CA2463588C - Supported polymerization catalysts comprising a polyvalent lewis base ligand - Google Patents
Supported polymerization catalysts comprising a polyvalent lewis base ligand Download PDFInfo
- Publication number
- CA2463588C CA2463588C CA2463588A CA2463588A CA2463588C CA 2463588 C CA2463588 C CA 2463588C CA 2463588 A CA2463588 A CA 2463588A CA 2463588 A CA2463588 A CA 2463588A CA 2463588 C CA2463588 C CA 2463588C
- Authority
- CA
- Canada
- Prior art keywords
- process according
- group
- alkyl
- metal complex
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
-
- 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
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/147—Copolymers of propene with monomers containing other atoms than carbon or hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
- D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
-
- 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
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0617—Polyalkenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0617—Polyalkenes
- C09K2200/062—Polyethylene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Abstract
A supported catalyst composition and process for preparing high molecular weight polymers of one or more addition polymerizable monomers, especially propylene, said composition comprising: 1) a substrate comprising the reaction product of a solid, particulated, high surface area, metal oxide, metalloid oxide, or a mixture thereof and an organoaluminum compound, 2) a Group 4 metal complex of a polyvalent, Lewis base ligand; and optionally, 3) an activating cocatalyst for the metal complex.
Description
SUPPORTED POLYMERIZATION CATALYSTS COMPRISING
A POLYVALENT LEWIS BASE LIGAND
Background of the Invention The present invention relates to supported olefin polymerization catalysts and to a process for preparing polypropylene and other olefin polymers therefrom. The resulting polymers are well known commercially and may be usefully employed in the preparation of solid articles such as moldings, films, sheets and foamed objects by molding, extruding or other processes. The resulting products include components for automobiles, such as bumpers; packaging materials; and other applications.
In USP's 6,320,005 and 6,103,657 certain transition metal amine donor complexes for use as components of olefin polymerization catalysts were disclosed. In WO
02/38628 additional description of such Group 4 metal complexes containing "spectator ligands"
such as amino-substituted cyclic amine compounds were disclosed. In the latter publication the use of supports such as silica or alumina for preparing heterogeneous versions of such metal complexes was taught.
Summary of the Invention According to the present invention there are now provided a supported, heterogeneous catalyst composition for use in polymerization of addition polymerizable monomers, especially propylene, to form high molecular weight polymers, comprising:
1) a substrate comprising the reaction product of a solid, particulated, high surface area, metal oxide, metalloid oxide, or a mixture thereof and an organoaluminum compound, 2) a Group 4 metal complex of a polyvalent, Lewis base ligand; and optionally, 3) an activating cocatalyst for the metal complex.
In a further embodiment of the present invention there is provided a process for preparing high molecular weight polymers of one or more addition polymerizable monomers, especially propylene or mixtures of ethylene and propylene, comprising contacting one or more addition polymerizable monomers under addition polymerization conditions with a catalyst composition comprising:
1) a substrate comprising the reaction product of a solid, particulated, high surface area, metal oxide, metalloid oxide, or a mixture thereof and an organoaluminum compound, 2) a Group 4 metal complex of a polyvalent, Lewis base ligand; and optionally, 3) an activating cocatalyst for the metal complex.
In an embodiment of the invention, there is provided a process for preparing high molecular weight propylene homopolymers or copolymers of propylene and ethylene, said process comprising contacting propylene and optionally from 0.001 to 10 percent of the total monomer weight of ethylene under addition polymerization conditions with a supported, heterogeneous catalyst composition comprising: 1) a substrate comprising the reaction product of a solid, particulated, high surface area, metal oxide, metalloid oxide, or a miture thereof and an organoaluminum compound, 2) a Group 4 metal complex of a polyvalent, Lewis base ligand; and optionally, 3) an activating cocatalyst for the metal complex.
Detailed Description of the Invention All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1999. Also, any references to a Group or Groups shall be to the Groups or Groups reflected in this Periodic Table of the Elements using the ILrPAC system for numbering groups.
The term "comprising" and derivatives thereof is not intended to exclude the presence of any additional component, step or procedure, whether or not the same is disclosed herein. In order to avoid any doubt, all compositions claimed herein through use of the term "comprising" may include any additional additive, adjuvant, or compound whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, "consisting essentially of"
excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term "consisting of excludes any component, step or procedure not specifically delineated or listed. The term "or", unless stated otherwise, refers to the listed members individually as well as in any combination.
The term "polymer", includes both homopolymers, that is, polymers prepared from a single reactive compound, and copolymers, meaning polymers prepared by reaction of at least two polymer forming, reactive, monomeric compounds. More specifically, the term "polypropylene"
includes homopolymers of propylene and copolymers of propylene and one or more olefins, with the proviso that if the comonomer comprises ethylene, at least 60 percent of the polymer units must be derived from propylene, that is, a methyl- substituted ethylene group. The term "crystalline" if employed, refers to a polymer that exhibits an X-ray diffraction pattern at 25 C and possesses a first order transition or crystalline melting point (Tm). The term may be used interchangeably with the term "semicrystalline".
Suitable solid, particulated, high surface area, metal oxide, metalloid oxide, or mixtures thereof (interchangeably referred to herein as an inorganic oxide) for use in the preparation of component 1) include: talc, silica, alumina, magnesia, titania, zirconia, Sn203, aluminosilicates, borosilicates, clays, and mixtures thereof. Inorganic oxides suitable for the present invention preferably have a surface area as determined by nitrogen porosimetry using the B.E.T. method from 10 to 1000 m2/g, and preferably from 100 to 600 m2/g. The pore volume of the inorganic oxide as well as the resulting catalyst composition, as determined by nitrogen adsorption, is typically up to 5 -2a-cm3/g, advantageously between 0.1 and 3 cm3/g, preferably from 0.2 to 2 cm3/g.
The average particle size is chosen to fit the desired application, as explained here-in-after, and typically is from 0.1 to 500 m, preferably from 1 to 200 m, more preferably 10 to 100 m.
Preferred inorganic oxides for use in the present invention include highly porous silicas, aluminas, aluminosilicates, and mixtures thereof. The most preferred support material is silica.
The support material may be in granular, agglomerated, pelletized, or any other physical form.
Suitable materials include, but are not limited to, silicas available from Grace Davison (division of W.R. Grace & Co.) under the designations SD 3216.30, Davison Syloid TM245, Davison 948 and Davison 952, and from Crossfield Corporation under the designation ES70, and from Degussa AG
under the designation Aerosil TM812; and aluminas available from Akzo Chemicals Inc. under the designation KetzenTM.
The inorganic oxide is preferably first dehydrated or dried, by heating at temperatures up to 800 C, as is well known in the art, to remove physi-sorbed water, oxygen, carbon dioxide, or other molecules. Alternatively however, in one embodiment the inorganic oxide may initially contain small quantities of water, up to 20 weight percent, which are carefully reacted with a trialkylaluminum compound, especially trimethylaluminum, to prepare alumoxane in situ on the surface of the inorganic oxide. Suitable thermal treatments, if employed, are heating at 100 C to 1000 C, preferably at 200 C to 850 C in an inert atmosphere or under reduced pressure. Typically, this treatment is carried out for 10 minutes to 72 hours, preferably from 0.5 hours to 24 hours.
The solid inorganic oxide is thereafter treated with the organoaluminum compound according to known techniques. Suitable organoaluminum compounds include the well known trihydrocarbyl aluminum compounds, such as trialkylaluminums, especially trimethylaluminum, triethylaluminum, and triisbutylaluminum; trihalohydrocarbyl aluminum compounds, such as tris(pentaflurorphenyl)aluminum; and oxygen containing aluminum compounds, such as alumoxanes.
Suitable alumoxanes for treatment of the inorganic oxide supports herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, and neutral Lewis acid modified polymeric or oligomeric alumoxanes, such as alkylalumoxanes modified by addition of a C1_30 hydrocarbyl substituted Group 13 compound, especially a tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compound, or a halogenated (including perhalogenated) derivative thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially a trialkylaluminum compound, a perfluorinated tri(aryl)boron compound, or a perfluorinated tri(aryl)aluminum compound. Examples include triisobutyl aluminum- or tri-n-butyl aluminum-modified methylalumoxane, sometimes referred to as modified methalumoxane, or MMAO. The most preferred alumoxane for treatment of the inorganic oxide support is methalumoxane.
The inorganic oxide is treated with the organoaluminum compound by contacting a solution or dispersion thereof with the solid inorganic oxide, optionally at an elevated temperature, in the substantial absence of interfering substances such as oxygen, water or carbon dioxide. The organoaluminum compound is desirably dissolved or dispersed in an inert liquid, such as a hydrocarbon, and the inorganic oxide material immersed, coated, sprayed, or otherwise brought into contact with the solution or dispersion for an appropriate contact period from one minute to several days. The resulting solid may be recovered and devolatilized or rinsed with an inert diluent, especially an aliphatic hydrocarbon to remove excess organoaluminum compound, if desired, prior to use. Typically the quantity of organoaluminum compound used with respect to inorganic oxide is sufficient to provide a concentration of from 0.1 to 50 mol per g of inorganic oxide, preferably from 1 to 10 gmol/g. The quantity of organoaluminum compound employed is desirably sufficient to saturate the available surface of the support without depositing a significant quantity of material that is capable of being removed by contact with an aliphatic hydrocarbon liquid. Desirably no more than 10 percent, preferably no more than 5 percent, and most preferably no more than 1 percent of the treated support is removed by contacting with hexane at 25 C
for 15 minutes.
Suitable metal complexes of polyvalent Lewis base ligands for use in the present invention include Group 4 metal derivatives, especially hafnium derivatives of hydrocarbylamine substituted heteroaryl compounds of the formula R'HN-T-R2 (I), said complexes corresponding to the formula:
NI., TNI R2 Rl (IA) MXx wherein:
Rl is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives thereof containing from 1 to 30 atoms not counting hydrogen;
T is a divalent bridging group of from 1 to 20 atoms other than hydrogen, preferably a mono- or di- C1_20 hydrocarbyl substituted methylene or silane group, and R2 is a C6_20 heteroaryl group containing Lewis base functionality, especially a pyridin-2-yl-or substituted pyridin-2-yl group, and in the metal complex, M is the Group 4 metal, preferably hafnium, X is an anionic, neutral or dianionic ligand group, x is a number from 0 to 5 indicating the number of such X groups, and bonds, optional bonds and electron donative interactions are represented by lines, dotted lines and arrows respectively.
Preferred complexes are those wherein ligand formation results from hydrogen elimination from the amine group and optionally from the loss of one or more additional groups, especially from R2. In addition, electron donation from the Lewis base functionality, preferably an electron pair, provides additional stability to the metal center. Preferred examples of the foregoing polyfunctional Lewis base compounds and the resulting metal complexes correspond to the formulas:
(IIA) OT RS RS
R1-Ng N R1N N
A POLYVALENT LEWIS BASE LIGAND
Background of the Invention The present invention relates to supported olefin polymerization catalysts and to a process for preparing polypropylene and other olefin polymers therefrom. The resulting polymers are well known commercially and may be usefully employed in the preparation of solid articles such as moldings, films, sheets and foamed objects by molding, extruding or other processes. The resulting products include components for automobiles, such as bumpers; packaging materials; and other applications.
In USP's 6,320,005 and 6,103,657 certain transition metal amine donor complexes for use as components of olefin polymerization catalysts were disclosed. In WO
02/38628 additional description of such Group 4 metal complexes containing "spectator ligands"
such as amino-substituted cyclic amine compounds were disclosed. In the latter publication the use of supports such as silica or alumina for preparing heterogeneous versions of such metal complexes was taught.
Summary of the Invention According to the present invention there are now provided a supported, heterogeneous catalyst composition for use in polymerization of addition polymerizable monomers, especially propylene, to form high molecular weight polymers, comprising:
1) a substrate comprising the reaction product of a solid, particulated, high surface area, metal oxide, metalloid oxide, or a mixture thereof and an organoaluminum compound, 2) a Group 4 metal complex of a polyvalent, Lewis base ligand; and optionally, 3) an activating cocatalyst for the metal complex.
In a further embodiment of the present invention there is provided a process for preparing high molecular weight polymers of one or more addition polymerizable monomers, especially propylene or mixtures of ethylene and propylene, comprising contacting one or more addition polymerizable monomers under addition polymerization conditions with a catalyst composition comprising:
1) a substrate comprising the reaction product of a solid, particulated, high surface area, metal oxide, metalloid oxide, or a mixture thereof and an organoaluminum compound, 2) a Group 4 metal complex of a polyvalent, Lewis base ligand; and optionally, 3) an activating cocatalyst for the metal complex.
In an embodiment of the invention, there is provided a process for preparing high molecular weight propylene homopolymers or copolymers of propylene and ethylene, said process comprising contacting propylene and optionally from 0.001 to 10 percent of the total monomer weight of ethylene under addition polymerization conditions with a supported, heterogeneous catalyst composition comprising: 1) a substrate comprising the reaction product of a solid, particulated, high surface area, metal oxide, metalloid oxide, or a miture thereof and an organoaluminum compound, 2) a Group 4 metal complex of a polyvalent, Lewis base ligand; and optionally, 3) an activating cocatalyst for the metal complex.
Detailed Description of the Invention All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1999. Also, any references to a Group or Groups shall be to the Groups or Groups reflected in this Periodic Table of the Elements using the ILrPAC system for numbering groups.
The term "comprising" and derivatives thereof is not intended to exclude the presence of any additional component, step or procedure, whether or not the same is disclosed herein. In order to avoid any doubt, all compositions claimed herein through use of the term "comprising" may include any additional additive, adjuvant, or compound whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, "consisting essentially of"
excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term "consisting of excludes any component, step or procedure not specifically delineated or listed. The term "or", unless stated otherwise, refers to the listed members individually as well as in any combination.
The term "polymer", includes both homopolymers, that is, polymers prepared from a single reactive compound, and copolymers, meaning polymers prepared by reaction of at least two polymer forming, reactive, monomeric compounds. More specifically, the term "polypropylene"
includes homopolymers of propylene and copolymers of propylene and one or more olefins, with the proviso that if the comonomer comprises ethylene, at least 60 percent of the polymer units must be derived from propylene, that is, a methyl- substituted ethylene group. The term "crystalline" if employed, refers to a polymer that exhibits an X-ray diffraction pattern at 25 C and possesses a first order transition or crystalline melting point (Tm). The term may be used interchangeably with the term "semicrystalline".
Suitable solid, particulated, high surface area, metal oxide, metalloid oxide, or mixtures thereof (interchangeably referred to herein as an inorganic oxide) for use in the preparation of component 1) include: talc, silica, alumina, magnesia, titania, zirconia, Sn203, aluminosilicates, borosilicates, clays, and mixtures thereof. Inorganic oxides suitable for the present invention preferably have a surface area as determined by nitrogen porosimetry using the B.E.T. method from 10 to 1000 m2/g, and preferably from 100 to 600 m2/g. The pore volume of the inorganic oxide as well as the resulting catalyst composition, as determined by nitrogen adsorption, is typically up to 5 -2a-cm3/g, advantageously between 0.1 and 3 cm3/g, preferably from 0.2 to 2 cm3/g.
The average particle size is chosen to fit the desired application, as explained here-in-after, and typically is from 0.1 to 500 m, preferably from 1 to 200 m, more preferably 10 to 100 m.
Preferred inorganic oxides for use in the present invention include highly porous silicas, aluminas, aluminosilicates, and mixtures thereof. The most preferred support material is silica.
The support material may be in granular, agglomerated, pelletized, or any other physical form.
Suitable materials include, but are not limited to, silicas available from Grace Davison (division of W.R. Grace & Co.) under the designations SD 3216.30, Davison Syloid TM245, Davison 948 and Davison 952, and from Crossfield Corporation under the designation ES70, and from Degussa AG
under the designation Aerosil TM812; and aluminas available from Akzo Chemicals Inc. under the designation KetzenTM.
The inorganic oxide is preferably first dehydrated or dried, by heating at temperatures up to 800 C, as is well known in the art, to remove physi-sorbed water, oxygen, carbon dioxide, or other molecules. Alternatively however, in one embodiment the inorganic oxide may initially contain small quantities of water, up to 20 weight percent, which are carefully reacted with a trialkylaluminum compound, especially trimethylaluminum, to prepare alumoxane in situ on the surface of the inorganic oxide. Suitable thermal treatments, if employed, are heating at 100 C to 1000 C, preferably at 200 C to 850 C in an inert atmosphere or under reduced pressure. Typically, this treatment is carried out for 10 minutes to 72 hours, preferably from 0.5 hours to 24 hours.
The solid inorganic oxide is thereafter treated with the organoaluminum compound according to known techniques. Suitable organoaluminum compounds include the well known trihydrocarbyl aluminum compounds, such as trialkylaluminums, especially trimethylaluminum, triethylaluminum, and triisbutylaluminum; trihalohydrocarbyl aluminum compounds, such as tris(pentaflurorphenyl)aluminum; and oxygen containing aluminum compounds, such as alumoxanes.
Suitable alumoxanes for treatment of the inorganic oxide supports herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, and neutral Lewis acid modified polymeric or oligomeric alumoxanes, such as alkylalumoxanes modified by addition of a C1_30 hydrocarbyl substituted Group 13 compound, especially a tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compound, or a halogenated (including perhalogenated) derivative thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially a trialkylaluminum compound, a perfluorinated tri(aryl)boron compound, or a perfluorinated tri(aryl)aluminum compound. Examples include triisobutyl aluminum- or tri-n-butyl aluminum-modified methylalumoxane, sometimes referred to as modified methalumoxane, or MMAO. The most preferred alumoxane for treatment of the inorganic oxide support is methalumoxane.
The inorganic oxide is treated with the organoaluminum compound by contacting a solution or dispersion thereof with the solid inorganic oxide, optionally at an elevated temperature, in the substantial absence of interfering substances such as oxygen, water or carbon dioxide. The organoaluminum compound is desirably dissolved or dispersed in an inert liquid, such as a hydrocarbon, and the inorganic oxide material immersed, coated, sprayed, or otherwise brought into contact with the solution or dispersion for an appropriate contact period from one minute to several days. The resulting solid may be recovered and devolatilized or rinsed with an inert diluent, especially an aliphatic hydrocarbon to remove excess organoaluminum compound, if desired, prior to use. Typically the quantity of organoaluminum compound used with respect to inorganic oxide is sufficient to provide a concentration of from 0.1 to 50 mol per g of inorganic oxide, preferably from 1 to 10 gmol/g. The quantity of organoaluminum compound employed is desirably sufficient to saturate the available surface of the support without depositing a significant quantity of material that is capable of being removed by contact with an aliphatic hydrocarbon liquid. Desirably no more than 10 percent, preferably no more than 5 percent, and most preferably no more than 1 percent of the treated support is removed by contacting with hexane at 25 C
for 15 minutes.
Suitable metal complexes of polyvalent Lewis base ligands for use in the present invention include Group 4 metal derivatives, especially hafnium derivatives of hydrocarbylamine substituted heteroaryl compounds of the formula R'HN-T-R2 (I), said complexes corresponding to the formula:
NI., TNI R2 Rl (IA) MXx wherein:
Rl is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives thereof containing from 1 to 30 atoms not counting hydrogen;
T is a divalent bridging group of from 1 to 20 atoms other than hydrogen, preferably a mono- or di- C1_20 hydrocarbyl substituted methylene or silane group, and R2 is a C6_20 heteroaryl group containing Lewis base functionality, especially a pyridin-2-yl-or substituted pyridin-2-yl group, and in the metal complex, M is the Group 4 metal, preferably hafnium, X is an anionic, neutral or dianionic ligand group, x is a number from 0 to 5 indicating the number of such X groups, and bonds, optional bonds and electron donative interactions are represented by lines, dotted lines and arrows respectively.
Preferred complexes are those wherein ligand formation results from hydrogen elimination from the amine group and optionally from the loss of one or more additional groups, especially from R2. In addition, electron donation from the Lewis base functionality, preferably an electron pair, provides additional stability to the metal center. Preferred examples of the foregoing polyfunctional Lewis base compounds and the resulting metal complexes correspond to the formulas:
(IIA) OT RS RS
R1-Ng N R1N N
(II) R M---------R6 (X)X , wherein M, X, x, R1 and T are as previously defined, R3, R4, R5 and R6 are hydrogen, halo, or an alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, or silyl group of up to 20 atoms not counting hydrogen, or adjacent R3, R4, R5 or R6 groups may be joined together thereby forming fused ring derivatives, and bonds, optional bonds and electron pair donative interactions are represented by lines, dotted lines and arrows respectively.
More preferred examples of the foregoing difunctional Lewis base compounds and metal complexes correspond to the formula:
More preferred examples of the foregoing difunctional Lewis base compounds and metal complexes correspond to the formula:
7 R8 R3 R4 7 R~ R3 R4 R\ R\
Q-NH N N N
(R R6 (R a aj 6 M-------------R
(nI) and (-K)X (IRA) wherein M, X, x, R' and T are as previously defined, R3, R4, R5 and R6 are as previously defined, preferably R3, R4, and R5 are hydrogen, or C14 alkyl, and R6 is C6-2o aryl, most preferably naphthalenyl;
Ra independently each occurrence is C1 alkyl, and a is 1-5, most preferably Ra in two ortho- positions is isopropyl or t-butyl;
RR and R8 independently each occurrence are hydrogen, halogen, or a C1_20 alkyl or aryl group, most preferably one of R7 and R8 is hydrogen and the other is a C6_20 aryl group, especially a fused polycyclic aryl group, most preferably an anthracenyl group, and bonds, optional bonds and electron pair donative interactions are represented by lines, dotted lines and arrows respectively.
Highly preferred polyfunctional Lewis base compounds and metal complexes for use herein correspond to the formula:
(IV) (IVA) IR (Rb)b (Rb)b H '\N (R )c (H3C)2HC H 2\N/ (Rc)c (H3C)2HC H
CH(CH3)2 (H3C)2HC
and 2 wherein X each occurrence is halide, N,N-dimethylamido, or C14 alkyl, and preferably each occurrence X is methyl;
Rb independently each occurrence is hydrogen, halogen, C1_20 alkyl, or C6_20 aryl, or two adjacent Rb groups are joined together thereby forming a ring, and b is 1-5;
and R independently each occurrence is hydrogen, halogen, C1_20 alkyl, or C6_20 aryl, or two adjacent R groups are joined together thereby forming a ring, and c is 1-5.
Most highly preferred examples of metal complexes for use according to the present invention are complexes of the following formulas:
o CH3 (H3C)2H H (H3C)2HC H N/ O
HIS
Hf O O o (H3C)2HC and (H3C)2HC
wherein X each occurrence is halide, N,N-dimethylamido, or C,14 alkyl, and preferably each occurrence X is methyl.
Examples of metal complexes usefully employed according to the present invention include:
[N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(a-naphthalen-2-diyl(6-pyridin-diyl)methane)]hafnium dimethyl;
[N-(2,6-di(1-methylethyl)phenyl)amido)( o-tolyl)(a-naphthalen-2-diyl(6-pyridin-diyl)methane)]hafnium di(N,N-dimethylamido);
[N-(2,6-di(1-methylethyl)phenyl)amido)( o-tolyl)(a-naphthalen-2-diyl(6-pyridin-diyl)methane)]hafnium dichloride;
[N-(2,6-di(1-methyl ethyl)phenyl)amido)(phenanthren-5-yl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl;
[N-(2,6-di(1-methylethyl)phenyl)amido)((henanthren-5-yl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium di(N,N-dimethylamido); and [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5 -yl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dichloride.
Under the reaction conditions used to prepare the metal complexes used in the present invention, it has been discovered that the hydrogen of the 2-position of the a-naphthalene group substituted at the 6-position of the pyridin-2-yl group is subject to elimination, thereby uniquely forming metal complexes wherein the metal is covalently bonded to both the resulting amide group and to the 2-position of the a-naphthalenyl group, as well as stabilized by coordination to the pyridinyl nitrogen atom through the electron pair of the nitrogen atom.
The foregoing metal complexes are conveniently prepared by standard metallation and ligand exchange procedures involving a source of the Group 4 metal and the neutral polyfunctional ligand source. The complexes may also be prepared by means of an amide elimination and hydrocarbylation process starting from the corresponding Group 4 metal tetraamide and a hydrocarbylating agent, such as trimethylaluminum, as disclosed in WO
02/38628. Other techniques may be used as well.
The Group 4 metal complexes may be activated to form the actual catalyst composition by combination with a cocatalyst, preferably an aluminoxane, a cation forming cocatalyst, or a combination thereof. Preferably, the sole activating cocatalyst is an alumoxane which is a portion of the alumoxane used to treat the surface of the metal- or metalloid- oxide support, or generated in situ, on the surface of the support by reaction of an aluminum trialkyl compound, especially trimethylaluminum, with water present on the surface of the metal oxide. In this event, additional activating cocatalyst is not required to be separately combined with the metal complex before supporting the metal complex, and for this reason component 3) is stated as being optionally added to the composition.
Suitable alumoxanes for activation of the metal complexes herein include the same compounds used for treatment of the inorganic oxide supports, namely polymeric or oligomeric alumoxanes, especially methylalumoxane, and neutral Lewis acid modified polymeric or oligomeric alumoxanes, such as alkylalumoxanes modified by addition of a C,-30 hydrocarbyl substituted Group 13 compound, especially a tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compound, or a halogenated (including perhalogenated) derivative thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially a trialkylaluminum compound, a perfluorinated tri(aryl)boron compound, or a perfluorinated tri(aryl)aluminum compound.
Examples include triisobutyl aluminum- or tri-n-butyl aluminum- modified methylalumoxane, sometimes referred to as modified methalumoxane, or MMAO.
The Group 4 metal complexes may also be rendered catalytically active by combination with a cation forming cocatalyst, such as those previously known in the art for use with Group 4 metal olefin polymerization complexes. Suitable cation forming cocatalysts for use herein include neutral Lewis acids, such as C1-3o hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluoro-phenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium- or sulfonium- salts of compatible, noncoordinating anions, or ferrocenium-, lead- or silver salts of compatible, noncoordinating anions; and combinations of the foregoing cation forming cocatalysts and techniques. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes for olefin polymerizations in the following references: EP-A-277,003, US-A-5,153,157, US-A-5,064,802, US-A-5,321,106, US-A-5,721,185, US-A-5,350,723, US-A-5,425,872, US-A-5,625,087, US-A-5,883,204, US-A-5,919,983, US-A-5,783,512, WO
99/15534, and W099/42467.
It should be noted that the foregoing activating cocatalysts other than an alumoxane, are not preferably included in the invented composition, in as much as the best results have generally been obtained by the use of inorganic oxide supports that have been treated with methalumoxane, and optionally, additional methalumoxane cocatalyst.
During the polymerization, a mixture of monomers is contacted with the supported, activated catalyst composition according to any suitable polymerization conditions. The process is characterized by use of elevated temperatures and pressures. Hydrogen may be employed as a chain transfer agent for molecular weight control according to known techniques if desired. As in other similar polymerizations, it is highly desirable that the monomers and solvents employed be of sufficiently high purity that catalyst deactivation does not occur. Any suitable technique for monomer purification such as devolatilization at reduced pressures, contacting with molecular sieves or high surface area alumina, or a combination of the foregoing processes may be employed.
In a preferred embodiment of the invention the supported catalysts are employed in either a solution, slurry or gas phase polymerization. It has been discovered that if a minor proportion of ethylene is present or is first present in a polymerization of propylene using the catalysts of the present invention, polymers having very high molecular weights can be prepared. Moreover, the process for preparing such interpolymers is more efficient, compared to processes in which ethylene is completely absent. The quantity of ethylene added to the reactor is a minor amount compared to the quantity of propylene, and may be extremely small, preferably greater than 0.001 mole percent, based on total monomer content, more preferably from 0.01 to 10 mole percent.
Desirably the resulting copolymer possesses in polymerized form from 0.1 to 25 mole percent ethylene. Further desirably such copolymers also possess a molecular weight distribution, Mw/Mn, greater than 4.0, preferably greater than 5Ø Additionally the polymers desirably possess very rapid crystallization rates, as evidenced by an isothermal crystallization half time (ICHT) of less than about 1 minute at 120 C. Additionally, they are characterized by unique 13C NMR spectrum, showing peaks corresponding to such regio-error at about 14.6 and about 15.7 ppm, with the peaks being of equal or approximately equal intensity (that is, the integrated areas of the two peaks differ by less than 10 percent).
Q-NH N N N
(R R6 (R a aj 6 M-------------R
(nI) and (-K)X (IRA) wherein M, X, x, R' and T are as previously defined, R3, R4, R5 and R6 are as previously defined, preferably R3, R4, and R5 are hydrogen, or C14 alkyl, and R6 is C6-2o aryl, most preferably naphthalenyl;
Ra independently each occurrence is C1 alkyl, and a is 1-5, most preferably Ra in two ortho- positions is isopropyl or t-butyl;
RR and R8 independently each occurrence are hydrogen, halogen, or a C1_20 alkyl or aryl group, most preferably one of R7 and R8 is hydrogen and the other is a C6_20 aryl group, especially a fused polycyclic aryl group, most preferably an anthracenyl group, and bonds, optional bonds and electron pair donative interactions are represented by lines, dotted lines and arrows respectively.
Highly preferred polyfunctional Lewis base compounds and metal complexes for use herein correspond to the formula:
(IV) (IVA) IR (Rb)b (Rb)b H '\N (R )c (H3C)2HC H 2\N/ (Rc)c (H3C)2HC H
CH(CH3)2 (H3C)2HC
and 2 wherein X each occurrence is halide, N,N-dimethylamido, or C14 alkyl, and preferably each occurrence X is methyl;
Rb independently each occurrence is hydrogen, halogen, C1_20 alkyl, or C6_20 aryl, or two adjacent Rb groups are joined together thereby forming a ring, and b is 1-5;
and R independently each occurrence is hydrogen, halogen, C1_20 alkyl, or C6_20 aryl, or two adjacent R groups are joined together thereby forming a ring, and c is 1-5.
Most highly preferred examples of metal complexes for use according to the present invention are complexes of the following formulas:
o CH3 (H3C)2H H (H3C)2HC H N/ O
HIS
Hf O O o (H3C)2HC and (H3C)2HC
wherein X each occurrence is halide, N,N-dimethylamido, or C,14 alkyl, and preferably each occurrence X is methyl.
Examples of metal complexes usefully employed according to the present invention include:
[N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(a-naphthalen-2-diyl(6-pyridin-diyl)methane)]hafnium dimethyl;
[N-(2,6-di(1-methylethyl)phenyl)amido)( o-tolyl)(a-naphthalen-2-diyl(6-pyridin-diyl)methane)]hafnium di(N,N-dimethylamido);
[N-(2,6-di(1-methylethyl)phenyl)amido)( o-tolyl)(a-naphthalen-2-diyl(6-pyridin-diyl)methane)]hafnium dichloride;
[N-(2,6-di(1-methyl ethyl)phenyl)amido)(phenanthren-5-yl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl;
[N-(2,6-di(1-methylethyl)phenyl)amido)((henanthren-5-yl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium di(N,N-dimethylamido); and [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5 -yl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dichloride.
Under the reaction conditions used to prepare the metal complexes used in the present invention, it has been discovered that the hydrogen of the 2-position of the a-naphthalene group substituted at the 6-position of the pyridin-2-yl group is subject to elimination, thereby uniquely forming metal complexes wherein the metal is covalently bonded to both the resulting amide group and to the 2-position of the a-naphthalenyl group, as well as stabilized by coordination to the pyridinyl nitrogen atom through the electron pair of the nitrogen atom.
The foregoing metal complexes are conveniently prepared by standard metallation and ligand exchange procedures involving a source of the Group 4 metal and the neutral polyfunctional ligand source. The complexes may also be prepared by means of an amide elimination and hydrocarbylation process starting from the corresponding Group 4 metal tetraamide and a hydrocarbylating agent, such as trimethylaluminum, as disclosed in WO
02/38628. Other techniques may be used as well.
The Group 4 metal complexes may be activated to form the actual catalyst composition by combination with a cocatalyst, preferably an aluminoxane, a cation forming cocatalyst, or a combination thereof. Preferably, the sole activating cocatalyst is an alumoxane which is a portion of the alumoxane used to treat the surface of the metal- or metalloid- oxide support, or generated in situ, on the surface of the support by reaction of an aluminum trialkyl compound, especially trimethylaluminum, with water present on the surface of the metal oxide. In this event, additional activating cocatalyst is not required to be separately combined with the metal complex before supporting the metal complex, and for this reason component 3) is stated as being optionally added to the composition.
Suitable alumoxanes for activation of the metal complexes herein include the same compounds used for treatment of the inorganic oxide supports, namely polymeric or oligomeric alumoxanes, especially methylalumoxane, and neutral Lewis acid modified polymeric or oligomeric alumoxanes, such as alkylalumoxanes modified by addition of a C,-30 hydrocarbyl substituted Group 13 compound, especially a tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compound, or a halogenated (including perhalogenated) derivative thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially a trialkylaluminum compound, a perfluorinated tri(aryl)boron compound, or a perfluorinated tri(aryl)aluminum compound.
Examples include triisobutyl aluminum- or tri-n-butyl aluminum- modified methylalumoxane, sometimes referred to as modified methalumoxane, or MMAO.
The Group 4 metal complexes may also be rendered catalytically active by combination with a cation forming cocatalyst, such as those previously known in the art for use with Group 4 metal olefin polymerization complexes. Suitable cation forming cocatalysts for use herein include neutral Lewis acids, such as C1-3o hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluoro-phenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium- or sulfonium- salts of compatible, noncoordinating anions, or ferrocenium-, lead- or silver salts of compatible, noncoordinating anions; and combinations of the foregoing cation forming cocatalysts and techniques. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes for olefin polymerizations in the following references: EP-A-277,003, US-A-5,153,157, US-A-5,064,802, US-A-5,321,106, US-A-5,721,185, US-A-5,350,723, US-A-5,425,872, US-A-5,625,087, US-A-5,883,204, US-A-5,919,983, US-A-5,783,512, WO
99/15534, and W099/42467.
It should be noted that the foregoing activating cocatalysts other than an alumoxane, are not preferably included in the invented composition, in as much as the best results have generally been obtained by the use of inorganic oxide supports that have been treated with methalumoxane, and optionally, additional methalumoxane cocatalyst.
During the polymerization, a mixture of monomers is contacted with the supported, activated catalyst composition according to any suitable polymerization conditions. The process is characterized by use of elevated temperatures and pressures. Hydrogen may be employed as a chain transfer agent for molecular weight control according to known techniques if desired. As in other similar polymerizations, it is highly desirable that the monomers and solvents employed be of sufficiently high purity that catalyst deactivation does not occur. Any suitable technique for monomer purification such as devolatilization at reduced pressures, contacting with molecular sieves or high surface area alumina, or a combination of the foregoing processes may be employed.
In a preferred embodiment of the invention the supported catalysts are employed in either a solution, slurry or gas phase polymerization. It has been discovered that if a minor proportion of ethylene is present or is first present in a polymerization of propylene using the catalysts of the present invention, polymers having very high molecular weights can be prepared. Moreover, the process for preparing such interpolymers is more efficient, compared to processes in which ethylene is completely absent. The quantity of ethylene added to the reactor is a minor amount compared to the quantity of propylene, and may be extremely small, preferably greater than 0.001 mole percent, based on total monomer content, more preferably from 0.01 to 10 mole percent.
Desirably the resulting copolymer possesses in polymerized form from 0.1 to 25 mole percent ethylene. Further desirably such copolymers also possess a molecular weight distribution, Mw/Mn, greater than 4.0, preferably greater than 5Ø Additionally the polymers desirably possess very rapid crystallization rates, as evidenced by an isothermal crystallization half time (ICHT) of less than about 1 minute at 120 C. Additionally, they are characterized by unique 13C NMR spectrum, showing peaks corresponding to such regio-error at about 14.6 and about 15.7 ppm, with the peaks being of equal or approximately equal intensity (that is, the integrated areas of the two peaks differ by less than 10 percent).
The polymerization is desirably carried out as a continuous polymerization, in which catalyst components, monomers, and optionally solvent, adjuvants, scavengers, and polymerization aids are continuously supplied to the reaction zone and polymer product continuously removed therefrom. Within the scope of the terms "continuous" and "continuously" as used in this context are those processes in which there are intermittent additions of reactants and removal of products at small regular intervals, so that, over time, the overall process is continuous.
The catalyst compositions can be advantageously employed in a high pressure, solution, slurry, or gas phase polymerization process. For a solution polymerization process it is desirable to employ homogeneous dispersions of the catalyst components in liquid diluent in which the polymer is soluble under the polymerization conditions employed. One such process utilizing an extremely fine silica or similar dispersing agent to produce such a homogeneous catalyst dispersion is disclosed in US-A-5,783,512. A high pressure process is usually carried out at temperatures from 100 C to 400 C and at pressures above 500 bar (50 MPa). A slurry process typically uses an inert hydrocarbon diluent and temperatures of from 0 C up to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium.
Preferred temperatures in a slurry polymerization are from 30 C, preferably from 60 C up to 115 C, preferably up to 100 C. Pressures typically range from atmospheric (100 kPa) to 500 psi (3.4 MPa).
Preferably for use in gas phase polymerization processes, the support material and resulting catalyst has a median particle diameter from 20 to 200 gm, more preferably from 30 gm to 150 gm, and most preferably from 50 gm to 100 gm. Preferably for use in slurry polymerization processes, the support has a median particle diameter from 1 pun to 200 gm, more preferably from 5 gm to 100 gm, and most preferably from 10 gm to 80 gm. Preferably for use in solution or high pressure polymerization processes, the support has a median particle diameter from 0.1 gm to 40 gm, more preferably from 1 gm to 30 gm, and most preferably from 2 gm to 20 gm.
The supported catalyst composition of the present invention can also be employed to advantage in a gas phase polymerization process. Such processes are used commercially on a large scale for the manufacture of polypropylene, ethylene/propylene copolymers, and other olefin polymerizaitons. The gas phase process employed can be, for example, of the type which employs a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone. Preferred is the process wherein the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported or suspended above a perforated plate, the fluidization grid, by a flow of fluidization gas.
The gas employed to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed. The hot gases emerge from the top of the reactor, normally via a tranquilization zone, also known as a velocity reduction zone, having a wider diameter than the fluidized bed and wherein fine particles entrained in the gas stream have an opportunity to gravitate back into the bed. It can also be advantageous to use a cyclone to remove ultra-fine particles from the hot gas stream. The gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to strip the gas of the heat of polymerization.
A preferred method of cooling of the bed, in addition to the cooling provided by the cooled recycle gas, is to feed a volatile liquid to the bed to provide an evaporative cooling effect, often referred to as operation in the condensing mode. The volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having 3 to 8, preferably 4 to 6, carbon atoms. In the case that the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, this can suitably be fed to the bed to provide an evaporative cooling effect. The volatile liquid evaporates in the hot fluidized bed to form gas which mixes with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will undergo some polymerization in the bed. The evaporated liquid then emerges from the reactor as part of the hot recycle gas, and enters the compression/heat exchange part of the recycle loop. The recycle gas is cooled in the heat exchanger and, if the temperature to which the gas is cooled is below the dew point, liquid will precipitate from the gas. This liquid is desirably recycled continuously to the fluidized bed. It is possible to recycle the precipitated liquid to the bed as liquid droplets carried in the recycle gas stream. This type of process is described, for example in EP-89691; U.S. 4,543,399;
WO-94/25495 and U.S. 5,352,749. A particularly preferred method of recycling the liquid to the bed is to separate the liquid from the recycle gas stream and to reinject this liquid directly into the bed, preferably using a method which generates fine droplets of the liquid within the bed. This type of process is described in WO-94/28032.
The polymerization reaction occurring in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst composition. The catalyst composition may be subjected to a prepolymerization step, for example, by polymerizing a small quantity of olefin monomer in a liquid inert diluent, to provide a catalyst composite comprising supported catalyst particles embedded in olefin polymer particles if desired as well.
The polymer is produced directly in the fluidized bed by polymerization of the monomer or mixture of monomers on the fluidized particles of catalyst composition, supported catalyst composition or prepolymerized catalyst composition within the bed. Start-up of the polymerization reaction is achieved using a bed of preformed polymer particles, which are preferably similar to the desired polymer, and conditioning the bed by drying with inert gas or nitrogen prior to introducing the catalyst composition, the monomers and any other gases which it is desired to have in the recycle gas stream, such as a diluent gas, hydrogen chain transfer agent, or an inert condensable gas when operating in gas phase condensing mode. The produced polymer is discharged continuously or semi-continuously from the fluidized bed as desired.
The gas phase processes most suitable for the practice of this invention are continuous processes which provide for the continuous supply of reactants to the reaction zone of the reactor and the removal of products from the reaction zone of the reactor, thereby providing a steady-state environment on the macro scale in the reaction zone of the reactor. Products are readily recovered by exposure to reduced pressure and optionally elevated temperatures (devolatilization) according to known techniques. Typically, the fluidized bed of the gas phase process is operated at temperatures greater than 50 C, preferably from 60 C to 110 C, more preferably from 70 C to 110 C.
Suitable gas phase processes which are adaptable for use in the process of this invention are disclosed in US-A's: 4,588,790; 4,543,399; 5,352,749; 5,436,304; 5,405,922;
5,462,999; 5,461,123;
5,453,471; 5,032,562; 5,028,670; 5,473,028; 5,106,804; 5,556,238; 5,541,270;
5,608,019; and 5,616,661.
The skilled artisan will appreciate that the invention disclosed herein may be practiced in the absence of any component which has not been specifically disclosed.
The following examples are provided as further illustration of the invention and are not to be construed as limiting. Unless stated to the contrary all parts and percentages are expressed on a weight basis. The term "overnight", if used, refers to a time of approximately 16-18 hours, the term "room temperature", refers to a temperature of 20-25 C, and the term "mixed alkanes" refers to a commercially obtained mixture of C6_9 aliphatic hydrocarbons available under the trade designation Isopar E , from Exxon Chemicals Inc. In the event the name of a compound herein does not conform to the structural representation thereof, the structural representation shall control. The synthesis of all metal complexes and the preparation of all screening experiments were carried out in a dry nitrogen atmosphere using dry box techniques. All solvents used were HPLC grade and were dried before their use.
Examples 1-6 and Comparatives 1 and 2 Component 1) Preparation 1A) Davison 948TM silica (949 g, available from Grace Davison Company) which had been heated at 600 C for 3 hours under a nitrogen purge was added to toluene (2400 g) containing methylalumoxane (MAO, Akzo Nobel, Inc. 1314 mL of a 13.7 percent toluene solution). The mixture was stirred for 30 minutes, and the temperature of the mixture was increased to 70 C and the volatiles were removed in vacuo. The resulting dry powder was heated an additional 1 hour under vacuum. The resulting alumoxane modified silica, was a free flowing solid having an aluminum content of 4.5 mmol/g. Contacting with hexane at 25 C resulted in less than 1 percent weight loss.
1B) Davison 948TM silica (370 g) which had been heated at 500 C for 3 hours under a nitrogen purge was slurried in enough isopentane to obtain a easily stirred mixture. 549 ml of a 12.9 percent (4.14 M Al) toluene solution of a tri(n-octyl)aluminum modified methylalumoxane (MMAO-12, Akzo-Noble, Inc.) was added at room temperature. The mixture was stirred for 1 hour, the supernatant was removed via cannula, and the treated silica was washed with isopentane (1000 ml) and dried under high vacuum. The resulting free flowing, powder had an aluminum content of 4.5 mmol/g. Contacting with hexane at 25 C resulted in less than 1 percent weight loss.
1C) Davison 948TM silica (6.00 g) which had been heated at 500 C for 3 hours under a nitrogen purge was slurried in hexane (24 g) and then treated with 8.00 ml of a 21 percent triethylaluminum/hexane solution at room temperature. The mixture was stirred for 30 minutes, collected on a filter, and the treated silica was washed with hexane (2x10 ml) and dried under high vacuum. The resulting free flowing, powder had an aluminum content of approximately 1.1 mmol/g. Contacting with hexane at 25 C resulted in less than 1 percent weight loss.
1D) Davison 948TM silica (6.00 g) was heated at 500 C for 3 hours under a nitrogen purge prior to use.
Component 2) Preparation 2A) To a flask containing toluene and (2,6-di(1-methylethyl)phenylamino)(o-tolyl)(((X-naphthalenyl(6-pyridin-2-diyl))methane, one equivalent of n-butyllithium is added. After deprotonation is complete, one equivalent of hafnium tetrachloride is added and the mixture is heated to reflux for at least 1 hour. After cooling, a minimum of 3 equivalents of methyl , magnesium bromide is added. After methylation is complete, the crude product is separated from the inorganic salts by filtration, washed with hexane, and isolated by removal of the volatiles in vacuo.
2B) [N-(2,6-di(1-methylethyl)phenylamido)(o-tolyl)((a-naphthalen-2-diyl(6-pyridin-2-diyl))methane)]hafnium dichloride, is obtained by treatment of a toluene solution of 2A with 2 equivalents of anhydrous triethylammonium chloride. After protonolysis is complete, the product is filtered to remove insolubles, isolated by removing volatiles in vacuo, and washing the product with hexane before final drying in vacuo.
Component 3) Preparation 3A) In a glass ampoule, 16.5 pL of a 19.6 percent toluene solution of triethylaluminum were combined with 260 mg of a 10.4 percent toluene solution of the methylbis-(C18_22a1ky1)ammonium salt of p-hydroxyphenyltris(pentafluorophenyl)borate:
[(p-HOC6H4)B(C6F5)3][NHMe(C18-22H32-45)2] (0.024 pmol) and stirred for 15 minutes.
Prior to use the product was diluted with 400 mg toluene.
3B) Methylbis(C18-22alky1)ammonium tetrakis(pentafluorophenyl)borate:
[N Me(C18.22H37-45)2]+[B(C6F5)4]" was prepared according to US-A-5,919,983.
Supported Catalyst Preparation Example 1 (No separately added cocatalyst) In a glass flask containing 40 mL
hexane, 10.13 g of the treated support lA (45.6 mmol Al) was added and stirred to form a slurry.
Component 2A (70.0 mg, 0.101 mmol Hf) was added and the resulting mixture stirred for 3 hours.
The solids were allowed to settle, the supernatant was removed by decantation, and the solids were dried under high vacuum, leaving the catalyst composition as a free flowing powder, in quantitative yield. Hf content = 1 Opmol Hf/g. Al/Hf (molar ratio) = 450:1.
Example 2 (No separately added cocatalyst; supported catalyst generated in situ and used without isolation) In a vial, 0.2 mL of a 0.005 M hexane solution of component 2A was added to a slurry of 0.26 g of support lA in 2 mL of hexane. After stirring for 1 h, the mixture was injected directly into the polymerization vessel. Hf content = 3.85 gmol/g. Al/Hf (molar ratio) = 1170:1 Example 3 (No separately added cocatalyst; supported catalyst generated in situ and used without isolation) In a vial, 0.2 mL of a 0.005 M hexane solution of component 2A was added to a slurry of 0.222 g of support lB in 2 mL of hexane. After stirring for 60 minutes, the mixture was injected directly into the polymerization vessel. Hf content = 4.50 pmol/g.
Al/Hf (molar ratio) _ 1000:1 Example 4 (with ammonium borate cocatalyst 3A) To 1.00 g of the triethylaluminum treated support component 1C (1.1 mmol Al) in a flask, component 3A (680 mg) was added dropwise with stirring. Additional toluene (200 mg) was added and stirring continued for 1 h.
Component 2A (13.8 mg, 20 mol Hf) in 500 mg toluene was added and the resulting mixture stirred for one hour. Hexane (25 ml) was added and stirring continued for 2 h.
The solids were collected by filtration, washed with 20 mL hexane and dried, leaving the catalyst composition as a free flowing powder, in quantitative yield. Hf content = 20 gmol Hf/g. Al/Hf (molar ratio) = 55:1.
B:Hf (molar ratio) = 1.2:1.
Example 5 (with ammonium borate cocatalyst 3B) To a mixture of 1.00 g of the triethylaluminum treated support component 1 C (1.1 mmol Al) and 4.0 mL of hexane in a flask, a mixture of 2.50 g of a 1.06 percent methylcyclohexane solution of component 3B
and 13.9 mg of component 2A which was premixed for 30 minutes, was added dropwise with stirring. The combined mixtures were stirred for 30 minutes and the volatiles were removed in vacuo, leaving the catalyst composition as a free flowing powder, in quantitative yield. Hf content = 20 pmol Hf/g.
Al/Hf (molar ratio) = 55:1. B:Hf (molar ratio) = 1.1:1.
Example 6 (No separately added cocatalyst) In a glass vial containing 4.0 mL
hexane, 0.44 g of the treated support 1A was added and stirred to form a slurry. Component 2B (0.4 mL of a 0.005 M toluene solution) was added and the mixture stirred for 1 h. The resulting mixture was injected directly into the reactor without isolation of the supported catalyst. Hf content = 4.5 mol Hf/g. Al/Hf (molar ratio) = 1000:1.
Comparative 1 (Untreated silica, not an example of the invention) In a glass flask containing 5 mL hexane, 1.00 g of Davison 948TM silica which had been heated at 500 C for 3 hours under a nitrogen purge, was added and stirred to form a slurry. A
premixed hexane solution of Component 2A (4.15 mg, 6.0 mmol Hf, 1.0 mL hexane) and the MMAO-12 methalumoxane cocatalyst as a 12.9 percent aluminum/toluene solution (1.09 mL, 4500 mol Al, Akzo-Noble) was added and the resulting mixture stirred overnight. The volatiles were removed under high vacuum leaving the catalyst composition as a free flowing powder, in quantitative yield. Hf content = 3.53 gmol Hf/g. Al:Hf (molar ratio) = 750:1.
Comparative 2 (Untreated silica, not an example of the invention) In a glass flask containing 5 mL hexane, 1.00 g.of Davison 948TM silica which had been heated at 500 C for 3 hours under a nitrogen purge, was added and stirred to form a slurry. A
premixed toluene solution of Component 2A (4.15 mg, 6.0 mmol Hf, 1.0 mL toluene) and methalumoxane cocatalyst as a 13.7 percent aluminum/toluene solution (0.96 mL, 4500 mol Al, MAO-3, Albemarle) was added and the resulting mixture stirred overnight. The volatiles were removed under high vacuum leaving the catalyst composition as a free flowing powder, in quantitative yield. Hf content = 4.72 mol Hf/g.
Al:Hf (molar ratio) = 750:1.
Polymerization A 1 liter stirred, jacketed, polymerization reactor was charged with 400 g propylene and heated to 60 C, resulting in an internal pressure of 375 psi (2.8 MPa).
Triisobutylaluminum (0.4 g, 2 mmol) in 10 ml hexane solvent was added to the reactor contents and circulated for 10 minutes to scavenge impurities. Next, the desired quantity of catalyst slurry followed by an additional 10 ml hexane to purge the line was added via a transfer line. The reaction temperature was maintained at 60 C. After 30 minutes polymerization time, the reactor was vented and cooled and the resulting polymer removed from the reactor. Results are contained in Table 1.
The catalyst compositions can be advantageously employed in a high pressure, solution, slurry, or gas phase polymerization process. For a solution polymerization process it is desirable to employ homogeneous dispersions of the catalyst components in liquid diluent in which the polymer is soluble under the polymerization conditions employed. One such process utilizing an extremely fine silica or similar dispersing agent to produce such a homogeneous catalyst dispersion is disclosed in US-A-5,783,512. A high pressure process is usually carried out at temperatures from 100 C to 400 C and at pressures above 500 bar (50 MPa). A slurry process typically uses an inert hydrocarbon diluent and temperatures of from 0 C up to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium.
Preferred temperatures in a slurry polymerization are from 30 C, preferably from 60 C up to 115 C, preferably up to 100 C. Pressures typically range from atmospheric (100 kPa) to 500 psi (3.4 MPa).
Preferably for use in gas phase polymerization processes, the support material and resulting catalyst has a median particle diameter from 20 to 200 gm, more preferably from 30 gm to 150 gm, and most preferably from 50 gm to 100 gm. Preferably for use in slurry polymerization processes, the support has a median particle diameter from 1 pun to 200 gm, more preferably from 5 gm to 100 gm, and most preferably from 10 gm to 80 gm. Preferably for use in solution or high pressure polymerization processes, the support has a median particle diameter from 0.1 gm to 40 gm, more preferably from 1 gm to 30 gm, and most preferably from 2 gm to 20 gm.
The supported catalyst composition of the present invention can also be employed to advantage in a gas phase polymerization process. Such processes are used commercially on a large scale for the manufacture of polypropylene, ethylene/propylene copolymers, and other olefin polymerizaitons. The gas phase process employed can be, for example, of the type which employs a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone. Preferred is the process wherein the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported or suspended above a perforated plate, the fluidization grid, by a flow of fluidization gas.
The gas employed to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed. The hot gases emerge from the top of the reactor, normally via a tranquilization zone, also known as a velocity reduction zone, having a wider diameter than the fluidized bed and wherein fine particles entrained in the gas stream have an opportunity to gravitate back into the bed. It can also be advantageous to use a cyclone to remove ultra-fine particles from the hot gas stream. The gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to strip the gas of the heat of polymerization.
A preferred method of cooling of the bed, in addition to the cooling provided by the cooled recycle gas, is to feed a volatile liquid to the bed to provide an evaporative cooling effect, often referred to as operation in the condensing mode. The volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having 3 to 8, preferably 4 to 6, carbon atoms. In the case that the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, this can suitably be fed to the bed to provide an evaporative cooling effect. The volatile liquid evaporates in the hot fluidized bed to form gas which mixes with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will undergo some polymerization in the bed. The evaporated liquid then emerges from the reactor as part of the hot recycle gas, and enters the compression/heat exchange part of the recycle loop. The recycle gas is cooled in the heat exchanger and, if the temperature to which the gas is cooled is below the dew point, liquid will precipitate from the gas. This liquid is desirably recycled continuously to the fluidized bed. It is possible to recycle the precipitated liquid to the bed as liquid droplets carried in the recycle gas stream. This type of process is described, for example in EP-89691; U.S. 4,543,399;
WO-94/25495 and U.S. 5,352,749. A particularly preferred method of recycling the liquid to the bed is to separate the liquid from the recycle gas stream and to reinject this liquid directly into the bed, preferably using a method which generates fine droplets of the liquid within the bed. This type of process is described in WO-94/28032.
The polymerization reaction occurring in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst composition. The catalyst composition may be subjected to a prepolymerization step, for example, by polymerizing a small quantity of olefin monomer in a liquid inert diluent, to provide a catalyst composite comprising supported catalyst particles embedded in olefin polymer particles if desired as well.
The polymer is produced directly in the fluidized bed by polymerization of the monomer or mixture of monomers on the fluidized particles of catalyst composition, supported catalyst composition or prepolymerized catalyst composition within the bed. Start-up of the polymerization reaction is achieved using a bed of preformed polymer particles, which are preferably similar to the desired polymer, and conditioning the bed by drying with inert gas or nitrogen prior to introducing the catalyst composition, the monomers and any other gases which it is desired to have in the recycle gas stream, such as a diluent gas, hydrogen chain transfer agent, or an inert condensable gas when operating in gas phase condensing mode. The produced polymer is discharged continuously or semi-continuously from the fluidized bed as desired.
The gas phase processes most suitable for the practice of this invention are continuous processes which provide for the continuous supply of reactants to the reaction zone of the reactor and the removal of products from the reaction zone of the reactor, thereby providing a steady-state environment on the macro scale in the reaction zone of the reactor. Products are readily recovered by exposure to reduced pressure and optionally elevated temperatures (devolatilization) according to known techniques. Typically, the fluidized bed of the gas phase process is operated at temperatures greater than 50 C, preferably from 60 C to 110 C, more preferably from 70 C to 110 C.
Suitable gas phase processes which are adaptable for use in the process of this invention are disclosed in US-A's: 4,588,790; 4,543,399; 5,352,749; 5,436,304; 5,405,922;
5,462,999; 5,461,123;
5,453,471; 5,032,562; 5,028,670; 5,473,028; 5,106,804; 5,556,238; 5,541,270;
5,608,019; and 5,616,661.
The skilled artisan will appreciate that the invention disclosed herein may be practiced in the absence of any component which has not been specifically disclosed.
The following examples are provided as further illustration of the invention and are not to be construed as limiting. Unless stated to the contrary all parts and percentages are expressed on a weight basis. The term "overnight", if used, refers to a time of approximately 16-18 hours, the term "room temperature", refers to a temperature of 20-25 C, and the term "mixed alkanes" refers to a commercially obtained mixture of C6_9 aliphatic hydrocarbons available under the trade designation Isopar E , from Exxon Chemicals Inc. In the event the name of a compound herein does not conform to the structural representation thereof, the structural representation shall control. The synthesis of all metal complexes and the preparation of all screening experiments were carried out in a dry nitrogen atmosphere using dry box techniques. All solvents used were HPLC grade and were dried before their use.
Examples 1-6 and Comparatives 1 and 2 Component 1) Preparation 1A) Davison 948TM silica (949 g, available from Grace Davison Company) which had been heated at 600 C for 3 hours under a nitrogen purge was added to toluene (2400 g) containing methylalumoxane (MAO, Akzo Nobel, Inc. 1314 mL of a 13.7 percent toluene solution). The mixture was stirred for 30 minutes, and the temperature of the mixture was increased to 70 C and the volatiles were removed in vacuo. The resulting dry powder was heated an additional 1 hour under vacuum. The resulting alumoxane modified silica, was a free flowing solid having an aluminum content of 4.5 mmol/g. Contacting with hexane at 25 C resulted in less than 1 percent weight loss.
1B) Davison 948TM silica (370 g) which had been heated at 500 C for 3 hours under a nitrogen purge was slurried in enough isopentane to obtain a easily stirred mixture. 549 ml of a 12.9 percent (4.14 M Al) toluene solution of a tri(n-octyl)aluminum modified methylalumoxane (MMAO-12, Akzo-Noble, Inc.) was added at room temperature. The mixture was stirred for 1 hour, the supernatant was removed via cannula, and the treated silica was washed with isopentane (1000 ml) and dried under high vacuum. The resulting free flowing, powder had an aluminum content of 4.5 mmol/g. Contacting with hexane at 25 C resulted in less than 1 percent weight loss.
1C) Davison 948TM silica (6.00 g) which had been heated at 500 C for 3 hours under a nitrogen purge was slurried in hexane (24 g) and then treated with 8.00 ml of a 21 percent triethylaluminum/hexane solution at room temperature. The mixture was stirred for 30 minutes, collected on a filter, and the treated silica was washed with hexane (2x10 ml) and dried under high vacuum. The resulting free flowing, powder had an aluminum content of approximately 1.1 mmol/g. Contacting with hexane at 25 C resulted in less than 1 percent weight loss.
1D) Davison 948TM silica (6.00 g) was heated at 500 C for 3 hours under a nitrogen purge prior to use.
Component 2) Preparation 2A) To a flask containing toluene and (2,6-di(1-methylethyl)phenylamino)(o-tolyl)(((X-naphthalenyl(6-pyridin-2-diyl))methane, one equivalent of n-butyllithium is added. After deprotonation is complete, one equivalent of hafnium tetrachloride is added and the mixture is heated to reflux for at least 1 hour. After cooling, a minimum of 3 equivalents of methyl , magnesium bromide is added. After methylation is complete, the crude product is separated from the inorganic salts by filtration, washed with hexane, and isolated by removal of the volatiles in vacuo.
2B) [N-(2,6-di(1-methylethyl)phenylamido)(o-tolyl)((a-naphthalen-2-diyl(6-pyridin-2-diyl))methane)]hafnium dichloride, is obtained by treatment of a toluene solution of 2A with 2 equivalents of anhydrous triethylammonium chloride. After protonolysis is complete, the product is filtered to remove insolubles, isolated by removing volatiles in vacuo, and washing the product with hexane before final drying in vacuo.
Component 3) Preparation 3A) In a glass ampoule, 16.5 pL of a 19.6 percent toluene solution of triethylaluminum were combined with 260 mg of a 10.4 percent toluene solution of the methylbis-(C18_22a1ky1)ammonium salt of p-hydroxyphenyltris(pentafluorophenyl)borate:
[(p-HOC6H4)B(C6F5)3][NHMe(C18-22H32-45)2] (0.024 pmol) and stirred for 15 minutes.
Prior to use the product was diluted with 400 mg toluene.
3B) Methylbis(C18-22alky1)ammonium tetrakis(pentafluorophenyl)borate:
[N Me(C18.22H37-45)2]+[B(C6F5)4]" was prepared according to US-A-5,919,983.
Supported Catalyst Preparation Example 1 (No separately added cocatalyst) In a glass flask containing 40 mL
hexane, 10.13 g of the treated support lA (45.6 mmol Al) was added and stirred to form a slurry.
Component 2A (70.0 mg, 0.101 mmol Hf) was added and the resulting mixture stirred for 3 hours.
The solids were allowed to settle, the supernatant was removed by decantation, and the solids were dried under high vacuum, leaving the catalyst composition as a free flowing powder, in quantitative yield. Hf content = 1 Opmol Hf/g. Al/Hf (molar ratio) = 450:1.
Example 2 (No separately added cocatalyst; supported catalyst generated in situ and used without isolation) In a vial, 0.2 mL of a 0.005 M hexane solution of component 2A was added to a slurry of 0.26 g of support lA in 2 mL of hexane. After stirring for 1 h, the mixture was injected directly into the polymerization vessel. Hf content = 3.85 gmol/g. Al/Hf (molar ratio) = 1170:1 Example 3 (No separately added cocatalyst; supported catalyst generated in situ and used without isolation) In a vial, 0.2 mL of a 0.005 M hexane solution of component 2A was added to a slurry of 0.222 g of support lB in 2 mL of hexane. After stirring for 60 minutes, the mixture was injected directly into the polymerization vessel. Hf content = 4.50 pmol/g.
Al/Hf (molar ratio) _ 1000:1 Example 4 (with ammonium borate cocatalyst 3A) To 1.00 g of the triethylaluminum treated support component 1C (1.1 mmol Al) in a flask, component 3A (680 mg) was added dropwise with stirring. Additional toluene (200 mg) was added and stirring continued for 1 h.
Component 2A (13.8 mg, 20 mol Hf) in 500 mg toluene was added and the resulting mixture stirred for one hour. Hexane (25 ml) was added and stirring continued for 2 h.
The solids were collected by filtration, washed with 20 mL hexane and dried, leaving the catalyst composition as a free flowing powder, in quantitative yield. Hf content = 20 gmol Hf/g. Al/Hf (molar ratio) = 55:1.
B:Hf (molar ratio) = 1.2:1.
Example 5 (with ammonium borate cocatalyst 3B) To a mixture of 1.00 g of the triethylaluminum treated support component 1 C (1.1 mmol Al) and 4.0 mL of hexane in a flask, a mixture of 2.50 g of a 1.06 percent methylcyclohexane solution of component 3B
and 13.9 mg of component 2A which was premixed for 30 minutes, was added dropwise with stirring. The combined mixtures were stirred for 30 minutes and the volatiles were removed in vacuo, leaving the catalyst composition as a free flowing powder, in quantitative yield. Hf content = 20 pmol Hf/g.
Al/Hf (molar ratio) = 55:1. B:Hf (molar ratio) = 1.1:1.
Example 6 (No separately added cocatalyst) In a glass vial containing 4.0 mL
hexane, 0.44 g of the treated support 1A was added and stirred to form a slurry. Component 2B (0.4 mL of a 0.005 M toluene solution) was added and the mixture stirred for 1 h. The resulting mixture was injected directly into the reactor without isolation of the supported catalyst. Hf content = 4.5 mol Hf/g. Al/Hf (molar ratio) = 1000:1.
Comparative 1 (Untreated silica, not an example of the invention) In a glass flask containing 5 mL hexane, 1.00 g of Davison 948TM silica which had been heated at 500 C for 3 hours under a nitrogen purge, was added and stirred to form a slurry. A
premixed hexane solution of Component 2A (4.15 mg, 6.0 mmol Hf, 1.0 mL hexane) and the MMAO-12 methalumoxane cocatalyst as a 12.9 percent aluminum/toluene solution (1.09 mL, 4500 mol Al, Akzo-Noble) was added and the resulting mixture stirred overnight. The volatiles were removed under high vacuum leaving the catalyst composition as a free flowing powder, in quantitative yield. Hf content = 3.53 gmol Hf/g. Al:Hf (molar ratio) = 750:1.
Comparative 2 (Untreated silica, not an example of the invention) In a glass flask containing 5 mL hexane, 1.00 g.of Davison 948TM silica which had been heated at 500 C for 3 hours under a nitrogen purge, was added and stirred to form a slurry. A
premixed toluene solution of Component 2A (4.15 mg, 6.0 mmol Hf, 1.0 mL toluene) and methalumoxane cocatalyst as a 13.7 percent aluminum/toluene solution (0.96 mL, 4500 mol Al, MAO-3, Albemarle) was added and the resulting mixture stirred overnight. The volatiles were removed under high vacuum leaving the catalyst composition as a free flowing powder, in quantitative yield. Hf content = 4.72 mol Hf/g.
Al:Hf (molar ratio) = 750:1.
Polymerization A 1 liter stirred, jacketed, polymerization reactor was charged with 400 g propylene and heated to 60 C, resulting in an internal pressure of 375 psi (2.8 MPa).
Triisobutylaluminum (0.4 g, 2 mmol) in 10 ml hexane solvent was added to the reactor contents and circulated for 10 minutes to scavenge impurities. Next, the desired quantity of catalyst slurry followed by an additional 10 ml hexane to purge the line was added via a transfer line. The reaction temperature was maintained at 60 C. After 30 minutes polymerization time, the reactor was vented and cooled and the resulting polymer removed from the reactor. Results are contained in Table 1.
Table 1 run Catalyst Com lex Su ort Activator** Efficiency k / Hf) 1 Ex.l 2A 1A - 254 2 Ex.2 1A - 969 3 Ex.3 1B - 214 4 Ex. 4 14 1 C 3A 117 Ex. 5 1 C 3B 171 6 Ex.6 2B lA - 168 7* Com . 1 2A 1D MMAO-12 62 8* Com .2 1D MAO 2 * comparative not an example of the invention, support not pretreated with organoaluminum compound prior to contacting with metal complex ** activator combined with metal complex prior to contact with support As may be seen by reference to the results contained in table 1, the use of silica that has been modified by treatment with an aluminum compound, especially an alumoxane, gives the best results, particularly when used immediately following preparation without isolation of the supported solid catalyst; and use of unmodified silica support, even in combination with use of an alumoxane cocatalyst gave extremely poor results.
Polymer Characterization The following analytical studies were performed on the polymers prepared according to the invention. Results are reported for the polymer of Run 3 in Tables 2 and 3.
GPC, xylene solubles (XS), and NMR measurements were performed according to standard procedures.
Morphology (polymer particle integrity and lack of lumping or friability) was determined qualitatively by observation.
Melt flow rate (MFR) (g/10 minutes) was determined in accordance with ASTM D-condition L.
Differential Scanning Calorimetry (DSC) heat-cool-heat experiments were performed using a Perkin-Elmer DSC7 instrument. The first heating was done at 10 C/minute, then cooling at 10 C/min to crystallize the polymer, then second heating was done at 10 C/minute.
Percent crystallinity was determined from DSC data using the equation:
Xc = 100 AHf / AHfo where AHf is the measured heat of fusion of the sample, and OHfo is the heat of fusion of 100 percent crystalline polymer, namely 39.4 calories/gm.
For measuring ICHT (isothermal crystallization half time) by differential scanning calorimeter (Perkin Elmer DSC7) the following procedure was used. The polymer was melted at 250 C (for 3 minutes), then cooled rapidly (200 C/minute) to 120 C
(crystallization temperature), then held isothermally in time mode at 120 C until it crystallized. The time to the peak of the crystallization exotherm was taken as the ICHT. Lower ICHT indicates faster crystallization rate.
Table 2. General Characteristics - Run 3 Mn Mw Mz Mw/Mn Morphology MFR XS (percent) 249,500 1,275,000 3,825,000 5.11 Good to excellent 0.04 0.64 Table 3. Melting and crystallization data - Run 3 Tm, C Tc, C Heat of fusion Percent ICHT 120 C
(J/gm) Crystallinity (min) 146 112 89.6 54.1 <1 As can be seen from the Tables, the polypropylene resin from run 3 has a broad molecular weight distribution (MWD) and a rapid crystallization rate. The broad MWD is a particularly surprising feature of this polypropylene and is believed to result from the interaction of the active catalyst components of the invention. While only homopolymer polypropylenes were made, it is believed that propylene/ethylene copolymers made with the present supported catalyst composition will exhibit a similar broad MWD.
The polypropylene of runs 1 through 4 also had regio-errors as determined by spectroscopy. In particular, the regio-error frequency was 8 to 14 per 1000 propylene units. The regio-error shows up as a twin peaks at about 14.6 and about 15.7 ppm in the 13C NMR spectrum, with the peaks having about equal intensity. Polypropylene homopolymers made from the active catalyst of the invention typically have at least 50 percent more of this regio-error than a comparable polypropylene homopolymer prepared with a Ziegler-Natta catalyst.
Propylene/
ethylene copolymers made with the present catalyst composition also are characterized by 13C NMR
spectra exhibiting a similar regio-error.
Isothermal crystallization half time (ICHT) at 120 C for the polypropylene resins made in runs 1-4 were surprisingly fast (1 min or less). This indicates the polymers possess a crystallization rate faster than commercially available polypropylenes made using zirconium based metallocene catalysts.
Polymer Characterization The following analytical studies were performed on the polymers prepared according to the invention. Results are reported for the polymer of Run 3 in Tables 2 and 3.
GPC, xylene solubles (XS), and NMR measurements were performed according to standard procedures.
Morphology (polymer particle integrity and lack of lumping or friability) was determined qualitatively by observation.
Melt flow rate (MFR) (g/10 minutes) was determined in accordance with ASTM D-condition L.
Differential Scanning Calorimetry (DSC) heat-cool-heat experiments were performed using a Perkin-Elmer DSC7 instrument. The first heating was done at 10 C/minute, then cooling at 10 C/min to crystallize the polymer, then second heating was done at 10 C/minute.
Percent crystallinity was determined from DSC data using the equation:
Xc = 100 AHf / AHfo where AHf is the measured heat of fusion of the sample, and OHfo is the heat of fusion of 100 percent crystalline polymer, namely 39.4 calories/gm.
For measuring ICHT (isothermal crystallization half time) by differential scanning calorimeter (Perkin Elmer DSC7) the following procedure was used. The polymer was melted at 250 C (for 3 minutes), then cooled rapidly (200 C/minute) to 120 C
(crystallization temperature), then held isothermally in time mode at 120 C until it crystallized. The time to the peak of the crystallization exotherm was taken as the ICHT. Lower ICHT indicates faster crystallization rate.
Table 2. General Characteristics - Run 3 Mn Mw Mz Mw/Mn Morphology MFR XS (percent) 249,500 1,275,000 3,825,000 5.11 Good to excellent 0.04 0.64 Table 3. Melting and crystallization data - Run 3 Tm, C Tc, C Heat of fusion Percent ICHT 120 C
(J/gm) Crystallinity (min) 146 112 89.6 54.1 <1 As can be seen from the Tables, the polypropylene resin from run 3 has a broad molecular weight distribution (MWD) and a rapid crystallization rate. The broad MWD is a particularly surprising feature of this polypropylene and is believed to result from the interaction of the active catalyst components of the invention. While only homopolymer polypropylenes were made, it is believed that propylene/ethylene copolymers made with the present supported catalyst composition will exhibit a similar broad MWD.
The polypropylene of runs 1 through 4 also had regio-errors as determined by spectroscopy. In particular, the regio-error frequency was 8 to 14 per 1000 propylene units. The regio-error shows up as a twin peaks at about 14.6 and about 15.7 ppm in the 13C NMR spectrum, with the peaks having about equal intensity. Polypropylene homopolymers made from the active catalyst of the invention typically have at least 50 percent more of this regio-error than a comparable polypropylene homopolymer prepared with a Ziegler-Natta catalyst.
Propylene/
ethylene copolymers made with the present catalyst composition also are characterized by 13C NMR
spectra exhibiting a similar regio-error.
Isothermal crystallization half time (ICHT) at 120 C for the polypropylene resins made in runs 1-4 were surprisingly fast (1 min or less). This indicates the polymers possess a crystallization rate faster than commercially available polypropylenes made using zirconium based metallocene catalysts.
Claims (14)
1. A process for preparing high molecular weight propylene homopolymers or copolymers of propylene and ethylene, said process comprising contacting propylene and optionally from 0.00 t to 10 percent of the total monomer weight of ethylene under addition polymerization conditions with a supported, heterogeneous catalyst composition comprising:
1) a substrate comprising the reaction product of a-solid, particulated, high surface area, metal oxide, metalloid oxide, or a mixture thereof and an organoaluminum compound, 2) a Group 4 metal complex of a polyvalent, Lewis base ligand; and optionally, 3) an activating cocatalyst for the metal complex.
1) a substrate comprising the reaction product of a-solid, particulated, high surface area, metal oxide, metalloid oxide, or a mixture thereof and an organoaluminum compound, 2) a Group 4 metal complex of a polyvalent, Lewis base ligand; and optionally, 3) an activating cocatalyst for the metal complex.
2. A process according to claim 1 wherein propylene is homopolymerized.
3. A process according to claim 1, wherein ethylene in an amount from 0.001 to 10 percent of the total monomer weight is copolymerized with propylene.
4. A process according to any one of claims 1 to 3 wherein the metal complex corresponds to the formula IA:
wherein R1 is alkyl ; cycloalkyl, heteroalkyl, cycloheteroalkyl or aryl, or an inertly substituted derivative thereof containing from 1 to 30 atoms not counting hydrogen;
T is a divalent bridging group of from 1 to 20 atoms other than hydrogen, and R2 is a C6-20 heteroaryl group containing Lewis base functionality, M is the Group 4 metal, X is an anionic, neutral or dianionic ligand group, x is a number from 0 to 5 indicating the number of such X groups, and bonds, optional bonds and electron donative interactions are represented bylines, dotted lines and arrows respectively.
wherein R1 is alkyl ; cycloalkyl, heteroalkyl, cycloheteroalkyl or aryl, or an inertly substituted derivative thereof containing from 1 to 30 atoms not counting hydrogen;
T is a divalent bridging group of from 1 to 20 atoms other than hydrogen, and R2 is a C6-20 heteroaryl group containing Lewis base functionality, M is the Group 4 metal, X is an anionic, neutral or dianionic ligand group, x is a number from 0 to 5 indicating the number of such X groups, and bonds, optional bonds and electron donative interactions are represented bylines, dotted lines and arrows respectively.
5. A process according to claim 4 wherein T is a mono- or di- C1-19 hydrocarbyl substituted methylene or silane group.
6. A process according to claim 4 or 5 wherein M is hafnium.
7. A process according to any one of claims 4 to 6 wherein R2 is a pyridin-2-yl- or substituted pyridin-2-yl group.
8. A process according claim 7 wherein the metal complex corresponds to the formula IIA:
wherein M, X, x, R1 and T are as defined with reference to claim 7, aqd R3, R4, R5 and R6 are hydrogen, halo, or an optionally substituted alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, or silyl group of up to 15 atoms not counting hydrogen, or adjacent R5 or R6 groups may be joined together thereby forming fused ring derivatives.
wherein M, X, x, R1 and T are as defined with reference to claim 7, aqd R3, R4, R5 and R6 are hydrogen, halo, or an optionally substituted alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, or silyl group of up to 15 atoms not counting hydrogen, or adjacent R5 or R6 groups may be joined together thereby forming fused ring derivatives.
9. A process according claim 8 wherein the metal complex corresponds to the formula IIIA:
wherein M, X and x are defined with reference to claim 7;
R3, R4, and R5 are hydrogea or C1-4 alkyl, and R6 is optionally substituted C6-15 aryl, R a independently each occurrence is C1-4 alkyl, and a is 1-5; and one of R7 and R8 is hydrogen and the other is a C6-19 aryl group.
wherein M, X and x are defined with reference to claim 7;
R3, R4, and R5 are hydrogea or C1-4 alkyl, and R6 is optionally substituted C6-15 aryl, R a independently each occurrence is C1-4 alkyl, and a is 1-5; and one of R7 and R8 is hydrogen and the other is a C6-19 aryl group.
10. A process according claim 9 wherein the metal complex corresponds to the formula IVA:
wherein X each occurrence is halide, N,N-dimethylamido, or C1-4 alkyl;
R b independently each occurrence is hydrogen, halogen, C1-13 alkyl, or C6-13 aryl, or two adjacent R b groups are joined together thereby forming a ring, and b is 1-5;
and R c independently each occurrence is hydrogen, halogen, C1-9 alkyl, or C6-9 aryl, or two adjacent R c groups are joined together thereby forming a ring, and c is 1-5.
wherein X each occurrence is halide, N,N-dimethylamido, or C1-4 alkyl;
R b independently each occurrence is hydrogen, halogen, C1-13 alkyl, or C6-13 aryl, or two adjacent R b groups are joined together thereby forming a ring, and b is 1-5;
and R c independently each occurrence is hydrogen, halogen, C1-9 alkyl, or C6-9 aryl, or two adjacent R c groups are joined together thereby forming a ring, and c is 1-5.
11. A process according to claim 10 wherein the metal complex is:
wherein X each occurrence is halide, N,N-dimethylamido, or C1-4 alkyl.
wherein X each occurrence is halide, N,N-dimethylamido, or C1-4 alkyl.
12. A process according to Claim 11 wherein X each occurrence is halide or methyl.
13. A process according to any one of claims 1 to 12 wherein the substrate is the reaction product of silica and an organoaluminum compound.
14. A process according to any one of claims 1 to 13 wherein the organoaluminum compound is an alumoxane.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US33888101P | 2001-11-06 | 2001-11-06 | |
US60/338,881 | 2001-11-06 | ||
US10/139,786 | 2002-05-05 | ||
US10/139,786 US6960635B2 (en) | 2001-11-06 | 2002-05-05 | Isotactic propylene copolymers, their preparation and use |
PCT/US2002/035617 WO2003040195A1 (en) | 2001-11-06 | 2002-11-05 | Supported catalysts for manufacture of polymers |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2463588A1 CA2463588A1 (en) | 2003-05-15 |
CA2463588C true CA2463588C (en) | 2012-04-10 |
Family
ID=26837536
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2463588A Expired - Fee Related CA2463588C (en) | 2001-11-06 | 2002-11-05 | Supported polymerization catalysts comprising a polyvalent lewis base ligand |
Country Status (7)
Country | Link |
---|---|
US (3) | US6960635B2 (en) |
EP (2) | EP1448630A2 (en) |
JP (4) | JP5027378B2 (en) |
CN (1) | CN100467501C (en) |
CA (1) | CA2463588C (en) |
DE (1) | DE60229426D1 (en) |
WO (2) | WO2003040195A1 (en) |
Families Citing this family (449)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6576583B1 (en) | 2000-02-11 | 2003-06-10 | Phillips Petroleum Company | Organometal catalyst composition |
US6843595B2 (en) * | 2001-01-26 | 2005-01-18 | Waters Investment Limited | Differential scanning calorimeter accounting for heat leakage |
US6960635B2 (en) * | 2001-11-06 | 2005-11-01 | Dow Global Technologies Inc. | Isotactic propylene copolymers, their preparation and use |
JP2003176321A (en) * | 2001-12-12 | 2003-06-24 | Sumitomo Chem Co Ltd | Polypropylene-based oriented film |
ES2305371T3 (en) | 2002-06-26 | 2008-11-01 | Avery Dennison Corporation | POLYMERIC FILMS ORIENTED IN THE DIRECTION OF MACHINING. |
US8003725B2 (en) | 2002-08-12 | 2011-08-23 | Exxonmobil Chemical Patents Inc. | Plasticized hetero-phase polyolefin blends |
US7998579B2 (en) | 2002-08-12 | 2011-08-16 | Exxonmobil Chemical Patents Inc. | Polypropylene based fibers and nonwovens |
US7662885B2 (en) * | 2002-08-12 | 2010-02-16 | Exxonmobil Chemical Patents Inc. | Method to make an article comprising polymer concentrate |
US7271209B2 (en) | 2002-08-12 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Fibers and nonwovens from plasticized polyolefin compositions |
CN100345896C (en) | 2002-08-12 | 2007-10-31 | 埃克森美孚化学专利公司 | Plasticized polyolefin compositions |
US7531594B2 (en) | 2002-08-12 | 2009-05-12 | Exxonmobil Chemical Patents Inc. | Articles from plasticized polyolefin compositions |
US7476441B2 (en) * | 2002-08-30 | 2009-01-13 | Ishida Co., Ltd. | Display strip and display strip and product assembly |
DE60304778T2 (en) * | 2002-08-30 | 2006-09-21 | Ishida Co., Ltd. | Display Strip |
DE60301234T2 (en) | 2002-08-30 | 2006-05-24 | Ishida Co., Ltd. | display strip |
US20060004157A1 (en) * | 2002-09-17 | 2006-01-05 | Arriola Daniel J | Process for manufacture of polymers |
US7294681B2 (en) | 2002-10-15 | 2007-11-13 | Exxonmobil Chemical Patents Inc. | Mutliple catalyst system for olefin polymerization and polymers produced therefrom |
US8653169B2 (en) | 2002-10-15 | 2014-02-18 | Exxonmobil Chemical Patents Inc. | Propylene copolymers for adhesive applications |
US8618219B2 (en) | 2002-10-15 | 2013-12-31 | Exxonmobil Chemical Patents Inc. | Propylene copolymers for adhesive applications |
US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
US7459500B2 (en) * | 2002-11-05 | 2008-12-02 | Dow Global Technologies Inc. | Thermoplastic elastomer compositions |
WO2004054895A1 (en) * | 2002-12-17 | 2004-07-01 | Ishida Co., Ltd. | Display strip |
DE602004032419D1 (en) † | 2003-01-08 | 2011-06-09 | Exxonmobil Chem Patents Inc | ELASTIC ARTICLES AND MANUFACTURING METHOD THEREFOR |
EP1597305B1 (en) * | 2003-02-26 | 2012-10-10 | Omlidon Technologies LLC | Polymer gel-processing techniques and high modulus products |
EP1620504A1 (en) * | 2003-05-05 | 2006-02-01 | Dow Global Technologies Inc. | Filled thermoplastic olefin composition |
US8192813B2 (en) | 2003-08-12 | 2012-06-05 | Exxonmobil Chemical Patents, Inc. | Crosslinked polyethylene articles and processes to produce same |
US8158711B2 (en) | 2003-08-25 | 2012-04-17 | Dow Global Technologies Llc | Aqueous dispersion, its production method, and its use |
US8946329B2 (en) | 2003-08-25 | 2015-02-03 | Dow Global Technologies Llc | Coating compositions |
US8357749B2 (en) | 2003-08-25 | 2013-01-22 | Dow Global Technologies Llc | Coating composition and articles made therefrom |
US7763676B2 (en) * | 2003-08-25 | 2010-07-27 | Dow Global Technologies Inc. | Aqueous polymer dispersions and products from those dispersions |
US8779053B2 (en) | 2003-08-25 | 2014-07-15 | Dow Global Technologies Llc | Coating compositions |
US9169406B2 (en) | 2003-08-25 | 2015-10-27 | Dow Global Technologies Llc | Coating compositions |
US8722787B2 (en) | 2003-08-25 | 2014-05-13 | Dow Global Technologies Llc | Coating composition and articles made therefrom |
US8349929B2 (en) | 2003-08-25 | 2013-01-08 | Dow Global Technologies Llc | Coating composition and articles made therefrom |
US7803865B2 (en) | 2003-08-25 | 2010-09-28 | Dow Global Technologies Inc. | Aqueous dispersion, its production method, and its use |
EP1514893A1 (en) * | 2003-09-12 | 2005-03-16 | Borealis Technology OY | Polypropylene blown film |
WO2005049672A1 (en) | 2003-11-14 | 2005-06-02 | Exxonmobil Chemical Patents Inc. | Transparent and translucent crosslinked propylenebased elastomers, and their production and use |
US20050106978A1 (en) | 2003-11-18 | 2005-05-19 | Cheng Chia Y. | Elastic nonwoven fabrics made from blends of polyolefins and processes for making the same |
EP1942152A1 (en) | 2003-12-24 | 2008-07-09 | Dow Gloval Technologies Inc. | Polymeric composition |
US8273826B2 (en) | 2006-03-15 | 2012-09-25 | Dow Global Technologies Llc | Impact modification of thermoplastics with ethylene/α-olefin interpolymers |
WO2005090426A1 (en) | 2004-03-17 | 2005-09-29 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for higher olefin multi-block copolymer formation |
US8273838B2 (en) * | 2004-03-17 | 2012-09-25 | Dow Global Technologies Llc | Propylene/α-olefins block interpolymers |
RU2381240C2 (en) * | 2004-03-17 | 2010-02-10 | Дау Глобал Текнолоджиз Инк. | Catalyst composition containing shuttling agent for formation of ethylene multi-block copolymer |
MXPA06010485A (en) | 2004-03-17 | 2006-12-19 | Dow Global Technologies Inc | Catalyst composition comprising shuttling agent for ethylene copolymer formation. |
US7101623B2 (en) * | 2004-03-19 | 2006-09-05 | Dow Global Technologies Inc. | Extensible and elastic conjugate fibers and webs having a nontacky feel |
US8182456B2 (en) * | 2004-03-29 | 2012-05-22 | The Procter & Gamble Company | Disposable absorbent articles with components having both plastic and elastic properties |
US20050215972A1 (en) | 2004-03-29 | 2005-09-29 | Roe Donald C | Disposable absorbent articles with zones comprising elastomeric components |
US7820875B2 (en) | 2004-03-29 | 2010-10-26 | The Procter & Gamble Company | Disposable absorbent articles being adaptable to wearer's anatomy |
US7598328B2 (en) | 2004-04-07 | 2009-10-06 | Dow Global Technologies, Inc. | Supported catalysts for manufacture of polymers |
US7645829B2 (en) | 2004-04-15 | 2010-01-12 | Exxonmobil Chemical Patents Inc. | Plasticized functionalized propylene copolymer adhesive composition |
ES2311221T3 (en) * | 2004-04-19 | 2009-02-01 | Dow Global Technologies Inc. | SUITABLE COMPOSITION FOR A STRETCHING ADHERENT FILM, LOW NOISE OF A SINGLE FACE AND FILMS MANUFACTURED FROM THE SAME. |
ATE499465T1 (en) * | 2004-04-30 | 2011-03-15 | Dow Global Technologies Inc | IMPROVED NON-WOVEN FABRIC AND IMPROVED FIBERS |
JP4928939B2 (en) * | 2004-06-11 | 2012-05-09 | 株式会社イシダ | Display strip and product display |
ATE504349T1 (en) * | 2004-06-16 | 2011-04-15 | Dow Global Technologies Inc | METHOD FOR SELECTING POLYMERIZATION MODIFIERS |
GB2438843B (en) * | 2004-07-08 | 2009-04-29 | Ishida Seisakusho | Display strip and commodity display unit |
WO2006020624A1 (en) * | 2004-08-09 | 2006-02-23 | Dow Global Technologies Inc. | Supported bis(hydroxyarylaryloxy) catalysts for manufacture of polymers |
JP5065022B2 (en) * | 2004-08-09 | 2012-10-31 | ダウ グローバル テクノロジーズ エルエルシー | Functionalized poly (4-methyl-1-pentene) |
CA2577290C (en) * | 2004-08-13 | 2011-03-08 | Srivatsan Srinivas Iyer | Polymeric compositions including their uses and methods of production |
WO2006018813A1 (en) * | 2004-08-18 | 2006-02-23 | Basell Poliolefine Italia S.R.L. | Stretch blow-molded containers from ziegler natta propylene polymer compositions |
SG156639A1 (en) * | 2004-10-13 | 2009-11-26 | Exxonmobil Chem Patents Inc | Elastomeric reactor blend compositions |
US20080265464A1 (en) * | 2004-10-22 | 2008-10-30 | D Hooghe Edward L | Apparatus and Process for Manufacturing Shaped Plastic Reinforced Composite Articles |
JP4043471B2 (en) | 2004-10-26 | 2008-02-06 | 株式会社イシダ | Display strip and product display |
US7745526B2 (en) | 2004-11-05 | 2010-06-29 | Exxonmobil Chemical Patents Inc. | Transparent polyolefin compositions |
US7829623B2 (en) * | 2004-11-05 | 2010-11-09 | Exxonmobil Chemical Patents Inc. | Thermoplastic vulcanizates having improved fabricability |
US7473750B2 (en) * | 2004-12-07 | 2009-01-06 | Fina Technology, Inc. | Random copolymers and formulations useful for thermoforming and blow molding applications |
CN101076621A (en) * | 2004-12-13 | 2007-11-21 | 巴塞尔聚烯烃意大利有限责任公司 | Polyolefin composition, fibres and nonwoven fabrics |
US20070202285A1 (en) * | 2004-12-15 | 2007-08-30 | Fina Technology, Inc. | Articles having improved clarity, prepared from propylene-ethylene copolymers |
US8709560B2 (en) * | 2004-12-16 | 2014-04-29 | Exxonmobil Chemical Patents Inc. | Polymeric compositions including their uses and methods of production |
DE602005016302D1 (en) | 2004-12-17 | 2009-10-08 | Exxonmobil Chem Patents Inc | HETEROGENIC POLYMER BLENDS AND FORM BODY THEREOF |
ATE440909T1 (en) | 2004-12-17 | 2009-09-15 | Exxonmobil Chem Patents Inc | POLYMER BLENDS AND NON-WOVEN MATERIALS THEREOF |
US8389615B2 (en) | 2004-12-17 | 2013-03-05 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin |
EP1831304B1 (en) | 2004-12-17 | 2010-05-12 | ExxonMobil Chemical Patents Inc. | Homogeneous polymer blend and articles therefrom |
US7683129B2 (en) | 2004-12-17 | 2010-03-23 | Exxonmobil Chemical Patents Inc. | Films from polymer blends |
US8536268B2 (en) | 2004-12-21 | 2013-09-17 | Dow Global Technologies Llc | Polypropylene-based adhesive compositions |
US8013069B2 (en) * | 2005-01-31 | 2011-09-06 | Exxonmobil Chemical Patents Inc. | Polymer blends and pellets and methods of producing same |
US7803876B2 (en) * | 2005-01-31 | 2010-09-28 | Exxonmobil Chemical Patent Inc. | Processes for producing polymer blends and polymer blend pellets |
US7855263B2 (en) * | 2005-02-03 | 2010-12-21 | Basell Polyolefine Gmbh | Process for producing thermoformed articles |
US7414006B2 (en) * | 2005-03-09 | 2008-08-19 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins |
WO2006099053A1 (en) * | 2005-03-09 | 2006-09-21 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins |
US7910658B2 (en) * | 2005-03-17 | 2011-03-22 | Dow Global Technologies Llc | Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates |
US9410009B2 (en) | 2005-03-17 | 2016-08-09 | Dow Global Technologies Llc | Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation |
KR101263966B1 (en) | 2005-03-17 | 2013-05-13 | 다우 글로벌 테크놀로지스 엘엘씨 | Catalyst composition comprising shuttling agent for regio-irregular multi-block copolymer formation |
CN101466752B (en) | 2005-03-17 | 2012-09-26 | 陶氏环球技术有限责任公司 | Compositions of ethylene/alpha-olefin multi-block interpolymer suitable for films |
US20060210741A1 (en) * | 2005-03-17 | 2006-09-21 | Cryovac, Inc. | Retortable packaging film with having seal/product-contact layer containing blend of polyethylenes and skin layer containing propylene-based polymer blended with polyethylene |
BRPI0609825B1 (en) | 2005-03-17 | 2023-05-16 | Dow Global Technologies Inc | COMPOSITION AND ARTICLE |
BRPI0609835A2 (en) | 2005-03-17 | 2010-05-04 | Dow Global Technologies Inc | copolymer, process for preparing a multiblock copolymer, multiblock copolymer, functionalized derivative, homogeneous polymer blend, and polymer |
ZA200707881B (en) | 2005-03-17 | 2008-12-31 | Dow Global Technologies Inc | Impact modification of thermoplastics with ethylene/alpha-olefin interpolymers |
MX2007013072A (en) * | 2005-04-19 | 2008-01-14 | Dow Global Technologies Inc | Composition suitable for high gloss blown film and films made therefrom. |
US7517569B2 (en) | 2005-06-06 | 2009-04-14 | Cryovac, Inc. | Shrink packaging barrier film |
EP1896537B1 (en) | 2005-06-24 | 2017-10-11 | ExxonMobil Chemical Patents Inc. | Functionalized propylene copolymer adheside composition |
US8287949B2 (en) | 2005-07-07 | 2012-10-16 | Dow Global Technologies Inc. | Aqueous dispersions |
WO2007011541A1 (en) | 2005-07-15 | 2007-01-25 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions |
US7935301B2 (en) | 2005-08-01 | 2011-05-03 | Cryovac, Inc. | Method of thermoforming |
TW200713336A (en) * | 2005-08-05 | 2007-04-01 | Dow Global Technologies Inc | Polypropylene-based wire and cable insulation or jacket |
US7858707B2 (en) | 2005-09-15 | 2010-12-28 | Dow Global Technologies Inc. | Catalytic olefin block copolymers via polymerizable shuttling agent |
JP5230426B2 (en) | 2005-09-15 | 2013-07-10 | ダウ グローバル テクノロジーズ エルエルシー | Control of polymer structure and molecular weight distribution by multi-center shuttling agent (MULTI-CENTERRED SHUTTLINGAGENT) |
EP1931686B1 (en) * | 2005-09-28 | 2012-08-01 | Dow Global Technologies LLC | High activity, low molecular weight olefin polymerization process |
TWI386310B (en) * | 2005-10-07 | 2013-02-21 | Dow Global Technologies Llc | Multilayer elastic film structures |
JP2009513396A (en) | 2005-10-26 | 2009-04-02 | ダウ グローバル テクノロジーズ インコーポレイティド | Multilayer elastic article |
US7807593B2 (en) * | 2005-10-26 | 2010-10-05 | Dow Global Technologies Inc. | Multi-layer, pre-stretched elastic articles |
KR101353124B1 (en) * | 2005-10-31 | 2014-01-17 | 다우 글로벌 테크놀로지스 엘엘씨 | Propylene-based elastomeric composition |
US7737206B2 (en) | 2005-11-18 | 2010-06-15 | Exxonmobil Chemical Patents Inc. | Polyolefin composition with high filler loading capacity |
US8153243B2 (en) | 2005-12-09 | 2012-04-10 | Dow Global Technologies Llc | Interpolymers suitable for multilayer films |
KR20080080526A (en) * | 2005-12-09 | 2008-09-04 | 다우 글로벌 테크놀로지스 인크. | Processes of controlling molecular weight distribution in ethylene/alpha-olefin compositions |
US8282776B2 (en) | 2005-12-15 | 2012-10-09 | Kimberly-Clark Worldwide, Inc. | Wiping product having enhanced oil absorbency |
US7879191B2 (en) | 2005-12-15 | 2011-02-01 | Kimberly-Clark Worldwide, Inc. | Wiping products having enhanced cleaning abilities |
KR101353189B1 (en) * | 2005-12-22 | 2014-01-17 | 다우 글로벌 테크놀로지스 엘엘씨 | Blends of Styrenic Block Copolymers and Propylene-Alpha Olefin Copolymers |
WO2007092136A2 (en) * | 2006-02-03 | 2007-08-16 | Exxonmobil Chemical Patents, Inc. | Process for generating alpha olefin comonomers |
US7982085B2 (en) * | 2006-02-03 | 2011-07-19 | Exxonmobil Chemical Patents Inc. | In-line process for generating comonomer |
US8003839B2 (en) * | 2006-02-03 | 2011-08-23 | Exxonmobil Chemical Patents Inc. | Process for generating linear apha olefin comonomers |
AU2007226554A1 (en) * | 2006-03-15 | 2007-09-20 | Dow Global Technologies Inc. | Propylene/alpha-olefins block interpolymers |
EP1840164A1 (en) * | 2006-03-30 | 2007-10-03 | SOLVAY INDUSTRIAL FOILS MANAGEMENT AND RESEARCH (Société Anonyme) | Retortable composition |
CN101583476A (en) * | 2006-04-19 | 2009-11-18 | 陶氏环球技术公司 | Thermoplastic articles and improved processes for making the same |
US9163141B2 (en) * | 2006-04-27 | 2015-10-20 | Cryovac, Inc. | Polymeric blend comprising polylactic acid |
US8206796B2 (en) * | 2006-04-27 | 2012-06-26 | Cryovac, Inc. | Multilayer film comprising polylactic acid |
JP2009536202A (en) * | 2006-05-05 | 2009-10-08 | ダウ グローバル テクノロジーズ インコーポレイティド | Improved hafnium complexes of heterocyclic organic ligands |
EP2021381B1 (en) * | 2006-05-05 | 2015-12-23 | Dow Global Technologies LLC | Hafnium complexes of heterocyclic organic ligands |
RU2008147910A (en) * | 2006-05-05 | 2010-06-10 | Дау Глобал Текнолоджиз Инк. (Us) | ORTHO-METALED HAPHNIC COMPLEXES OF IMIDAZOLE LIGANES |
US20080003332A1 (en) * | 2006-05-12 | 2008-01-03 | Dimitrios Ginossatis | Multilayer heat shrinkable cook-in film |
KR101397337B1 (en) | 2006-05-17 | 2014-05-19 | 다우 글로벌 테크놀로지스 엘엘씨 | High Efficiency Solution Polymerization Process |
EP2049333B1 (en) | 2006-06-14 | 2012-12-05 | Avery Dennison Corporation | Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing |
WO2007149900A2 (en) * | 2006-06-20 | 2007-12-27 | Avery Dennison Corporation | Multilayered polymeric film for hot melt adhesive labeling and label stock and label thereof |
EP2041221B1 (en) | 2006-06-29 | 2014-06-04 | Dow Global Technologies LLC | PROCESSES and kit FOR MAKING THERMOPLASTIC ARTICLES USING AN IMPROVED MASTERBATCH |
US8785531B2 (en) * | 2006-07-06 | 2014-07-22 | Dow Global Technologies Llc | Dispersions of olefin block copolymers |
WO2008016518A2 (en) | 2006-08-02 | 2008-02-07 | Exxonmobil Chemical Patents Inc. | Propylene-based polymer article |
US8404915B2 (en) * | 2006-08-30 | 2013-03-26 | Exxonmobil Chemical Patents Inc. | Phosphine ligand-metal compositions, complexes, and catalysts for ethylene trimerizations |
US8476326B2 (en) * | 2006-09-22 | 2013-07-02 | Dow Global Technologies Llc | Fibrillated polyolefin foam |
EP2079813B1 (en) * | 2006-10-30 | 2012-09-26 | Dow Global Technologies LLC | Adhesive films |
JP5061842B2 (en) * | 2006-11-01 | 2012-10-31 | 王子製紙株式会社 | Biaxially stretched polypropylene film |
CA2668397A1 (en) | 2006-11-01 | 2008-05-15 | Dow Global Technologies Inc. | Articles comprising nonpolar polyolefin and polyurethane, and methods for their preparation and use |
CN101595252A (en) | 2006-11-30 | 2009-12-02 | 陶氏环球技术公司 | The olefin block compositions that is used for heavy weight stretch fabrics |
US7776770B2 (en) * | 2006-11-30 | 2010-08-17 | Dow Global Technologies Inc. | Molded fabric articles of olefin block interpolymers |
CN101589081A (en) * | 2006-11-30 | 2009-11-25 | 陶氏环球技术公司 | Olefin block compositions for stretch fabric with wrinkle resistance |
US20100093937A1 (en) * | 2006-12-05 | 2010-04-15 | Pham Hoang T | Polar group functionalized co-polymers |
US7785443B2 (en) * | 2006-12-07 | 2010-08-31 | Kimberly-Clark Worldwide, Inc. | Process for producing tissue products |
US8075830B2 (en) * | 2006-12-15 | 2011-12-13 | Fina Technology, Inc. | Polypropylene blown film |
US8242237B2 (en) | 2006-12-20 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Phase separator and monomer recycle for supercritical polymerization process |
BRPI0719500B1 (en) | 2006-12-21 | 2023-10-10 | Dow Global Technologies Inc | PROCESS FOR PREPARING A FUNCTIONALIZED MULTIBLOCK OLEFIN INTERPOLYMER AND PROCESS FOR PREPARING AN IMIDE FUNCTIONALIZED MULTIBLOCK INTERPOLYMER |
JP5007116B2 (en) * | 2006-12-27 | 2012-08-22 | 日本ポリプロ株式会社 | Process for producing olefin copolymer |
WO2008082975A1 (en) * | 2006-12-29 | 2008-07-10 | Dow Global Technologies Inc. | Compositions |
ES2348323T3 (en) * | 2007-01-12 | 2010-12-02 | Dow Global Technologies Inc. | SUITABLE COMPOSITION FOR THIN-WALL INJECTION-MOLDED ARTICLES. |
US20080184498A1 (en) * | 2007-01-16 | 2008-08-07 | Dow Global Technologies Inc. | Colorfast fabrics and garments of olefin block compositions |
EP2122023A1 (en) | 2007-01-16 | 2009-11-25 | Dow Global Technologies Inc. | Cone dyed yarns of olefin block compositions |
US8728960B2 (en) * | 2007-01-19 | 2014-05-20 | Exxonmobil Chemical Patents Inc. | Spunbond fibers and fabrics from polyolefin blends |
US7951732B2 (en) | 2007-01-26 | 2011-05-31 | Exxonmobil Chemical Patents Inc. | Elastomeric laminates for consumer products |
US8247512B2 (en) * | 2007-03-05 | 2012-08-21 | Fina Technology, Inc. | Metallocene random copolymers with cool temperature impact properties |
JP2010520366A (en) * | 2007-03-06 | 2010-06-10 | エクソンモービル・ケミカル・パテンツ・インク | Polymer produced under supersolution conditions |
US8362163B2 (en) | 2007-03-07 | 2013-01-29 | Dow Global Technologies, Llc | Tethered supported transition metal complex |
CN101679697B (en) * | 2007-04-24 | 2014-05-21 | 陶氏环球技术有限责任公司 | Thermoforming, scratch-resistant, low gloss compositions comprising interpolymers of ethylene/alpha-olefins |
ES2380973T3 (en) * | 2007-04-26 | 2012-05-22 | Flexopack S.A. Plastics Industry | Overlay sealable shrink film |
WO2008134173A1 (en) * | 2007-05-01 | 2008-11-06 | Advanced Elastomer Systems, L.P. | Method for preparing thermoplastic vulcanizates |
ITMI20070878A1 (en) | 2007-05-02 | 2008-11-03 | Dow Global Technologies Inc | PROCESS FOR POLYMERIZZAINE OF TACTICAL POLYMERS USING CHIRAL CATALYSTS |
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 |
US8241753B2 (en) | 2007-06-04 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Composite thermoplastic elastomer structures with high adhesion performance and uses for the same |
KR20100041818A (en) * | 2007-07-09 | 2010-04-22 | 다우 글로벌 테크놀로지스 인크. | Olefin block interpolymer composition suitable for fibers |
CN104212538A (en) * | 2007-07-13 | 2014-12-17 | 陶氏环球技术有限责任公司 | Viscosity index improver for lubricant compositions |
CN101802086B (en) | 2007-07-13 | 2013-10-02 | 陶氏环球技术有限责任公司 | Catalytic olefin block copolymers with controlled block sequence distribution and at least one low crystallinity hard block |
WO2009012215A1 (en) | 2007-07-13 | 2009-01-22 | Dow Global Technologies Inc. | Ethylene/a-olefin interpolymers containing low crystallinity hard blocks |
US8492322B2 (en) * | 2007-07-13 | 2013-07-23 | Dow Global Technologies, Llc | Viscosity index improver for lubricant compositions |
ATE492396T1 (en) | 2007-08-13 | 2011-01-15 | Tesa Se | RELEASE AGENT BASED ON ETHYLENE MULTI-BLOCK COPOLYMER |
ES2353038T3 (en) | 2007-08-13 | 2011-02-24 | Tesa Se | ADHESIVE BAND WITH A SUPPORT OF AT LEAST A FOAM COAT. |
GB0717376D0 (en) | 2007-09-07 | 2007-10-17 | Exxonmobil Chem Patents Inc | Composition and manufacture thereof |
JP5201923B2 (en) * | 2007-09-19 | 2013-06-05 | 日本ポリプロ株式会社 | Propylene polymer production method |
EP2042552A1 (en) * | 2007-09-27 | 2009-04-01 | Borealis Technology Oy | Polyolefin compositions having improved optical and mechanical properties |
EP2203512A1 (en) * | 2007-09-28 | 2010-07-07 | Dow Global Technologies Inc. | Thermoplastic olefin composition with improved heat distortion temperature |
CN101835838B (en) | 2007-10-22 | 2014-03-12 | 陶氏环球技术公司 | Polymeric compositions and method for molding articles |
US8609772B2 (en) | 2007-10-23 | 2013-12-17 | Exxonmobil Chemical Patents Inc. | Elastic films having improved mechanical and elastic properties and methods for making the same |
US8420760B2 (en) * | 2007-11-19 | 2013-04-16 | Dow Global Technologies Llc | Long chain branched propylene-alpha-olefin copolymers |
BRPI0819051A2 (en) * | 2007-12-05 | 2015-05-05 | Dow Global Technologies Inc | Resin, film and retort pouch composition |
US8138269B2 (en) | 2007-12-20 | 2012-03-20 | Exxonmobil Research And Engineering Company | Polypropylene ethylene-propylene copolymer blends and in-line process to produce them |
EP2077297B1 (en) * | 2008-01-02 | 2012-04-04 | Flexopack S A | PVDC formulation and heat shrinkable film |
AU2008264215A1 (en) * | 2008-01-03 | 2009-07-23 | Flexopack S.A. | Thermoforming film |
EP2085216B1 (en) * | 2008-01-29 | 2016-04-20 | Flexopack S A | Thin film for waste packing cassettes |
KR20160125531A (en) * | 2008-01-30 | 2016-10-31 | 다우 글로벌 테크놀로지스 엘엘씨 | PROPYLENE/α-OLEFIN BLOCK INTERPOLYMERS |
US20110039082A1 (en) | 2008-02-29 | 2011-02-17 | Yun Xiaobing B | Oriented Films Comprising Ethylene/a-Olefin Block Interpolymer |
US7858817B2 (en) | 2008-03-10 | 2010-12-28 | Exxonmobil Chemical Patents Inc. | Metallocene-substituted pyridyl amines, their metal complexes, and processes for production and use thereof |
BRPI0906178B1 (en) * | 2008-03-14 | 2021-07-20 | Dow Global Technologies Inc. | PROCESS FOR MANUFACTURING A MOLDED ARTICLE |
ATE541699T1 (en) * | 2008-04-21 | 2012-02-15 | Flexopack S A Plastics Industry | STACK SEAL SHRINK FILM |
US8669329B2 (en) | 2008-04-24 | 2014-03-11 | Sumitomo Chemical Company, Limited | Thermoplastic elastomer composition, a method for producing a molded body, and a molded body |
US7867433B2 (en) | 2008-05-30 | 2011-01-11 | Exxonmobil Chemical Patents Inc. | Polyolefin-based crosslinked articles |
US8765832B2 (en) | 2011-10-14 | 2014-07-01 | Exxonmobil Chemical Patents Inc. | Polyolefin-based crosslinked compositions and methods of making them |
US8242198B2 (en) | 2008-06-09 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions |
US8283400B2 (en) * | 2008-06-09 | 2012-10-09 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions |
US8431642B2 (en) * | 2008-06-09 | 2013-04-30 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
SG10201805188YA (en) | 2008-06-18 | 2018-07-30 | Dow Global Technologies Inc | Processes to control fouling and improve compositions |
WO2009158100A2 (en) | 2008-06-27 | 2009-12-30 | Exxonmobil Chemical Patents Inc. | High shrinkage propylene-based films |
WO2010003047A1 (en) * | 2008-07-02 | 2010-01-07 | Dow Global Technologies Inc. | Films and articles with good taste and/or odor performance |
PL2147783T3 (en) * | 2008-07-23 | 2018-10-31 | Flexopack S.A. | Stack sealable heat shrinkable film |
WO2010016847A1 (en) | 2008-08-08 | 2010-02-11 | Exxonmobil Chemical Patents Inc. | Improved olefinic copolymer compositions for viscosity modification of motor oil |
WO2010022228A2 (en) * | 2008-08-21 | 2010-02-25 | Dow Global Technologies, Inc. | Metal-ligand complexes and catalysts |
US8664129B2 (en) | 2008-11-14 | 2014-03-04 | Exxonmobil Chemical Patents Inc. | Extensible nonwoven facing layer for elastic multilayer fabrics |
US9498932B2 (en) | 2008-09-30 | 2016-11-22 | Exxonmobil Chemical Patents Inc. | Multi-layered meltblown composite and methods for making same |
US9168718B2 (en) | 2009-04-21 | 2015-10-27 | Exxonmobil Chemical Patents Inc. | Method for producing temperature resistant nonwovens |
US10161063B2 (en) | 2008-09-30 | 2018-12-25 | Exxonmobil Chemical Patents Inc. | Polyolefin-based elastic meltblown fabrics |
US8709610B2 (en) | 2008-10-17 | 2014-04-29 | Dow Global Technologies Llc | Biaxially oriented film which could be thermally laminated with paper and other substrates |
US20100119855A1 (en) * | 2008-11-10 | 2010-05-13 | Trazollah Ouhadi | Thermoplastic Elastomer with Excellent Adhesion to EPDM Thermoset Rubber and Low Coefficient of Friction |
US8088872B2 (en) * | 2008-11-25 | 2012-01-03 | Dow Global Technologies Llc | Procatalyst composition including silyl ester internal donor and method |
EP2356158B1 (en) | 2008-12-12 | 2018-12-26 | Dow Global Technologies LLC | Coating composition, a process of producing a coating composition, a coated article, and a method of forming such articles |
US8829083B2 (en) | 2008-12-16 | 2014-09-09 | Dow Global Technologies Llc | Coating composition, a process of producing a coating composition, a coated article, and a method of making such articles |
CN104438026B (en) | 2008-12-22 | 2018-05-15 | 陶氏环球技术有限责任公司 | Woven carpet coating compound, relevant application method and the product as made from the mixture |
TW201035411A (en) * | 2008-12-25 | 2010-10-01 | Mitsui Chemicals Inc | Aqueous dispersion for treatment of fibers |
SG172447A1 (en) | 2008-12-31 | 2011-08-29 | Dow Global Technologies Llc | Procatalyst composition with substituted 1,2-phenylene aromatic diester internal donor and method |
RU2522435C2 (en) | 2008-12-31 | 2014-07-10 | ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи | Improved procatalyst composition and method for production thereof |
CN102300922B (en) | 2009-01-30 | 2013-07-31 | 陶氏环球技术有限责任公司 | Polymeric compositions and filled tpo articles having improved aesthetics |
EP2401324B1 (en) | 2009-02-25 | 2013-08-21 | Dow Global Technologies LLC | Phylon processes of making foam articles comprising ethylene/ -olefins block interpolymers |
JP5650138B2 (en) | 2009-02-27 | 2015-01-07 | エクソンモービル・ケミカル・パテンツ・インク | Multilayer nonwoven in situ laminate and method for producing the same |
CN102414258B (en) | 2009-03-16 | 2014-03-26 | 陶氏环球技术有限责任公司 | A dispersion, and a process for producing the same |
US8105463B2 (en) | 2009-03-20 | 2012-01-31 | Kimberly-Clark Worldwide, Inc. | Creped tissue sheets treated with an additive composition according to a pattern |
EP2995449A1 (en) | 2009-03-20 | 2016-03-16 | Dow Global Technologies LLC | Multilayer structure and method of making the same |
US20120046409A1 (en) | 2009-03-30 | 2012-02-23 | Dow Global Technologies Llc | Hybrid dispersions and methods for producing the same |
WO2010138253A2 (en) * | 2009-05-29 | 2010-12-02 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and method of making thereof |
US8318874B2 (en) | 2009-06-26 | 2012-11-27 | Dow Global Technologies Llc | Process of selectively polymerizing ethylene and catalyst therefor |
CN102497981B (en) * | 2009-07-16 | 2016-12-07 | 陶氏环球技术有限责任公司 | Based on polyolefinic dermatine |
US8158733B2 (en) | 2009-07-22 | 2012-04-17 | Equistar Chemicals, Lp | Catalysts based on 2-(2-aryloxy)quinoline or 2-(2-aryloxy)dihydroquinoline ligands |
US8153544B2 (en) * | 2009-07-22 | 2012-04-10 | Equistar Chemicals, Lp | Method for preparing non-metallocene catalysts |
US7858718B1 (en) | 2009-07-22 | 2010-12-28 | Equistar Chemicals, Lp | Catalysts based on 2-aryl-8-anilinoquinoline ligands |
US8975334B2 (en) | 2009-07-23 | 2015-03-10 | Exxonmobil Chemical Patents Inc. | Crosslinkable propylene-based copolymers, methods for preparing the same, and articles made therefrom |
EP3202681B1 (en) | 2009-07-24 | 2021-04-21 | Dow Global Technologies LLC | Method of making a coated container device |
BR112012000451B1 (en) | 2009-07-24 | 2019-09-03 | Dow Global Technologies Llc | coated container device and method for making a coated container device |
ES2894689T3 (en) | 2009-07-29 | 2022-02-15 | Dow Global Technologies Llc | Chain transfer agents and their use for the preparation of block copolymers |
KR101621703B1 (en) | 2009-07-29 | 2016-05-17 | 다우 글로벌 테크놀로지스 엘엘씨 | Multifunctional chain shuttling agents |
DE112010003197T5 (en) | 2009-08-06 | 2012-06-28 | Dow Global Technologies Llc | "High frequency sealable film, sealed film structure and method of making the same |
US20110054117A1 (en) * | 2009-08-27 | 2011-03-03 | Hall Gregory K | Polyolefin Adhesive Compositions and Method of Making Thereof |
US20110054122A1 (en) * | 2009-08-31 | 2011-03-03 | Jerzy Klosin | Catalyst and process for polymerizing an olefin and polyolefin prepared thereby |
US8394892B2 (en) * | 2009-09-14 | 2013-03-12 | Sumitomo Chemical Company, Ltd. | High performance thermoplastic elastomer composition |
CN102791251B (en) * | 2009-09-15 | 2015-07-01 | 联合碳化化学品及塑料技术公司 | Personal care compositions with ethylene acrylic acid copolymer aqueous dispersions |
JP5937511B2 (en) * | 2009-09-15 | 2016-06-22 | ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー | Silicone replacement for personal care compositions |
US8686087B2 (en) | 2009-10-02 | 2014-04-01 | Dow Global Technologies Llc | Block composites in soft compounds |
US20120208946A1 (en) | 2009-10-02 | 2012-08-16 | Dow Global Technologies Llc | Block copolymers in soft compounds |
SG178395A1 (en) * | 2009-10-02 | 2012-03-29 | Exxonmobil Chem Patents Inc | Crosslinked polyolefin polymer blends |
US8802774B2 (en) | 2009-10-02 | 2014-08-12 | Dow Global Technologies Llc | Block composites and impact modified compositions |
CN102770487B (en) | 2009-10-02 | 2014-10-01 | 陶氏环球技术有限责任公司 | Block composites in thermoplastic vulcanizate applications |
US9458310B2 (en) | 2009-10-16 | 2016-10-04 | Exxonmobil Chemical Patents Inc. | Modified polyethylene film compositions |
US9200177B2 (en) * | 2009-10-30 | 2015-12-01 | Dow Global Technologies Llc | Alkyd dispersion, and a process for producing the same |
US8829106B2 (en) | 2009-11-20 | 2014-09-09 | Dow Global Technologies Llc | Thermoplastic elastomer for cold and wet applications |
US8668975B2 (en) | 2009-11-24 | 2014-03-11 | Exxonmobil Chemical Patents Inc. | Fabric with discrete elastic and plastic regions and method for making same |
GB2475961B (en) * | 2009-12-02 | 2015-07-08 | Flexopack Sa | Thin film for waste packing cassettes |
WO2011068525A1 (en) | 2009-12-04 | 2011-06-09 | Dow Global Technologies Inc. | Extruder screw |
EP2516708B1 (en) | 2009-12-23 | 2016-02-17 | Invista Technologies S.à.r.l. | Polyolefin elastic fiber |
MX337858B (en) | 2009-12-23 | 2016-03-18 | INVISTA Technologies S à r l | Fabric including polylefin elastic fiber. |
WO2011087693A2 (en) | 2009-12-23 | 2011-07-21 | Invista Technologies S.A R.1. | Elastic fiber containing an anti-tack additive |
CN107411883A (en) | 2009-12-23 | 2017-12-01 | 英威达技术有限公司 | Elastic article including polyolefin elastic fiber |
WO2011079457A1 (en) | 2009-12-31 | 2011-07-07 | Dow Global Technologies Inc. | Halogen-free, flame retardant thermoplastic compositions for wire and cable applications |
EP2529044B1 (en) * | 2010-01-28 | 2014-04-09 | Borealis AG | Melt blown fiber |
US8729201B2 (en) * | 2010-02-19 | 2014-05-20 | Dow Global Technologies Llc | Process for polymerizing an olefin monomer and catalyst therefor |
EP2536735B1 (en) * | 2010-02-19 | 2018-08-01 | Dow Global Technologies LLC | Metal-ligand complexes and catalysts |
KR101167172B1 (en) | 2010-02-26 | 2012-07-24 | 현대제철 주식회사 | Method for calculating length and width in rolling process |
US20110218283A1 (en) * | 2010-03-02 | 2011-09-08 | Nadeem Akhtar Bokhari | Reactor thermoplastic polyolefin elastomer composition |
BR112012022587B1 (en) * | 2010-03-26 | 2019-06-18 | Union Carbide Chemicals & Plastics Technology Llc | COMPOSITION FOR HAIR COLORING AND METHOD FOR REDUCING CAPILLARY DAMAGE FROM COMPOSITION FOR HAIR COLORING |
EP2569368B1 (en) | 2010-05-10 | 2017-06-14 | Dow Global Technologies LLC | Adhesion promoter system, and method of producing the same |
US20130059165A1 (en) | 2010-05-10 | 2013-03-07 | Dow Global Technologies Llc | Adhesion promoter system, and method of producing the same |
WO2011142946A1 (en) | 2010-05-10 | 2011-11-17 | Dow Global Technologies Llc | Adhesion promoter system, and method of producing the same |
JP2013532197A (en) | 2010-05-10 | 2013-08-15 | ダウ グローバル テクノロジーズ エルエルシー | Adhesion promoter system and method of manufacturing the same |
EP3150375A1 (en) | 2010-05-18 | 2017-04-05 | Dow Global Technologies LLC | A multilayer sheet, a thermoformed article, and a method for making the same |
WO2011156579A2 (en) | 2010-06-10 | 2011-12-15 | Union Carbide Chemicals & Plastics Technology Llc | Personal care compositions with ethylene acrylic acid copolymer aqueous dispersions |
KR20190141798A (en) | 2010-06-18 | 2019-12-24 | 다우 글로벌 테크놀로지스 엘엘씨 | Coated polymeric particulates, and a process for coating polymeric particulates |
JP5860043B2 (en) | 2010-06-21 | 2016-02-16 | ダウ グローバル テクノロジーズ エルエルシー | Crystalline block composites as compatibilizers |
SG186414A1 (en) | 2010-06-21 | 2013-01-30 | Dow Global Technologies Llc | Crystalline block composites as compatibilizers |
WO2011163189A1 (en) | 2010-06-21 | 2011-12-29 | Dow Global Technologies Llc | Crystalline block composites as compatibilizers |
US8822599B2 (en) | 2010-06-21 | 2014-09-02 | Dow Global Technologies Llc | Crystalline block composites as compatibilizers |
CN103068894A (en) | 2010-06-23 | 2013-04-24 | 陶氏环球技术有限责任公司 | Masterbatch composition |
US20120016092A1 (en) | 2010-07-14 | 2012-01-19 | Sandor Nagy | Catalysts based on quinoline precursors |
WO2012015624A1 (en) | 2010-07-27 | 2012-02-02 | Dow Global Technologies Llc | Low-density web and method of applying an additive composition thereto |
US8445393B2 (en) | 2010-07-27 | 2013-05-21 | Kimberly-Clark Worldwide, Inc. | Low-density web and method of applying an additive composition thereto |
WO2012027448A1 (en) | 2010-08-25 | 2012-03-01 | Dow Global Technologies Llc | Process for polymerizing a polymerizable olefin and catalyst therefor |
CN103328565B (en) | 2010-09-15 | 2015-08-26 | 陶氏环球技术有限责任公司 | There is the propylene-alpha-olefin copolymers composition of the foaming window of improvement |
WO2012037180A1 (en) | 2010-09-16 | 2012-03-22 | Dow Global Technologies Llc | Coextruded multilayer film structure |
US8907034B2 (en) | 2010-09-30 | 2014-12-09 | Dow Global Technologies Llc | Comb architecture olefin block copolymers |
BR112013008316A2 (en) | 2010-10-20 | 2016-06-14 | Rohm & Haas | hair fixative makeup, use of makeup and method for styling hair |
WO2012061168A1 (en) | 2010-11-02 | 2012-05-10 | Dow Global Technologies Llc | A sealant composition, method of producing the same |
US8986663B2 (en) | 2010-11-04 | 2015-03-24 | Rohm And Haas Company | Skin care compositions |
WO2012061706A1 (en) | 2010-11-04 | 2012-05-10 | Dow Global Technologies Llc | Double shuttling of polyolefin polymeryl chains |
US20120116034A1 (en) * | 2010-11-08 | 2012-05-10 | Dow Global Technologies, Inc. | Solution polymerization process and procatalyst carrier systems useful therein |
CN103328564B (en) | 2010-11-24 | 2016-08-24 | 陶氏环球技术有限责任公司 | Including propylene-alpha-olefin copolymers, olefin block copolymers and the compositions of DPO-BSA molecule melt |
WO2012082624A2 (en) | 2010-12-17 | 2012-06-21 | Dow Global Technologies Llc | Ethylene acrylic acid copolymer aqueous dispersions for fragrance release in laundry detergents |
WO2012079243A1 (en) | 2010-12-17 | 2012-06-21 | Dow Global Technologies Llc | Halogen-free, flame retardant composition for wire and cable applications |
KR101843217B1 (en) | 2010-12-30 | 2018-03-28 | 다우 글로벌 테크놀로지스 엘엘씨 | Thermoplastic vulcanizate composition, method of producing the same, and articles made therefrom |
WO2012094315A1 (en) | 2011-01-03 | 2012-07-12 | Dow Global Technologies Llc | Microcapillary films and foams containing functional filler materials |
WO2012094317A1 (en) | 2011-01-03 | 2012-07-12 | Dow Global Technologies Llc | Reinforced microcapillary films and foams |
WO2012103080A1 (en) | 2011-01-26 | 2012-08-02 | Dow Global Technologies Llc | Process for making a polyolefin-polysiloxane block copolymer |
US9631115B2 (en) | 2011-04-08 | 2017-04-25 | Dow Global Technologies Llc | Coating composition, and a process for producing the same |
EP2520518B1 (en) | 2011-05-03 | 2020-09-23 | Flexopack S.A. | Waste packaging device |
WO2012155022A1 (en) | 2011-05-12 | 2012-11-15 | Dow Global Technologies Llc | Non-cyclopentadienyl-based chromium catalysts for olefin polymerization |
EP2535279B1 (en) | 2011-06-16 | 2016-11-16 | Flexopack S.A. | Waste packaging system and film |
JP5768184B2 (en) | 2011-06-21 | 2015-08-26 | ダウ グローバル テクノロジーズ エルエルシー | Halogen-free flame retardant polymer composition containing piperazine-based expansive flame retardant |
MX344487B (en) | 2011-06-27 | 2016-12-16 | Fuller H B Co | Propylene-alpha-olefin polymers, hot melt adhesive compositions that include propylene-alpha-olefin polymers and articles that include the same. |
CN103649258B (en) | 2011-06-27 | 2016-07-06 | H.B.富勒公司 | What radical initiator was modified comprises functional polyethylene and the hot-melt adhesive composition of propylene-alpha-olefin polymer |
CA2789611C (en) | 2011-06-30 | 2020-04-28 | Dow Global Technologies Llc | Clear graphic cling films |
CN103649101A (en) * | 2011-07-08 | 2014-03-19 | 博瑞立斯有限公司 | Catalysts |
WO2013016398A1 (en) | 2011-07-28 | 2013-01-31 | Dow Global Technologies Llc | Polymeric blend formulations suitable for synthetic leather applications |
JP5960831B2 (en) * | 2011-09-23 | 2016-08-02 | エクソンモービル ケミカル パテンツ インコーポレイテッド | Modified polyethylene composition |
US20160272798A1 (en) | 2011-09-23 | 2016-09-22 | Exxonmobil Chemical Patents Inc. | Modified Polyethylene Compositions with Enhanced Melt Strength |
WO2013048754A1 (en) | 2011-09-30 | 2013-04-04 | Dow Global Technologies Llc | Flame retardant thermoplastic composition of polycarbonate and polypropylene |
JP5600219B2 (en) | 2011-10-24 | 2014-10-01 | 三菱化学株式会社 | Thermoplastic elastomer composition and method for producing the same |
US8629217B2 (en) | 2011-11-22 | 2014-01-14 | Exxonmobil Chemical Patents Inc. | Modified polyethylene blown film compositions having excellent bubble stability |
EP2602367B1 (en) * | 2011-12-06 | 2015-05-13 | Borealis AG | PP copolymers for melt blown/pulp fibrous nonwoven structures with improved mechanical properties and lower hot air consumption |
SG11201402933PA (en) | 2011-12-14 | 2014-07-30 | Dow Global Technologies Llc | Functionalized block composite and crystalline block composite compositions as compatibilizers |
JP6346566B2 (en) | 2011-12-14 | 2018-06-20 | ダウ グローバル テクノロジーズ エルエルシー | Functionalized block composite and crystalline block composite composition |
WO2013096696A1 (en) | 2011-12-20 | 2013-06-27 | Dow Global Technologies Llc | A rotomolding composition |
BR112014015134A2 (en) | 2011-12-21 | 2017-06-13 | Dow Global Technologies Llc | method for improving the formation of a polyolefin-based article and polyolefin article |
WO2013096711A1 (en) | 2011-12-21 | 2013-06-27 | Dow Global Technologies Llc | High frequency weldable polyolefin compositions including polar polymers |
WO2013096714A1 (en) | 2011-12-22 | 2013-06-27 | Dow Global Technologies Llc | Microcapillary films and foams suitable for capillary action fluid transport |
US20130165354A1 (en) | 2011-12-22 | 2013-06-27 | Exxonmobil Research And Engineering Company | Method for improving engine fuel efficiency |
US9604430B2 (en) | 2012-02-08 | 2017-03-28 | Flexopack S.A. | Thin film for waste packing cassettes |
BR112014019935B1 (en) | 2012-03-07 | 2021-03-09 | Dow Global Technologies Llc | multilayer structure |
WO2013154860A1 (en) | 2012-04-12 | 2013-10-17 | Dow Global Technologies Llc | Polyolefin blend composition and articles made therefrom |
US8691916B2 (en) | 2012-05-07 | 2014-04-08 | Dow Global Technologies Llc | Retortable easy opening seals for film extrusion |
BR112014029687B1 (en) | 2012-06-19 | 2021-01-19 | Dow Global Technologies Llc | water based mix composition, process for producing a water based mix composition, film, multilayer film and container device |
JP6298812B2 (en) | 2012-06-19 | 2018-03-20 | ダウ グローバル テクノロジーズ エルエルシー | Aqueous blend composition and process for producing the same |
ES2708300T3 (en) | 2012-06-28 | 2019-04-09 | Dow Global Technologies Llc | System and method for producing a multilayer microcapillary film |
WO2014003758A1 (en) | 2012-06-28 | 2014-01-03 | Dow Global Technologies Llc | Method and apparatus for producing a multi - layer microcapillary film |
US9676532B2 (en) | 2012-08-15 | 2017-06-13 | Avery Dennison Corporation | Packaging reclosure label for high alcohol content products |
US11292234B2 (en) | 2012-09-13 | 2022-04-05 | Dow Global Technologies Llc | Polyolefin based films suitable for thermoforming |
BR112015006442B1 (en) | 2012-09-24 | 2019-11-26 | Dow Global Technologies Llc | skin care oil-like gel makeup |
US9834712B2 (en) | 2012-10-09 | 2017-12-05 | Dow Global Technologies Llc | Sealant composition |
EP2732963A1 (en) | 2012-11-15 | 2014-05-21 | Dow Global Technologies LLC | Extrusion coated textile laminate with improved peel strength |
WO2014081516A1 (en) | 2012-11-21 | 2014-05-30 | Dow Global Technologies Llc | A film composition, film made from the film composition and a multi-layer film including the film and articles made therefrom |
CN104769048B (en) | 2012-11-21 | 2017-07-07 | 陶氏环球技术有限公司 | Coating composition |
WO2014081777A1 (en) | 2012-11-21 | 2014-05-30 | Dow Global Technologies Llc | A film composition, film made from the film composition and a multi-layer film including the film and articles made therefrom |
US9840613B1 (en) | 2012-11-29 | 2017-12-12 | K. Jabat, Inc. | Elastomeric composition having high impact strength |
EP2925797B1 (en) * | 2012-11-30 | 2019-01-09 | Dow Global Technologies LLC | Ethylene/alpha-olefin/nonconjugated polyene based compositions and foams formed from the same |
CN105189105B (en) | 2012-12-17 | 2017-04-19 | 陶氏环球技术有限责任公司 | A multi-layered structure and a method of sealing or shaping using a multi-layered structure |
WO2014099305A1 (en) | 2012-12-19 | 2014-06-26 | Dow Global Technologies Llc | Flexible film composition forheat seals and container with same |
CN104903070B (en) | 2012-12-27 | 2018-05-01 | 陶氏环球技术有限责任公司 | Manufacture thermoplastic polyolefin roof film is extruded by reversely rotating |
US20140187114A1 (en) | 2012-12-28 | 2014-07-03 | Dow Brasil S.A. | Elastic nonwovens with improved haptics and mechanical properties |
CN104968736B (en) | 2012-12-28 | 2017-09-05 | 陶氏环球技术有限责任公司 | Coating composition |
BR112015015417B1 (en) | 2012-12-28 | 2021-08-17 | Dow Global Technologies Llc | COATING COMPOSITION |
WO2014101154A1 (en) | 2012-12-31 | 2014-07-03 | Dow Global Technologies Llc | Thermoplastic vulcanizate with crosslinked olefin block copolymer |
US9267060B2 (en) | 2013-02-15 | 2016-02-23 | H.B. Fuller Company | Reaction product of propylene polymer and wax, graft copolymers derived from polypropylene polymer and wax, hot melt adhesive compositions including the same, and methods of using and making the same |
US9593235B2 (en) | 2013-02-15 | 2017-03-14 | H.B. Fuller Company | Reaction product of propylene polymer and wax, graft copolymers derived from polypropylene polymer and wax, hot melt adhesive compositions including the same, and methods of using and making the same |
US20140235127A1 (en) * | 2013-02-21 | 2014-08-21 | Henkel Corporation | Elastic attachment adhesive and use thereof |
US20150353718A1 (en) | 2013-02-28 | 2015-12-10 | Dow Global Technologies Llc | A blend composition suitable for injection molding applications |
US9034477B2 (en) | 2013-03-05 | 2015-05-19 | Dow Global Technologies Llc | Coating composition, a film containing the same, and a method for forming a sealable film |
TWI617489B (en) | 2013-04-09 | 2018-03-11 | 陶氏全球科技有限責任公司 | Process for producing ultrasonic seal, and film structures and flexible containers with same |
WO2014186953A1 (en) | 2013-05-22 | 2014-11-27 | Dow Global Technologies Llc | Paper composition and process for making the same |
EP2813362B1 (en) | 2013-06-14 | 2019-05-22 | Flexopack S.A. | Heat shrinkable film |
US20160102429A1 (en) * | 2013-07-02 | 2016-04-14 | Exxonmobil Chemical Patents Inc. | Carpet Backing Compositions and Carpet Backing Comprising the Same |
US9469753B2 (en) | 2013-07-22 | 2016-10-18 | Exxonmobil Chemical Patents Inc. | Propylene copolymers in elastomeric compositions |
WO2015021201A1 (en) | 2013-08-08 | 2015-02-12 | Dow Global Technologies Llc | A composite material, articles made therefrom |
WO2015042820A1 (en) | 2013-09-26 | 2015-04-02 | Dow Global Technologies Llc | A polymeric blend composition |
US9752024B2 (en) | 2013-10-15 | 2017-09-05 | Dow Global Technologies Llc | Compatibilized polyolefin blends |
EP2862712A1 (en) | 2013-10-16 | 2015-04-22 | Dow Global Technologies LLC | Flexible film composition for heat seals and container thereof |
WO2015061440A1 (en) | 2013-10-25 | 2015-04-30 | Dow Global Technologies Llc | Polyethylene and polypropylene composition suitable for the use as retortable easy opening seals |
WO2015066899A1 (en) | 2013-11-08 | 2015-05-14 | Dow Global Technologies Llc | Primerless paint composition, methods of manufacture thereof and articles comprising the same |
KR102296621B1 (en) * | 2013-11-15 | 2021-08-31 | 더블유.알. 그레이스 앤드 캄파니-콘. | Propylene-based polymer with reduced high-molecular weight portion |
KR102243786B1 (en) * | 2013-11-21 | 2021-04-22 | 더블유.알. 그레이스 앤드 캄파니-콘. | Producing high comonomer content propylene-based polymers |
US9708488B2 (en) | 2013-11-22 | 2017-07-18 | Trinseo Europe Gmbh | Polycarbonate containing compositions |
US10066102B2 (en) | 2013-11-22 | 2018-09-04 | Trinseo Europe Gmbh | Polycarbonate containing compositions |
CN105793330A (en) | 2013-12-16 | 2016-07-20 | 陶氏环球技术有限责任公司 | Process to make storage stable polymer formulations |
JP2017501905A (en) | 2013-12-31 | 2017-01-19 | ダウ グローバル テクノロジーズ エルエルシー | Multilayered film, method for producing the same, and article including them |
US10723824B2 (en) | 2014-02-07 | 2020-07-28 | Eastman Chemical Company | Adhesives comprising amorphous propylene-ethylene copolymers |
US10308740B2 (en) | 2014-02-07 | 2019-06-04 | Eastman Chemical Company | Amorphous propylene-ethylene copolymers |
US9399686B2 (en) | 2014-02-07 | 2016-07-26 | Eastman Chemical Company | Amorphous propylene-ethylene copolymers |
US10647795B2 (en) | 2014-02-07 | 2020-05-12 | Eastman Chemical Company | Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins |
US11267916B2 (en) | 2014-02-07 | 2022-03-08 | Eastman Chemical Company | Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins |
US10696765B2 (en) | 2014-02-07 | 2020-06-30 | Eastman Chemical Company | Adhesive composition comprising amorphous propylene-ethylene copolymer and propylene polymer |
US20150231862A1 (en) | 2014-02-19 | 2015-08-20 | Dow Global Technologies Llc | Multilayered polyolefin films, methods of manufacture thereof and articles comprising the same |
WO2015123827A1 (en) | 2014-02-19 | 2015-08-27 | Dow Global Technologies Llc | High performance sealable co-extruded oriented film, methods of manufacture thereof and articles comprising the same |
US20150231861A1 (en) | 2014-02-19 | 2015-08-20 | Dow Global Technologies Llc | Multilayered polyolefin films, methods of manufacture thereof and articles comprising the same |
WO2015123829A1 (en) | 2014-02-19 | 2015-08-27 | Dow Global Technologies Llc | Multilayer film, methods of manufacture thereof and articles comprising the same |
EP3116468B1 (en) | 2014-03-10 | 2018-11-14 | Dow Global Technologies LLC | Hair care sensory agents |
EP2921519A1 (en) | 2014-03-17 | 2015-09-23 | Dow Global Technologies LLC | A multilayer structure |
CN106163800B (en) | 2014-04-01 | 2019-12-06 | 陶氏环球技术有限责任公司 | Multilayer films and articles made therefrom |
US9694564B2 (en) | 2014-05-30 | 2017-07-04 | Inteplast Group Corporation | Peelable puncture-resistant film for packaging |
BR112016028445B1 (en) | 2014-06-02 | 2022-05-31 | Avery Dennison Corporation | Oriented film with abrasion resistance, clarity and conformability, label assembly comprising the film and method for producing a labeled article |
WO2015188358A1 (en) | 2014-06-12 | 2015-12-17 | Dow Global Technologies Llc | Coated substrates and articles made therefrom |
KR20170026500A (en) | 2014-07-03 | 2017-03-08 | 다우 글로벌 테크놀로지스 엘엘씨 | A composition, injection molded article made therefrom and process to make injection molded article |
US10421258B2 (en) | 2014-08-13 | 2019-09-24 | Performance Materials Na, Inc. | Multilayer structure comprising polypropylene |
MX2017003105A (en) | 2014-09-26 | 2017-06-14 | Dow Global Technologies Llc | A multilayer structure. |
EP3202731B1 (en) * | 2014-09-30 | 2023-12-27 | Sekisui Chemical Co., Ltd. | Interlayer film for laminated glass, and laminated glass |
WO2016069089A1 (en) | 2014-10-29 | 2016-05-06 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions for elastic applications |
AU2015258191B2 (en) | 2014-11-19 | 2020-02-27 | Flexopack S.A. | Oven skin packaging process |
SG11201704288RA (en) | 2014-12-02 | 2017-06-29 | Dow Global Technologies Llc | Dynamic vulcanization of a blend composition, methods of manufacture thereof and articles comprising the same |
SG11201705166WA (en) | 2014-12-23 | 2017-07-28 | Dow Global Technologies Llc | Thermoplastic vulcanizate including a block composite |
JP6734278B2 (en) | 2014-12-23 | 2020-08-05 | ダウ グローバル テクノロジーズ エルエルシー | Thermoplastic vulcanizate containing rubber block interpolymer |
ES2863574T3 (en) | 2015-03-18 | 2021-10-11 | Dow Global Technologies Llc | Protective films, mixtures and manufacturing methods thereof |
KR101953799B1 (en) | 2015-05-08 | 2019-03-04 | 주식회사 엘지화학 | Ligand compound and transition metal compound |
WO2017003762A1 (en) | 2015-06-30 | 2017-01-05 | Dow Global Technologies Llc | Polypropylene/inorganic particle blend composition for pvc-free wear layer in resilient flooring |
EP3317347B1 (en) | 2015-06-30 | 2023-05-10 | Dow Global Technologies LLC | Blends for foams, foams manufactured therefrom and articles comprising the same |
AR105371A1 (en) | 2015-07-27 | 2017-09-27 | Dow Global Technologies Llc | ELASTIC COMPOSITIONS BASED ON POLYOLEFINE, METHODS FOR THEIR MANUFACTURING AND ARTICLES THAT INCLUDE THEM |
CN107949602B (en) | 2015-09-17 | 2020-11-27 | 陶氏环球技术有限责任公司 | Polymer coating compositions having reduced ignition sensitivity |
BR112018005199B1 (en) | 2015-09-30 | 2020-12-15 | Dow Global Technologies Llc | PROCESS FOR THE PREPARATION OF A COMPOSITION, COMPOSITION AND PROCESS FOR POLYMERIZATION OF AT LEAST ONE POLYMERIZABLE MONOMER BY ADDITION TO FORM A POLYMER COMPOSITION |
EP3368602B1 (en) | 2015-10-29 | 2020-07-08 | Dow Global Technologies, LLC | Crosslinkable polymeric compositions for flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation |
WO2017088168A1 (en) | 2015-11-27 | 2017-06-01 | Dow Global Technologies Llc | Adhesive formulations for fabric/poe adhesion |
MX2018006358A (en) | 2015-12-10 | 2018-09-05 | Dow Global Technologies Llc | High modulus olefin compounds for fiber optic cable buffer tubes. |
US10952936B2 (en) | 2015-12-11 | 2021-03-23 | Dow Global Technologies Llc | Concentrated polyolefin emulsions and personal care compositions containing them |
CN108289798A (en) | 2015-12-11 | 2018-07-17 | 罗门哈斯公司 | Concentrate polyolefin emulsion and the Haircare composition containing it |
EP3390475A1 (en) | 2015-12-15 | 2018-10-24 | Dow Global Technologies, LLC | Cross-linked foams made from interpolymers of ethylene/alpha-olefins |
TW201723001A (en) | 2015-12-16 | 2017-07-01 | 陶氏全球科技有限責任公司 | Package with peelable and non-peelable heat seals |
MX2018006965A (en) | 2015-12-18 | 2018-09-21 | Dow Global Technologies Llc | Multilayer films suitable for use in thermoforming applications. |
KR101910232B1 (en) * | 2015-12-24 | 2018-12-19 | 주식회사 엘지화학 | Catalyst composition comprising novel transition metal compound |
KR20180100339A (en) | 2016-01-05 | 2018-09-10 | 다우 글로벌 테크놀로지스 엘엘씨 | Thermoformed microcapillary sheeting |
US10654997B2 (en) | 2016-03-25 | 2020-05-19 | Dow Global Technologies Llc | Buffer tubes for fiber optic cables |
US11279780B2 (en) | 2016-05-27 | 2022-03-22 | Cornell University | Polyethylene and polypropylene block copolymers |
CN109195667A (en) | 2016-06-15 | 2019-01-11 | 陶氏环球技术有限责任公司 | improved hair care composition |
BR112018074590A2 (en) | 2016-06-15 | 2019-03-12 | Dow Brasil Sudeste Ind Ltda | method for making a hair treatment composition. |
EP3260295A1 (en) | 2016-06-22 | 2017-12-27 | Dow Global Technologies LLC | Multilayer films and packages formed from same |
JP7011654B2 (en) | 2016-09-29 | 2022-01-26 | ダウ グローバル テクノロジーズ エルエルシー | Blends for foams, foams produced from them and articles containing them |
CN109963888A (en) | 2016-09-30 | 2019-07-02 | 陶氏环球技术有限责任公司 | It is used to prepare the method for being suitable for bull or double end composition that chain shuttle moves |
JP7029448B2 (en) | 2016-09-30 | 2022-03-03 | ダウ グローバル テクノロジーズ エルエルシー | A sealed multi- or dual-head composition useful for chain shuttling, and the process of preparing it. |
TW201840572A (en) | 2016-09-30 | 2018-11-16 | 美商陶氏全球科技有限責任公司 | Multi- or dual-headed compositions useful for chain shuttling and process to prepare the same |
BR112019007278B1 (en) | 2016-10-12 | 2022-09-06 | Dow Global Technologies Llc | MULTI-LAYER STRUCTURE AND METHOD TO PREPARE THE MULTI-LAYER STRUCTURE |
AR110303A1 (en) | 2016-12-01 | 2019-03-13 | Dow Global Technologies Llc | MULTI-PATH FILMS |
US10221267B2 (en) | 2016-12-13 | 2019-03-05 | Afton Chemical Corporation | Microstructure-controlled copolymers of ethylene and C3-C10 alpha-olefins |
US10584297B2 (en) | 2016-12-13 | 2020-03-10 | Afton Chemical Corporation | Polyolefin-derived dispersants |
JP7028885B2 (en) | 2017-03-15 | 2022-03-02 | ダウ グローバル テクノロジーズ エルエルシー | Catalyst system for forming multi-block copolymers |
BR112019019129A2 (en) | 2017-03-15 | 2020-04-14 | Dow Global Technologies Llc | catalyst system for multi-block copolymer formation |
JP7179750B2 (en) | 2017-03-15 | 2022-11-29 | ダウ グローバル テクノロジーズ エルエルシー | Catalyst system for forming multi-block copolymers |
SG11201908414YA (en) | 2017-03-15 | 2019-10-30 | Dow Global Technologies Llc | Catalyst system for multi-block copolymer formation |
JP7101185B2 (en) | 2017-03-15 | 2022-07-14 | ダウ グローバル テクノロジーズ エルエルシー | Catalyst system for forming multi-block copolymers |
US20200247009A1 (en) | 2017-08-31 | 2020-08-06 | Exxonmobil Chemical Patents Inc. | Methods of Making Thermoplastic Vulcanizates |
WO2019125989A1 (en) | 2017-12-20 | 2019-06-27 | Dow Global Technologies Llc | Multilayer cast films and methods of making thereof |
EP3501822A1 (en) | 2017-12-22 | 2019-06-26 | Flexopack S.A. | Fibc liner film |
KR102644634B1 (en) | 2017-12-29 | 2024-03-07 | 다우 글로벌 테크놀로지스 엘엘씨 | Capped double head organic aluminum composition |
CN111511557A (en) * | 2018-01-05 | 2020-08-07 | 巴克斯特国际公司 | Multilayer article and method for producing same |
EP3752538A1 (en) | 2018-02-12 | 2020-12-23 | ExxonMobil Chemical Patents Inc. | Metallocene catalyst feed system for solution polymerization process |
EP3768687A1 (en) | 2018-03-19 | 2021-01-27 | Dow Global Technologies LLC | Silicon-terminated organo-metal compounds and processes for preparing the same |
SG11202009138QA (en) | 2018-03-19 | 2020-10-29 | Dow Global Technologies Llc | Silicon-terminated organo-metal compounds and processes for preparing the same |
CN112074547A (en) | 2018-03-19 | 2020-12-11 | 陶氏环球技术有限责任公司 | Method for functionalizing organometallic compounds with silane-based functionalizing agents and silane-functionalized compounds prepared thereby |
JP2021518330A (en) | 2018-03-19 | 2021-08-02 | ダウ グローバル テクノロジーズ エルエルシー | Silicon-terminated telechelic polyolefin composition and the process for preparing it |
WO2020005942A1 (en) | 2018-06-29 | 2020-01-02 | Dow Global Technologies Llc | Shelf stable aqueous dispersions suitable for use in food contact applications |
CN112703131B (en) | 2018-10-17 | 2024-01-30 | 陶氏环球技术有限责任公司 | Coating composition, coated fabric, method of making coated fabric, and articles made from coated fabric |
WO2020081279A1 (en) | 2018-10-17 | 2020-04-23 | Dow Global Technologies Llc | A coating composition, a coated fabric, a method of making a coated fabric, and an article made from the coated fabric |
US20220001829A1 (en) | 2018-10-17 | 2022-01-06 | Dow Global Technologies Llc | A coating composition, a coated fabric, a method of making a coated fabric, and an article made from the coated fabric |
US20220098034A1 (en) * | 2018-12-17 | 2022-03-31 | King Abdullah University Of Science And Technology | Heterogeneous catalysts for hydrogen generation from formic acid |
JP2022516119A (en) | 2018-12-28 | 2022-02-24 | ダウ グローバル テクノロジーズ エルエルシー | Curable composition containing telechelic polyolefin |
KR20210121026A (en) | 2018-12-28 | 2021-10-07 | 다우 글로벌 테크놀로지스 엘엘씨 | Telechelic polyolefin and method for preparing same |
KR20210121027A (en) | 2018-12-28 | 2021-10-07 | 다우 글로벌 테크놀로지스 엘엘씨 | Curable composition comprising unsaturated polyolefin |
EP3902809A1 (en) | 2018-12-28 | 2021-11-03 | Dow Global Technologies LLC | Curable compositions comprising unsaturated polyolefins |
BR112021012777A2 (en) | 2018-12-28 | 2021-09-08 | Dow Global Technologies Llc | ORGANOMETALLIC COMPOSITION |
CN113993977A (en) | 2019-05-24 | 2022-01-28 | 伊士曼化工公司 | Mixing a small amount of pyrolysis oil into the liquid flow entering the gas cracker for processing |
CN114269829A (en) | 2019-08-20 | 2022-04-01 | 埃克森美孚化学专利公司 | Film and method for producing same |
BR112022003180A2 (en) | 2019-08-29 | 2022-05-17 | Dow Global Technologies Llc | Polymer blend and molded article |
CN110575758B (en) * | 2019-09-26 | 2024-01-26 | 中海石油气电集团有限责任公司 | Novel detection tube permeable membrane and preparation method and application thereof |
EP3797988A1 (en) * | 2019-09-30 | 2021-03-31 | Dow Global Technologies Llc | Plastomer toughened/stiffened polyolefin multilayer films and laminates comprising same |
US11945998B2 (en) | 2019-10-31 | 2024-04-02 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
US11939534B2 (en) | 2019-11-07 | 2024-03-26 | Eastman Chemical Company | Recycle content alpha olefins and fatty alcohols |
US11518154B2 (en) | 2020-01-27 | 2022-12-06 | Exxonmobil Chemical Patents Inc. | Barrier films for packaging |
CN115362198B (en) * | 2020-03-30 | 2023-07-21 | 东洋纺株式会社 | Polyolefin resin film and laminate using same |
AR121793A1 (en) | 2020-04-14 | 2022-07-13 | Dow Global Technologies Llc | ABSORBENT LAYERS SUITABLE FOR USE IN ABSORBENT ARTICLES AND METHODS OF MAKING THEM |
CN115885010A (en) | 2020-05-12 | 2023-03-31 | 国际人造丝公司 | Thermoplastic elastomer composition for pharmaceutical articles |
US20230248585A1 (en) | 2020-07-16 | 2023-08-10 | Dow Global Technologies Llc | Reusable outer cover formed from a nonwoven |
WO2022015368A1 (en) | 2020-07-17 | 2022-01-20 | Dow Global Technologies Llc | Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes |
BR112023000641A2 (en) | 2020-07-17 | 2023-01-31 | Dow Global Technologies Llc | POLYMERIZATION PROCESS OF OLEFIN MONOMERS |
US20240010771A1 (en) | 2020-07-17 | 2024-01-11 | Dow Global Technologies Llc | Hydrocarbyl-modified methylaluminoxane cocatalyst for bis-phenylphenoxy metal-ligand complexes |
JPWO2022075350A1 (en) * | 2020-10-06 | 2022-04-14 | ||
KR20230132560A (en) | 2021-01-25 | 2023-09-15 | 다우 글로벌 테크놀로지스 엘엘씨 | Hydrocarbyl-modified methylaluminoxane cocatalyst for bis-phenylphenoxy metal-ligand complexes |
WO2022240932A1 (en) | 2021-05-12 | 2022-11-17 | Dow Global Technologies Llc | Rheology modified olefin-based polymer composition and method for making it |
CN117659239A (en) * | 2022-09-08 | 2024-03-08 | 中国石油天然气股份有限公司 | Main catalyst for preparing poly (4-methyl-1-pentene) and application thereof |
CN115710326A (en) * | 2022-10-27 | 2023-02-24 | 万华化学集团股份有限公司 | Dibenzofuran bridged aryloxy metal complex catalyst, and method and application thereof |
Family Cites Families (139)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USB632416I5 (en) | 1956-03-01 | 1976-03-09 | ||
US3485706A (en) | 1968-01-18 | 1969-12-23 | Du Pont | Textile-like patterned nonwoven fabrics and their production |
US3520861A (en) | 1968-12-26 | 1970-07-21 | Dow Chemical Co | Copolymers of ethylene |
US4330646A (en) | 1979-08-13 | 1982-05-18 | Asahi Kasei Kogyo Kabushiki Kaisha | Polymerization of an α-olefin |
US4322027A (en) | 1980-10-02 | 1982-03-30 | Crown Zellerbach Corporation | Filament draw nozzle |
US4413110A (en) | 1981-04-30 | 1983-11-01 | Allied Corporation | High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore |
DE3127133A1 (en) | 1981-07-09 | 1983-01-27 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING POLYOLEFINS AND THEIR COPOLYMERISATS |
US4430563A (en) | 1982-04-30 | 1984-02-07 | Minnesota Mining And Manufacturing Company | Data processing form |
DE3240383A1 (en) | 1982-11-02 | 1984-05-03 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING OLIGOMER ALUMINOXANES |
CA1216700A (en) | 1983-01-25 | 1987-01-13 | Masaki Kohyama | Film-forming propylene copolymer, film thereof and process for production of the film |
US5324800A (en) | 1983-06-06 | 1994-06-28 | Exxon Chemical Patents Inc. | Process and catalyst for polyolefin density and molecular weight control |
US4599392A (en) | 1983-06-13 | 1986-07-08 | The Dow Chemical Company | Interpolymers of ethylene and unsaturated carboxylic acids |
US4612300A (en) | 1985-06-06 | 1986-09-16 | The Dow Chemical Company | Novel catalyst for producing relatively narrow molecular weight distribution olefin polymers |
US4663220A (en) | 1985-07-30 | 1987-05-05 | Kimberly-Clark Corporation | Polyolefin-containing extrudable compositions and methods for their formation into elastomeric products including microfibers |
US4668566A (en) | 1985-10-07 | 1987-05-26 | Kimberly-Clark Corporation | Multilayer nonwoven fabric made with poly-propylene and polyethylene |
US5384299A (en) | 1987-01-30 | 1995-01-24 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
US5153157A (en) | 1987-01-30 | 1992-10-06 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
US5408017A (en) | 1987-01-30 | 1995-04-18 | Exxon Chemical Patents Inc. | High temperature polymerization process using ionic catalysts to produce polyolefins |
US5198401A (en) | 1987-01-30 | 1993-03-30 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
US4874880A (en) | 1987-03-10 | 1989-10-17 | Chisso Corporation | Bis(di-, tri- or tetra-substituted-cyclopentadienyl)-zirconium dihalides |
US4988781A (en) | 1989-02-27 | 1991-01-29 | The Dow Chemical Company | Process for producing homogeneous modified copolymers of ethylene/alpha-olefin carboxylic acids or esters |
US5093415A (en) | 1987-05-19 | 1992-03-03 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing stereoregular polymers having a narrow molecular weight distribution |
US5015749A (en) | 1987-08-31 | 1991-05-14 | The Dow Chemical Company | Preparation of polyhydrocarbyl-aluminoxanes |
IT1221653B (en) | 1987-11-27 | 1990-07-12 | Ausimonti Spa | PROPYLENE CRYSTALLINE COPOLYMERS |
US5229478A (en) | 1988-06-16 | 1993-07-20 | Exxon Chemical Patents Inc. | Process for production of high molecular weight EPDM elastomers using a metallocene-alumoxane catalyst system |
US5041584A (en) | 1988-12-02 | 1991-08-20 | Texas Alkyls, Inc. | Modified methylaluminoxane |
US4960878A (en) | 1988-12-02 | 1990-10-02 | Texas Alkyls, Inc. | Synthesis of methylaluminoxanes |
US5218071A (en) | 1988-12-26 | 1993-06-08 | Mitsui Petrochemical Industries, Ltd. | Ethylene random copolymers |
AU661456B2 (en) | 1989-02-27 | 1995-07-27 | Dow Chemical Company, The | Process for producing homogeneous modified copolymers of ethylene/alpha-olefin carboxylic acids or esters |
NZ235032A (en) | 1989-08-31 | 1993-04-28 | Dow Chemical Co | Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component |
US5057475A (en) | 1989-09-13 | 1991-10-15 | Exxon Chemical Patents Inc. | Mono-Cp heteroatom containing group IVB transition metal complexes with MAO: supported catalyst for olefin polymerization |
US5064802A (en) | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
US6001933A (en) | 1989-11-28 | 1999-12-14 | Idemitsupetrochemical Co., Ltd. | Flexible polypropylene resins, propylene based elastomer compositions and process for production of olefin polymers |
US6156846A (en) | 1989-11-28 | 2000-12-05 | Idemitsu Petrochemical Co., Ltd. | Flexible polypropylene resins, propylene bases elastomer compositions and process for production of olefin polymers |
US5044438A (en) | 1990-03-16 | 1991-09-03 | Young Joe A | Wellhead bowl protector and retrieving tool |
PL166690B1 (en) | 1990-06-04 | 1995-06-30 | Exxon Chemical Patents Inc | Method of obtaining polymers of olefins |
US5041585A (en) | 1990-06-08 | 1991-08-20 | Texas Alkyls, Inc. | Preparation of aluminoxanes |
US5041583A (en) | 1990-06-28 | 1991-08-20 | Ethyl Corporation | Preparation of aluminoxanes |
US5272236A (en) | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
IL99741A0 (en) * | 1990-11-01 | 1992-08-18 | Himont Inc | Propylene polymer films and laminates |
US5134209A (en) | 1990-12-26 | 1992-07-28 | Shell Oil Company | Process of producing ethylene-propylene rubbery copolymer |
MX9200724A (en) | 1991-02-22 | 1993-05-01 | Exxon Chemical Patents Inc | HEAT SEALABLE MIX OF POLYETHYLENE OR PLASTOMER OF VERY LOW DENSITY WITH POLYMERS BASED ON POLYPROPYLENE AND THERMAL SEALABLE FILM AS WELL AS ARTICLES MADE WITH THOSE. |
US5721185A (en) | 1991-06-24 | 1998-02-24 | The Dow Chemical Company | Homogeneous olefin polymerization catalyst by abstraction with lewis acids |
US5710224A (en) | 1991-07-23 | 1998-01-20 | Phillips Petroleum Company | Method for producing polymer of ethylene |
US6448355B1 (en) | 1991-10-15 | 2002-09-10 | The Dow Chemical Company | Elastic fibers, fabrics and articles fabricated therefrom |
US5525695A (en) | 1991-10-15 | 1996-06-11 | The Dow Chemical Company | Elastic linear interpolymers |
US5278272A (en) | 1991-10-15 | 1994-01-11 | The Dow Chemical Company | Elastic substantialy linear olefin polymers |
BE1006840A5 (en) | 1992-05-04 | 1995-01-03 | Solvay | Catalyst system for olefin polymerisation; method for the polymerization and polymers therefrom. |
ES2108861T3 (en) | 1991-11-25 | 1998-01-01 | Exxon Chemical Patents Inc | POLYTONIC CATALYTIC COMPOSITIONS OF TRANSITIONAL METALS. |
ATE142681T1 (en) * | 1992-03-03 | 1996-09-15 | Exxon Chemical Patents Inc | HEAT SEALED, STERILIZABLE CONTAINER MADE OF HIGH ETHYLENE STATISTICAL COPOLYMER FILM AND METHOD |
US5296433A (en) | 1992-04-14 | 1994-03-22 | Minnesota Mining And Manufacturing Company | Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom |
US5350723A (en) | 1992-05-15 | 1994-09-27 | The Dow Chemical Company | Process for preparation of monocyclopentadienyl metal complex compounds and method of use |
ES2190567T3 (en) | 1992-07-01 | 2003-08-01 | Exxonmobil Chem Patents Inc | PRECURSORS OF TRANSITION METAL CATALYSTS OF GROUPS 5 AND 6. |
CA2102542A1 (en) * | 1992-11-12 | 1994-05-13 | Thaddeus W. Klimek | Gas-phase process for producing copolymer of propylene and ethylene and polyolefin films made therefrom |
US5322728A (en) | 1992-11-24 | 1994-06-21 | Exxon Chemical Patents, Inc. | Fibers of polyolefin polymers |
JP3417023B2 (en) * | 1992-12-22 | 2003-06-16 | 住友化学工業株式会社 | Polyolefin composition and film comprising the composition |
IT1256260B (en) | 1992-12-30 | 1995-11-29 | Montecatini Tecnologie Srl | ATACTIC POLYPROPYLENE |
US5883188A (en) | 1993-04-28 | 1999-03-16 | The Dow Chemical Company | Paintable olefinic interpolymer compositions |
DE4317655A1 (en) | 1993-05-27 | 1994-12-01 | Basf Ag | Multi-phase block copolymers of propylene |
DE69434709T2 (en) * | 1993-06-07 | 2006-10-19 | Mitsui Chemicals, Inc. | propylene elastomers |
EP0705269B1 (en) * | 1993-06-24 | 1997-01-15 | The Dow Chemical Company | Titanium(ii) or zirconium(ii) complexes and addition polymerization catalysts therefrom |
US6005049A (en) | 1993-07-19 | 1999-12-21 | Union Carbide Chemicals & Plastics Technology Corporation | Process for the production of polypropylene |
CA2128920C (en) | 1993-07-28 | 1999-06-01 | Akihiko Yamamoto | Propylene polymer compositions |
US5472775A (en) | 1993-08-17 | 1995-12-05 | The Dow Chemical Company | Elastic materials and articles therefrom |
US5504223A (en) | 1994-01-25 | 1996-04-02 | The Dow Chemical Company | Synthesis of cyclopentadienyl metal coordination complexes from metal hydrocarbyloxides |
DE4416876A1 (en) | 1994-05-13 | 1995-11-16 | Basf Ag | Process for the production of bridged half-sandwich complexes |
IT1270256B (en) | 1994-06-20 | 1997-04-29 | Himont Inc | POLYOLEFINIC COMPOSITIONS FOR SHEETS AND FILM WELDABLE WITH RADIOFREQUENCES |
AU689895B2 (en) | 1994-07-11 | 1998-04-09 | Tonen Chemical Corporation | Polypropylene resin composition |
US5616664A (en) | 1994-08-02 | 1997-04-01 | The Dow Chemical Company | Polymerization process with biscyclopentadienyl diene complex containing catalysts |
US5625087A (en) | 1994-09-12 | 1997-04-29 | The Dow Chemical Company | Silylium cationic polymerization activators for metallocene complexes |
CA2164461C (en) * | 1994-12-06 | 2000-08-08 | Tatsuya Tanizaki | Polypropylene composition and uses thereof |
CA2183419A1 (en) | 1994-12-20 | 1996-07-04 | Luigi Resconi | Reactor blend polypropylene, process for the preparation thereof and process for preparing metallocene ligands |
US5645542A (en) | 1994-12-29 | 1997-07-08 | Kimberly-Clark Worldwide, Inc. | Elastomeric absorbent structure |
IT1275857B1 (en) | 1995-03-03 | 1997-10-24 | Spherilene Srl | ATACTIC PROPYLENE COPOLYMERS WITH ETHYLENE |
US5637660A (en) | 1995-04-17 | 1997-06-10 | Lyondell Petrochemical Company | Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety |
EP0745638A1 (en) * | 1995-05-31 | 1996-12-04 | Hoechst Aktiengesellschaft | Biaxially oriented film of polypropylene with improved tear-through resistance |
TW420692B (en) | 1995-06-26 | 2001-02-01 | Japan Polyolefins Co Ltd | Propylene block copolymer, process for preparation thereof and propylene resin composition comprising same |
US5731253A (en) | 1995-07-27 | 1998-03-24 | Albemarle Corporation | Hydrocarbylsilloxy - aluminoxane compositions |
US5869575A (en) | 1995-08-02 | 1999-02-09 | The Dow Chemical Company | Ethylene interpolymerizations |
US5962714A (en) | 1995-10-02 | 1999-10-05 | Mccullough; Laughlin Gerard | Monocyclopentadienyl transition metal catalyst and olefin polymerization process |
AT405286B (en) | 1995-10-16 | 1999-06-25 | Danubia Petrochem Polymere | POLYPROPYLENE WITH REDUCED WHITE BREAKAGE |
US5728855A (en) | 1995-10-19 | 1998-03-17 | Akzo Nobel Nv | Modified polyalkylaluminoxane composition formed using reagent containing carbon-oxygen double bond |
US5767208A (en) | 1995-10-20 | 1998-06-16 | Exxon Chemical Patents Inc. | High temperature olefin polymerization process |
EP0876407B1 (en) | 1996-01-26 | 2000-12-27 | The Dow Chemical Company | Improved olefin addition polymerization catalyst composition |
DE19606510A1 (en) * | 1996-02-22 | 1997-08-28 | Hoechst Ag | High molecular weight polypropylene with a broad molecular weight distribution |
KR100437238B1 (en) | 1996-03-27 | 2004-08-16 | 다우 글로벌 테크놀로지스 인크. | Highly soluble olefin polymerization catalyst activator |
JP2000517349A (en) | 1996-03-27 | 2000-12-26 | ザ ダウ ケミカル カンパニー | Solution polymerization with dispersed catalytic activators. |
US5929147A (en) | 1996-06-18 | 1999-07-27 | Montell North America Inc. | Embrittlement-resistant polyolefin composition and flexible articles therefrom |
CZ20999A3 (en) | 1996-07-22 | 1999-04-14 | The Dow Chemical Company | Metal complexes containing bridge non-aromatic anionic dienyl groups, addition polymerization catalysts based on such complexes and polymerization process |
EP0854155A4 (en) | 1996-07-31 | 2002-01-02 | Japan Polyolefins Co Ltd | Highly crystalline polypropylene |
US6015868A (en) | 1996-10-03 | 2000-01-18 | The Dow Chemical Company | Substituted indenyl containing metal complexes and olefin polymerization process |
US5910224A (en) | 1996-10-11 | 1999-06-08 | Kimberly-Clark Worldwide, Inc. | Method for forming an elastic necked-bonded material |
TW442528B (en) | 1996-12-02 | 2001-06-23 | Chisso Corp | Polypropylene composition |
US6245856B1 (en) | 1996-12-17 | 2001-06-12 | Exxon Chemical Patents, Inc. | Thermoplastic olefin compositions |
WO1998027155A1 (en) | 1996-12-17 | 1998-06-25 | Advanced Elastomer Systems, L.P. | Thermoplastic elastomeric compositions |
US5783512A (en) | 1996-12-18 | 1998-07-21 | The Dow Chemical Company | Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same |
US5965756A (en) | 1996-12-19 | 1999-10-12 | The Dow Chemical Company | Fused ring substituted indenyl metal complexes and polymerization process |
JPH10202720A (en) * | 1997-01-22 | 1998-08-04 | Mitsui Chem Inc | Extruded polypropylene film |
US5994482A (en) | 1997-03-04 | 1999-11-30 | Exxon Chemical Patents, Inc. | Polypropylene copolymer alloys and process for making |
US5922822A (en) | 1997-04-09 | 1999-07-13 | Eastman Kodak Company | (2-(sulfonamidomethylene)-2-cyanoacetamido)phenyl acrylate polymers |
TW420693B (en) * | 1997-04-25 | 2001-02-01 | Mitsui Chemicals Inc | Olefin polymerization catalysts, transition metal compounds, and <alpha>-olefin/conjugated diene copolymers |
US6103657A (en) * | 1997-07-02 | 2000-08-15 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
CA2210131C (en) | 1997-07-09 | 2005-08-02 | Douglas W. Stephan | Supported phosphinimine-cp catalysts |
US6921794B2 (en) | 1997-08-12 | 2005-07-26 | Exxonmobil Chemical Patents Inc. | Blends made from propylene ethylene polymers |
US6635715B1 (en) | 1997-08-12 | 2003-10-21 | Sudhin Datta | Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers |
US6525157B2 (en) * | 1997-08-12 | 2003-02-25 | Exxonmobile Chemical Patents Inc. | Propylene ethylene polymers |
US6153702A (en) | 1997-09-12 | 2000-11-28 | Eastman Chemical Company | Polymers, and novel compositions and films therefrom |
US6150297A (en) | 1997-09-15 | 2000-11-21 | The Dow Chemical Company | Cyclopentaphenanthrenyl metal complexes and polymerization process |
US6117962A (en) | 1997-12-10 | 2000-09-12 | Exxon Chemical Patents Inc. | Vinyl-containing stereospecific polypropylene macromers |
JPH11255825A (en) * | 1997-12-26 | 1999-09-21 | Tokuyama Corp | Non-stretched film polypropylene based resin and non-stretched film |
US6034240A (en) | 1998-03-09 | 2000-03-07 | Symyx Technologies, Inc. | Substituted aminomethylphosphines, coordination complexes of aminomethylphosphines and their synthesis |
JP2002519497A (en) | 1998-07-01 | 2002-07-02 | エクソンモービル・ケミカル・パテンツ・インク | Elastic blend comprising a crystalline propylene polymer and a crystallizable propylene polymer |
US6288171B2 (en) | 1998-07-01 | 2001-09-11 | Advanced Elastomer Systems, L.P. | Modification of thermoplastic vulcanizates using random propylene copolymers |
JP2000044003A (en) * | 1998-07-27 | 2000-02-15 | Monteru J P O Kk | Container bag for waste transport equipment |
US6037417A (en) | 1998-08-18 | 2000-03-14 | Montell Technology Company Bv | Polypropylene composition useful for making solid state oriented film |
US6258903B1 (en) * | 1998-12-18 | 2001-07-10 | Univation Technologies | Mixed catalyst system |
US6362309B1 (en) | 1999-04-01 | 2002-03-26 | Symyx Technologies, Inc. | Polymerization catalyst ligands, catalytic metal complexes and compositions and processes using and method of making same |
US6500563B1 (en) | 1999-05-13 | 2002-12-31 | Exxonmobil Chemical Patents Inc. | Elastic films including crystalline polymer and crystallizable polymers of propylene |
US6750284B1 (en) | 1999-05-13 | 2004-06-15 | Exxonmobil Chemical Patents Inc. | Thermoplastic filled membranes of propylene copolymers |
DE60040697D1 (en) | 1999-05-13 | 2008-12-11 | Exxonmobil Chem Patents Inc | Elastic fibers and articles made therefrom containing crystalline and crystallizable propylene polymers |
CZ20014144A3 (en) | 1999-05-19 | 2002-10-16 | Exxon Chemical Patents Inc. | Elastomeric mixture based on isobutylene exhibiting improved strength and elasticity and reduced permeability |
JP2001048911A (en) * | 1999-08-13 | 2001-02-20 | Mitsui Chemicals Inc | PRODUCTION OF alpha-OLEFIN RANDOM COPOLYMER |
BR0014148A (en) | 1999-09-01 | 2002-05-07 | Exxon Chemical Patents Inc | Breathable films and method for their production |
JP2003511427A (en) * | 1999-10-12 | 2003-03-25 | ダウ グローバル テクノロジーズ インコーポレーテッド | Dicationic non-metallocene group 4 metal complexes |
CA2387877C (en) * | 1999-10-22 | 2006-12-19 | Univation Technologies, Llc | Catalyst systems and their use in a polymerization process |
US6399722B1 (en) * | 1999-12-01 | 2002-06-04 | Univation Technologies, Llc | Solution feed of multiple catalysts |
US6340730B1 (en) * | 1999-12-06 | 2002-01-22 | Univation Technologies, Llc | Multiple catalyst system |
WO2001046201A1 (en) * | 1999-12-21 | 2001-06-28 | The Dow Chemical Company | Gallium or indium-bridged group 4 metal complexes |
CA2395532A1 (en) | 1999-12-22 | 2001-06-28 | A. G. Karandinos | Polypropylene-based adhesive compositions |
US20020049288A1 (en) | 2000-04-04 | 2002-04-25 | Christopher Goh | Ether-amine based polymerization catalysts, compositions and processes using same |
US6458738B1 (en) * | 2000-09-22 | 2002-10-01 | Union Carbide Chemicals & Plastics Technology Corporation | Spray-drying compositions and methods of spray-drying |
WO2002046249A2 (en) | 2000-11-07 | 2002-06-13 | Symyx Technologies, Inc. | Methods of copolymerizing ethylene and isobutylene and polymers made thereby |
CA2432916A1 (en) | 2000-12-22 | 2002-07-04 | Exxonmobil Chemical Patents Inc. | Composites comprising semicrystalline random ethylene / propylenecopolymers |
KR20030064415A (en) | 2000-12-22 | 2003-07-31 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | Multicomponent thermoset structures |
US6653417B2 (en) * | 2001-10-12 | 2003-11-25 | Univation Technologies, Llc | Catalyst precursor and olefin polymerization processes |
US6960635B2 (en) | 2001-11-06 | 2005-11-01 | Dow Global Technologies Inc. | Isotactic propylene copolymers, their preparation and use |
WO2004035681A2 (en) | 2002-10-17 | 2004-04-29 | Exxonmobil Chemical Patents Inc. | Hetero phase polymer compositions |
AU2003297134A1 (en) | 2002-12-17 | 2004-07-29 | Exxonmobil Chemical Patents Inc. | Elastic blends comprising elastic crystalline polymer and crystallizable polymers for ethylene |
DE602004032419D1 (en) | 2003-01-08 | 2011-06-09 | Exxonmobil Chem Patents Inc | ELASTIC ARTICLES AND MANUFACTURING METHOD THEREFOR |
-
2002
- 2002-05-05 US US10/139,786 patent/US6960635B2/en not_active Expired - Lifetime
- 2002-11-05 DE DE60229426T patent/DE60229426D1/en not_active Expired - Lifetime
- 2002-11-05 JP JP2003542247A patent/JP5027378B2/en not_active Expired - Fee Related
- 2002-11-05 EP EP02780584A patent/EP1448630A2/en not_active Withdrawn
- 2002-11-05 JP JP2003542240A patent/JP5118286B2/en not_active Expired - Fee Related
- 2002-11-05 EP EP02776467A patent/EP1448615B1/en not_active Expired - Fee Related
- 2002-11-05 WO PCT/US2002/035617 patent/WO2003040195A1/en active Application Filing
- 2002-11-05 US US10/492,139 patent/US7115689B2/en not_active Expired - Lifetime
- 2002-11-05 CA CA2463588A patent/CA2463588C/en not_active Expired - Fee Related
- 2002-11-05 CN CNB028268474A patent/CN100467501C/en not_active Expired - Fee Related
- 2002-11-05 WO PCT/US2002/035566 patent/WO2003040202A2/en active Application Filing
-
2004
- 2004-11-15 US US10/988,964 patent/US7238759B2/en not_active Expired - Lifetime
-
2009
- 2009-02-04 JP JP2009023872A patent/JP2009173936A/en active Pending
- 2009-02-04 JP JP2009023845A patent/JP5179395B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP5179395B2 (en) | 2013-04-10 |
WO2003040202A2 (en) | 2003-05-15 |
WO2003040195A1 (en) | 2003-05-15 |
EP1448615A1 (en) | 2004-08-25 |
US20030204017A1 (en) | 2003-10-30 |
CA2463588A1 (en) | 2003-05-15 |
JP2009173936A (en) | 2009-08-06 |
EP1448630A2 (en) | 2004-08-25 |
US7115689B2 (en) | 2006-10-03 |
JP5027378B2 (en) | 2012-09-19 |
CN1612902A (en) | 2005-05-04 |
US20050113524A1 (en) | 2005-05-26 |
JP2005508413A (en) | 2005-03-31 |
JP5118286B2 (en) | 2013-01-16 |
WO2003040195B1 (en) | 2003-08-28 |
WO2003040202A3 (en) | 2003-08-28 |
US20040220051A1 (en) | 2004-11-04 |
DE60229426D1 (en) | 2008-11-27 |
JP2005508416A (en) | 2005-03-31 |
CN100467501C (en) | 2009-03-11 |
JP2009138205A (en) | 2009-06-25 |
US6960635B2 (en) | 2005-11-01 |
US7238759B2 (en) | 2007-07-03 |
EP1448615B1 (en) | 2008-10-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2463588C (en) | Supported polymerization catalysts comprising a polyvalent lewis base ligand | |
EP0507876B1 (en) | Supported ionic metallocene catalysts for olefin polymerization | |
JP2994746B2 (en) | Monocyclopentadienyl transition metal olefin polymerization catalyst | |
US5547675A (en) | Modified monocyclopentadienyl transition metal/alumoxane catalyst system for polymerization of olefins | |
EP1091968B1 (en) | Production of half-sandwich substituted catalyst precursors | |
JP2003515628A (en) | Multi-component catalyst system | |
WO2000004058A1 (en) | Aluminum-based lewis acid cocatalysts for olefin polymerization | |
EP0618931B1 (en) | A modified monocyclopentadienyl transition metal/alumoxane catalyst system for polymerization of olefins | |
EP0705283B1 (en) | PROCESS FOR PRODUCING AMORPHOUS POLY-$g(a)-OLEFINS WITH A MONOCYCLOPENTADIENYL TRANSITION METAL CATALYST SYSTEM | |
EP1543049B1 (en) | Improved process for manufacture of polymers | |
CA2338472C (en) | Functionalized catalyst supports and supported catalyst systems | |
JP2004504420A (en) | Catalyst systems and their use in polymerization processes | |
JP2002519359A (en) | Metal complexes containing one or more silsesquioxane ligands | |
CA2356261C (en) | Process for preparing a supported polymerization catalyst using reduced amounts of solvent and polymerization process | |
TW200523312A (en) | Polymerization process and control of polymer composition properties | |
AU784134B2 (en) | Chemically-modified supports and supported catalyst systems prepared therefrom | |
JP3872757B2 (en) | Method for producing catalyst system and use thereof in polymerization method | |
JP2004528276A (en) | Catalyst composition and polymerization method | |
US7598328B2 (en) | Supported catalysts for manufacture of polymers | |
JP2004531618A (en) | Catalyst system and its use in polymerization processes | |
US6852811B1 (en) | Process for preparing a supported polymerization catalyst using reduced amounts of solvent and polymerization process | |
JP2004523603A (en) | Process for producing catalyst composition and its use in polymerization process | |
JP3302415B2 (en) | Internal olefin polymerization catalyst and method for producing internal olefin polymer | |
US20110251362A1 (en) | Olefin polymerization catalysts | |
WO2001053361A1 (en) | Siloxy-substituted monocyclopentadienyl ligated constrained geometry olefin polymerisation catalysts |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKLA | Lapsed |
Effective date: 20191105 |