies, Inc. | Catalyst ligands, catalytic metal complexes and processes using same |
US6225427B1 (en) | 1998-10-15 | 2001-05-01 | Uniroyal Chemical Company, Inc. | Olefin polymerization process employing metallocene catalyst provided by cocatalyst activation of a metallocene procatalyst |
US6340651B1 (en) | 1999-04-26 | 2002-01-22 | Phillips Petroleum Company | Multicyclic metallocycle metallocenes and their use |
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 |
US6673735B1 (en) | 1999-11-24 | 2004-01-06 | Dow Global Technologies Inc. | Preparation of catalyst compositions |
US6281306B1 (en) | 1999-12-16 | 2001-08-28 | Univation Technologies, Llc | Method of polymerization |
US20020013224A1 (en) * | 2000-02-08 | 2002-01-31 | Diamond Gary M. | Catalysts, metal complexes, compositions and arrays containing erbium |
US6448424B1 (en) * | 2000-05-01 | 2002-09-10 | Solvay Polyolefins Europe-Belgium (Société Anonyme) | Tetrahydrofluorenyl containing group 4 metallocenes useful as catalysts for the polymerization of olefins, process for their preparation and use of said metallocenes for the polymerization of olefins |
US7078164B1 (en) | 2000-06-19 | 2006-07-18 | Symyx Technologies, Inc. | High throughput screen for identifying polymerization catalysts from potential catalysts |
US6559230B2 (en) | 2000-09-29 | 2003-05-06 | Dupont Dow Elastomers L.L.C. | Thermosetting ethylene/alpha-olefin composition and safety glass interlayer film made from the composition |
US6713577B2 (en) | 2000-11-07 | 2004-03-30 | Symyx Technologies, Inc. | Substituted pyridyl amine catalysts and processes for polymerizing and polymers |
US6538082B2 (en) * | 2000-12-05 | 2003-03-25 | Solvay Polyolefins Europe-Belgium | Asymmetric silicon-bridged metallocenes useful as catalysts in the polymerization of α-olefins, process for their preparation and use of said metallocenes for the polymerization of α-olefins |
US6590034B2 (en) | 2001-01-02 | 2003-07-08 | Dow Global Technologies Inc. | Peelable seal and method of making and using same |
ES2232767T3 (en) * | 2001-08-31 | 2005-06-01 | Dow Global Technologies Inc. | MULTIMODAL POLYETHYLENE MATERIAL. |
WO2003037937A1 (en) * | 2001-10-18 | 2003-05-08 | The Dow Chemical Company | Diene functionalized catalyst supports and supported catalyst compositions |
US7122689B2 (en) | 2001-11-06 | 2006-10-17 | Symyx Technologies, Inc. | Titanium substituted pyridyl amine complexes, catalysts and processes for polymerizing ethylene and stryene |
US6794514B2 (en) | 2002-04-12 | 2004-09-21 | Symyx Technologies, Inc. | Ethylene-styrene copolymers and phenol-triazole type complexes, catalysts, and processes for polymerizing |
US7060848B2 (en) * | 2002-04-24 | 2006-06-13 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
US7091292B2 (en) * | 2002-04-24 | 2006-08-15 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
AU2003225156A1 (en) * | 2002-04-24 | 2003-11-10 | Symyx Technologies, Inc. | Bridged bi-aromatic ligands, complexes, catalysts and processes for polymerizing and poymers therefrom |
US6846884B2 (en) * | 2002-09-27 | 2005-01-25 | Union Carbide Chemicals & Plastics Technology Corporation | Control of resin properties |
US7223822B2 (en) | 2002-10-15 | 2007-05-29 | Exxonmobil Chemical Patents Inc. | Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom |
AU2003302033A1 (en) | 2002-10-15 | 2004-06-15 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
JP4768992B2 (en) * | 2002-12-13 | 2011-09-07 | ダウ グローバル テクノロジーズ エルエルシー | Olefin polymerization catalyst composition containing a group 13 amide derivative |
JP4090389B2 (en) * | 2003-06-10 | 2008-05-28 | 株式会社日立製作所 | Nuclear magnetic resonance apparatus |
CA2558251A1 (en) | 2004-03-17 | 2005-09-29 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for ethylene copolymer formation |
TW200604224A (en) | 2004-03-17 | 2006-02-01 | Dow Global Technologies Inc | Catalyst composition comprising shuttling agent for ethylene copolymer formation |
JP4879882B2 (en) | 2004-03-17 | 2012-02-22 | 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 higher order olefin multi-block copolymers |
CN102321201B (en) * | 2004-06-16 | 2013-06-26 | 陶氏环球技术有限责任公司 | Method for selecting polymerization modifiers |
KR101195320B1 (en) * | 2004-08-09 | 2012-10-29 | 다우 글로벌 테크놀로지스 엘엘씨 | Supported bishydroxyarylaryloxy catalysts for manufacture of polymers |
WO2006036748A2 (en) * | 2004-09-22 | 2006-04-06 | Symyx Technologies, Inc. | Heterocycle-amine ligands, compositions, complexes, and catalysts, and methods of making and using the same |
US7256296B2 (en) * | 2004-09-22 | 2007-08-14 | Symyx Technologies, Inc. | Heterocycle-amine ligands, compositions, complexes, and catalysts |
US7399874B2 (en) | 2004-10-29 | 2008-07-15 | Exxonmobil Chemical Patents Inc. | Catalyst compound containing divalent tridentate ligand |
US7705157B2 (en) * | 2004-12-16 | 2010-04-27 | Symyx Solutions, Inc. | Phenol-heterocyclic ligands, metal complexes, and their uses as catalysts |
KR20070087670A (en) * | 2004-12-21 | 2007-08-28 | 다우 글로벌 테크놀로지스 인크. | Polypropylene-based adhesive compositions |
CA2600140A1 (en) | 2005-03-17 | 2006-09-28 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation |
WO2006101595A1 (en) | 2005-03-17 | 2006-09-28 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for regio-irregular multi-block copolymer formation |
US9410009B2 (en) | 2005-03-17 | 2016-08-09 | Dow Global Technologies Llc | Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation |
MY148274A (en) * | 2005-07-08 | 2013-03-29 | Dow Global Technologies Inc | Layered film compositions, packages prepared therefrom, and methods of use |
CA2622599A1 (en) * | 2005-09-15 | 2007-03-29 | Dow Global Technolgies Inc. | Control of polymer architecture and molecular weight distribution via multi-centered shuttling agent |
TW200722441A (en) | 2005-09-15 | 2007-06-16 | Dow Global Technologies Inc | Catalytic olefin block copolymers via polymerizable shuttling agent |
US8153243B2 (en) | 2005-12-09 | 2012-04-10 | Dow Global Technologies Llc | Interpolymers suitable for multilayer films |
AU2006329980A1 (en) | 2005-12-16 | 2007-07-05 | Dow Global Technologies Inc. | Polydentate heteroatom ligand containing metal complexes, catalysts and methods of making and using the same |
EP1803747A1 (en) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films |
JP4988754B2 (en) * | 2005-12-30 | 2012-08-01 | エルジー・ケム・リミテッド | Catalyst composition containing group 4 transition metal compound and method for producing polyolefin using the same |
KR100874032B1 (en) * | 2006-02-01 | 2008-12-17 | 주식회사 엘지화학 | Catalyst composition comprising a transition metal compound and olefin polymerization using the same |
US7601255B2 (en) | 2006-09-06 | 2009-10-13 | Chemtura Corporation | Process for removal of residual catalyst components |
EP2067079B1 (en) | 2006-09-21 | 2020-03-18 | Union Carbide Chemicals & Plastics Technology LLC | Method of controlling properties in multimodal systems |
CA2680181A1 (en) * | 2007-03-07 | 2008-09-12 | Dow Global Technologies Inc. | Tethered supported transition metal complex |
ITMI20070877A1 (en) | 2007-05-02 | 2008-11-03 | Dow Global Technologies Inc | PROCESS FOR THE PRODUCTION OF MULTI-BLOCKED COPOLYMERS WITH THE USE OF POLAR SOLVENTS |
ITMI20070878A1 (en) | 2007-05-02 | 2008-11-03 | Dow Global Technologies Inc | PROCESS FOR POLYMERIZZAINE OF TACTICAL POLYMERS USING CHIRAL CATALYSTS |
US8281332B2 (en) * | 2007-05-02 | 2012-10-02 | Google Inc. | Animated video overlays |
TW200932762A (en) | 2007-10-22 | 2009-08-01 | Univation Tech Llc | Polyethylene compositions having improved properties |
US8420760B2 (en) * | 2007-11-19 | 2013-04-16 | Dow Global Technologies Llc | Long chain branched propylene-alpha-olefin copolymers |
US20090286944A1 (en) * | 2008-05-15 | 2009-11-19 | Symyx Technologies, Inc. | Select phenol-heterocycle ligands, metal complexes formed therefrom, and their uses as catalysts |
CN102257017B (en) | 2008-12-18 | 2014-02-12 | 尤尼威蒂恩技术有限责任公司 | Method for seed bed treatment for polymerization reaction |
EP2411424A2 (en) | 2009-03-06 | 2012-02-01 | Dow Global Technologies LLC | Catalysts, processes for making catalysts, processes for making polyolefin compositions and polyolefin compositions |
WO2011016992A2 (en) | 2009-07-29 | 2011-02-10 | Dow Global Technologies Inc. | Polymeric chain transfer/shuttling agents |
ES2858349T3 (en) | 2009-07-29 | 2021-09-30 | Dow Global Technologies Llc | Multi-headed chain transport agents and their use for the preparation of block copolymers |
US8067652B2 (en) | 2009-08-13 | 2011-11-29 | Chemtura Corporation | Processes for controlling the viscosity of polyalphaolefins |
IN2012DN03367A (en) | 2009-10-19 | 2015-10-23 | Sasol Technolgoy Pty Ltd | |
JP2013529720A (en) | 2010-07-06 | 2013-07-22 | ティコナ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Molded high molecular weight polyethylene articles, their manufacture and use |
JP5937071B2 (en) | 2010-07-06 | 2016-06-22 | ティコナ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for producing high molecular weight polyethylene |
JP5916724B2 (en) | 2010-07-06 | 2016-05-11 | ティコナ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for producing high molecular weight polyethylene |
KR20130124170A (en) | 2010-07-06 | 2013-11-13 | 티코나 게엠베하 | Process for producing high molecular weight polyethylene |
EP2591018A2 (en) | 2010-07-06 | 2013-05-15 | Ticona GmbH | Process for producing high molecular weight polyethylene |
KR20130089165A (en) | 2010-07-06 | 2013-08-09 | 티코나 게엠베하 | Ultra-high molecular weight polyethylene, its production and use |
JP2013531111A (en) | 2010-07-06 | 2013-08-01 | ティコナ ゲゼルシャフト ミット ベシュレンクテル ハフツング | High molecular weight polyethylene fibers and membranes, their manufacture and use |
CN103228682B (en) | 2010-11-30 | 2015-07-22 | 尤尼威蒂恩技术有限责任公司 | Processes for the polymerization of olefins with extracted metal carboxylate salts |
SG190429A1 (en) | 2010-11-30 | 2013-06-28 | Univation Tech Llc | Catalyst composition having improved flow characteristics and methods of making and using the same |
US8893725B2 (en) | 2011-01-28 | 2014-11-25 | R. J. Reynolds Tobacco Company | Polymeric materials derived from tobacco |
CN103534279B (en) | 2011-05-13 | 2016-08-17 | 尤尼威蒂恩技术有限责任公司 | The carbon monoxide-olefin polymeric being spray-dried and the polymerization using it |
US8658556B2 (en) | 2011-06-08 | 2014-02-25 | Exxonmobil Chemical Patents Inc. | Catalyst systems comprising multiple non-coordinating anion activators and methods for polymerization therewith |
WO2012170202A2 (en) | 2011-06-08 | 2012-12-13 | Exxonmobil Chemical Patents Inc. | Catalyst systems comprising multiple non-coordinating anion activators and methods for polymerization therewith |
CN106397636B (en) | 2011-09-30 | 2019-09-20 | 埃克森美孚化学专利公司 | The dynamics of metalloscene catalyst is modulated |
US8841379B2 (en) | 2011-11-07 | 2014-09-23 | E I Du Pont De Nemours And Company | Method to form an aqueous dispersion of an ionomer-polyolefin blend |
CN104105720A (en) | 2011-12-19 | 2014-10-15 | 提克纳有限公司 | Process for producing high molecular weight polyethylene |
WO2014074981A1 (en) | 2012-11-12 | 2014-05-15 | Univation Technologies, Llc | Recycle gas cooler systems for gas-phase polymerization processes |
WO2014099303A1 (en) | 2012-12-21 | 2014-06-26 | Exxonmobil Chemical Patents Inc. | Bridged metallocene compounds, catalyst systems and processes for polymerization therewith |
CN105121015A (en) | 2013-01-14 | 2015-12-02 | 尤尼威蒂恩技术有限责任公司 | Methods for preparing catalyst systems with increased productivity |
US20150353651A1 (en) | 2013-01-30 | 2015-12-10 | Univation Technologies, Llc | Processes for making catalyst compositions having improved flow |
EP3301119B1 (en) | 2013-07-17 | 2021-03-17 | ExxonMobil Chemical Patents Inc. | Isotactic propylene polymers |
EP3022233B1 (en) | 2013-07-17 | 2019-05-01 | ExxonMobil Chemical Patents Inc. | Cyclopropyl substituted metallocene catalysts |
CA2943378C (en) | 2014-04-02 | 2023-09-12 | Univation Technologies, Llc | Continuity compositions and methods of making and using the same |
EP3578578A1 (en) | 2014-07-24 | 2019-12-11 | Dow Global Technologies Llc | Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers |
WO2016094843A2 (en) | 2014-12-12 | 2016-06-16 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system comprising mesoporous organosilica support |
CN107001945B (en) | 2014-12-12 | 2020-12-18 | 埃克森美孚研究工程公司 | Aromatic hydrogenation catalyst and use thereof |
WO2016094870A1 (en) | 2014-12-12 | 2016-06-16 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system comprising mesoporous organosilica support |
WO2016094866A1 (en) | 2014-12-12 | 2016-06-16 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system comprising mesoporous organosilica support |
US10155826B2 (en) | 2014-12-12 | 2018-12-18 | Exxonmobil Research And Engineering Company | Olefin polymerization catalyst system comprising mesoporous organosilica support |
EP3268399B1 (en) | 2015-03-10 | 2021-01-20 | Univation Technologies, LLC | Spray dried catalyst compositions, methods for preparation and use in olefin polymerization processes |
US10195589B2 (en) | 2015-04-20 | 2019-02-05 | Univation Technologies, Llc | Bridged bi-aromatic ligands and olefin polymerization catalysts prepared therefrom |
CN107531601A (en) | 2015-04-20 | 2018-01-02 | 尤尼威蒂恩技术有限责任公司 | Bridging biaryl perfume base ligand and transistion metal compound prepared therefrom |
EP3288984B1 (en) | 2015-04-27 | 2023-08-09 | Univation Technologies, LLC | Supported catalyst compositions having improved flow properties and preparation thereof |
WO2016195824A1 (en) | 2015-05-29 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Polymerization process using bridged metallocene compounds supported on organoaluminum treated layered silicate supports |
EP3303423A1 (en) | 2015-06-05 | 2018-04-11 | ExxonMobil Chemical Patents Inc. | Single reactor production of polymers in gas or slurry phase |
EP3885373A1 (en) | 2015-06-05 | 2021-09-29 | ExxonMobil Chemical Patents Inc. | Production of heterophasic polymers in gas or slurry phase |
WO2017003565A1 (en) | 2015-06-30 | 2017-01-05 | Exxonmobil Chemical Patents Inc. | Transition metal complexes of tridentate dianionic cnn ligands, production and use thereof |
EP3356374A1 (en) | 2015-09-30 | 2018-08-08 | Dow Global Technologies LLC | Multi- or dual-headed compositions useful for chain shuttling and process to prepare the same |
CN108348905A (en) | 2015-10-02 | 2018-07-31 | 埃克森美孚化学专利公司 | The Salan catalyst of asymmetric fluorenyl substitution |
WO2017069854A1 (en) | 2015-10-22 | 2017-04-27 | Exxonmobil Chemical Patents Inc. | Catalysts for the formation of multimodal polymers |
WO2017069851A1 (en) | 2015-10-23 | 2017-04-27 | Exxonmobil Chemical Patents Inc. | Production of polyolefins with internal unsaturation structures using a metallocene catalyst system |
US9803037B1 (en) | 2016-05-03 | 2017-10-31 | Exxonmobil Chemical Patents Inc. | Tetrahydro-as-indacenyl catalyst composition, catalyst system, and processes for use thereof |
EP3464390A1 (en) | 2016-05-27 | 2019-04-10 | ExxonMobil Chemical Patents Inc. | Metallocene catalyst compositions and polymerization process therewith |
WO2018022249A1 (en) | 2016-07-29 | 2018-02-01 | Exxonmobil Chemical Patents Inc. | Heterocyclic amido transition metal complexes, production and use thereof |
KR102444560B1 (en) | 2016-09-30 | 2022-09-20 | 다우 글로벌 테크놀로지스 엘엘씨 | Multi- or dual-head components useful for chain shuttling and the process of preparing them |
CN109952324B (en) | 2016-09-30 | 2023-06-09 | 陶氏环球技术有限责任公司 | Blocked multi-or double-headed compositions suitable for chain shuttling and methods of making the same |
JP7123040B2 (en) | 2016-09-30 | 2022-08-22 | ダウ グローバル テクノロジーズ エルエルシー | Method for preparing multi-headed or double-headed compositions useful for chain shuttling |
WO2018067289A1 (en) | 2016-10-05 | 2018-04-12 | Exxonmobil Chemical Patents Inc. | Sterically hindered metallocenes, synthesis and use |
WO2018075243A1 (en) | 2016-10-19 | 2018-04-26 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and methods of using same |
CA3049111A1 (en) | 2017-01-06 | 2018-07-12 | Univation Technologies, Llc | Synthesis of benzylanilinyl phenyl phenol ligands |
CN110114363B (en) | 2017-01-06 | 2023-01-20 | 尤尼威蒂恩技术有限责任公司 | Synthesis of benzyl oxyphenoxyphenol ligand |
WO2018151790A1 (en) | 2017-02-20 | 2018-08-23 | Exxonmobil Chemical Patents Inc. | Hafnocene catalyst compounds and process for use thereof |
WO2018151904A1 (en) | 2017-02-20 | 2018-08-23 | Exxonmobil Chemical Patents Inc. | Group 4 catalyst compounds and process for use thereof |
KR20190112293A (en) | 2017-02-20 | 2019-10-04 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | Group 4 catalyst compound and method of using the same |
US11028196B2 (en) | 2017-12-22 | 2021-06-08 | Exxonmobil Chemical Patents Inc. | Polyolefin compositions |
WO2019156968A1 (en) | 2018-02-07 | 2019-08-15 | Exxonmobil Chemical Patents Inc. | Supported catalysts systems and polymerization processes for using the same |
US11440979B2 (en) | 2018-02-19 | 2022-09-13 | Exxonmobil Chemical Patents Inc. | Catalysts, catalyst systems, and methods for using the same |
EP3768734A1 (en) | 2018-03-19 | 2021-01-27 | ExxonMobil Chemical Patents Inc. | Elastomeric propylene-alpha-olefin-diene terpolymer compositions |
US11369949B2 (en) | 2018-06-04 | 2022-06-28 | Exxonmobil Chemical Patents Inc. | Metallocenes with Si—Si bridges |
WO2020041096A1 (en) | 2018-08-22 | 2020-02-27 | Exxonmobil Research And Engineering Company | Manufacturing hydrocarbons |
WO2020041084A1 (en) | 2018-08-22 | 2020-02-27 | Exxonmobil Research And Engineering Company | Manufacturing a base stock from ethanol |
US20210179827A1 (en) | 2018-08-29 | 2021-06-17 | Exxonmobil Chemical Patents Inc. | Methods of Making Polymer Compositions with Enhanced Elasticity by Employing VTP and HMP Catalyst Systems in Parallel Processes |
WO2020069086A2 (en) | 2018-09-27 | 2020-04-02 | Exxonmobil Chemical Patents Inc. | C1,c2-bridged ligands and catalysts |
CN113498413A (en) | 2018-12-28 | 2021-10-12 | 陶氏环球技术有限责任公司 | Curable compositions comprising unsaturated polyolefins |
BR112021012786A2 (en) | 2018-12-28 | 2021-09-14 | Dow Global Technologies Llc | CURABLE FORMULATION |
CN113454130A (en) | 2018-12-28 | 2021-09-28 | 陶氏环球技术有限责任公司 | Telechelic polyolefins and process for preparing telechelic polyolefins |
KR20210121028A (en) | 2018-12-28 | 2021-10-07 | 다우 글로벌 테크놀로지스 엘엘씨 | organometallic chain transfer agent |
SG11202107057WA (en) | 2018-12-28 | 2021-07-29 | Dow Global Technologies Llc | Curable compositions comprising unsaturated polyolefins |
WO2020146375A2 (en) | 2019-01-08 | 2020-07-16 | Exxonmobil Chemical Patents Inc | Olefin polymerization processes featuring in situ blending of an oil extension |
US11180580B2 (en) | 2019-03-29 | 2021-11-23 | Exxonmobil Chemical Patents Inc. | Benzazole and pseudoindole diamido transition metal complexes and use thereof in olefin polymerization |
US20220267649A1 (en) | 2019-07-17 | 2022-08-25 | Exxonmobil Chemical Patents Inc. | Pressure Sensitive Adhesives Comprising Propylene-Ethylene(-Diene) Copolymers |
CN114450336B (en) | 2019-08-05 | 2024-01-09 | 埃克森美孚化学专利公司 | Propylene-alpha-olefin-diene terpolymer additives for improved rubber adhesion |
US11649256B2 (en) | 2019-10-11 | 2023-05-16 | Exxonmobil Chemical Patents Inc. | Catalysts for olefin polymerization |
EP4073131A1 (en) | 2019-12-11 | 2022-10-19 | ExxonMobil Chemical Patents Inc. | Low aromatic polyolefins |
WO2021126692A1 (en) | 2019-12-16 | 2021-06-24 | Exxonmobil Chemical Patents Inc. | Iron bis(imino) aryl catalysts and methods thereof |
WO2021173361A1 (en) | 2020-02-24 | 2021-09-02 | Exxonmobil Chemical Patents Inc. | Ansa-bis(inden-2-yl) catalysts for producing vinylidene-terminated polyalphaolefins |
WO2021173362A1 (en) | 2020-02-24 | 2021-09-02 | Exxonmobil Chemical Patents Inc. | Lewis base catalysts and methods thereof |
US11760814B2 (en) | 2020-03-03 | 2023-09-19 | Exxonmobil Chemical Patents Inc. | 1,5 diazabicyclooctane ligand systems and methods therewith |
WO2021188361A1 (en) | 2020-03-20 | 2021-09-23 | Exxonmobil Chemical Patents Inc. | Linear alpha-olefin copolymers and impact copolymers thereof |
EP4127061A1 (en) | 2020-03-30 | 2023-02-08 | ExxonMobil Chemical Patents Inc. | Comb-block copolymers and methods thereof |
US20230242745A1 (en) | 2020-06-03 | 2023-08-03 | Exxonmobil Chemical Patents Inc | Process for Production of Thermoplastic Vulcanizates using Supported Catalyst Systems and Compositions Made Therefrom |
US20230212330A1 (en) | 2020-06-16 | 2023-07-06 | Exxonmobil Chemical Patents Inc. | Metallocene Catalysts for Producing Vinyl-Terminated Polyalphaolefins and Methods Associated Therewith |
WO2021262842A1 (en) | 2020-06-26 | 2021-12-30 | Exxonmobil Chemical Patents Inc. | COPOLYMERS OF ETHYLENE, α-OLEFIN, NON-CONJUGATED DIENE, AND ARYL-SUBSTITUTED CYCLOALKENE, METHODS TO PRODUCE, BLENDS, AND ARTICLES THEREFROM |
WO2021262838A1 (en) | 2020-06-26 | 2021-12-30 | Exxonmobil Chemical Patents Inc. | Copolymers composed of ethylene, a-olefin, non-conjugated diene, and substituted styrene and articles therefrom |
US20240018279A1 (en) | 2020-08-13 | 2024-01-18 | Exxonmobil Chemical Patents Inc. | Cyclic Containing Polymer Compositions Obtained Using Transition Metal Bis(Phenolate) Catalyst Complexes and Process for Production Thereof |
EP4222180B1 (en) | 2020-09-30 | 2024-04-10 | ExxonMobil Chemical Patents Inc. | Bis(heterocyclic-olate) lewis base catalysts and methods thereof |
US11919981B2 (en) | 2020-10-22 | 2024-03-05 | Exxonmobil Chemical Patents Inc. | Monocyclopentadienyl pyridyl hydroxyl amine catalyst compounds and systems for olefin polymerization |
US11814460B2 (en) | 2020-10-22 | 2023-11-14 | Exxonmobil Chemical Patents Inc. | Pyridyl hydroxyl amine catalyst compounds and systems for Olefin Polymerization |
CN117043198A (en) | 2020-10-22 | 2023-11-10 | 埃克森美孚化学专利公司 | Multidentate lewis base catalysts and methods of use thereof |
US20230406967A1 (en) | 2020-10-28 | 2023-12-21 | Exxonmobil Chemical Patents Inc. | Non-Aromatic Hydrocarbon Soluble Olefin Polymerization Catalysts and Use Thereof |
EP4271718A1 (en) | 2020-12-29 | 2023-11-08 | ExxonMobil Chemical Patents Inc. | Polyolefin-based ionomers and production thereof |
CA3216256A1 (en) | 2021-05-14 | 2022-11-17 | Jo Ann M. Canich | Ethylene-propylene branched copolymers as viscosity modifiers |
EP4347670A1 (en) | 2021-05-24 | 2024-04-10 | ExxonMobil Chemical Patents Inc. | Biphasic polymerization processes |
WO2023034889A1 (en) | 2021-09-02 | 2023-03-09 | Exxonmobil Chemical Patents Inc. | C1 symmetric metallocene catalysts tailored for production of vinyl-terminated polypropylene oligomers and macromonomers |
WO2023044215A1 (en) | 2021-09-14 | 2023-03-23 | Exxonmobil Chemical Patents Inc. | Catalyst feeder and processes thereof |
WO2023177957A1 (en) | 2022-03-14 | 2023-09-21 | Exxonmobil Chemical Patents Inc. | Metal-containing bis(imino) per-substituted aryl compounds and methods thereof |
WO2023177956A1 (en) | 2022-03-14 | 2023-09-21 | Exxonmobil Chemical Patents Inc. | Metal bis(imino) aryl compounds and methods thereof |
WO2023250268A1 (en) | 2022-06-24 | 2023-12-28 | Exxonmobil Chemical Patents Inc. | Constrained geometry metal-ligand complexes and use thereof in olefin polymerization |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0418044A2 (en) * | 1989-09-14 | 1991-03-20 | The Dow Chemical Company | Metal complex compounds, process for preparation and method of use |
EP0426638A2 (en) * | 1989-10-30 | 1991-05-08 | Fina Technology, Inc. | Addition of aluminium alkyl for improved metallocene catalyst |
WO1992000333A2 (en) * | 1990-06-22 | 1992-01-09 | Exxon Chemical Patents Inc. | Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization |
EP0481480A1 (en) * | 1990-10-17 | 1992-04-22 | Idemitsu Kosan Company Limited | Process for producing propylene based oligomers |
EP0513380A1 (en) * | 1990-11-30 | 1992-11-19 | Idemitsu Kosan Company Limited | Process for producing olefinic polymer |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US5026798A (en) * | 1989-09-13 | 1991-06-25 | Exxon Chemical Patents Inc. | Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system |
US5077367A (en) * | 1989-09-29 | 1991-12-31 | The Dow Chemical Company | Crystalline syndiotactic copolymers from arylcyclobutene functional monomers and vinyl aromatic monomers |
-
1992
- 1992-12-01 KR KR1019930702664A patent/KR100262023B1/en not_active IP Right Cessation
- 1992-12-01 DE DE69232297T patent/DE69232297T2/en not_active Expired - Lifetime
- 1992-12-01 DE DE69224287T patent/DE69224287T2/en not_active Expired - Lifetime
- 1992-12-01 EP EP92925471A patent/EP0574561B1/en not_active Expired - Lifetime
- 1992-12-01 JP JP51243193A patent/JP3275078B2/en not_active Expired - Lifetime
- 1992-12-01 WO PCT/US1992/010360 patent/WO1993014132A1/en active IP Right Grant
- 1992-12-01 ES ES97201982T patent/ES2165562T3/en not_active Expired - Lifetime
- 1992-12-01 CA CA002105555A patent/CA2105555C/en not_active Expired - Lifetime
- 1992-12-01 ES ES92925471T patent/ES2111656T3/en not_active Expired - Lifetime
- 1992-12-01 US US08/108,693 patent/US5453410A/en not_active Expired - Lifetime
- 1992-12-01 EP EP97201982A patent/EP0802204B1/en not_active Expired - Lifetime
-
1993
- 1993-01-05 TW TW082100035A patent/TW211018B/zh active
- 1993-09-03 FI FI933861A patent/FI114641B/en active IP Right Grant
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0418044A2 (en) * | 1989-09-14 | 1991-03-20 | The Dow Chemical Company | Metal complex compounds, process for preparation and method of use |
EP0426638A2 (en) * | 1989-10-30 | 1991-05-08 | Fina Technology, Inc. | Addition of aluminium alkyl for improved metallocene catalyst |
WO1992000333A2 (en) * | 1990-06-22 | 1992-01-09 | Exxon Chemical Patents Inc. | Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization |
EP0481480A1 (en) * | 1990-10-17 | 1992-04-22 | Idemitsu Kosan Company Limited | Process for producing propylene based oligomers |
EP0513380A1 (en) * | 1990-11-30 | 1992-11-19 | Idemitsu Kosan Company Limited | Process for producing olefinic polymer |
Cited By (85)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6355592B1 (en) | 1990-03-20 | 2002-03-12 | Exxonmobil Chemical Patents Inc | Catalyst system of enhanced productivity and its use in polymerization process |
US6294625B1 (en) | 1990-03-20 | 2001-09-25 | Exxonmobil Chemical Patents Inc. | Catalyst system of enhanced productivity and its use in polymerization process |
US5801113A (en) * | 1990-06-22 | 1998-09-01 | Exxon Chemical Patents, Inc. | Polymerization catalyst systems, their production and use |
WO1994007927A1 (en) * | 1992-10-05 | 1994-04-14 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity and its use in polymerization process |
EP0705849A1 (en) * | 1993-06-15 | 1996-04-10 | Idemitsu Kosan Company Limited | Process for producing olefin polymer and catalyst for olefin polymerization |
US6462154B1 (en) | 1993-06-15 | 2002-10-08 | Idemitsu Kosan Co., Ltd. | Process for preparing olefin polymer and catalyst for polymerization of olefin |
EP0705849A4 (en) * | 1993-06-15 | 1996-10-23 | Idemitsu Kosan Co | Process for producing olefin polymer and catalyst for olefin polymerization |
WO1995007941A1 (en) * | 1993-09-17 | 1995-03-23 | Exxon Chemical Patents Inc. | Olefin polymerisation process |
BE1007614A3 (en) * | 1993-10-11 | 1995-08-22 | Dsm Nv | Process for the polymerization of an olefin in the presence of a catalyst formed from HALOGEENMETALLOCEEN. |
EP0708117A1 (en) * | 1994-10-03 | 1996-04-24 | Sumitomo Chemical Company Limited | Process for producing copolymer rubber |
US6066603A (en) * | 1996-06-17 | 2000-05-23 | Exxon Chemical Patents Inc. | Polar monomer containing copolymers derived from olefins useful as lubricant and useful as lubricant and fuel oil additivies process for preparation of such copolymers and additives and use thereof |
US5811379A (en) * | 1996-06-17 | 1998-09-22 | Exxon Chemical Patents Inc. | Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof (PT-1267) |
US6468948B1 (en) | 1996-06-17 | 2002-10-22 | Infineum Usa L.P. | Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof (PT-1267) |
US6355819B1 (en) | 1997-04-14 | 2002-03-12 | Borealis Technology Oy | Substituted metallocene compounds for olefin polymerization catalyst systems, their intermediates and methods for preparing them |
US6172015B1 (en) | 1997-07-21 | 2001-01-09 | Exxon Chemical Patents, Inc | Polar monomer containing copolymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such copolymers and additives and use thereof |
US6211312B1 (en) | 1998-06-12 | 2001-04-03 | Univation Technologies | Olefin polymerization process using activated lewis acid-base complexes |
US6476166B1 (en) | 1998-07-16 | 2002-11-05 | Univation Technologies, Llc | Aluminum-based lewis acid cocatalysts for olefin polymerization |
US6147174A (en) * | 1998-07-16 | 2000-11-14 | Univation Technologies, Llc | Aluminum based lewis acid cocatalysts for olefin polymerization |
US6984722B2 (en) | 1998-09-30 | 2006-01-10 | Exxonmobil Chemical Patents Inc. | Cationic group 3 catalyst system |
US6403773B1 (en) | 1998-09-30 | 2002-06-11 | Exxon Mobil Chemical Patents Inc. | Cationic group 3 catalyst system |
US6677441B2 (en) | 1998-09-30 | 2004-01-13 | Exxonmobil Chemical Patents Inc. | Cationic group 3 catalyst system |
US6806220B2 (en) | 1998-10-23 | 2004-10-19 | Exxonmobil Chemical Patents Inc. | High activity carbenium-activated polymerization catalysts |
US6486088B1 (en) | 1998-10-23 | 2002-11-26 | Exxonmobil Chemical Patents Inc. | High activity carbenium-activated polymerization catalysts |
US6562919B2 (en) | 1998-10-23 | 2003-05-13 | Exxonmobil Chemical Patents Inc. | High activity carbenium-activated polymerization catalysts |
US6476164B1 (en) | 1999-10-22 | 2002-11-05 | Exxonmobil Chemical Patents Inc. | Carbenium cationic complexes suitable for polymerization catalysts |
US6475946B1 (en) | 1999-10-22 | 2002-11-05 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalysis with aryl substituted carbenium cationic complexes |
US6838411B2 (en) | 1999-10-22 | 2005-01-04 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalysis with aryl substituted carbenium cationic complexes |
US6489480B2 (en) | 1999-12-09 | 2002-12-03 | Exxonmobil Chemical Patents Inc. | Group-15 cationic compounds for olefin polymerization catalysts |
US6822057B2 (en) | 1999-12-09 | 2004-11-23 | Exxon Mobil Chemical Patents Inc. | Olefin polymerization catalysts derived from Group-15 cationic compounds and processes using them |
US6977287B2 (en) | 1999-12-10 | 2005-12-20 | Exxonmobil Chemical Patents Inc. | Propylene diene copolymers |
US6809168B2 (en) | 1999-12-10 | 2004-10-26 | Exxonmobil Chemical Patents Inc. | Articles formed from propylene diene copolymers |
US7005491B2 (en) | 1999-12-10 | 2006-02-28 | Exxonmobil Chemical Patents Inc. | Propylene diene copolymerized polymers |
US7163993B2 (en) | 1999-12-20 | 2007-01-16 | Exxonmobil Chemical Patents Inc. | Electrical devices from polymer resins prepared with ionic catalysts |
US6590055B2 (en) | 1999-12-20 | 2003-07-08 | Exxonmobil Chemical Patents Inc. | Electrical devices from polymer resins prepared with ionic catalysts |
US6562920B2 (en) | 1999-12-20 | 2003-05-13 | Exxonmobil Chemical Patents Inc. | Processes for the preparation polyolefin resins using supported ionic catalysts |
US6627723B2 (en) | 1999-12-22 | 2003-09-30 | Exxonmobil Chemical Patents Inc. | Adhesive alpha-olefin inter-polymers |
US7521507B2 (en) | 1999-12-22 | 2009-04-21 | Exxonmobil Chemical Patents Inc. | Polypropylene-based adhesive compositions |
US7067603B1 (en) | 1999-12-22 | 2006-06-27 | Exxonmobil Chemical Patents Inc. | Adhesive alpha-olefin inter-polymers |
EP2045304A2 (en) | 1999-12-22 | 2009-04-08 | ExxonMobil Chemical Patents Inc. | Polypropylene-Based Adhesive Compositions |
US6809209B2 (en) | 2000-04-07 | 2004-10-26 | Exxonmobil Chemical Patents Inc. | Nitrogen-containing group-13 anionic compounds for olefin polymerization |
WO2003000740A2 (en) | 2001-06-20 | 2003-01-03 | Exxonmobil Chemical Patents Inc. | Polyolefins made by catalyst comprising a noncoordinating anion and articles comprising them |
US7220801B2 (en) | 2001-06-22 | 2007-05-22 | Exxonmobil Chemical Patents Inc. | Metallocene-produced very low density polyethylenes or linear low density polyethylenes as impact modifiers |
US7153571B2 (en) | 2002-07-31 | 2006-12-26 | Exxonmobil Chemical Patents Inc. | Silane crosslinkable polyethylene |
US7235607B2 (en) | 2002-09-05 | 2007-06-26 | Exxonmobil Chemical Patents Inc. | Shrink film |
US7601409B2 (en) | 2002-09-05 | 2009-10-13 | Exxonmobil Chemical Patents Inc. | Stretch film |
WO2005118605A1 (en) | 2004-05-26 | 2005-12-15 | Exxonmobil Chemical Patents, Inc. | Transition metal compounds for olefin polymerization and oligomerization |
WO2007070041A1 (en) | 2005-12-14 | 2007-06-21 | Exxonmobil Chemical Patents Inc. | Halogen substituted metallocene compounds for olefin polymerization |
US7951873B2 (en) | 2006-05-05 | 2011-05-31 | Exxonmobil Chemical Patents Inc. | Linear low density polymer blends and articles made therefrom |
WO2007136497A3 (en) * | 2006-05-17 | 2008-01-31 | Dow Global Technologies Inc | High temperature solution polymerization process |
EP2112173A1 (en) | 2008-04-16 | 2009-10-28 | ExxonMobil Chemical Patents Inc. | Catalyst compounds and use thereof |
WO2011087692A2 (en) | 2009-12-23 | 2011-07-21 | Invista Technologies S.A R.L. | Stretch articles including polyolefin elastic fiber |
WO2011087695A2 (en) | 2009-12-23 | 2011-07-21 | Invista Technologies S.A R.L. | Polyolefin elastic fiber |
US10041190B2 (en) | 2009-12-23 | 2018-08-07 | Invista North America S.A.R.L. | Fabric including polyolefin elastic fiber |
WO2011087693A2 (en) | 2009-12-23 | 2011-07-21 | Invista Technologies S.A R.1. | Elastic fiber containing an anti-tack additive |
US10039855B2 (en) | 2009-12-23 | 2018-08-07 | Invista North America S.A.R.L. | Elastic fiber containing an anti-tack additive |
WO2011079042A2 (en) | 2009-12-24 | 2011-06-30 | Exxonmobil Chemical Patents Inc. | Process for producing novel synthetic basestocks |
WO2011087729A2 (en) | 2010-01-14 | 2011-07-21 | Exxonmobil Chemical Patents Inc. | Processes and apparatus for polymer finishing and packaging |
WO2011087728A2 (en) | 2010-01-14 | 2011-07-21 | Exxonmobil Chemical Patents Inc. | Processes and apparatus for continuous solution polymerization |
WO2011087731A1 (en) | 2010-01-14 | 2011-07-21 | Exxonmobil Chemical Patents Inc. | Processes and apparatus for continuous solution polymerization |
EP2368896A1 (en) | 2010-03-01 | 2011-09-28 | ExxonMobil Chemical Patents Inc. | Mono-indenyl transition metal compounds and polymerization therewith |
WO2015073132A1 (en) | 2013-10-31 | 2015-05-21 | Exxonmobil Chemical Patents Inc. | Process and apparatus for continuous solution polymerization |
WO2015073157A1 (en) | 2013-11-15 | 2015-05-21 | Exxonmobil Chemical Patents Inc. | Process to produce polymers from pyridyldiamido transition metal complexes and use thereof |
WO2016171810A1 (en) | 2015-04-20 | 2016-10-27 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and processes for use thereof |
WO2016172197A1 (en) | 2015-04-20 | 2016-10-27 | Exxonmobil Chemical Patents Inc. | Multimodal and broad molecular weight high density polyethylene |
WO2016171809A1 (en) | 2015-04-20 | 2016-10-27 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and processes for use thereof |
WO2018022263A1 (en) | 2016-07-29 | 2018-02-01 | Exxonmobil Chemical Patents Inc. | Polymerization processes using high molecular weight polyhydric quenching agents |
WO2018044395A1 (en) | 2016-08-31 | 2018-03-08 | Exxonmobil Chemical Patents Inc. | Spiral heat exchanger as a preheater in polymer devolatilization processes |
WO2018151903A1 (en) | 2017-02-20 | 2018-08-23 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and processes for use thereof |
WO2019027605A1 (en) | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | Films made from polyethylene compositions and processes for making the same |
WO2019027585A1 (en) | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | Mixed catalysts with unbridged hafnocenes with -ch2-sime3 moieties |
WO2019027587A1 (en) | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions and films prepared therefrom |
WO2019108327A1 (en) | 2017-12-01 | 2019-06-06 | Exxonmobil Chemical Patents Inc. | Films comprising polyethylene composition |
WO2019108977A1 (en) | 2017-12-01 | 2019-06-06 | Exxonmobil Chemical Patents Inc. | Catalyst systems and polymerization processes for using the same |
WO2019162760A1 (en) | 2018-02-05 | 2019-08-29 | Exxonmobil Chemical Patents Inc. A Corporation Of State Of Delaware | Enhanced processability of lldpe by addition of ultra-high molecular weight high density polyethylene |
WO2019173605A1 (en) | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Ethylene-propylene branched copolymers as viscosity modifiers with enhanced fuel economy |
WO2019173598A1 (en) | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Ethylene-propylene linear copolymers as viscosity modifiers |
WO2019246069A1 (en) | 2018-06-19 | 2019-12-26 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions and films prepared therefrom |
WO2020060745A1 (en) | 2018-09-19 | 2020-03-26 | Exxonmobil Chemical Patents Inc. | Devolatilization processes |
WO2020167399A1 (en) | 2019-02-11 | 2020-08-20 | Exxonmobil Chemical Patents Inc. | Biphasic polymerization processes and ethylene-based polyolefins therefrom |
WO2021041406A1 (en) | 2019-08-27 | 2021-03-04 | Chevron Oronite Company Llc | Ethylene copolymers and use as viscosity modifiers |
WO2021126443A2 (en) | 2019-12-17 | 2021-06-24 | Exxonmobil Chemical Patents Inc. | Solution polymerization process for making high-density polyethylene long-chain branching |
WO2021222280A2 (en) | 2020-05-01 | 2021-11-04 | Exxonmobil Chemical Patents Inc. | Linear low density polyethylene for film applications |
WO2021222016A2 (en) | 2020-05-01 | 2021-11-04 | Exxonmobil Chemical Patents Inc. | Linear low density polyethylene for film applications |
WO2022076216A1 (en) | 2020-10-08 | 2022-04-14 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and processes for use thereof |
WO2023097161A1 (en) | 2021-11-23 | 2023-06-01 | Exxonmobil Chemical Patents Inc. | Plants and processes for forming polymers |
Also Published As
Publication number | Publication date |
---|---|
JPH06505767A (en) | 1994-06-30 |
FI114641B (en) | 2004-11-30 |
TW211018B (en) | 1993-08-11 |
FI933861A (en) | 1993-09-03 |
CA2105555C (en) | 2003-12-30 |
EP0574561A1 (en) | 1993-12-22 |
FI933861A0 (en) | 1993-09-03 |
JP3275078B2 (en) | 2002-04-15 |
ES2165562T3 (en) | 2002-03-16 |
DE69224287D1 (en) | 1998-03-05 |
EP0802204A2 (en) | 1997-10-22 |
EP0802204B1 (en) | 2001-12-12 |
US5453410A (en) | 1995-09-26 |
DE69224287T2 (en) | 1998-08-27 |
KR100262023B1 (en) | 2000-07-15 |
ES2111656T3 (en) | 1998-03-16 |
DE69232297D1 (en) | 2002-01-24 |
CA2105555A1 (en) | 1993-07-07 |
DE69232297T2 (en) | 2002-08-14 |
EP0802204A3 (en) | 2000-03-15 |
EP0574561B1 (en) | 1998-01-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0802204B1 (en) | Improved catalyst composition | |
EP0561479B1 (en) | Catalysts, method of preparing these catalysts and method of using said catalysts | |
CA2133990C (en) | Process for preparation of monocyclopentadienyl metal complex compounds and method of use | |
US5132380A (en) | Metal complex compounds | |
EP1135419B1 (en) | Nitrogen-containing group 13 anionic complexes for olefin polymerization | |
CA2046075C (en) | Addition polymerization catalyst with oxidative activation | |
JPH0586120A (en) | Manufacture of addition polymerization catalyst by metal center oxidation | |
JP2002517571A (en) | Olefin polymerization method using activated Lewis acid-base complex | |
US6262201B1 (en) | Aryl substituted metallocene catalysts and their use | |
JPH08502094A (en) | Catalyst systems with improved productivity and their use in polymerization processes | |
US6291610B1 (en) | Haloaryl containing group 13 substituents on bridged metallocene polyolefin catalysts | |
US6268448B1 (en) | Iminophosphonamide complexes for olefin | |
US6825369B1 (en) | Metal complex compounds | |
AU2001294965B2 (en) | A method for preparing a catalyst composition and its use in a polymerization process | |
JP3120601B2 (en) | Olefin polymerization catalyst and olefin polymerization method | |
WO2006052427A1 (en) | Highly soluble ferrocenyl compounds | |
JP3302415B2 (en) | Internal olefin polymerization catalyst and method for producing internal olefin polymer | |
WO2001053361A1 (en) | Siloxy-substituted monocyclopentadienyl ligated constrained geometry olefin polymerisation catalysts | |
JP2001525425A (en) | Olefin polymerization catalyst and olefin polymerization method using the catalyst | |
AU2002352741A1 (en) | Bidentate Ligand Based Catalyst for the Polymerization of Olefins | |
EP1379561A2 (en) | Transition metal donor complexes and olefin polymerization process | |
CZ449690A3 (en) | Compound for preparing catalyst for addition polymerization of monomers, process of its preparation and monomer preparation process |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA FI JP KR US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 08108693 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2105555 Country of ref document: CA Ref document number: 933861 Country of ref document: FI |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1992925471 Country of ref document: EP Ref document number: 1019930702664 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 1992925471 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1992925471 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 933861 Country of ref document: FI |