Modified phosphinimine catalysts for olefin polymerization

Olefin polymerization is carried out with a supported phosphinimine catalyst which has been treated with a long chain substituted amine compound.

Ti catalyst systems comprising substituted cyclopentadienyl, amidine and diene ligand

The invention relates to a catalyst system for the polymerization of olefins comprising a metal complex of formula CyLMD and an activating cocatalyst, wherein M is titanium, Cy is a cyclopentadienyl-type ligand, D is a diene, L is an amidinate-containing ligand of formula (1), wherein the amidinate-containing ligand is covalently bonded to the titanium via the imine nitrogen atom, Sub 1 is a substituent, which comprises a group 14 atom through which Sub 1 is bonded to the imine carbon atom, Sub 2 is a substituent, which comprises a nitrogen atom, through which Sub 2 is bonded to the imine carbon atom, and Cy is a mono- or polysubstituted cyclopentadienyl-type ligand, wherein the one or more substituents of Cy are selected from the group consisting of halogen, hydrocarbyl, silyl and germyl residues, optionally substituted with one or more halogen, amido, phosphido, alkoxy, or aryloxy residues. The invention further relates to a process for the preparation of a polymer comprising at least one aliphatic or aromatic hydrocarbyl C 2-20 olefin wherein the at least one aliphatic or aromatic olefin is contacted with the catalyst system of the present invention.

Process for Preparing a Polyethylene in at Least One Continuously Stirred Tank Reactor

Processes for preparing a polyethylene in at least one continuously stirred tank reactor are described herein. The process may comprise the step of: polymerizing ethylene in the presence of at least one supported metallocene catalyst, a diluent, optionally one or more co-monomers, and optionally hydrogen, thereby obtaining the polyethylene, wherein the supported metallocene catalyst comprises a solid support, a co-catalyst and at least one metallocene, wherein the solid support has a surface area within the range of from 100 to 500 m2/g, and has a D50 value within the range of from 4 μm to 18 μm, with D50 being defined as the particle size for which fifty percent by weight of the particles has a size lower than the D50; and D50 being measured by laser diffraction analysis on a Malvern type analyzer. Polyethylene obtained by the disclosed process and articles comprising the polyethylene are also described. 115.-. (canceled)16. An article comprising a polyethylene resin prepared by a process in at least one continuously stirred tank reactor , the process comprising:polymerizing ethylene in the presence of at least one supported metallocene catalyst, a diluent, optionally one or more co-monomers, and optionally hydrogen, thereby obtaining the polyethylene resin,{'sup': '2', 'wherein the supported metallocene catalyst comprises a solid support, a co-catalyst and at least one metallocene, wherein the solid support has a surface area within the range of from 100 to 350 m/g, and has a D50 value within the range of from 4 μm to 18 μm, with D50 being defined as the particle size for which fifty percent by weight of the particles has a size lower than the D50; and D50 being measured by laser diffraction analysis on a Malvern type analyzer.'}17. The article according to claim 16 , wherein the polyethylene resin at the end of the process has a D50 of at least 100 and at most 400 μm; and Si content lower than 60 ppm by weight.18. The article according to claim 16 , wherein the ...

Polyethylene composition and film

In some embodiments disclosed herein are polyethylene composition including a first polyethylene which is an ethylene copolymer having a weight average molecular weight of from 70,000 to 250,000 and a molecular weight distribution Mw/Mn of <2.3, a second polyethylene which is an ethylene copolymer or homopolymer having a weight average molecular weight of less than 75,000 and a molecular weight distribution Mw/Mn of <2.3, a third polyethylene which is an ethylene copolymer or homopolymer having a weight average molecular weight of less than 75,000 and a molecular weight distribution Mw/Mn of <2.3, and a fourth polyethylene which is an ethylene copolymer or homopolymer having a weight average molecular weight of from 100,000 to 250,000 and a molecular weight distribution Mw/Mn of >2.3, where the first polyethylene has more short chain branching than the second polyethylene or the third polyethylene. The polyethylene composition may have a soluble fraction in a CEF analysis of at least 7.5 weight percent. Film made from the polyethylene composition may have a machine direction 1% secant modulus of ≥200 MPa (at a film thickness of about 1 mil) and an oxygen transmission rate (OTR) of ≥550 cm3 per 100 inch2 (at a film thickness of about 1 mil). Film made from the polyethylene composition retains much of its dart impact performance on downgauging from a thickness of 1 mil to a thickness of 0.75 mil.

Methods for Determining Transition Metal Compound Concentrations in Multicomponent Liquid Systems

Methods for determining the concentration of transition metal compounds in a solution containing more than one transition metal compound are described. Polymerization reactor systems providing real-time monitoring and control of the concentrations of the transition metal components of a multicomponent catalyst system are disclosed, as well as methods for operating such polymerization reactor systems and for improving methods of preparing the multicomponent catalyst system.

CATALYST SYSTEM FOR THE POLYMERISATION AND/OR OLIGOMERISATION OF OLEFINS AND PROCESS UTILIZING THE CATALYST SYSTEM

The present invention relates to a synergistic dual olefin copolymerization catalyst system comprising a solid support material having, on its surface, two or more catalytic metal complexes wherein the two or more catalytic metal complexes comprise at least one first transition metal complex and a second transition metal complex different from the first transition metal complex; use of such a system as a catalyst; a process for producing a polymer of an olefin utilizing the catalyst system. 1. A synergistic dual olefin copolymerisation catalyst system comprising a solid support material having , on its surface , two or more catalytic metal complexes wherein the two or more catalytic metal complexes comprise at least one first transition metal complex and a second transition metal complex different from the first transition metal complex.2. The synergistic dual olefin copolymerisation catalyst system according to wherein the first transition metal complex is an olefin polymerisation catalyst and the second transition metal complex is an olefin oligomerisation catalyst.3. The system according to claim 1 , wherein the second transition metal complex is a chromium containing complex.4. The system according to claim 1 , wherein the second transition metal complex is a chromium-permethylpentalene derived complex or a chromium cyclopentadienyl complex.5. The system according to claim 1 , wherein the first transition metal complex is at least one complex of a metal selected from zirconium claim 1 , iron claim 1 , chromium claim 1 , cobalt claim 1 , nickel claim 1 , titanium and hafnium containing one or more aromatic or heteroaromatic ligands.7. The system according to claim 1 , wherein the second transition metal complex is a complex of chromium and a ligand derived from permethylpentalene having the formula [Pn*(H)CrCl] claim 1 , where Pn* is a permethylpentalene moiety.8. The system according to claim 1 , wherein the solid support material is selected from a layered ...

Polyethylene blend compositions and film

A polymer blend comprising first and second polyethylene copolymers is presented which has good processability, and which when made into film shows good toughness-stiffness balance, reasonable MD tear, as well as good optical properties.

Titanium Phosphinimide and Titanium Iminoimidazolidide Catalyst Systems With Activator-Supports

Catalyst compositions containing activator-supports and half-metallocene titanium phosphinimide complexes or half-metallocene titanium iminoimidazolidide complexes are disclosed. These catalyst compositions can be used to produce olefin polymers having relatively broad molecular weight distributions and low levels of long chain branching.

Dual Catalyst System for Producing LLDPE Copolymers with Improved Processability

Disclosed herein are ethylene-based polymers generally characterized by a density from 0.89 to 0.93 g/cm 3 , a ratio of Mw/Mn from 3 to 6.5, a Mz from 200,000 to 650,000 g/mol, a CY-a parameter at 190° C. from 0.2 to 0.4, and a reverse short chain branching distribution. The ATREF profile of these polymers can have a high temperature peak from 92 to 102° C., and a low temperature peak from 18 to 36° C. less than that of the high temperature peak. These polymers can have comparable physical properties to that of a metallocene-catalyzed LLDPE, but with improved processability, shear thinning, and melt strength, and can be used in blown film and other end-use applications.

Dilution index

This disclosure relates to ethylene interpolymer compositions. Specifically, ethylene interpolymer products having: a Dilution Index (Y d ) greater than 0; total catalytic metal≧3.0 ppm; ≧0.03 terminal vinyl unsaturations per 100 carbon atoms, and; optionally a Dimensionless Modulus (X d ) greater than 0. The disclosed ethylene interpolymer products have a melt index from about 0.3 to about 500 dg/minute, a density from about 0.869 to about 0.975 g/cm 3 , a polydispersity (M w /M n ) from about 2 to about 25 and a CDBI 50 from about 20% to about 97%. Further, the ethylene interpolymer products are a blend of at least two ethylene interpolymers; where one ethylene interpolymer is produced with a single-site catalyst formulation and at least one ethylene interpolymer is produced with a heterogeneous catalyst formulation.

Metal complex with a lewis base ligand

A metal complex of the formula (1) CyAMX(L) n   (1) wherein Cy is a cyclopentadienyl-type ligand, M is a metal of group 4; A is an amidine-containing ligand moiety, represented by formula 2: wherein the amidine-containing ligand is covalently bonded to the metal M via the imine nitrogen atom, and Sub1 is a substituent comprising a group 14 atom through which Sub1 is bonded to the imine carbon atom and Sub2 is a substituent comprising a heteroatom of group 15, through which Sub2 is bonded to the imine carbon atom; X is an allyl borate ligand derived from a conjugated diene ligand, D, and a borane, B and L is a neutral Lewis basic ligand wherein the number of said metal ligands “n” is in the range of 1 to the amount that specifies the 18-electron rule.

Process for Preparing a Polyethylene in at Least One Continuously Stirred Tank Reactor

Processes for preparing a polyethylene in at least one continuously stirred tank reactor are described herein. The process may comprise the step of: polymerizing ethylene in the presence of at least one supported metallocene catalyst, a diluent, optionally one or more co-monomers, and optionally hydrogen, thereby obtaining the polyethylene, wherein the supported metallocene catalyst comprises a solid support, a co-catalyst and at least one metallocene, wherein the solid support has a surface area within the range of from 100 to 500 m2/g, and has a D50 value within the range of from 4 μm to 18 μm, with D50 being defined as the particle size for which fifty percent by weight of the particles has a size lower than the D50; and D50 being measured by laser diffraction analysis on a Malvern type analyzer. Polyethylene obtained by the disclosed process and articles comprising the polyethylene are also described. 1. A process for preparing a polyethylene resin in at least one continuously stirred tank reactor , comprising the step of:polymerizing ethylene in the presence of at least one supported metallocene catalyst, a diluent, optionally one or more co-monomers, and optionally hydrogen, thereby obtaining the polyethylene resin,{'sup': '2', 'wherein said supported metallocene catalyst comprises a solid support, a co-catalyst and at least one metallocene, wherein the solid support has a surface area within the range of from 100 to 350 m/g, and has a D50 value within the range of from 4 μm to 18 μm, with D50 being defined as the particle size for which fifty percent by weight of the particles has a size lower than the D50; and D50 being measured by laser diffraction analysis on a Malvern type analyzer.'}2. The process according to claim 1 , wherein the polyethylene resin at the end of said process has a D50 of at least 100 and at most 400 μm; and Si content lower than 60 ppm by weight.3. The process according to claim 1 , wherein said at least one supported metallocene ...

Metallic Complex Catalyst And Polymerization Methods Employing Same

Metallic complexes having indenyl ligands can be used as an ingredient of a catalyst system. The catalyst system can be used in polymerizations of ethylenically unsaturated hydrocarbon monomers that include both olefins and polyenes. Embodiments of the catalyst system can provide interpolymers that include polyene mer and up to about 40 mole percent ethylene mer. The catalyst system also can be used in solution polymerizations conducted in C-Calkanes. 18-. (canceled)10. The process of wherein said at least one polyene comprises a conjugated diene.11. (canceled)12. The process of wherein said at least one α-olefin comprises ethylene.13. The process of wherein said at least one α-olefin is ethylene.14. The process of wherein said polymer comprises from more than zero up to 40% mole percent ethylene mer.15. The process of wherein said polymer comprises less than 2% polyene mer incorporated in a vinyl configuration.16. The process of wherein z in said general formula is 0.17. The process of wherein M in said general formula is a lanthanide metal atom.18. The process of wherein n in said general formula is 2.19. The process of wherein each Rin said general formula is a haloalkyl group.20. The process of wherein each haloalkyl group is a trifluoromethyl group.21. The process of wherein m in said general formula is 2.22. The process of wherein m in said general formula is 2.23. The process of wherein each Rin said general formula is an electron rich group independently selected from C-Calkyl groups.24. The process of wherein each Rin said general formula is a tert-butyl group.25. The process of wherein m in said general formula is 1.26. The process of wherein m in said general formula is 1.27. The process of wherein said catalyst activator comprises an alkylating agent.28. The process of wherein said catalyst activator comprises a non-coordinating anion or a non-coordinating anion precursor. This application claims the benefit of U.S. provisional patent application No. 62/ ...

VERY LOW DENSITY POLYETHYLENE PRODUCED WITH SINGLE SITE CATALYST

Provided herein are VLDPE polymer compositions suitable for use in the manufacture of flexible films or sheets. In one embodiment, the copolymer comprises a polyethylene VLDPE resin with M/Mof greater than 2, CDBIof greater than 55 and a single melting peak in DSC measurement. The polymer compositions disclosed herein may be suitable for use in the manufacture of films with improved balance of film toughness, processability and sealability in monolayer and multi-layer film structures. 147-. (canceled)48. A continuous polymerization process for production of an ethylene copolymer made from ethylene and one or more Calpha olefin comonomers , wherein the continuous solution polymerization process comprises at least two reactorsa first stirred tank polymerization reactor having a mean reactor temperature from 100° C. to less than 140° C., and,a second stirred tank reactor having a mean temperature of at least 20° C. greater than the mean reactor temperature of the first reactor; andwherein said process provides a polymer having a density from 0.890 to 0.915 g/cm3.49. The continuous polymerization process of claim 48 , wherein said process provides a polymer havinga) a molecular weight distribution Mw/Mn from about 2.2 to about 4.5,b) a molecular weight distribution Mz/Mw of greater than 2, provided that when the Mz/Mw is greater than 3, the copolymer further has a normal to flat comonomer distribution,c) a CDBI50 from about 55 to about 98, andd) a single peak in a DSC measurement.50. The continuous polymerization process of claim 48 , wherein at least one single site catalyst is used.51. The continuous polymerization process of claim 48 , wherein a single site catalyst is in the first reactor.52. The continuous polymerization process of claim 48 , wherein a single site catalyst is in the second reactor.53. The continuous polymerization process of claim 48 , wherein a single site catalyst is in the first reactor and a single site catalyst is in the second reactor.54. The ...

SPHEROIDAL CATALYST FOR OLEFIN POLYMERIZATION

A solid, spheroidal polymerization catalyst having a particle size distribution characterized by a Dm*/Dn of less than 3.0, the catalyst comprising a phosphinimine catalyst, a cocatalyst and a magnesium chloride support. A process for the polymerization of ethylene with one or more alpha olefin catalyzed by a solid, spheroidal polymerization catalyst having a particle size distribution characterized by a Dm*/Dn of less than 3.0, the catalyst comprising a phosphinimine catalyst, a cocatalyst and a magnesium chloride support. 111-. (canceled)12. A method of making a spheroidal olefin polymerization catalyst having a particle size distribution characterized by a Dm*/Dn of less than 3.0 , wherein said method comprises:i) combining a dialkylmagnesium compound with a non-protic ether,ii) combining the product of step i) with a source of chloride anion,iii) treating the product of step ii) to substantially remove the non-protic ether,iv) combining the product of step iii) with a phosphinimine catalyst and a cocatalyst.13. The method of wherein treating the product of step ii) to remove the non-protic ether comprises heating the product of step ii).14. The method of wherein treating the product of step ii) to remove the non-protic ether comprises adding an alkylaluminumchloride compound.15. The method of wherein the phosphinimine catalyst has the formula: (L)(PI)MX claim 12 , where M is Ti claim 12 , Zr or Hf; PI is a phosphinimine ligand having the formula RP═N— claim 12 , where R is independently selected from the group consisting of hydrogen claim 12 , halogen claim 12 , and C-Chydrocarbyl; L is a ligand selected from the group consisting of cyclopentadienyl claim 12 , substituted cyclopentadienyl claim 12 , indenyl claim 12 , substituted indenyl claim 12 , fluorenyl claim 12 , and substituted fluorenyl; and X is an activatable ligand.16. The method of wherein the phosphinimine catalyst has the formula: (L)((t-Bu)P═N)TiX claim 12 , where L is a cyclopentadienyl ligand ...

Ethylene copolymers produced with single site catalyst

Embodiments of the invention described herein relate to a polyethylene polymer composition suitable for use in the manufacture of packaging articles, flexible films and/or sheets. In one embodiment, the copolymer comprises a polyethylene resin with density 0.918 g/cm3 to about 0.935 g/cm3, G′ at G″(500 Pa) value, as determined from Dynamic Mechanical Analysis at 190° C., of less than 40 Pa, Mz/Mw of greater than 2, CDBI50 of greater than 60. Other embodiments relate to polymer compositions with defined molecular characteristics and formulations suitable for use in the manufacture of articles including films, sheets, bags and pouches with improved creep resistance and high toughness and a good balance of film stiffness and processability in monolayer and/or multi-layer film structures.

Ethylene interpolymers having improved color

This disclosure relates to a continuous solution polymerization process where ethylene interpolymer products having an improved color index; for example, products having higher whiteness (Whiteness Index (WI)) and lower yellowness (Yellowness Index (YI)). Product color was improved by adjusting selected solution polymerization reaction conditions. The disclosed ethylene interpolymer products have improved color relative to comparative polyethylene compositions.

Formed article

Provided is a film, sheet, plate, or other such formed article having excellent transparency made of a copolymer obtained from a cyclic olefin monomer and an α-olefin monomer. The present invention provides a formed article made from a copolymer having Tg of 170° C. or higher and an Al content of 50 ppm or less that is a copolymer including a structural unit of a cyclic olefin monomer (A) derived from norbornene and a structural unit of a monomer (B) derived from at least one C4-C12 α-olefin.

Solution polymerization process

A solution polymerization process uses a reactor system in which a first stage is operated in a non adiabatic (cooled) manner and is connected to a second stage containing a downstream reactor that is operated adiabatically. In an embodiment, the first reactor stage includes at least one loop reactor and the second stage includes a tubular reactor. In an embodiment, the first stage is operated with a single site catalyst and at least one downstream reactor uses a Ziegler Natta catalyst.

Cyclic Olefin Copolymers and Methods of Making Them

A process for making a branched cyclic olefin copolymer (bCOC), and the bCOC therefrom, comprising combining at a temperature within a range from 60° C. to 140° C. a catalyst precursor and an activator with a feed comprising ethylene and at least one cyclic olefin; where the catalyst precursor is selected from the group consisting of C-symmetric Group 4 metallocenes comprising any two ligands selected from cyclopentadienyl and ligands isolobal to the cyclopentadienyl group. The resulting bCOC is desirably semi-crystalline and useful in such articles as tubing, thermoformed and foamed articles. 1. A process for making a branched cyclic olefin copolymer (bCOC) comprising combining at a temperature within a range from 60° C. to 140° C. a catalyst precursor and an activator with a feed comprising ethylene and at least one cyclic olefin; where the catalyst precursor is selected from the group consisting of C-symmetric Group 4 metallocenes comprising any two ligands selected from cyclopentadienyl and ligands isolobal to the cyclopentadienyl group , and isolating a bCOC.2. The process of claim 1 , wherein the ligands isolobal to the cyclopentadienyl group are selected from indenyl claim 1 , benzindenyl claim 1 , fluorenyl claim 1 , octahydrofluorenyl claim 1 , cyclooctatetraenyl claim 1 , cyclopentaphenanthrenyl claim 1 , hydrogenated or partially hydrogenated versions thereof claim 1 , substituted versions thereof claim 1 , and heterocyclic versions thereof.3. The process of claim 1 , wherein at least one of the two ligands is mono- or di-substituted with groups selected from C1 to C12 alkyls claim 1 , C3 to C16 iso-alkyls claim 1 , C6 to C24 aryls claim 1 , C9 to C24 fused multi-ring aryls claim 1 , C5 to C20 nitrogen and/or sulfur heterocycles claim 1 , and combinations thereof.4. The process of claim 1 , wherein at least one of the two ligands is mono- or di-substituted with groups selected from iso-propyl claim 1 , iso-butyl claim 1 , tert-butyl claim 1 , phenyl claim ...

CATALYST SYSTEM

A catalyst system comprising a supported catalyst containing a) a solid support, which is a solid methylaluminoxane composition wherein: i) the aluminum content is in the range of 36 to 41 wt % and ii) the mole fraction of methyl groups derived from the trimethylaluminum component relative to the total number of moles of methyl groups is 12 mol % or lower and b) a catalyst thereon which is a metal complex of the formula (1) CyLMZ(1), wherein M is titanium Z is an anionic ligand, p is number of 1 to 2, preferably 2, Cy is a cyclopentadienyl-type ligand and L is an amidinate ligand of the formula (2) wherein the amidine-containing ligand is covalently bonded to the metal M via the imine nitrogen atom, and Sub1 is a substituent comprising a group 14 atom through which Sub 1 is bonded to the imine carbon atom and Sub2 is a substituent comprising a heteroatom of group, through which Sub2 is bonded to the imine carbon atom. 2. The catalyst system according to claim 1 , wherein the solid methylaluminoxane composition has a particulate form with a volume-based median diameter of 1 to 50 μm.3. The catalyst system according to claim 1 , wherein the solid methylaluminoxane composition has a homogeneity of 0.45 or lower as denoted by the following equation:{'br': None, 'i': Xi|d', 'Di|/d', 'Xi, 'Homogeneity=Σ(SIGMA)(0.5)−(0.5)Σ(SIGMA)'}wherein Xi denotes the histogram value of a particle i, d(0.5) denotes the median diameter based on volume, and Di denotes the diameter based on volume of particle i.4. The catalyst system according to claim 1 , wherein the solid methylaluminoxane composition has a specific surface area of 10 to 25 m/mmol-Al.5. The catalyst system according to claim 1 , wherein the solid methylaluminoxane composition comprises polymethylaluminoxane containing the unit denoted by general formula (I) below and trimethylaluminum:{'br': None, '—[(Me)AlO]n—\u2003\u2003(I)'}wherein n denotes an integer of 10 to 50.6. The catalyst system according to claim 1 , further ...

Dual Catalyst System for Producing LLDPE Copolymers with Improved Processability

Disclosed herein are ethylene-based polymers generally characterized by a density from 0.89 to 0.93 g/cm, a ratio of Mw/Mn from 3 to 6.5, a Mz from 200,000 to 650,000 g/mol, a CY-a parameter at 190° C. from 0.2 to 0.4, and a reverse short chain branching distribution. The ATREF profile of these polymers can have a high temperature peak from 92 to 102° C., and a low temperature peak from 18 to 36° C. less than that of the high temperature peak. These polymers can have comparable physical properties to that of a metallocene-catalyzed LLDPE, but with improved processability, shear thinning, and melt strength, and can be used in blown film and other end-use applications. 118-. (canceled)19. An olefin polymerization process , the process comprising contacting a catalyst composition with an olefin monomer and an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer , wherein:the catalyst composition comprises a half-metallocene titanium compound, a bridged metallocene compound, an activator, and a co-catalyst; and [{'sup': '3', 'a density in a range from about 0.89 to about 0.93 g/cm;'}, 'a ratio of Mw/Mn in a range from about 3 to about 6.5;', 'a Mz in a range from about 200,000 to about 650,000 g/mol;', 'a CY-a parameter at 190° C. in a range from about 0.2 to about 0.4; and', "a number of short chain branches (SCB's) per 1000 total carbon atoms of the polymer at Mz that is greater than at Mn."], 'the olefin polymer is characterized by20. The process of claim 19 , wherein:the olefin monomer comprises ethylene;{'sub': 3', '10, 'the olefin comonomer comprises a C-Calpha-olefin; and'}the polymerization reactor system comprises a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof21. The process of claim 20 , wherein the olefin polymer is an ethylene polymer having the following polymer fractions in an ATREF test:from about 0.1 to about 8 wt. % of the polymer eluted below a temperature ...

Passivated supports: catalyst, process, product and film

Ethylene copolymers made in the gas phase using a phosphinimine based single site catalyst supported on a passivated inorganic oxide support. The ethylene copolymers have a relatively narrow molecular weight distribution and good rheological parameters.

Thermally tunable phosphinimine catalysts

A new phosphinimine polymerization catalyst exhibits restricted rotation about a carbon-phosphorous bond. The restricted rotation is demonstrated using variable temperature 1 H NMR. Ethylene copolymers made using the catalysts have microstructures which are dependent on the temperature at which polymerization takes place.

Modified phosphinimine catalysts for olefin polymerization

Olefin polymerization is carried out with a supported phosphinimine catalyst which has been treated with a long chain substituted amine compound.

Rotomolded articles

This disclosure relates to rotomolded articles, having a wall structure, where the wall structure contains at least one layer containing an ethylene interpolymer product, or a blend containing an ethylene interpolymer product and an ethylene polymer, where the ethylene interpolymer product has a Dilution Index (Y d ) greater than 0 and improved Environmental Stress Crack Resistance (ESCR). The ethylene interpolymer product has a melt index from about 0.5 to about 15 dg/minute, a density from about 0.930 to about 0.955 g/cm 3 , a polydispersity (M w /M n ) from about 2 to about 6 and a CDBI 50 from about 50% to about 98%. Further, the ethylene interpolymer products are a blend of at least two ethylene interpolymers; where one ethylene interpolymer is produced with a single-site catalyst formulation and at least one ethylene interpolymer is produced with a heterogeneous catalyst formulation.

Modified phosphinimine catalysts for olefin polymerization

Olefin polymerization is carried out with a supported phosphinimine catalyst which has been treated with a long chain substituted amine compound.

Catalyst Systems Containing Low Valent Titanium-Aluminum Complexes and Polymers Produced Therefrom

Disclosed herein are methods for synthesizing low valence, titanium-aluminum complexes from half-metallocene titanium compounds and alkylaluminum compounds. The titanium-aluminum complexes can be used as components in catalyst systems for the polymerization of olefins.

DILUTION INDEX

This disclosure relates to ethylene interpolymer compositions. Specifically, ethylene interpolymer products having: a Dilution Index (Y) greater than 0; total catalytic metal ≥3.0 ppm; ≥0.03 terminal vinyl unsaturations per 100 carbon atoms, and; optionally a Dimensionless Modulus (X) greater than 0. The disclosed ethylene interpolymer products have a melt index from about 0.3 to about 500 dg/minute, a density from about 0.869 to about 0.975 g/cm, a polydispersity (M/M) from about 2 to about 25 and a CDBIfrom about 20% to about 97%. Further, the ethylene interpolymer products are a blend of at least two ethylene interpolymers; where one ethylene interpolymer is produced with a single-site catalyst formulation and at least one ethylene interpolymer is produced with a heterogeneous catalyst formulation. 1102-. (canceled)103. An ethylene interpolymer product comprising:(i) a first ethylene interpolymer;(ii) a second ethylene interpolymer, and;{'sub': 'd', '(iii) optionally a third ethylene interpolymer; wherein said ethylene interpolymer product has a Dilution Index, Y, greater than 0; a density of from 0.910 to 0.912 g/cc, wherein density is measured according to ASTM D792 and a melt index of from 1.5 to 4.5 dg/minute, wherein said melt index is measured according to ASTM D1238 (2.16 kg load and 190° C.).'}104. The ethylene interpolymer product of synthesized using a solution polymerization process.105. The ethylene interpolymer product of ; wherein said interpolymer product comprises ethylene and one or more α-olefins selected from 1-hexene and 1-octene.106. The ethylene interpolymer product of ; wherein said first ethylene interpolymer is synthesized using a single-site catalyst formulation.107. The ethylene interpolymer product of ; wherein said second ethylene interpolymer is synthesized using a first heterogeneous catalyst formulation.108. The ethylene interpolymer product of ; wherein said third ethylene interpolymer is synthesized using a first heterogeneous ...

NOVEL METALLOCENE CATALYST COMPOUND FOR PRODUCTION OF POLYOLEFIN RESIN OR METHOD OF PREPARING SAME

The present invention relates to a novel metallocene catalyst compound for the production of a polyolefin resin having a high molecular weight and a wide molecular weight distribution or a method of preparing the same, and more particularly to a metallocene catalyst compound using a ligand containing a Group 15 or 16 element having a bulky substituent or a method of preparing the same. The present invention provides a novel metallocene catalyst compound represented by Chemical Formula 1 below.

Titanium Phosphinimide and Titanium Iminoimidazolidide Catalyst Systems with Activator-Supports

Catalyst compositions containing activator-supports and half-metallocene titanium phosphinimide complexes or half-metallocene titanium iminoimidazolidide complexes are disclosed. These catalyst compositions can be used to produce olefin polymers having relatively broad molecular weight distributions and low levels of long chain branching. 2. The process of claim 1 , wherein:the catalyst composition comprises an organoaluminum co-catalyst; andthe activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide.3. The process of claim 1 , wherein the polymerization reactor system comprises a slurry reactor claim 1 , gas-phase reactor claim 1 , solution reactor claim 1 , or a combination thereof.4. The process of claim 1 , wherein the olefin monomer comprises ethylene or propylene.5. The process of claim 1 , wherein:the catalyst composition comprises an organoaluminum co-catalyst comprising trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof; andthe activator-support comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof6. The process of claim 1 , wherein:the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof;the polymerization reactor system comprises a loop slurry reactor; andthe polymerization conditions comprise a polymerization temperature in a range from about 65° C. to about 110° C.7. The ...

PREPARATION OF ULTRA HIGH MOLECULAR WEIGHT POLYETHYLENE

Particulate ultra high molecular weight polyethylene (pUHMWPE) are disclosed having an intrinsic viscosity (IV) of at least 4 dl/g, a molecular weight distribution M/Mof less than 4.0, a median particle size D50 of between 50 and 200 μm, a residual Ti-content of less than 10 ppm, a residual Si-content of less than 50 ppm, and a total ash content of less than 1000 ppm. 1. A particulate ultra high molecular weight polyethylene (pUHMWPE) havingan intrinsic viscosity (IV) of at least 4 dl/g,{'sub': w', 'n, 'a molecular weight distribution M/Mof less than 4.0,'}a median particle size D50 of between 50 and 200 μm,a residual Ti-content of less than 10 ppm,a residual Si-content of less than 50 ppm, anda total ash content of less than 1000 ppm.2. The pUHMWPE according to claim 1 , wherein the polymer has a M/Mof less than 3.5.3. The pUHMWPE according to claim 1 , wherein the polymer has a M/Mof less than 3.4. The pUHMWPE according to claim 1 , wherein the polymer has a M/Mof less than 2.8.5. The pUHMWPE according to claim 1 , wherein the polymer has an IV of at least about 8 dl/g.6. The pUHMWPE according to claim 1 , wherein the polymer has an IV of at least about 12 dl/g.7. The pUHMWPE according to claim 1 , wherein the pUHMWPE has a SPAN of at most 3.8. The pUHMWPE according to wherein the pUHMWPE has an apparent bulk density of at least 300 kg/m.9. A process for manufacturing a molded UHMWPE article comprising the step of molding the pUHMWPE of to obtain a molded article therefrom.10. The process according to claim 9 , wherein the molded article is a fiber claim 9 , tape or film.11. A molded article comprising the pUHMWPE according to claim 1 , wherein the molded article is selected from the group consisting of ropes claim 1 , cables claim 1 , nets claim 1 , fabrics claim 1 , and protective appliances.12. The molded article according to claim 11 , wherein the molded article is a ballistic resistant article. This application is a divisional of commonly owned copending U.S. ...

Feeding highly active phosphinimine catalysts to a gas phase reactor

A highly active, supported phosphinimine catalyst is fed to a gas phase reactor as a slurry in a liquid hydrocarbon. The supported polymerization catalyst comprises: i) a phosphinimine catalyst having the formula ((R*)(Ar-F) C5H3)Ti(N=P(.tau.-Bu)3)X2; where R* is hydrogen or a hydrocarbyl group; Ar-F is a perfluorinated aryl group, a 2,6 fluoro substituted phenyl group, a 2,4,6 fluoro substituted phenyl group, or a 2,3,5,6 fluoro substituted phenyl group; and X is an activatable ligand; ii) a cocatalyst, and iii) an inert support. Feeding the catalyst to a gas phase reactor in a viscous liquid hydrocarbon modifies catalyst initiation kinetics.

Transition metal olefin polymerization processes

This invention relates to processes using non-Group 4 transition metal compositions useful as olefin polymerization catalysts, wherein the transition metal is in a high oxidation state. The invention further relates to design of new ligand systems and methods of preparing and using the same. Compositions useful as catalyst precursors are neutral transition metal complexes comprising the unique ligand systems of the invention. The inventive compositions may be activated to a catalytic state by ion-exchange reagents or by Lewis acids.

CATALYST COMPONENTS FOR OLEFIN POLYMERIZATION, POLYMERIZATION CATALYSTS AND OLEFIN POLYMERIZATION PROCEDURES USING THE SAME

Solution polymerization process

This disclosure relates to a continuous solution polymerization process wherein production rate is increased. Process solvent, ethylene, optional comonomers, optional hydrogen and a single site catalyst formulation are injected into a first reactor forming a first ethylene interpolymer. Process solvent, ethylene, optional comonomers, optional hydrogen and a heterogeneous catalyst formulation are injected into a second reactor forming a second ethylene interpolymer. The first and second reactors may be configured in series or parallel modes of operation. Optionally, a third ethylene interpolymer is formed in an optional third reactor, wherein an optional heterogeneous catalyst formulation may be employed. In a solution phase, the first, second and optional third ethylene interpolymers are combined, the catalyst is deactivated, the solution is passivated and following a phase separation process an ethylene interpolymer product is recovered.

Catalyst composition, method of polymerization, and polymer therefrom

Catalyst compositions and methods, useful in polymerization processes, utilizing at least two metal compounds are disclosed. At least one of the metal compounds is a Group 15 containing metal compound and the other metal compound is preferably a bulky ligand metallocene-type catalyst. The invention also discloses a new polyolefin, generally polyethylene, particularly a multimodal polymer and more specifically, a bimodal polymer, and its use in various end-use applications such as film, molding and pipe.

Bulky amido group substituted group 4 metal compounds and polymerization process

A metal compound corresponding to the formula: MXx Lt (I), wherein X is hydride or a monovalent anionic ligand group having up to 60 atoms not counting hydrogen, or optionally, two X groups are joined together to form a divalent ligand group; with the proviso that in at least one occurrence, X is a group of the formula, -NR12, wherein R1 is a C¿1-20? hydrocarbyl group, or a halo, alkoxy, trihydrocarbylsilyl or dihydrocarbylamino substituted derivative thereof, with the further proviso that in at least one occurrence, R?1¿ is a bulky hydrocarbyl group selected from alkyl, aryl, aralkyl, or cycloalkyl groups containing from 4 to 20 carbon atoms; M is a group 4 metal, preferably Ti; L independently each occurrence is a neutral ligating compound having up to 20 atoms; x is a number from 2 to 4 equal to the formal oxidation state of M; and t is a number from 0 to 2.

Methods for determining transition metal compound concentrations in multicomponent liquid systems

Methods for determining the concentration of transition metal compounds in a solution containing more than one transition metal compound are described. Polymerization reactor systems providing real-time monitoring and control of the concentrations of the transition metal components of a multicomponent catalyst system are disclosed, as well as methods for operating such polymerization reactor systems and for improving methods of preparing the multicomponent catalyst system.

Method for producing metallocene-supported catalyst

Transition metal olefin polymerization catalysts

This invention relates to non-Group 4 transition metal compositions useful as olefin polymerization catalysts, wherein the transition metal is in a high oxidation state. The invention further relates to design of new ligand systems and methods of preparing and using the same. Compositions useful as catalyst precursors are neutral transition metal complexes comprising the unique ligand systems of the invention. The inventive compositions may be activated to a catalytic state by ion-exchange reagents or by Lewis acids.

Dual catalyst system for producing LLDPE copolymers with improved processability

Disclosed herein are ethylene-based polymers generally characterized by a density from 0.89 to 0.93 g/cm 3 , a ratio of Mw/Mn from 3 to 6.5, a Mz from 200,000 to 650,000 g/mol, a CY-a parameter at 190° C. from 0.2 to 0.4, and a reverse short chain branching distribution. The ATREF profile of these polymers can have a high temperature peak from 92 to 102° C., and a low temperature peak from 18 to 36° C. less than that of the high temperature peak. These polymers can have comparable physical properties to that of a metallocene-catalyzed LLDPE, but with improved processability, shear thinning, and melt strength, and can be used in blown film and other end-use applications.

Method for producing metallocene-supported catalyst

A method of preparing a supported metallocene catalyst capable of more effectively preparing a polyolefin which may be preferably used for blow molding, etc., because its molecular weight distribution is such that polymer elasticity is increased to improve swell, is provided.

Improving reactor operability in a gas phase polymerization process

Olefin polymerization is carried out with a single site polymerization catalyst in the presence of a continuity additive. The continuity additive is a cocktail containing one or more dialkanolamide derived from a fatty acid, an oil soluble sulfonic acid and a dialkanolamine.

Modified phosphinimine catalysts for olefin polymerization

Olefin polymerization is carried out with a supported phosphinimine catalyst which has been treated with a long chain substituted amine compound.

Modified phosphinimine catalysts for olefin polymerization

Olefin polymerization is carried out with a supported phosphinimine catalyst which has been treated with a long chain substituted amine compound.

Methods for controlling ethylene copolymer properties

A method for altering the polymer architecture of ethylene copolymers made with a supported phosphinimine polymerization catalyst. The method involves changing the amount of a catalyst modifier added to a reactor separately from or together with a supported phosphinimine polymerization catalyst.

Modified phosphinimine catalysts for olefin polymerization

Olefin polymerization is carried out with a supported phosphinimine catalyst which has been treated with a long chain substituted amine compound.

溶液聚合法

用於乙烯之(共)聚合之溶液聚合法係在i)膦亞胺觸媒、ii)共觸媒及iii)長鏈胺改質劑存在下實施。

Modified phosphinimine catalysts for olefin polymerization

Olefin polymerization is carried out with a supported phosphinimine catalyst which has been treated with a long chain substituted amine compound.

Modified phosphinimine catalysts for olefin polymerization

Olefin polymerization is carried out with a supported phosphinimine catalyst which has been treated with a long chain substituted amine compound.

Modified phosphinimine catalysts for olefin polymerization

Olefin polymerization is carried out with a supported phosphinimine catalyst which has been treated with a long chain substituted amine compound.

Modified phosphinimine catalysts for olefin polymerization

Olefin polymerization is carried out with a supported phosphinimine catalyst which has been treated with a long chain substituted amine compound.

Passivated supports for use with olefin polymerization catalysts

A phosphinimine catalyst immobilized on a passivated inorganic oxide support, had high activity at low co-catalyst concentrations and gave, under gas phase polymerization conditions, ethylene copolymer with a high molecular weight. A method of making a passivated silica support involves treatment of silica with an organoaluminum compound, a diorganomagnesium compound and a source of chloride (to make MgCl2) under anhydrous conditions and in the absence of polar solvents.

Feeding highly active phosphinimine catalysts to a gas phase reactor

The present invention provides a gas phase copolymerization process that includes the step of introducing a catalyst slurry comprising a supported polymerization catalyst and a liquid hydrocarbon carrier into a gas phase reactor. The catalyst comprises (i) a phosphinimine catalyst having the formula ((R*)(Ar- F)C 5 H 3 Ti(N=P(t-Bu) 3 )X 2 where R* is hydrogen or a hydrocarbyl group; Ar-F is a perfluorinated aryl group, a 2,6 fluoro substituted phenyl group, a 2,4,6 fluoro substituted phenyl group, or a 2,3,5,6 fluoro substituted phenyl group; and X is an activatable ligand; ii) a cocatalyst, and iii) an inert support.

OLEFIN POLYMERIZATION CATALYSTS BASED ON TRANSITIONAL METALS

Feeding highly active phosphinimine catalysts to a gas phase reactor

A highly active, supported phosphinimine catalyst is fed to a gas phase reactor as a slurry in a liquid hydrocarbon. Feeding the catalyst to a gas phase reactor in a viscous liquid hydrocarbon modifies catalyst initiation kinetics.

Ethylene copolymer compositions, film and polymerization processes

Ethylene copolymers having a relatively high melt flow ratio and a multimodal profile in a temperature rising elution fractionation (TREF) plot are disclosed. The copolymers can be made into film having good dart impact values and good stiffness properties under decreased extruder pressures.

Polyethylene blend compositions

A polymer blend comprising first and second polyethylene copolymers is presented which has good processability, and which when made into film shows good toughness-stiffness balance, reasonable MD tear, as well as good optical properties and seal properties.

Process for polymerization in a fluidized bed reactor

Provided is an improved process by which to start-up a gas phase reactor which involves starting at high temperature and hydrogen concentration, followed by making targeted product at lower temperature and hydrogen concentration. Process steps include: a) fluidizing a bed of polymer particles in a reactor with a gas mixture comprising ethylene and one or more alpha olefin at a first hydrogen concentration [H2r; b) introducing a single site catalyst system to the reactor to initiate a polymerization reaction; c) polymerizing the ethylene and the one or more alpha olefin at a first reactor temperature, TA to give a first ethylene copolymer with a first melt index, I2A, a first melt flow ratio, (121/12)A, and a first density, dA, until at least one reactor bed volume has turned over, where a reactor bed volume is defined as the volume of the reactor from a reactor distributor bed plate to the top of the fluidized bed; and d) subsequently reducing the hydrogen concentration and the reaction temperature to a second hydrogen concentration [I-12r and a second reactor temperature TB, respectively, to give a second ethylene copolymer with a second melt index, I2B, a second melt flow ratio, (121/12)B, and a second density, dB ; wherein the first melt index, I2A is greater than the second melt index, I2B.

Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety

Disclosed is a novel bidentate pyridine transition metal catalyst having the general formula ##STR1## where Y is O, S, NR, ##STR2## each R is independently selected from hydrogen or C 1 to C 6 alkyl, each R' is independently selected from C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 6 to C 16 aryl, halogen, or CF 3 , M is titanium, zirconium, or hafnium, each X is independently selected from halogen, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, or ##STR3## L is X, cyclopentadienyl, C 1 to C 6 alkyl substituted cyclopentadienyl, indenyl, fluorenyl, or ##STR4## and "n" is 1 to 4. Also disclosed is a method of making a poly-α-olefin comprising polymerizing an α-olefin monomer using that catalyst or a catalyst that has the general formula ##STR5## where Y, M, L, X, and R' were previously defined.

Reactor continuity

A supported catalyst system comprising a phosphinimine ligand containing catalyst on an alumina support treated with a metal salt has improved reactor continuity in a dispersed phase reaction in terms of initial activation and subsequent deactivation. The resulting catalyst has a lower consumption of ethylene during initiation and a lower rate of deactivation. Preferably the catalyst is used with an antistatic agent.

Methods for controlling molecular weight and molecular weight distribution

Methods for controlling or adjusting the molecular weight and molecular weight distribution of an olefin polymer, such as an ethylene polymer, using an alkylaluminum compound are disclosed. In addition to the alkylaluminum compound, the catalyst systems contain a half-metallocene titanium phosphinimide compound and an activator.

Catalyst systems containing low valent titanium compounds and polymers produced therefrom

Disclosed herein are methods for synthesizing low valence, bimetallic titanium compounds from half-metallocene titanium compounds and alkylaluminum compounds. The bimetallic titanium compounds can be used as components in catalyst systems for the polymerization of olefins.

Methods for determining transition metal compound concentrations inc multicomponent liquid systems

Methods for determining the concentration of transition metal compounds in a solution containing more than one transition metal compound are described. Polymerization reactor systems providing real-time monitoring and control of the concentrations of the transition metal components of a multicomponent catalyst system are disclosed, as well as methods for operating such polymerization reactor systems and for improving methods of preparing the multicomponent catalyst system.

Dual catalyst system for producing lldpe copolymers with improved processability

Disclosed herein are ethylene-based polymers generally characterized by a density from 0.89 to 0.93 g/cm3, a ratio of Mw/Mn from 3 to 6.5, a Mz from 200,000 to 650,000 g/mol, a CY-a parameter at 190°C from 0.2 to 0.4, and a reverse short chain branching distribution. The ATREF profile of these polymers can have a high temperature peak from 92 to 102°C, and a low temperature peak from 18 to 36°C less than that of the high temperature peak. These polymers can have comparable physical properties to that of a metallocene-catalyzed LLDPE, but with improved processability, shear thinning, and melt strength, and can be used in blown film and other end-use applications.

Catalyst systems containing low valent titanium-aluminum complexes and polymers produced therefrom

Disclosed herein are methods for synthesizing low valence, titanium-aluminum complexes from half-metallocene titanium compounds and alkylaluminum compounds. The titanium-aluminum complexes can be used as components in catalyst systems for the polymerization of olefins.

Catalyst systems containing low valent titanium-aluminum complexes and polymers produced therefrom

Disclosed herein are methods for synthesizing low valence, titanium-aluminum complexes from half-metallocene titanium compounds and alkylaluminum compounds. The titanium-aluminum complexes can be used as components in catalyst systems for the polymerization of olefins.

Dual catalyst system for producing LLDPE copolymers with improved processability

Disclosed herein are ethylene-based polymers generally characterized by a density from 0.89 to 0.93 g/cm 3 , a ratio of Mw/Mn from 3 to 6.5, a Mz from 200,000 to 650,000 g/mol, a CY-a parameter at 190° C. from 0.2 to 0.4, and a reverse short chain branching distribution. The ATREF profile of these polymers can have a high temperature peak from 92 to 102° C., and a low temperature peak from 18 to 36° C. less than that of the high temperature peak. These polymers can have comparable physical properties to that of a metallocene-catalyzed LLDPE, but with improved processability, shear thinning, and melt strength, and can be used in blown film and other end-use applications.

Dual catalyst system for producing lldpe copolymers with improved processability

Disclosed herein are ethylene-based polymers generally characterized by a density from 0.89 to 0.93 g/cm³, a ratio of Mw/Mn from 3 to 6.5, a Mz from 200,000 to 650,000 g/mol, a CY-a parameter at 190 °C from 0.2 to 0.4, and a reverse short chain branching distribution. The ATREF profile of these polymers can have a high temperature peak from 92 to 102 °C, and a low temperature peak from 18 to 36 °C less than that of the high temperature peak. These polymers can have comparable physical properties to that of a metallocene-catalyzed LLDPE, but with improved processability, shear thinning, and melt strength, and can be used in blown film and other end-use applications.

Mixed phosphinimine catalyst

A supported catalyst for the polymerization of olefins, especially ethylene, has at least two catalyst components having different propagation and/or termination constants. Each catalyst component must have at least one phosphinimine ligand. The polymer produced according to this invention has a broad molecular weight distribution. Catalysts according to this invention have a very surprising and desirable hydrogen response.

Stereospecific living polymerization of olefins by a novel Ziegler-Natta catalyst composition

An olefin polymerization pre-catalyst and a method for preparing an activated olefin polymerization catalyst composition from the pre-catalyst are disclosed: wherein M, R 1 , R 2 , R 3 , R 4 and R 5 are defined herein.

Mixed phosphinimine catalyst

A supported catalyst for the polymerization of olefins, especially ethylene, has at least two catalyst components having different propagation and/or termination constants. Each catalyst component must have at least one phosphinimine ligand. The polymer produced according to this invention has a broad molecular weight distribution. Catalysts according to this invention have a very surprising and desirable hydrogen response.

Preparation of ultra high molecular weight ethylene copolymer

Passivated supports for use with olefin polymerization catalysts

A phosphinimine catalyst immobilized on a passivated inorganic oxide support, had high activity at low co-catalyst concentrations and gave, under gas phase polymerization conditions, ethylene copolymer with a high molecular weight. A method of making a passivated silica support involves treatment of silica with an organoaluminum compound, a diorganomagnesium compound and a source of chloride (to make MgCl 2 ) under anhydrous conditions and in the absence of polar solvents.

Continuity additives in gas phase polymerization processes

Ethylene ( co)polymerization is carried out with a single site polymerization catalyst in the presence of a multi-component continuity additive. The continuity additive is a mixture of one or more fatty acid dialkanolamides, an oil soluble sulfonic acid, and a dialkanolamine. The continuity additive, which reduces static in a gas phase reactor, can be used at relatively high loadings, such as 100 ppm, with less impact on catalyst productivity compared with equivalent amounts of conventional continuity additives which are mixtures of alkvldiethanolamines.

Catalyst constituents and catalyst system with a high degree of polymerisation activity for the production of polymers

In the present invention, catalyst systems with a high degree of polymerisation are described which contain at least one catalyst constituent of general formula (I): RnMXm, in which M1 is Ti, Zr or Hf, Ra is C5 (R?1, R2, R3, R4, R5¿) or C¿6? (R?1, R2, R3, R4, R5, R6¿) wherein R?1, R2, R3, R4, R5 and R6¿ are identical or different, and a hydrogen atom, a C¿1?-C20 alkyl group, a C1-C10 alkoxy group, a C1-C10 fluoroalkyl group, a C6-C20 aryl group, a C6-C10 aryloxy group, a C2-C10 alkenyl group, a C6-C10 fluoroaryl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a silyl group, a germyl group, or adjacent groups R?1, R2, R3, R4, R5 and R6¿ which form with the connecting atoms thereof a ring system; Rb is one fluorine atom when m = 1, at least one fluorine atom when m > 1 and can be identical or different, and be at least one hydrogen atom, a C¿1?-C20 alkyl group, a C1-C10 alkyoxy group, a C1-C10 fluoroalkyl group, a C6-C20 aryl group, a C6-C10 aryloxy group, a C2-C10 alkenyl group, a C6-C10 fluoroaryl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, or a C8-C40 arylalkenyl group, an OH group, a NR?7¿2 group or SR81 group, wherein R?7 and R8¿ are a C¿1?-C20 alkyl group, a C1-C10 alkoxy group, a C1-C10 fluoroalkyl group, a C6-C20 aryl group, a C6-C10 aryloxy group, a C2-C10 alkenyl group, a C6-C10 fluoroalryl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a silyl group, a germyl group or a halogen atom, m and n are integers, m + n = 2 to 4, and m is at least 1.

Metal complex with a Lewis base ligand

Process for the preparation of a polyolefin

The invention related to a process for the polymerization of at least one aliphatic C 2-20 or aromatic C 4-20 hydrocarbyl mono- or multiolefin in the presence of a catalyst and an aluminum comprising co-catalyst, wherein the catalyst comprises a composition of a metal-organic reagent, a spectator ligand and optionally at least one equivalent of a hydrocarbylating agent. The invention further relates to a polymer obtainable by the process of the invention.

Process for the preparation of a polyolefin

The invention related to a process for the polymerization of at least one aliphatic or aromatic hydrocarbyl C2-20 mono- or multiolefin in the presence of a catalyst and a boron comprising co-catalyst, wherein the catalyst comprises a composition of a metal-organic reagent, a spectator ligand and optionally at least one equivalent of a hydrocarbylating agent. The invention further relates to a polymer obtainable by the process of the invention.

Transition metal olefin polymerization catalysts

This invention relates to non-Group 4 transition metal compositions useful as olefin polymerization catalysts, wherein the transition metal is in a high oxidation state. The invention further relates to design of new ligand systems and methods of preparing and using the same. Compositions useful as catalyst precursors are neutral transition metal complexes comprising the unique ligand systems of the invention. The inventive compositions may be activated to a catalytic state by ion-exchange reagents or by Lewis acids.

Organometal compound catalyst

This invention provides catalyst compositions that are useful for polymerizing at least one monomer to produce a polymer. This invention also provides catalyst compositions that are useful for polymerizing at least one monomer to produce a polymer, wherein said catalyst composition comprises contacting an organometal compound, an organoaluminum compound, and a treated solid oxide compound.

Polyethylene film

Polyethylene films having a good balance of optical and mechanical properties are disclosed. The films are derived from ethylene copolymer compositions made with a suitably substituted phosphinimine catalyst. The ethylene copolymers have very narrow molecular weight distributions and broadened comonomer distributions.

Supported polymerisation catalysts

Ethylene copolymers having reverse comonomer incorporation

Ethylene copolymers having a relatively high melt flow ratio (I21/I2) and a multimodal profile in a temperature rising elution fractionation (TREF) plot. The ethylene copolymers have a composition distribution breadth index CDBI50 of between 35 wt% and 70 wt% and can be made into film having good dart impact values and good stiffness properties under decreased extruder pressures. The ethylene copolymers are made in a gas phase polymerization process using a group 4 phosphinimine catalyst having the formula (1-R2-Indenyl)Ti(N=P(t-Bu)3)X2; wherein R2 is a substituted or unsubstituted alkyl group, a substituted or an unsubstituted aryl group, or a substituted or unsubstituted benzyl group, wherein substituents for the alkyl, aryl or benzyl group are selected from the group consisting of alkyl, aryl, alkoxy, aryloxy, alkylaryl, arylalkyl and halide substituents; and wherein X is an activatable ligand.

Controlling resin properties in a gas phase polymerization process

Methods for dramatically altering the processability of ethylene copolymers made with a supported phosphinimine polymerization catalyst. The method involves changing the polymerization reactor temperature during the polymerization of ethylene and a least one alpha-olefin when a phosphinimine catalyst which comprises a substituted or unsubstituted indenyl ligand and a phosphinimine type ligand.

Passivated supports: catalyst, process and product

Ethylene copolymers made in the gas phase using a phosphinimine based single site catalyst supported on a passivated inorganic oxide support. The ethylene copolymers have a relatively narrow molecular weight distribution and good rheological parameters.

Spheroidal catalyst for olefin polymerization

A solid, spheroidal polymerization catalyst having a particle size distribution characterized by a Dm*/Dn of less than 3.0, the catalyst comprising a phosphinimine catalyst, a cocatalyst and a magnesium chloride support. A process for the polymerization of ethylene with one or more alpha olefin catalyzed by a solid, spheroidal polymerization catalyst having a particle size distribution characterized by a Dm*IDn of less than 3.0, the catalyst comprising a phosphinimine catalyst, a cocatalyst and a magnesium chloride support.

Ethylene/1-butene copolymers with enhanced resin processability

Ethylene/1-butene copolymers made with a single site catalyst system have high melt strength and good processability. The ethylene copolymer is niade by polymerizing ethylene and 1-butene with a single site catalyst system in a polymerization reactor, and in an embodiment has a density of from 0.912 to 0.94 g/cm3, a melt index (12) of from 0.5 to 10 g/10min, a melt flow ratio (121/12) of from 20 to 35, a molecular weight distribution (Mw/Mn) of from 2.0 to 4.5, and an accelerated haul-off melt strength (es), as determined by Rosand capillary rheometry at 190 C, of at least 3.0 cN.

Supported ketimide catalysts for improved reactor continuity

Ketimide ligand containing catalyst/reactor continuity in a dispersed phase reaction in terms of initial activation and subsequent deactivation may be improved by treating the support with a metal salt. The activator and catalyst are then deposited on the treated support. The resulting catalyst has a lower consumption of ethylene during initiation and a lower rate of deactivation. Preferably the catalyst is used with an antistatic agent.

Feeding highly active phosphinimine catalysts to a gas phase reactor

A highly active, supported phosphinimine catalyst is fed to a gas phase reactor as a slurry in a liquid hydrocarbon. Feeding the catalyst to a gas phase reactor in a viscous liquid hydrocarbon modifies catalyst initiation kinetics.

Titanium phosphinimide and titanium iminoimidazolidide catalyst systems with activator-supports

Catalyst compositions containing activator-supports and half-metallocene titanium phosphinimide complexes or half-metallocene titanium iminoimidazolidide complexes are disclosed. These catalyst compositions can be used to produce olefin polymers having relatively broad molecular weight distributions and low levels of long chain branching.

Transition metal complexes, catalyst compositions comprising the same, and method for preparing polyolefins therewith

본 발명은 올레핀 단량체의 중합 반응에서 높은 활성과 향상된 공중합 활성을 나타내어 저밀도 및 고분자량의 폴리올레핀의 제조를 가능케 하는 전이금속 화합물, 이를 포함하는 촉매 조성물 및 상기 조성물을 이용한 폴리올레핀의 제조 방법에 관한 것이다. The present invention relates to a transition metal compound capable of producing a low density and high molecular weight polyolefin exhibiting high activity and an improved copolymerization activity in the polymerization reaction of an olefin monomer, a catalyst composition containing the same, and a process for producing a polyolefin using the composition.

Polymerization process using a mixed catalyst system

Polyethylene is made by polymerizing ethylene in a gas-phase reactor using a mixed catalyst system comprising a chromium catalyst supported on silica and a transition metal catalyst, having at least one phosphinimide or ketimide ligand, separately supported on silica. The catalyst components can be premixed before being added to a polymerization reactor or they can be added to a reactor separately.

A co-supported catalyst system

Polyethylene is made by copolymerizing ethylene in a gas-phase reactor using a catalyst system comprising a chromium catalyst and a group 4 transition metal catalyst having at least one phosphinimide or ketimide ligand, co-supported on an inorganic oxide support.

Supported phosphinimine catalysts for reduced reactor fouling

Fouling in a dispersed phase reactor in the presence of a phosphinimine catalyst and MAO may be reduced by reducing the loading of the phosphinimine catalyst to provide from 0.02 to 0.031 mmol of transition M per g of catalyst while still maintaining a productivity of not less than 2500 g of polymer/ gram of catalyst. The catalyst may optionally be used in the presence of an antistatic agent.

Passivated supports for use with olefin polymerization catalysts

A phosphinimine catalyst immobilized on a passivated inorganic oxide support, had high activity at low co-catalyst concentrations and gave, under gas phase polymerization conditions, ethylene copolymer with a high molecular weight. A method of making a passivated silica support involves treatment of silica with an organoaluminum compound, a diorganomagnesium compound and a source of chloride (to make MgCl 2 ) under anhydrous conditions and in the absence of polar solvents.

Methods for controlling ethylene copolymer properties

A method for altering the polymer architecture of ethylene copolymers made with a supported phosphinimine polymerization catalyst. The method involves changing the amount of a catalyst modifier added to a reactor separately from or together with a supported phosphinimine polymerization catalyst.

Reactor operability in a gas phase polymerization process

Olefin polymerization is carried out with a single site polymerization catalyst in the presence of a continuity additive. The continuity additive is a cocktail containing one or more dialkanolamide derived from a fatty acid, an oil soluble sulfonic acid and a dialkanolamine.

用於流體化床反應器中的聚合方法

本發明係關於當製備具有相對高之分子量分佈及熔融流動比之乙烯共聚物時用於穩定的氣相反應器啟動之聚合方法。