WO2007136494A2 - Ethylene/ alpha-olefin/ diene solution polymerization process - Google Patents
Ethylene/ alpha-olefin/ diene solution polymerization process Download PDFInfo
- Publication number
- WO2007136494A2 WO2007136494A2 PCT/US2007/009842 US2007009842W WO2007136494A2 WO 2007136494 A2 WO2007136494 A2 WO 2007136494A2 US 2007009842 W US2007009842 W US 2007009842W WO 2007136494 A2 WO2007136494 A2 WO 2007136494A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phenyl
- methyl
- bis
- oxoyl
- phenoxy
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- 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
- Y10S526/905—Polymerization in presence of transition metal containing catalyst in presence of hydrogen
Definitions
- Catalyst compositions based on well defined donor ligand containing metal complexes referred to as post-metallocene complexes have been shown to give products having better comonomer incorporation and narrow molecular weight distribution.
- these catalysts often have poor high temperature stability and suffer from poor catalytic efficiencies, especially at elevated polymerization temperatures.
- ethylene, ⁇ -olefin and diene containing polymers especially ethylene, propylene, and ethyl idenenorbornene (ENB) containing polymers
- the resulting polymer molecular weight and comonomer incorporation ratio is often deficient.
- Examples .of one type of the foregoing post metallocene catalysts are disclosed in USP 6,827,976, where Group 3-6 or Lanthanide metal complexes, preferably Group 4 metal complexes, of bridged divalent aromatic ligands containing a divalent Lewis base chelating group are disclosed.
- Group 3-6 or Lanthanide metal complexes, preferably Group 4 metal complexes, of bridged divalent aromatic ligands containing a divalent Lewis base chelating group are disclosed.
- Higher solution reaction temperatures are particularly desired for ethylene/ ⁇ - olefin/diene polymerizations in order to improve operating efficiency.
- the use of higher reaction temperatures often results in poor ⁇ -olefin and diene conversions. Accordingly, selection of catalyst compositions capable of incorporating increased amounts of ⁇ -olefin and diene comonomers at elevated reaction temperatures is highly desired.
- metal complexes may be employed in a solution polymerization process to prepare high molecular weight ethylene containing interpolymers containing relatively large ⁇ -olefin and diene contents.
- the resulting polymer products possess desirable properties such as increased tensile properties, reduced density (greater comonomer incorporation) and improved high temperature performance.
- these catalyst compositions retain their high catalyst activity using relatively low molar ratios of conventional alumoxane cocatalysts.
- interpolymers possessing relatively high molecular weights (with correspondingly low melt indices) and high levels of comonomer incorporation (low densities), having relatively good high temperature resistance.
- This unique combination of polymer properties is also attainable by use of low molar ratios (200 or less, preferably 100 or less, more preferably 80 or less, based on zirconium) of an alkylalumoxa ⁇ e cocatalyst or a trialkylaluminum- modified alumoxane cocatalyst.
- the polymers are capable of preparation under high temperature, high conversion conditions at high catalyst efficiencies.
- the present invention is particularly advantageous for use under continuous solution polymerization conditions wherein a reaction mixture comprising a metal complex, an activating cocatalyst or cocatalyst mixture, optionally a chain transfer agent, ethylene, a C 3 . 30 ⁇ -olefin, especially propylene, and at least one C ⁇ . 2 0 conjugated or nonconjugated diene are continuously added to a reactor operating under solution polymerization conditions, and polymer product is continuously or semi-continuously removed therefrom.
- the invention is used to prepare copolymers of ethylene, propylene and 5-ethylidene-2-norbornene having increased polymerized propylene and diene monomer contents.
- the invention is particularly suitable for production of resins that are used in the preparation of adhesives, films (including membranes for roofing and architectural applications), and molded or extruded articles having improved high temperature use properties, with or without subsequent curing or cross-linking.
- 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.
- hexane includes all isomers of hexane individually or collectively.
- compound and “complex” are used interchangeably herein to refer to organic-, inorganic- and organometal compounds.
- atom refers to the smallest constituent of an element regardless of ionic state, that is, whether or not the same bears a charge or partial charge or is bonded to another atom.
- heteroatom refers to an atom other than carbon or hydrogen.
- Preferred heteroatoms include: F, Cl, Br, N, O, P, B, S, Si, Sb, Al, Sn, As, Se and Ge.
- amorphous refers to a polymer lacking a crystalline melting point as determined by differential scanning calorimetry (DSC) or equivalent technique.
- hydrocarbyl refers to univalent substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic or noncyclic species. Examples include alkyl-, cycloalkyl-, alkenyl-, alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, and alkynyl- groups. “Substituted hydrocarbyl” refers to a hydrocarbyl group that is substituted with one or more nonhydrocarbyl substituent groups.
- heteroatom containing hydrocarbyl or “heterohydrocarbyl” refer to univalent groups in which at least one atom other than hydrogen or carbon is present along with one or more carbon atom and one or more hydrogen atoms.
- heterocarbyl refers to groups containing one or more carbon atoms and one or more heteroatoms, but no hydrogen atoms.
- the bond between the carbon atom and any heteroatom as well as the bonds between any two heteroatoms may be a single or multiple covalent bond or a coordinating or other donative bond.
- an alkyl group substituted with a heterocycloalkyl-, aryl- substituted heterocycloalkyl-, heteroaryK alkyl- substituted heteroaryl-, alkoxy-, aryloxy-, dihydrocarbylboryl-, dihydrocarbylphosphino-, dihydrocarbylamino-, trihydrocarbylsilyl-, hydrocarbylthio-, or hydrocarbylseleno- group is within the scope of the term heteroalkyl.
- specific heteroalkyl groups include cyanornethyl-, benzoylmethyl-, (2- pyridyl)methyl-, and trifluoromethyl- groups.
- aromatic refers to a polyatomic, cyclic, conjugated ring system containing (45+2) ⁇ -electrons, wherein ⁇ is an integer greater than or equal to 1.
- fused as used herein with respect to a ring system containing two or more polyatomic, cyclic rings means that with respect to at least two rings thereof, at least one pair of adjacent atoms is included in both rings.
- aryl refers to a monovalent aromatic substituent which may be a single aromatic ring or multiple aromatic rings which are fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety. Examples of aromatic ring(s) include phenyl, naphthyl, anthracenyl, and biphenyl, among others.
- Substituted aryl refers to an aryl group in which one or more hydrogen atoms bound to any carbon is replaced by one or more functional groups such as alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, alkylhalos (for example, CF 3 ), hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, and both saturated and unsaturated cyclic hydrocarbons which are fused to the aromatic ring(s), linked covalently or linked to a common group such as a methylene or ethylene moiety.
- the common linking group may also be a carbonyl as in benzophenone, or oxygen as in diphenylether, or nitrogen as in diphenylamine.
- Embodiments of the invention provide a new solution process for making ethylene/ ⁇ - olefin/diene interpolymers using a catalyst composition comprising a transition metal complex at high temperature, high catalyst efficiency and high monomer conversion.
- the produced polymers are of high molecular weight (I 2 ⁇ 5.0).
- Such polymers are suitably employed where improved high temperature performance is desired, such as in molding and extrusion grades of polymer especially for extruded films and profiles or molded parts applications.
- polymer refers to a macromolecular compound prepared by polymerizing one or more monomers.
- a polymer refers to homopolymers, copolymers, terpolymers, interpolymers, and so on.
- interpolymer is used herein interchangeably with the term copolymer to refer to polymers incorporating in polymerized form at least two copolymerizable monomers, or incorporating long chain branching as a result of chain termination/olefin formation reactions in situ, and reincorporation of the in situ formed olefin. Accordingly, copolymers may result from the polymerization of a single monomer, under the correct operating conditions.
- the least prevalent monomer or monomers in the resulting interpolymer are generally referred to by the term "comonomer".
- the chain length of the resulting long chain branches referred to above is consequently longer than the carbon length resulting from polymerization of any deliberately added comonomer, and in particular, is longer than 6 carbons for ethylene/ 1-octene copolymers.
- the presence of long chain branching may also be detected by the increased shear sensitivity of the polymer, as disclosed in EP-A-608,369, and elsewhere, or determined by Melt Index Ratio (MIR), a ratio of polymer melt viscosities measured under differing loads, especially
- MIR Melt Index Ratio
- the process described herein may be employed to prepare any olefin interpolymer, especially copolymers of ethylene, one or more C 3-2 o olefins, and one or more C 4 . 20 diolefins, and especially, ethylene/propylene/5-ethylidene-2-norbornene (EPDM) interpolymers.
- EPDM ethylene/propylene/5-ethylidene-2-norbornene
- Polymerization conditions generally refer to temperature, pressure, monomer content (including comonomer concentration), catalyst concentration, cocatalyst concentration, monomer conversion, or other conditions that influence the properties of the resulting polymer.
- high molecular weight polymers may be prepared having relatively high comonomer incorporation with high catalyst activities, low cocatalyst usage and high molecular weights.
- activities based on weight of polymer to weight of transition metal
- activities greater than 0.5 g/ ⁇ g, preferably greater than 0.55 g/ ⁇ g, and even greater than 0.6 g/ ⁇ g are possible.
- Polymer weight-average molecular weight is measured by gel permeation chromatography, one technique of which as described in USP 5,272,236.
- melt index I 2 , 1 10 or I 2
- melt index is inversely related to the molecular weight of the polymer. The higher the molecular weight, the lower the melt index, although the relationship is not necessarily linear.
- Mooney viscosity ML 1+4 @ 100 0 C.
- Suitable polymers are those having a Mooney viscosity in the range from 10 to 135, more preferably from 25 to 100, and most preferably from 30 to 80.
- One embodiment of this invention entails a process which comprises contacting ethylene, one or more C 3 . 30 ⁇ -olefins, especially propylene, and a conjugated or non-conjugated diene, especially 5-ethylidene-2-norbornene in a solution polymerization process.
- the present invented process is particularly advantageous for use under polymerization conditions wherein a reaction mixture comprising metal complex, activating cocatalyst, ethylene, and at least one C 3-30 ⁇ -olef ⁇ n comonomer (or the individual components thereof) is continuously or intermittently added to a reactor operating under solution polymerization conditions, optionally in the additional presence of a chain transfer agent, and polymerized product is continuously or semi-continuously removed therefrom.
- the present process comprises polymerizing ethylene, one or more C 3 . 30 ⁇ -olefins, and a diolefin using a zirconium complex and from 10 to 200 moles per mole zirconium of an alumoxane, under continuous, solution polymerization conditions at a temperature from 120 to 250 0 C, preferably from 130 to 250 0 C, under high ethylene conversion conditions (>85 percent, preferably >90 percent) to prepare a polymer comprising from 0 to 99, preferably 50 to 90 percent ethylene, 9.5 to 99.5, preferably 10 to 50 percent ⁇ -olefin, and 0.1 to 50, preferably 0.1 to 20, more preferably 0.1 to 15 percent diene.
- the present metal complexes are capable of producing polymers from diene monomers having extremely high molecular weight under a variety of polymerization conditions, and catalyst efficiencies of greater than 0.5 gpoiy m cr/ ⁇ g met ai,, thereby allowing the use of a chain transfer agent to control molecular weight without sacrificing molecular weight distribution, ⁇ - olefin content or diene content.
- a sufficient quantity of chain transfer agent is preferably used so that a substantial decrease in molecular weight (>30 percent) occurs compared to a comparative polymerization without the use of chain transfer agent.
- the chain transfer agent is hydrogen
- at least 0.01 mol percent (based on ethylene) is used, and a maximum of about 2 mol percent is used.
- high comonomer content polymers can be prepared with high levels of chain transfer agents, while still affording narrow molecular weight distribution polymers using low levels of alumoxane activators.
- use of high levels of chain transfer agent and high levels of comonomer with conventional catalysts results in production of polymers having broadened molecular weight distributions.
- the metal complexes are activated in various ways to yield catalyst compounds having a vacant coordination site that will coordinate, insert, and polymerize addition polymerizable monomers, especially olefin(s).
- activator or "cocatalyst” is defined to be any compound or component or method which can activate the metal complex in the foregoing manner.
- suitable activators include Lewis acids, non-coordinating ionic activators, ionizing activators, organometal compounds, and combinations of the foregoing substances capable of converting the neutral metal complex to a catalytically active species.
- catalyst activation may involve formation of a cationic, partially cationic, or zwitterionic species, by means of proton transfer, oxidation, or other suitable activation process. It is to be understood that the present invention is operable and fully enabled regardless of whether or not such an identifiable cationic, partially cationic, or zwitterionic species actually results during the activation process, also interchangeably referred to herein as an "ionization” process or "ionic activation process".
- Ionizing cocatalysts may contain an active proton, or some other cation associated with, but not coordinated to or only loosely coordinated to, an anion of the ionizing compound.
- Such compounds are described in European publications EP-A-570982, EP-A-520732, EP-A-495375, EP- A-500944, EP-A-277 003 and EP-A-277004, and U.S. Patents: 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124.
- ammonium cation containing salts especially those containing trihydrocarbyl- substituted ammonium cations containing one or two Ci 0-40 alkyl groups, especially methylbis(octadecyl)- ammonium- and methylbis(tetradecyl)-amrnonium- cations and a non-coordinating anion, especially a tetrakis(perfluoro)arylborate anion, especially tetrakis( ⁇ entafluorophenyl)borate.
- the cation may comprise a mixture of hydrocarbyl groups of differing lengths.
- the protonated ammonium cation derived from the commercially available long-chain amine comprising a mixture of two Ci 4 , Ci ⁇ or Ci 8 alkyl groups and one methyl group.
- Such amines are available from Chemtura Corp., under the trade name KemamineTM T9701 , and from Akzo- Nobel under the trade name ArmeenTM M2HT.
- a most preferred ammonium salt activator is methyldi(C
- ionizing ionic compounds not containing an active proton but capable of forming active catalyst compositions are also contemplated for use herein, and are described in EP-A-426637, EP-A- 573403 and U.S. Patent 5,387,568.
- strong Lewis acids especially tris(perfluoro)aryl borane compounds, such as tris(pentafluorophenyl)borane, which are capable of abstraction of a ligand groups, especially a hydrocarbyl ligand, thereby forming a non-coordinating counter anion for the cationic derivative of the metal complex.
- a class of cocatalysts comprising non-coordinating anions generically referred to as expanded anions, further disclosed in U. S. Patent 6,395,671, may be suitably employed to activate the metal complexes of the present invention for olefin polymerization.
- these cocatalysts (illustrated by those having imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide anions) may be depicted as follows:
- A* + is a cation, especially a proton containing cation, and preferably is a trihydrocarbyl ammonium cation containing one or two Ci 0-40 alkyl groups, especially a methyldi(Ci ⁇ 2 oalkyl)ammonium- cation,
- R 4 independently each occurrence, is hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms not counting hydrogen, preferably C] -2O alkyl, and
- J*' is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane).
- these catalyst activators include trihydrocarbylammonium- salts, especially, methyldi(C I4-2 oalkyl)ammonium- salts of: bis(tris(pentafluorophenyl)borane)imidazolide, bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide, bis(tris(pentafluorophenyI)borane)-2-heptadecylimidazoIide, bis(tris(pentafluorophenyl)borane)- 4,5-bis(undecyl)imidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide, bis(tris
- 2-heptadecyIimidazolinide bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide, bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, and bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.
- activators include those described in PCT publication WO 98/07515 such as tris (2,
- activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, EP-A-O 573120, PCT publications WO 94/07928 and WO 95/14044 and US Patents 5, 153, 157 and
- WO 98/09996 describes activating catalyst compounds with perchlorates, periodates and iodates, including their hydrates.
- WO 99/18135 describes the use of organoboroaluminum activators.
- EP-A-781299 describes using a silylium salt in combination with a non-coordinating compatible anion.
- Other activators or methods for activating a catalyst compound are described in for example, U. S. Patents 5,849,852, 5,859, 653, 5,869,723, EP-A-615981, and PCT publication WO 98/32775.
- alumoxanes also referred to as alkylaluminoxanes.
- Alumoxanes are well known activators for use with metallocene type catalyst compounds to prepare addition polymerization catalysts.
- metallocene type catalyst compounds to prepare addition polymerization catalysts.
- methods for preparing alumoxanes and modified alumoxanes are described in U.S.
- Preferred alumoxanes are Lewis acid modified alumoxanes, especially tri(C 3 .
- alkylaluminum modified methylalumoxane including tri(isobutyl)aluminum modified methalumoxane, available commercially as JVIMAO-3A or tri(n-octyl)aluminum modified methalumoxane, available commercially as MMAO- 12, from Akzo Nobel, Inc. It is within the scope of this invention to use alumoxane(s) or modified alumoxane(s) as an activator or as a tertiary component in the invented process.
- the compound may be used alone or in combination with other activators, either neutral or ionic, such as tri(alkyl)ammonium tetrakis(pentafluorophenyl)borate compounds, trisperfluoroaryl compounds, polyhalogenated heteroborane anions as disclosed in WO 98/43983, and combinations thereof.
- activators either neutral or ionic, such as tri(alkyl)ammonium tetrakis(pentafluorophenyl)borate compounds, trisperfluoroaryl compounds, polyhalogenated heteroborane anions as disclosed in WO 98/43983, and combinations thereof.
- the amount of alumoxane employed is generally less than that necessary to effectively activate the metal complex when employed alone. In this embodiment, it is believed, without wishing to be bound by such belief, that the alumoxane does not contribute significantly to actual catalyst activation.
- Suitable alumoxanes include polymeric or oligomeric alumoxanes, especially methylalumoxane (MAO) as well as Lewis acid- modified alumoxanes, especially trihydrocarbylaluminum-, halogenated tri(hydrocarbyl)aluminum- or halogenated tri(hydrocarbyl)boron- modified alumoxanes, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group.
- MAO methylalumoxane
- Lewis acid- modified alumoxanes especially trihydrocarbylaluminum-, halogenated tri(hydrocarbyl)aluminum- or halogenated tri(hydrocarbyl)boron- modified alumoxanes, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group.
- Preferred Lewis acid- modified alumoxane compounds are tri(i-butyl)aluminum- modified methalumoxane and tri(n- octyl)aluminum- modified methalumoxane containing from 10 to 30, preferably 15 to 25 mole percent i-butyl content and 10 to 20, preferably 12 to 18 mole percent n-octyl contents, respectively, said molar percents based on total alkyl Iigand content.
- the alumoxane or Lewis acid- modified alumoxane activator is preferably utilized in molar ratios cocatalystxatalyst from 20-200, more preferably from 20-150, and most preferably from 20-80.
- the present zirconium complexes can achieve reduced levels of cocatalyst byproducts in the resulting polymer along with long chain branch formation in the resulting polymer. This in turn allows the polymers to be employed in demanding applications that have been previously unsuited for ethylene/ ⁇ -olefin interpolymers, such as wire and cable electrical insulation and extrusion forming process for profiles, pipes, and other applications, while retaining good flexibility and processing properties.
- Multiple reactor polymerization processes may be suitably employed in the present invention. Examples include such systems as are disclosed in USP 3,914,342, among others.
- the multiple reactors can be operated in series or in parallel, with at least one catalyst composition according to the present invention employed in at least one of the reactors.
- One or both reactors may also contain at least two catalysts which have different comonomer incorporation capability and/or different molecular weight capability.
- a relatively high molecular weight product (M w from 100,000 to over 1 ,000,000, more preferably 200,000 to 500,000) is formed while in the second reactor a product of a relatively low molecular weight (M w 2,000 to 300,000) is formed. Both of these reactor products can have similar or different densities and/or elastomer content.
- the final product is a mixture of the two reactor effluents which are combined prior to devolatilization to result in a uniform mixing of the two or more polymer products.
- one reactor may be used to prepare a high ethylene content copolymer optionally containing diene while the second reactor is employed to prepare a homopolymer of either ethylene or the ⁇ -olefin or a copolymer of ethylene and one or more ⁇ -olefins.
- the reactors are connected in series, that is, the effluent from the first reactor is charged to the second reactor and fresh monomer, solvent and hydrogen is optionally added to the second reactor.
- Reactor conditions are adjusted such that the weight ratio of polymer produced in the first reactor to that produced in the second reactor is ideally in the range from 5:95 to 95:5.
- the foregoing dual reactor process is capable of producing polymers having broadened molecular weight distribution or polydispersity index (PDI).
- Preferred polymers made in the foregoing manner have PDI from 2.8 to 10.0, more preferably from 3.0 to 7.0.
- the high molecular weight component contains higher quantities of ⁇ -olefin comonomer (lower density) than the low molecular weight component.
- one of the reactors in the polymerization process contains a heterogeneous Ziegler-Natta catalyst or a chromium containing catalyst, such as one of the numerous such catalysts known in the art.
- Ziegler-Natta catalysts include, but are not limited to, titanium-based catalysts supported on MgCl 2 , and additionally comprise compounds of aluminum containing at least one aluminum-alkyl bond.
- Suitable Ziegler-Natta catalysts and their preparation include, but are not limited to, those disclosed in USP's 4,612,300, 4,330,646, and 5,869,575.
- Suitable chromium based catalysts are those disclosed in USP's 4,981,927, 4,835,219, 4,564,660, 4,173,548, 3,953,413, and elsewhere.
- Single reactor, multiple catalyst processes are also useful in the present invention.
- two or more catalysts are introduced into a single reactor at the high monomer conversion conditions that are herein disclosed, wherein each catalyst inherently produces different interpolymer products.
- a relatively high molecular weight product (M w from 100,000 to over 1,000,000, more preferably 200,000 to 500,000) is formed from one catalyst while a product of a relatively low molecular weight (M w 2,000 to 300,000) is formed from the other catalyst.
- M w molecular weight product
- M w 2,000 to 300,000 a relatively low molecular weight
- Both of these catalyst compositions can have similar or different comonomer incorporation ability, at least one of which comprises a metal complex as set forth herein.
- the resulting polymer will have properties dependant on the ratio of the two catalysts that are employed in the single reactor.
- the second catalyst composition may comprise a metal complex as herein disclosed, a metallocene or other ⁇ -bonded ligand group containing metal complex (including constrained geometry metal complexes), or a polyvalent heteroatom ligand group containing metal complex, especially polyvalent pyridylamine or imidizolylamine based complexes and tetradendate oxygen-ligated biphenylphenol based Group 4 metal complexes.
- Suitable metal complexes for use according to the present invention include compounds corresponding to the formula:
- R 20 independently each occurrence is a divalent aromatic or inertly substituted aromatic group containing from 5 to 20 atoms not counting hydrogen
- T 3 is a divalent hydrocarbon or silane group having from 1 to 20 atoms not counting hydrogen, or an inertly substituted derivative thereof
- R D independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two R D groups together are a divalent ligand group of from 1 to 20 atoms, not counting hydrogen.
- Ar 2 independently each occurrence is an arylene or an alkyl-, aryl-, alkoxy- or amino- substituted arylene group of from 6 to 20 atoms not counting hydrogen or any atoms of any substituent;
- T 3 is a divalent hydrocarbon bridging group of from 2 to 20 atoms not counting hydrogen, preferably a divalent substituted or unsubstituted C 3-6 aliphatic, cycloaliphatic, or bis(alkylene)- substituted cycloaliphatic group; and
- R D independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two R D groups together are a divalent ligand group of from 1 to 40 atoms, not counting hydrogen.
- metal complexes suitable for use herein include compounds of the formula:
- Ar 4 independently each occurrence is Cg -2O aryl or inertly substituted derivatives thereof, especially 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, 3,5-di(tertbutyl)phenyl, dibenzo-lH- pyrrole-1-yl, ⁇ aphthyl, anthracen-5-yl, l,2,3,4,6,7,8,9-octahydroanthrace ⁇ -5-yl; T 4 independently each occurrence is a propylene-l,3-diyl group, a cyclohexan-l,2-diyl group, a bis(alkylene)cyclohexan-l,2-diyl group, a cyclohexen-4,5-diyl group, or an inertly substituted derivative thereof;
- R 21 independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen;
- R D independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R D groups together are a divalent hydrocarbylene, hydrocarbadiyl or trihydrocarbylsilyl group of up to 40 atoms not counting hydrogen.
- Especially preferred metal complexes are compounds of the formula:
- Ar 4 independently each occurrence, is 3,5-di(isopropyl)phenyl, 3,5- di(isobutyl)phenyl, 3,5-di(tertbutyl)phenyl, dibenzo-lH-pyrroIe-l-yl, or anthracen-5-yl,
- R 2 ' independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen;
- T 4 is propan-l,3-diyl, cyclohexanediyl, cyclohexen ⁇ 4,5-diyl, or bis(methylene)cyclohexan- 1,2-diyl;
- R D independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R D groups together are a hydrocarbylene, hydrocarbadiyl or hydrocarbyls ⁇ anediyl group of up to 40 atoms not counting hydrogen.
- metal complexes comprising a 1 ,4-butandiyl T 4 group
- the foregoing complexes demonstrate improved catalyst efficiencies, especially at elevated polymerization temperatures.
- Most highly preferred metal complexes according to the invention correspond to the formulas: wherein, R D independently each occurrence is chloro, methyl or benzyl.
- suitable metal complexes are the following compounds: A) bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-l,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l ,2,3 A6 J ⁇ octahydroanthracen-S-yO-SKmethyOphenyl ⁇ -phenoxy)- 1 ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2- ⁇ henoxy)-l,3- propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyr
- 1,3-propanediylzirconium (IV) dichloride bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-
- the foregoing metal complexes may be conveniently prepared by standard metallation and liga ⁇ d exchange procedures involving a source of the transition metal and a neutral polyfunctional ligand source.
- the complexes may also be prepared by means of an amide elimination and hydrocarbylation process starting from the corresponding transition metal tetraamide and a hydrocarbylating agent, such as trimethylaluminum.
- the techniques employed are the same as or analogous to those disclosed in USP's 6,320,005, 6,103,657, WO 02/38628, WO 03/40195, US-A- 2004/0220050, and elsewhere.
- the metal complex is activated to form the active catalyst composition by combination with the cocatalyst.
- the activation may occur prior to addition of the catalyst composition to the reactor with or without the presence of other components of the reaction mixture, or in situ through separate addition of the metal complex and activating cocatalyst to the reactor.
- Suitable olefin mixtures for use herein include mixtures of ethylene, one or more 0 3 . 30 ⁇ - olefins and one or more conjugated or nonconjugated dienes.
- Suitable ⁇ -olefin comonomers include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- octene, 1-nonene, 1-decene, and 1-dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene, 1- eicosene, 3-methyl- 1-butene, 3-methyl-l-pentene, 4-methyl- 1-pentene, 4,6-dimethyl- 1-heptene, and vinylcyclohexane.
- Suitable dienes for use herein include straight chain-, branched chain-, cyclic-, and polycyclic hydrocarbon dienes having from 6 to 15 carbon atoms.
- suitable non- conjugated dienes include, but are not limited to, straight chain acyclic dienes, such as 1,4- hexadiene, 1 ,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as 5- methyl- 1 ,4-hexadiene; 3,7-dimethyl-l,6-octadiene; 3,7-dimethyl- 1,7-octadiene and mixed isomers of dihydromyricene and dihydroocinene, single ring alicyclic dienes, such as 1 ,3-cyclopentadiene; 1 ,4-cyclohexadiene; 1 ,5-cyclooctadiene and 1,5-cyclododecad
- the particularly preferred dienes are 1 ,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2- norbornene (VNB), 5-methylene-2-norbornene (MNB), and dicyclopentadiene (DCPD).
- the most especially preferred diene is 5-ethylidene-2-norbornene (ENB).
- the polymerization may be accomplished at conditions well known in the prior art for olefin solution polymerization reactions.
- Preferred polymerization temperatures are from 80 to 250 0 C, more preferably from 100-200 0 C.
- Preferred polymerization pressures are from atmospheric to 3000 atmospheres (100 kPa to 300 MPa), more preferably from 1 MPa to 10 MPa.
- the molar ratio of catalyst: polymerizable compound employed is from 10 "12 :l to 10 1 :1 , more preferably from 10 " ": 1 to I0 "5 : L
- the reaction is conducted under continuous, solution polymerization conditions, that is, conditions wherein the monomer or monomers are continuously added to a reactor operating under solution polymerization conditions, and polymerized product is continuously or semi-continuously removed and recovered or forwarded to a second reactor.
- the polymerization mixture comprises an aliphatic or alicyclic liquid diluent.
- aliphatic or alicyclic liquid diluents include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcyclo- heptane, and mixtures thereof; and perfluorinated hydrocarbons such as perfluorinated C 4 . 10 alkanes, and the like.
- a preferred liquid diluent is a hydrogenated oligomeric aliphatic hydrocarbon mixture having a distillation, ASTM D 86, IBP of 118 0 C, distillation, ASTM D 86, Dry Point of 137 0 C, and Specific Gravity, 15.6 0 C, ASTM D 1250 of 0.72 sold commercially under the trade designation IsoparTM E, available from ExxonMobil Corporation.
- molecular weight control agents or chain transfer agents in the present process is desired.
- molecular weight control agents include hydrogen, trialkyl aluminum compounds, or other known chain transfer agents. Hydrogen is a most preferred molecular weight control agent or chain transfer agent.
- a particular benefit of the use of the present invention is the ability (depending on reaction conditions) to produce narrow molecular weight distribution ethylene/ ⁇ -olefin interpolymers.
- Preferred polymers have Mw/Mn of less than 3.0, more preferably less than 2.6.
- Such narrow molecular weight distribution polymer products are highly desirable due to improved tensile strength properties as well as reduced levels of extractables and metal values.
- one means for carrying out the present polymerization process is as follows.
- the monomers to be polymerized are introduced continuously together with any solvent or diluent.
- the reactor contains a liquid phase composed substantially of monomers together with any solvent or diluent and dissolved polymer.
- Catalyst along with cocatalyst and optionally chain transfer agent are continuously or intermittently introduced in the reactor liquid phase or any recycled portion thereof.
- the reactor temperature may be controlled by adjusting the solvent/monomer ratio, the catalyst addition rate, as well as by use of cooling or heating coils, jackets or both.
- the polymerization rate is controlled by the rate of catalyst addition.
- Pressure is controlled by the monomer flow rate and partial pressures of volatile components.
- the ethylene content of the polymer product is determined by the ratio of ethylene to comonomer in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor.
- the polymer product molecular weight is controlled, optionally, by controlling other polymerization variables such as the temperature, monomer concentration, or by the flow rate of he previously mentioned chain transfer agent.
- a catalyst kill agent such as water, steam or an alcohol.
- the polymer solution is optionally heated, and the polymer product is recovered by flashing off gaseous monomers as well as residual solvent or diluent at reduced pressure, and, if necessary, conducting further devolatilization in equipment such as a de volatilizing extruder.
- the mean residence time of the catalyst and polymer in the reactor generally is from 5 minutes to 8 hours, and preferably is from 10 minutes to 6 hours.
- the foregoing polymerization may be carried out in a continuous loop reactor with or without a monomer, comonomer, catalyst or cocatalyst gradient established between differing regions thereof, optionally accompanied by separate addition of catalysts and/or chain transfer agent, and operating under adiabatic or non-adiabatic solution polymerization conditions or combinations of the foregoing reactor conditions.
- suitable loop reactors and a variety of suitable operating conditions for use therewith are found in USFs 5,977,251 , 6, 319,989 and 6,683, 149.
- a process for polymerization of ethylene, one or more C 3 - 30 ⁇ -olefins and one or more conjugated or nonconjugated dienes under continuous, solution polymerization conditions to prepare a high molecular weight interpolymer comprising conducting the polymerization in the presence of a catalyst composition comprising a zirconium complex of a polyvalent aryloxyether corresponding to the formula:
- R 20 independently each occurrence is a divalent aromatic or inertly substituted aromatic group containing from 5 to 20 atoms not counting hydrogen;
- T 3 is a divalent hydrocarbon or silane group having from 1 to 20 atoms not counting hydrogen, or an inertly substituted derivative thereof;
- R D independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two R D groups together are a divalent ligand group of from 1 to 40 atoms, not counting hydrogen; and an activating cocatalyst at a temperature from 80 to 250 0 C and a pressure from 100 kPa to 300 MPa.
- 5-ethylidene-2-norbornene, 5-vinylidene-2-norbornene, 5-methylene ⁇ 2-norbornene, and dicyclopentadiene is polymerized.
- Ar 2 independently each occurrence is an arylene or an alkyl-, aryl-, alkoxy- or amino- substituted arylene group of from 6 to 20 atoms not counting hydrogen or any atoms of any substituent;
- T 3 is a divalent hydrocarbon bridging group of from 2 to 20 atoms not counting hydrogen, preferably a divalent substituted or unsubstituted C 3-6 aliphatic, cycloaliphatic, or bis(alkylene)- substituted cycloaliphatic group; and
- R D independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two R D groups together are a divalent ligand group of from 1 to 40 atoms, not counting hydrogen. 15.
- the process of embodiment 14 wherein the metal complex corresponds to the formula: , where
- Ar 4 independently each occurrence is C ⁇ . 2 o aryl or inertly substituted derivatives thereof, especially 3,5-di(isopropyl)phenyl, 3,5-di(isobutyI)phenyl, dibenzo-lH-pyrrole-1-y], naphthyl, anthracen-5-yl, 1 ,2,3,4,6,7,8,9-octahydroanthracen-5-yI ;
- T 4 independently each occurrence is a propylene- 1 ,3-diyl group, a cyclohexan-l,2-diyl group, a bis(alkylene)cyclohexan-],2-diyl group, a cyclohexen-4,5-diy] group, or an inertly substituted derivative thereof;
- R 21 independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen;
- R D independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R D groups together are a divalent hydrocarbylene, hydrocarbadiyl or trihydrocarbylsilyl group of up to 40 atoms not counting hydrogen.
- R D independently each occurrence is chloro, methyl or benzyl.
- ⁇ - propanediylzirconium (IV) dimethyl bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy)-1,3- propanediylzirconium (FV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrroIe- 1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(3,5-di-(I ,i-dimethyIethyl)phenyl)-5-(methyl)phenyI)-(4-methyl-2-phenoxy)-l ,3- propanediylzirconium (IV) dimethyl, , bis((2-oxoyl-3-(
- 4,5-cyclohexenediylzirconium (IV) dimethyl bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethyIethyl)phenyl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))-cis- 4,5-cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis- 4,5-cyclohexenediylzirconiutn (IV) dibenzyl,
- A3 bis((2-oxoyl-3-(3,5-bis-(l , 1 -dimethylethyl)
- A4 bis((2-oxoyl-3-(dibenzo-1 H-pyrrole- 1 -yl)-5- phenyl)-5-(methyl)phenyl)-2- phenoxy)- (methyl)phenyl)-2-phenoxy)-
- A5 bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-
- A6 bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -y ⁇ )-5- (methyI)phenyD-2-phenoxy)-cis- (methyI) ⁇ henyr)-2-phenoxymethyl)- cis- 1 ,3-cycfohexanediyl zirconium (IV) dimethyl 4,5-cyck)hexenediyl zirconium (IV) dimethyl
- A7 bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yI)-5-
- A8 bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- l-yl)-5- (niethyl)phenyl)-( ⁇ rrEthyl-2-phenoxyrnethyl))- (methyl)phenyI)-2- ⁇ henoxy)- trans 1 ⁇ -cyclohexanezirconium (TV) dimethyl 1 ,4-butanediylzirconium QV) dimethyl
- A9 bis((2-oxoyl-3-(dibenzo-lH-py ⁇ O le- l-yT)-5-
- A10 bis((2-oxoyl-3-(dibenzo-lH-py ⁇ Ole-l-yI)-5- (rrethyl)phenyI)-(5-(2-i ⁇ E thyI)pr O pane-2-yl)-2- (methyI)phenyI)-(5-(2-methyl)propane-2-yl)-2- phenoxy)- 1 ,3-propanediyI zirconium (IV) dirrethyl ptenoxy> 1 ,3-propanediyl zirconium (TV) dichloride
- Al 1 bis((2-oxoyl-3-(3,5-bis-(l,l-di ⁇ thylethyI) Conrp: bis((2-oxoyl-3-(dibenzD- 1 H-pyrrole- 1 -yI)-5- phenyI)-5-(methyI)phenyl)-(5-2- ⁇ iethyI)propane (methyl)phenyr>-2-phenoxy ⁇ Ethyl)-trdns- -2-yj)2- pbsnoxy)- 1 ,3-propanediyl zirconium (IV) 1 ,2-cyctobsxanediylha ⁇ hium (TV) dimethyl dimethyl dimethyl
- Continuous solution polymerizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer.
- Purified mixed alkanes solvent IsoparTM E available from ExxonMobil, Inc.
- ethylene, propylene, 5-ethylidene-2-norbornene, and hydrogen are continuously supplied to a 3.8 L reactor equipped with a jacket for temperature control and an internal thermocouple.
- the solvent feed to the reactor is measured by a mass-flow controller.
- a variable speed diaphragm pump controls the solvent flow rate and pressure to the reactor. At the discharge of the pump, a side stream is taken to provide flush flows for the catalyst and cocatalyst injection lines and the reactor agitator.
- the remaining solvent is combined with monomers and hydrogen and fed to the reactor.
- a mass flow controller is used to deliver hydrogen to the reactor as needed.
- the temperature of the solvent/monomer solution is controlled by use of a heat exchanger before entering the reactor. This stream enters the bottom of the reactor.
- the catalyst and cocatalyst component solutions are metered using pumps and mass flow meters and are combined with the catalyst flush solvent and introduced into the bottom of the reactor.
- the cocatalyst used in runs 1-12 is a long-chain alkyl ammonium borate of approximate stoichiometry equal to methyldi(octadecyl)ammonium tetrakis(pentafluorophenyl)borate (MDB) combined with a tertiary component, tri(isobutyl)aluminum modified methalumoxane (MMAO) containing a molar ratio of i-butyl/methyl groups of about 1/3 in a molar ratio based on transition metal of 5/1.
- MDB methyldi(octadecyl)ammonium tetrakis(pentafluorophenyl)borate
- MMAO tri(isobutyl)aluminum modified methalumoxane
- the cocatalyst is MAO alone in a molar ratio based on Zr of 50: 1.
- the reactor is run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.
- Product is removed through exit lines at the top of the reactor. All exit lines from the reactor are steam traced and insulated. Polymerization is stopped by the addition of a small amount of water into the exit line along with any stabilizers or other additives and passing the mixture through a static mixer.
- the product stream is then heated by passing through a heat exchanger before devolatilization.
- the polymer product is recovered by extrusion using a devolatilizing extruder and water cooled pelletizer.
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020087030629A KR101401785B1 (en) | 2006-05-17 | 2007-04-24 | Ethylene/α-Olefin/Diene Solution Polymerization Process |
AU2007254428A AU2007254428A1 (en) | 2006-05-17 | 2007-04-24 | Ethylene/ alpha-olefin/ diene solution polymerization process |
US12/300,863 US8299189B2 (en) | 2006-05-17 | 2007-04-24 | Ethylene/α-olefin/diene solution polymerization process and polymer |
MX2008014668A MX2008014668A (en) | 2006-05-17 | 2007-04-24 | Ethylene/ alpha-olefin/ diene solution polymerization process. |
JP2009510950A JP5603595B2 (en) | 2006-05-17 | 2007-04-24 | Ethylene / α-olefin / diene solution polymerization method and polymer |
EP07755918.5A EP2024399B1 (en) | 2006-05-17 | 2007-04-24 | Ethylene/ alpha-olefin/ diene solution polymerization process |
CN2007800233160A CN101472952B (en) | 2006-05-17 | 2007-04-24 | Ethylene/ alpha-olefin/ diene solution polymerization process and polymer |
ES07755918.5T ES2475159T3 (en) | 2006-05-17 | 2007-04-24 | Polymerization procedure in ethylene / alpha-olefin / diene solution |
CA002652456A CA2652456A1 (en) | 2006-05-17 | 2007-04-24 | Ethylene/ .alpha.-olefin/ diene solution polymerization process and polymer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US80118206P | 2006-05-17 | 2006-05-17 | |
US60/801,182 | 2006-05-17 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2007136494A2 true WO2007136494A2 (en) | 2007-11-29 |
WO2007136494A3 WO2007136494A3 (en) | 2008-01-10 |
Family
ID=38572813
Family Applications (6)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2007/009843 WO2007136495A2 (en) | 2006-05-17 | 2007-04-24 | High efficiency solution polymerization process |
PCT/US2007/009845 WO2007136497A2 (en) | 2006-05-17 | 2007-04-24 | High temperature solution polymerization process |
PCT/US2007/009842 WO2007136494A2 (en) | 2006-05-17 | 2007-04-24 | Ethylene/ alpha-olefin/ diene solution polymerization process |
PCT/US2007/009844 WO2007136496A2 (en) | 2006-05-17 | 2007-04-24 | High temperature polyethylene solution polymerization process |
PCT/US2007/010070 WO2007136506A2 (en) | 2006-05-17 | 2007-04-24 | Polyolefin solution polymerization process and polymer |
PCT/US2007/009841 WO2007136493A2 (en) | 2006-05-17 | 2007-04-24 | Polypropylene solution polymerization process |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2007/009843 WO2007136495A2 (en) | 2006-05-17 | 2007-04-24 | High efficiency solution polymerization process |
PCT/US2007/009845 WO2007136497A2 (en) | 2006-05-17 | 2007-04-24 | High temperature solution polymerization process |
Family Applications After (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2007/009844 WO2007136496A2 (en) | 2006-05-17 | 2007-04-24 | High temperature polyethylene solution polymerization process |
PCT/US2007/010070 WO2007136506A2 (en) | 2006-05-17 | 2007-04-24 | Polyolefin solution polymerization process and polymer |
PCT/US2007/009841 WO2007136493A2 (en) | 2006-05-17 | 2007-04-24 | Polypropylene solution polymerization process |
Country Status (14)
Country | Link |
---|---|
US (7) | US8101696B2 (en) |
EP (8) | EP2787013A1 (en) |
JP (6) | JP5666129B2 (en) |
KR (6) | KR101384380B1 (en) |
CN (8) | CN101490094B (en) |
AR (6) | AR060641A1 (en) |
AU (1) | AU2007254428A1 (en) |
BR (3) | BRPI0711819A2 (en) |
CA (5) | CA2652551A1 (en) |
ES (7) | ES2634440T3 (en) |
MX (4) | MX2008014668A (en) |
RU (4) | RU2450026C2 (en) |
SG (1) | SG158102A1 (en) |
WO (6) | WO2007136495A2 (en) |
Cited By (74)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010079906A3 (en) * | 2009-01-06 | 2010-08-26 | 에스케이에너지 주식회사 | Ethylene-propylene-diene copolymer production method |
WO2011025784A1 (en) | 2009-08-31 | 2011-03-03 | Dow Global Technologies Inc. | Catalyst and process for polymerizing an olefin and polyolefin prepared thereby |
WO2011066469A1 (en) | 2009-11-24 | 2011-06-03 | Dow Global Technologies Inc. | Extrusion coating composition |
WO2011079207A1 (en) | 2009-12-24 | 2011-06-30 | Dow Global Technologies Llc | Polymer compositions, methods of making the same, and articles prepared from the same |
WO2011146291A1 (en) | 2010-05-17 | 2011-11-24 | Dow Global Technologies Llc | Process for selectively polymerizing ethylene and catalyst therefor |
WO2012064630A2 (en) | 2010-11-08 | 2012-05-18 | Dow Global Technologies Llc | Solution polymerization process and procatalyst carrier systems useful therein |
WO2012074812A1 (en) | 2010-12-03 | 2012-06-07 | Dow Global Technologies Llc | Processes to prepare ethylene-based polymer compositions |
WO2012088235A2 (en) | 2010-12-21 | 2012-06-28 | Dow Global Technologies Llc | Olefin-based polymers and dispersion polymerizations |
WO2012088217A1 (en) | 2010-12-21 | 2012-06-28 | Dow Global Technologies Llc | Polymerization process and raman analysis for olefin-based polymers |
WO2012092491A2 (en) | 2010-12-30 | 2012-07-05 | Dow Global Technologies Llc | Compositions, methods of making the same, and articles prepared from the same |
WO2013039739A1 (en) | 2011-09-07 | 2013-03-21 | Dow Global Technologies Llc | Polymer compositions and articles prepared from the same |
WO2013039850A1 (en) | 2011-09-12 | 2013-03-21 | Dow Global Technologies Llc | Compositions and articles formed from the same |
WO2013043796A2 (en) * | 2011-09-23 | 2013-03-28 | Exxonmobil Chemical Patents Inc. | Modified polyethylene compositions |
WO2013055642A1 (en) | 2011-10-10 | 2013-04-18 | Dow Global Technologies Llc | Polymer compositions with improved retention of properties under mechanical and thermal stresses |
WO2013059391A1 (en) | 2011-10-20 | 2013-04-25 | Dow Global Technologies Llc | Ethylene-based polymer compositions and articles prepared therefrom |
JP2013521382A (en) * | 2010-03-02 | 2013-06-10 | ダウ グローバル テクノロジーズ エルエルシー | Ethylene polymer composition |
WO2013096418A1 (en) | 2011-12-19 | 2013-06-27 | Dow Global Technologies Llc | Ethylene-based polymers prepared by dispersion polymerization |
WO2013096573A1 (en) | 2011-12-20 | 2013-06-27 | Dow Global Technologies Llc | Ethylene/alpha-olefin/nonconjugated polyene interpolymers and processes to form the same |
JP2013528689A (en) * | 2010-06-14 | 2013-07-11 | ダウ グローバル テクノロジーズ エルエルシー | Ethylene-based polymer composition for use as a blend component in shrink film applications |
WO2014084893A1 (en) | 2012-11-30 | 2014-06-05 | Dow Global Technologies Llc | Ethylene/alpha-olefin/polyene based compositions |
US8784996B2 (en) | 2009-11-24 | 2014-07-22 | Dow Global Technologies Llc | Extrusion coating composition |
WO2014113046A1 (en) | 2013-01-18 | 2014-07-24 | Dow Global Technologies Llc | Polymerization processes for high molecular weight polyolefins |
CN104628920A (en) * | 2013-11-08 | 2015-05-20 | 中国石油天然气股份有限公司 | Preparation method of solution polymerized ethylene propylene (EP) rubber |
WO2015116382A1 (en) * | 2014-01-30 | 2015-08-06 | Exxonmobil Chemical Patents Inc. | Foamed polyethylene compositions |
WO2015116381A1 (en) * | 2014-01-30 | 2015-08-06 | Exxonmobil Chemical Patents Inc. | Crack-resistant polyethylene composiitions |
WO2016014749A1 (en) | 2014-07-24 | 2016-01-28 | Dow Global Technologies Llc | Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers |
WO2016209807A1 (en) | 2015-06-22 | 2016-12-29 | Dow Global Technologies Llc | Process for making ethylene-based polymers using carbon-carbon free radical initiators |
US9605098B2 (en) | 2013-06-28 | 2017-03-28 | Dow Global Technologies Llc | Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts |
WO2017210201A1 (en) | 2016-05-30 | 2017-12-07 | Dow Global Technologies Llc | Ethylene/alpha-olefin/diene interpolymers compositions |
WO2017210195A1 (en) | 2016-05-30 | 2017-12-07 | Dow Global Technologies Llc | Ethylene/alpha-olefin/diene interpolymer |
WO2018005852A1 (en) | 2016-06-30 | 2018-01-04 | Dow Global Technologies Llc | Ethylene/alpha-olefin/polyene based compositions |
WO2018005922A1 (en) | 2016-06-30 | 2018-01-04 | Dow Global Technologies Llc | Ethylene/alpha-olefin/polyene interpolymers and compositions containing the same |
WO2018005789A1 (en) | 2016-06-30 | 2018-01-04 | Dow Global Technologies Llc | Procatalyst compositions useful for low comonomer incorporation and process for preparing the same |
WO2018013285A1 (en) | 2016-07-14 | 2018-01-18 | Exxonmobil Chemical Patents Inc. | Dual metallocene-catalyzed bimodal copolymer compositions |
WO2018013284A2 (en) | 2016-07-13 | 2018-01-18 | Exxonmobil Chemical Patents Inc. | Dual metallocene catalyst copolymer compositions |
WO2018013283A2 (en) | 2016-07-13 | 2018-01-18 | Exxonmobil Chemical Patents Inc. | Dual metallocene catalyst copolymer compositions |
EP2523983B1 (en) * | 2010-01-14 | 2018-03-21 | ExxonMobil Chemical Patents Inc. | Processes and apparatus for continuous solution polymerization |
WO2018063900A1 (en) | 2016-09-29 | 2018-04-05 | Dow Global Technologies Llc | Method of polymerizing an olefin |
WO2018063898A1 (en) | 2016-09-29 | 2018-04-05 | Dow Global Technologies Llc | Modified ziegler-natta (pro)catalyst and system |
WO2018080690A1 (en) | 2016-10-27 | 2018-05-03 | Univation Technologies, Llc | Method of preparing a molecular catalyst |
US10059787B2 (en) | 2012-12-27 | 2018-08-28 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
WO2018231224A1 (en) | 2017-06-14 | 2018-12-20 | Exxonmobil Chemical Patents Inc. | Ethylene copolymer blends for cross-linking applications |
US10214602B2 (en) | 2012-12-27 | 2019-02-26 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US10214622B2 (en) | 2012-12-27 | 2019-02-26 | Dow Global Technologies Llc | Catalyst systems for olefin polymerization |
WO2019040845A1 (en) | 2017-08-24 | 2019-02-28 | Dow Global Technologies Llc | Ethylene/c5-c10 alpha-olefin/ polyene interpolymers |
US10336846B2 (en) | 2015-05-28 | 2019-07-02 | Dow Global Technologies Llc | Process to form ethylene/α-olefin interpolymers |
WO2019157687A1 (en) | 2018-02-14 | 2019-08-22 | Dow Global Technologies Llc | Ethylene/alpha-olefin interpolymer compositions with improved long term heat aging performance |
US10487200B2 (en) | 2015-10-29 | 2019-11-26 | Dow Global Technologies Llc | Crosslinkable polymeric compositions for flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation |
US10490319B2 (en) | 2015-09-02 | 2019-11-26 | Dow Global Technologies Llc | Flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation |
WO2020046597A1 (en) | 2018-08-29 | 2020-03-05 | Exxonmobil Chemical Patents Inc. | Methods of making polymer compositions with enhanced elasticity by employing vtp and hmp catalyst systems in parallel processes |
US10597473B2 (en) | 2015-06-30 | 2020-03-24 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US10647797B2 (en) | 2015-09-30 | 2020-05-12 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US10822479B2 (en) | 2012-09-20 | 2020-11-03 | Exxonmobil Chemical Patents Inc. | Foamed polyethylene compositions |
US10836853B2 (en) | 2012-09-20 | 2020-11-17 | Exxonmobil Chemical Patents Inc. | Crack-resistant polyethylene compositions |
US10870713B2 (en) | 2015-09-30 | 2020-12-22 | Dow Global Technologies Llc | Procatalyst and polymerization process using the same |
WO2021022014A1 (en) | 2019-07-31 | 2021-02-04 | Dow Global Technologies Llc | Polymerization of ethylene in solution processes using a ziegler-natta catalyst and a hydrogenation procatalyst |
WO2021041562A1 (en) | 2019-08-30 | 2021-03-04 | Dow Global Technologies Llc | Polyolefin compositions having improved electrical properties |
WO2021061580A1 (en) | 2019-09-24 | 2021-04-01 | Dow Global Technologies Llc | Polymer compositions for extruded profiles |
WO2021061577A1 (en) | 2019-09-24 | 2021-04-01 | Dow Global Technologies Llc | Ethylene/alpha-olefin/polyene interpolymer compositions |
US11041027B2 (en) | 2015-06-30 | 2021-06-22 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US11066428B2 (en) | 2017-09-29 | 2021-07-20 | Dow Global Technologies Llc | Bis-phenyl-phenoxy polyolefin catalysts having a methylenetrialkylsilicon ligand on the metal for improved solubility |
US11066489B2 (en) | 2017-09-29 | 2021-07-20 | Dow Global Technologies Llc | Bis-phenyl-phenoxy polyolefin catalysts having two methylenetrialkylsilicon ligands on the metal for improved solubility |
WO2021202091A1 (en) | 2020-03-30 | 2021-10-07 | Exxonmobil Chemical Patents Inc. | Comb-block copolymers and methods thereof |
US11155693B2 (en) | 2015-09-02 | 2021-10-26 | Dow Global Technologies Llc | Flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation |
US11180644B2 (en) | 2011-09-23 | 2021-11-23 | Exxonmobil Chemical Patents Inc. | Modified polyethylene compositions with enhanced melt strength |
WO2022015368A1 (en) | 2020-07-17 | 2022-01-20 | Dow Global Technologies Llc | Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes |
WO2022015370A1 (en) | 2020-07-17 | 2022-01-20 | Dow Global Technologies Llc | Hydrocarbyl-modified methylaluminoxane cocatalyst for bis-phenylphenoxy metal-ligand complexes |
WO2022015369A1 (en) | 2020-07-17 | 2022-01-20 | Dow Global Technologies Llc | Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes |
US11242415B2 (en) | 2017-09-29 | 2022-02-08 | Dow Global Technologies Llc | Bis-phenyl-phenoxy polyolefin catalysts having an alkoxy- or amido-ligand on the metal for improved solubility |
US11447584B2 (en) | 2018-03-30 | 2022-09-20 | Dow Global Technologies Llc | Olefin polymerization activators |
US11447586B2 (en) | 2018-03-30 | 2022-09-20 | Dow Global Technologies Llc | Olefin polymerization activators |
US11542350B2 (en) | 2018-03-30 | 2023-01-03 | Dow Global Technologies Llc | Binuclear olefin polymerization activators |
US11787880B2 (en) | 2018-03-30 | 2023-10-17 | Dow Global Technologies Llc | Highly soluble alkyl substituted carbenium borate as co-catalysts for olefin polymerizations |
US11970602B2 (en) | 2018-02-14 | 2024-04-30 | Dow Global Technologies Llc | Ethylene/alpha-olefin interpolymer compositions with improved long term heat aging performance |
Families Citing this family (146)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101384380B1 (en) * | 2006-05-17 | 2014-04-10 | 다우 글로벌 테크놀로지스 엘엘씨 | Polypropylene solution polymerization process |
EP2212359B1 (en) * | 2007-11-19 | 2013-08-28 | Dow Global Technologies LLC | Long chain branched propylene-alpha-olefin copolymers |
US8722817B2 (en) * | 2009-06-05 | 2014-05-13 | Dow Global Technologies Llc | Process to make long chain branched (LCB), block, or interconnected copolymers of ethylene |
WO2010141557A1 (en) | 2009-06-05 | 2010-12-09 | Dow Global Technologies Inc. | Process to make long chain branched (lcb), block, or interconnected copolymers of ethylene |
US9243087B2 (en) | 2009-06-11 | 2016-01-26 | Dow Global Technologies Llc | LDPE enabling high output and good optics when blended with other polymers |
US20110003940A1 (en) * | 2009-07-01 | 2011-01-06 | Dow Global Technologies Inc. | Ethylene-based polymer compositions for use as a blend component in shrinkage film applications |
US8629214B2 (en) | 2009-07-01 | 2014-01-14 | Dow Global Technologies Llc. | Ethylene-based polymer compositions for use as a blend component in shrinkage film applications |
ES2589766T3 (en) * | 2009-07-01 | 2016-11-16 | Dow Global Technologies Llc | Ethylene polymer and its use |
CN102471403A (en) * | 2009-07-01 | 2012-05-23 | 陶氏环球技术有限责任公司 | Ethylenic polymer and its use |
WO2011019563A1 (en) | 2009-08-10 | 2011-02-17 | Dow Global Technologies Inc. | Ldpe for use as a blend component in shrinkage film applications |
JP5623043B2 (en) * | 2009-09-04 | 2014-11-12 | 出光興産株式会社 | Polyolefin production method, production apparatus thereof, and polymerization apparatus |
BR112012005109A2 (en) | 2009-09-14 | 2023-04-25 | Dow Global Technologies Llc | POLYMER COMPRISING ETHYLENE AND POLYKYLENE DERIVATIVE UNITS, COMPOSITION AND ARTICLE |
CN102597029B (en) | 2009-09-14 | 2014-09-17 | 陶氏环球技术有限责任公司 | Polymers comprising units derived from ethylene and poly(alkoxide) |
KR101715435B1 (en) | 2009-09-14 | 2017-03-10 | 다우 글로벌 테크놀로지스 엘엘씨 | Polymers comprising units derived from ethylene and siloxane |
JP2013528241A (en) * | 2010-05-26 | 2013-07-08 | ダウ グローバル テクノロジーズ エルエルシー | Electronic device module comprising polyolefin copolymer with low unsaturation and optional vinyl silane |
EP2576639A1 (en) | 2010-06-04 | 2013-04-10 | Dow Global Technologies LLC | Electronic device module comprising film of homogeneous polyolefin copolymer and grafted silane |
BR112012030649A2 (en) | 2010-06-04 | 2016-08-16 | Dow Global Technologies Llc | electronic device module comprising homogeneous polyolefin copolymer film and adhesive enhancing graft polymer |
US8722819B2 (en) * | 2010-07-06 | 2014-05-13 | Ticona Gmbh | Process for producing high molecular weight polyethylene |
KR101849188B1 (en) | 2010-11-02 | 2018-04-17 | 다우 글로벌 테크놀로지스 엘엘씨 | A sealant composition, method of producing the same |
WO2014209927A1 (en) * | 2013-06-28 | 2014-12-31 | Dow Global Technologies Llc | Hyperbranched ethylene-based oligomers |
MX350943B (en) * | 2011-10-05 | 2017-09-26 | Dow Global Technologies Llc | Spunbond nonwoven fabrics. |
MX370571B (en) * | 2011-10-21 | 2019-12-17 | Dow Global Technologies Llc | Multi-layered shrink films. |
KR20140080502A (en) * | 2011-10-24 | 2014-06-30 | 다우 글로벌 테크놀로지스 엘엘씨 | Artificial grass yarn |
BR112014012380B1 (en) | 2011-12-13 | 2020-11-10 | Dow Global Technologies Llc | composition and article |
EP2797962B1 (en) * | 2011-12-29 | 2015-11-18 | Dow Global Technologies LLC | Process for producing low molecular weight ethylene- and alpha-olefin-based materials |
EP2797963B1 (en) * | 2011-12-29 | 2019-07-03 | Dow Global Technologies LLC | Hyperbranched olefin oil-based dielectric fluid |
EP2617741B1 (en) * | 2012-01-18 | 2016-01-13 | Borealis AG | Process for polymerizing olefin polymers in the presence of a catalyst system and a method of controlling the process |
EP2809695B1 (en) | 2012-02-03 | 2024-03-13 | Dow Global Technologies LLC | Silane-containing ethylene interpolymer formulation including films and electronic device module comprising same |
ES2694590T3 (en) | 2012-05-09 | 2018-12-21 | Dow Global Technologies Llc | Polyolefin polymerization process, semicrystalline ethylene-based polymer made from it, and articles made from the polymer |
EP2867296B1 (en) * | 2012-06-29 | 2018-10-24 | Dow Global Technologies LLC | Ethylene/alpha-olefin/nonconjugated polyene based compositions for thermoplastic vulcanizates |
WO2014012250A1 (en) * | 2012-07-20 | 2014-01-23 | Dow Global Technologies Llc | A linear low density polyethylene composition suitable for cast film |
EP2880098B1 (en) | 2012-08-03 | 2018-01-10 | ExxonMobil Chemical Patents Inc. | Halogenated catalysts comprising salan ligands |
EP2882810B1 (en) | 2012-08-03 | 2018-01-17 | ExxonMobil Chemical Patents Inc. | Catalysts comprising salan ligands |
US9382349B2 (en) | 2012-08-03 | 2016-07-05 | Exxonmobil Chemical Patents Inc. | Polyalphaolefins prepared using modified Salan catalyst compounds |
WO2014022010A2 (en) | 2012-08-03 | 2014-02-06 | Exxonmobil Chemical Patents Inc. | Non-symmetric catalysts comprising salan ligands |
CN104379680B (en) | 2012-08-03 | 2017-11-28 | 埃克森美孚化学专利公司 | The polyolefin of ethenyl blocking with long chain branching |
EP2880096B1 (en) | 2012-08-03 | 2018-01-03 | ExxonMobil Chemical Patents Inc. | Process for preparing polyalphaolefins using modified salan catalyst compounds and polyalphaolefins prepared therewith |
WO2014070502A1 (en) | 2012-11-02 | 2014-05-08 | Exxonmobil Chemical Patents Inc. | Supported salan catalysts |
JP6207336B2 (en) * | 2012-11-12 | 2017-10-04 | 日本ポリプロ株式会社 | Diol compound, catalyst for olefin polymerization, and method for producing olefin polymer |
ES2750524T3 (en) | 2012-12-27 | 2020-03-26 | Dow Global Technologies Llc | Procedure for the polymerization of ethylene and octene |
SG10201705303SA (en) | 2012-12-27 | 2017-07-28 | Dow Global Technologies Llc | An ethylene based polymer |
CN104968668B (en) | 2013-02-08 | 2017-11-17 | 三井化学株式会社 | Solid-like poly-aluminium silicone compositions, catalyst for olefines polymerizing, the manufacture method of the manufacture method of olefin polymer and solid-like poly-aluminium silicone compositions |
WO2014143202A1 (en) | 2013-03-13 | 2014-09-18 | Exxonmobil Chemical Patents Inc. | Diphenylamine salan catalyst |
KR101657262B1 (en) * | 2013-04-05 | 2016-09-13 | 한화케미칼 주식회사 | Catalyst for olefin polymerization and method for preparing polyolefin using the same |
WO2014204625A1 (en) | 2013-06-20 | 2014-12-24 | Exxonmobil Chemical Patents Inc. | Salenol catalyst |
WO2014204681A1 (en) | 2013-06-20 | 2014-12-24 | Exxonmobil Chemical Patents Inc. | Long-bridged salen catalyst |
CN105392776B (en) | 2013-06-20 | 2019-02-12 | 埃克森美孚化学专利公司 | Thio-Salalen catalyst |
EP2883890A4 (en) | 2013-06-28 | 2016-07-20 | Lg Chemical Ltd | Trinary elastic copolymer comprising diene and method for preparing same |
CN104768986A (en) | 2013-06-28 | 2015-07-08 | 株式会社Lg化学 | Ternary elastomeric copolymer comprising diene and method for preparing same |
EP2883889A4 (en) | 2013-06-28 | 2016-06-01 | Lg Chemical Ltd | Trinary elastic copolymer comprising diene and method for preparing same |
KR101585204B1 (en) | 2013-06-28 | 2016-01-13 | 주식회사 엘지화학 | Elastic diene terpolymer and preparation method thereof |
US10155831B2 (en) * | 2013-09-05 | 2018-12-18 | Univation Technologies, Llc | Process control for long chain branching control in polyethylene production |
CN105814015B (en) * | 2013-12-13 | 2019-04-02 | 埃克森美孚化学专利公司 | The Salan catalyst that cyclopentadienyl group replaces |
CN106103507B (en) | 2014-03-21 | 2019-04-05 | 埃克森美孚化学专利公司 | The preparation method of ethylene propylene copolymer |
WO2015152974A1 (en) | 2014-03-31 | 2015-10-08 | Exxonmobil Chemical Patents Inc. | Phenylene-bridged salalen catalysts |
RU2693453C2 (en) * | 2014-04-17 | 2019-07-03 | Бореалис Аг | Improved catalyst system for producing polyethylene copolymers in high-temperature solution polymerisation method |
JP6985015B2 (en) * | 2014-06-30 | 2021-12-22 | ダウ グローバル テクノロジーズ エルエルシー | Catalyst system for olefin polymerization |
JP6797694B6 (en) * | 2014-06-30 | 2021-01-20 | ダウ グローバル テクノロジーズ エルエルシー | Process for olefin polymerization |
CN107041138B (en) | 2014-12-04 | 2020-11-27 | 陶氏环球技术有限责任公司 | Pentacomplex bisphenylphenoxy catalyst for preparing vinyl polymer |
ES2820302T3 (en) * | 2014-12-31 | 2021-04-20 | Dow Global Technologies Llc | A polyolefin composition and method of producing the same |
CN107428878B (en) * | 2015-03-31 | 2020-08-28 | 陶氏环球技术有限责任公司 | Process for preparing high molecular weight ethylene/alpha-olefin/non-conjugated interpolymers with low content of long chain branching |
JP6895900B2 (en) * | 2015-06-17 | 2021-06-30 | ダウ グローバル テクノロジーズ エルエルシー | A method for producing a crosslinked cable insulator using a high melt strength ethylene polymer produced in a tubular reactor and optionally modified with a branching agent. |
US10800865B2 (en) | 2015-09-14 | 2020-10-13 | Exxonmobil Chemical Patents Inc. | Process for making branched EPDM and the EPDM therefrom |
WO2017058921A1 (en) | 2015-09-30 | 2017-04-06 | Dow Global Technologies Llc | A process for preparing functional polymers through addition of amino and polymeryl groups to aldehyde moieties |
CN108026115B (en) | 2015-09-30 | 2021-11-09 | 陶氏环球技术有限责任公司 | Multi-head or double-head composition capable of being used for chain shuttling and preparation method thereof |
BR112018013064B1 (en) | 2015-12-29 | 2023-05-09 | Dow Global Technologies Llc | PROCESS FOR FORMING A FUNCTIONALIZED ETHYLENE-BASED POLYMER COMPOSITION, FUNCTIONALIZED ETHYLENE-BASED POLYMER COMPOSITION AND ARTICLE |
EP3214115B1 (en) | 2016-03-03 | 2018-10-03 | Dow Global Technologies LLC | Polyethylene composition, method of making the same, and films made therefrom |
EP3487695A1 (en) | 2016-07-21 | 2019-05-29 | Dow Global Technologies LLC | Composite cushioning structures, and methods of manufacturing thereof |
WO2018022588A1 (en) | 2016-07-29 | 2018-02-01 | Dow Global Technologies Llc | Mixed catalyst systems for producing multimodal elastomers |
EP3491034A1 (en) | 2016-07-29 | 2019-06-05 | Dow Global Technologies, LLC | Silyl-bridged bis-biphenyl-phenoxy catalysts for olefin polymerization |
EP3519454A1 (en) | 2016-09-29 | 2019-08-07 | Dow Global Technologies LLC | Magnesium halide-supported titanium (pro) catalysts |
CN109937217B (en) | 2016-09-30 | 2021-09-14 | 陶氏环球技术有限责任公司 | Multi-or double-headed compositions suitable for chain shuttles and process for preparing same |
KR102490785B1 (en) | 2016-09-30 | 2023-01-20 | 다우 글로벌 테크놀로지스 엘엘씨 | Capped multi- or double-headed compositions useful for chain shuttling and methods of making the same |
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 |
WO2018089165A1 (en) * | 2016-11-11 | 2018-05-17 | Exxonmobil Chemical Patents Inc. | Catalyst compositions and use thereof |
US10280234B2 (en) | 2016-11-11 | 2019-05-07 | Exxonmobil Chemical Patents Inc. | Catalyst compositions and use thereof |
TW201829574A (en) | 2016-11-16 | 2018-08-16 | 美商陶氏全球科技有限責任公司 | Tie layer compositions and multilayer films incorporating same |
US11168155B2 (en) | 2017-02-28 | 2021-11-09 | Dow Global Technologies Llc | Phosphoramidate catalysts for ethylene-based interpolymers |
CN110603274B (en) | 2017-03-15 | 2022-09-30 | 陶氏环球技术有限责任公司 | Catalyst system for forming multi-block copolymers |
WO2018170056A1 (en) | 2017-03-15 | 2018-09-20 | Dow Global Technologies Llc | Catalyst system for multi-block copolymer formation |
WO2018170138A1 (en) | 2017-03-15 | 2018-09-20 | Dow Global Technologies Llc | Catalyst system for multi-block copolymer formation |
SG11201908307XA (en) | 2017-03-15 | 2019-10-30 | Dow Global Technologies Llc | Catalyst system for multi-block copolymer formation |
EP3596143B1 (en) | 2017-03-15 | 2023-04-26 | Dow Global Technologies LLC | Catalyst system for multi-block copolymer formation |
JP2018162231A (en) * | 2017-03-27 | 2018-10-18 | 三井化学株式会社 | Transition metal compound, catalyst for olefin polymerization and method for producing olefin polymer |
EP3409697A1 (en) | 2017-05-28 | 2018-12-05 | SABIC Global Technologies B.V. | Preparation of polymer dispersions |
US10683376B2 (en) | 2017-11-07 | 2020-06-16 | Nova Chemicals (International) S.A. | Manufacturing ethylene interpolymer products at higher production rate |
US10995166B2 (en) | 2017-11-07 | 2021-05-04 | Nova Chemicals (International) S.A. | Ethylene interpolymer products and films |
SG11202005775UA (en) | 2017-12-26 | 2020-07-29 | Dow Global Technologies Llc | Compositions with multimodal ethylene-based polymers having improved toughness at low temperatures |
US11680120B2 (en) | 2017-12-26 | 2023-06-20 | Dow Global Technologies Llc | Dual reactor solution process for the production of multimodal ethylene-based polymer |
BR112020012842B1 (en) | 2017-12-26 | 2024-01-02 | Dow Global Technologies Llc | METHOD FOR PRODUCING A TRIMODAL POLYMER IN A SOLUTION POLYMERIZATION PROCESS |
KR20200117996A (en) | 2017-12-26 | 2020-10-14 | 다우 글로벌 테크놀로지스 엘엘씨 | Method for producing multimodal ethylene polymer |
SG11202005754XA (en) | 2017-12-26 | 2020-07-29 | Dow Global Technologies Llc | Multimodal ethylene-based polymer compositions having improved toughness |
SG11202005779SA (en) | 2017-12-26 | 2020-07-29 | Dow Global Technologies Llc | Compositions comprising multimodal ethylene based polymers and low density polyethylene (ldpe) |
WO2019133699A1 (en) | 2017-12-29 | 2019-07-04 | Dow Global Technologies Llc | Capped dual-headed organoaluminum compositions |
EP3732181A1 (en) | 2017-12-29 | 2020-11-04 | Dow Global Technologies LLC | Dual-headed organoaluminum compositions |
US20190248934A1 (en) | 2018-02-09 | 2019-08-15 | Exxonmobil Chemical Patents Inc. | Ethylene-a-olefin-diene Elastomers and Methods of Making Them |
TW201938570A (en) | 2018-03-19 | 2019-10-01 | 美商陶氏全球科技有限責任公司 | Silicon-terminated organo-metal compounds and processes for preparing the same |
KR20200129126A (en) | 2018-03-19 | 2020-11-17 | 다우 글로벌 테크놀로지스 엘엘씨 | Hot-melt adhesive composition containing polyolefin-polydiorganosiloxane copolymer, and method for producing same and use thereof |
CN111741997B (en) | 2018-03-19 | 2022-08-09 | 美国陶氏有机硅公司 | Polyolefin-polydiorganosiloxane block copolymers and hydrosilylation reaction methods for their synthesis |
CN111868109A (en) | 2018-03-19 | 2020-10-30 | 陶氏环球技术有限责任公司 | Method for functionalizing organozinc compounds with halosilanes using basic nitrogen-containing heterocycles and silane-functionalized compounds prepared therefrom |
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 |
EP3768766A1 (en) | 2018-03-19 | 2021-01-27 | Dow Silicones Corporation | Polyolefin-polydiorganosiioxane block copolymer and method for the synthesis thereof |
KR20200135419A (en) | 2018-03-19 | 2020-12-02 | 다우 글로벌 테크놀로지스 엘엘씨 | Method for functionalizing an organo-metal compound with a silyl-based functionalizing agent, and a silyl-based functionalizing agent compound prepared thereby |
WO2019182983A1 (en) | 2018-03-19 | 2019-09-26 | Dow Global Technologies Llc | Silicon-terminated organo-metal compounds and processes for preparing the same |
CA3093558A1 (en) | 2018-03-19 | 2019-09-26 | Dow Silicones Corporation | Polyorganosiloxane hot melt adhesive compositions containing polyolefin - polydiorganoosiloxane copolymers and methods for the preparation and use thereof |
US20210115243A1 (en) | 2018-03-29 | 2021-04-22 | Dow Global Technologies Llc | Resins for use as tie layer in multilayer structure and multilayer structures comprising the same |
WO2019231916A1 (en) | 2018-05-31 | 2019-12-05 | E. I. Du Pont De Nemours And Company | Molded articles, and methods thereof |
MX2020013370A (en) | 2018-06-15 | 2021-03-09 | Dow Global Technologies Llc | Cast films comprising bimodal ethylene-based polymers having high molecular weight high density fractions. |
US11873377B2 (en) | 2018-06-15 | 2024-01-16 | Dow Global Technologies Llc | Blown films comprising bimodal ethylene-based polymers having high molecular weight high density fractions |
EP3807329A1 (en) | 2018-06-15 | 2021-04-21 | Dow Global Technologies Llc | Bimodal ethylene-based polymers having high molecular weight high density fractions |
JP7406513B2 (en) | 2018-06-15 | 2023-12-27 | ダウ グローバル テクノロジーズ エルエルシー | Production process of bimodal ethylene-based polymers with high molecular weight and high density fractions |
CN112334515B (en) | 2018-07-17 | 2022-08-09 | 美国陶氏有机硅公司 | Polysiloxane resin-polyolefin copolymers and methods of making and using the same |
CN113166449B (en) | 2018-11-30 | 2023-06-09 | 陶氏环球技术有限责任公司 | Polymer base film with balanced properties |
EP3902808A1 (en) | 2018-12-28 | 2021-11-03 | Dow Global Technologies LLC | Curable compositions comprising unsaturated polyolefins |
EP3902867A4 (en) | 2018-12-28 | 2022-09-14 | Dow Global Technologies LLC | Curable compositions comprising unsaturated polyolefins |
WO2020140064A1 (en) | 2018-12-28 | 2020-07-02 | Dow Global Technologies Llc | Organometallic chain transfer agents |
CN113454130A (en) | 2018-12-28 | 2021-09-28 | 陶氏环球技术有限责任公司 | Telechelic polyolefins and process for preparing telechelic polyolefins |
KR20210121029A (en) | 2018-12-28 | 2021-10-07 | 다우 글로벌 테크놀로지스 엘엘씨 | Curable composition comprising telechelic polyolefin |
US11028805B2 (en) | 2019-01-09 | 2021-06-08 | Saudi Arabian Oil Company | System and method for on-board catalytic upgrading of hydrocarbon fuels |
KR101995951B1 (en) * | 2019-03-12 | 2019-07-03 | 주식회사 라이온켐텍 | A continuous method for manufacturing polyolefin copolymer |
CN113631585B (en) | 2019-03-28 | 2023-10-20 | 陶氏环球技术有限责任公司 | Group III anionic complexes of weakly coordinating anions as olefin polymerization catalyst activators |
SG11202111068WA (en) | 2019-04-30 | 2021-11-29 | Dow Global Technologies Llc | Alkene functionalized activators |
WO2020220245A1 (en) | 2019-04-30 | 2020-11-05 | Dow Global Technologies Llc | Ethylene/propylene/nonconjugated diene interpolymer composition |
US11945888B2 (en) | 2019-05-15 | 2024-04-02 | Exxonmobil Chemical Patents Inc. | Solution polymerization process and product control using effluent density |
JP2022539097A (en) | 2019-06-26 | 2022-09-07 | ダウ グローバル テクノロジーズ エルエルシー | EPDM blends with long chain branching |
US20220275121A1 (en) | 2019-06-26 | 2022-09-01 | Dow Global Technologies Llc | Controlled Long Chain Branching in EPDM by Post-Reactor Modification |
EP3763745A1 (en) | 2019-07-10 | 2021-01-13 | Borealis AG | High temperature solution process for the copolymerization of alpha-olefins |
JP2023508106A (en) | 2019-12-30 | 2023-02-28 | ダウ グローバル テクノロジーズ エルエルシー | Process for preparing alpha-substituted acrylates |
US20220402855A1 (en) | 2019-12-30 | 2022-12-22 | Dow Global Technologies Llc | Process for preparing an alpha-substituted acrylate |
EP4127000A1 (en) | 2020-03-27 | 2023-02-08 | Dow Global Technologies LLC | Long-chain branched ethylene-based polymers |
CN115298234A (en) | 2020-03-27 | 2022-11-04 | 陶氏环球技术有限责任公司 | Long chain branched ethylene-based polymers |
JP2023518728A (en) | 2020-03-27 | 2023-05-08 | ダウ グローバル テクノロジーズ エルエルシー | Long-chain branched ethylene-based polymer |
EP4127001A1 (en) | 2020-03-27 | 2023-02-08 | Dow Global Technologies LLC | A process for producing long-chain branched ethylene-based polymers |
BR112022022017A2 (en) | 2020-04-29 | 2022-12-20 | Dow Global Technologies Llc | HIGH FLUID PROPYLENE-BASED INTERPOLYMER COMPOSITIONS |
CN111662403B (en) * | 2020-07-14 | 2022-08-05 | 万华化学集团股份有限公司 | Cascade catalytic system and method for preparing LLDPE (Linear Low Density polyethylene) by using same |
CN111909196B (en) * | 2020-08-10 | 2023-05-26 | 万华化学集团股份有限公司 | IVB-group-containing bimetallic complex catalyst, and preparation method and application thereof |
WO2022073805A1 (en) | 2020-10-05 | 2022-04-14 | Borealis Ag | High temperature solution process for the copolymerization of ethylene with one ore more α-Olefin comonomer(s) |
EP4244280A1 (en) | 2020-11-10 | 2023-09-20 | Dow Global Technologies LLC | Preparation of polyolefin-polyacrylate block copolymers additives for increasing surface energy of polyethylene |
JP2023552056A (en) | 2020-11-10 | 2023-12-14 | ダウ グローバル テクノロジーズ エルエルシー | Preparation of nonpolar-polar block copolymers via vinyl-terminated polyolefins |
US20240010773A1 (en) | 2020-11-24 | 2024-01-11 | Dow Global Technologies Llc | Process to Produce Long Chain Branching in EPDM and Product |
JP2024509386A (en) * | 2021-02-26 | 2024-03-01 | ダウ グローバル テクノロジーズ エルエルシー | Bis-phenoxy-ether ligands for Group IV polyolefin catalysts |
KR20240038800A (en) | 2021-08-04 | 2024-03-25 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Flexible polypropylene modified insulating material, manufacturing method and application thereof |
WO2023039514A1 (en) | 2021-09-10 | 2023-03-16 | Dow Global Technologies Llc | Hydrocarbon soluble borate cocatalysts for olefin polymerization |
WO2023039515A2 (en) | 2021-09-10 | 2023-03-16 | Dow Global Technologies Llc | Borate cocatalysts for polyolefin production |
CN114957530B (en) * | 2022-06-28 | 2023-09-29 | 杭州双安科技有限公司 | Solution polymerization method of ethylene and alpha-olefin |
CN115160472B (en) * | 2022-08-09 | 2023-07-11 | 万华化学集团股份有限公司 | High insertion rate ethylene copolymer solution polymerization method |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6686490B1 (en) * | 2000-11-06 | 2004-02-03 | Ramot University Authority For Applied Research & Industrial Development Ltd. | Active non-metallocene pre-catalyst and method for tactic catalytic polymerization of alpha-olefin monomers |
US20050164872A1 (en) * | 2002-04-24 | 2005-07-28 | Symyx Technologies, Inc. | Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom |
WO2006020624A1 (en) * | 2004-08-09 | 2006-02-23 | Dow Global Technologies Inc. | Supported bis(hydroxyarylaryloxy) catalysts for manufacture of polymers |
Family Cites Families (152)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3485706A (en) | 1968-01-18 | 1969-12-23 | Du Pont | Textile-like patterned nonwoven fabrics and their production |
US3914342A (en) | 1971-07-13 | 1975-10-21 | Dow Chemical Co | Ethylene polymer blend and polymerization process for preparation thereof |
US3953413A (en) | 1974-06-13 | 1976-04-27 | Chemplex Company | Supported chromium-containing catalyst and process of polymerizing 1-olefins |
US4173548A (en) | 1977-02-02 | 1979-11-06 | Chemplex Company | Ethylene polymerization catalyst and method |
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 |
DZ520A1 (en) | 1982-03-24 | 2004-09-13 | Union Carbide Corp | Improved process for increasing the space-time yield of an exothermic polymerization reaction in a fluidized bed. |
US4588790A (en) | 1982-03-24 | 1986-05-13 | Union Carbide Corporation | Method for fluidized bed polymerization |
US4543399A (en) | 1982-03-24 | 1985-09-24 | Union Carbide Corporation | Fluidized bed reaction systems |
US4430563A (en) | 1982-04-30 | 1984-02-07 | Minnesota Mining And Manufacturing Company | Data processing form |
US4564660A (en) | 1983-06-30 | 1986-01-14 | Union Carbide Corporation | Use of alkylaluminum compounds and hydroxyl-containing compounds to initiate polymerization of ethylene with chromium oxide catalysts |
US4612300A (en) | 1985-06-06 | 1986-09-16 | The Dow Chemical Company | Novel catalyst for producing relatively narrow molecular weight distribution olefin polymers |
US4665208A (en) | 1985-07-11 | 1987-05-12 | Exxon Chemical Patents Inc. | Process for the preparation of alumoxanes |
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 |
DE3752260T2 (en) | 1986-09-24 | 1999-09-02 | Mitsui Chemicals | Process for olefin polymerization |
JPH0780933B2 (en) | 1986-11-20 | 1995-08-30 | 三井石油化学工業株式会社 | Olefin Polymerization Method |
JPS63154753A (en) | 1986-12-18 | 1988-06-28 | Nippon Oil Co Ltd | Polyethylene composition |
IL85097A (en) | 1987-01-30 | 1992-02-16 | Exxon Chemical Patents Inc | Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes |
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 |
US5241025A (en) | 1987-01-30 | 1993-08-31 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
US5198401A (en) | 1987-01-30 | 1993-03-30 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
PL276385A1 (en) | 1987-01-30 | 1989-07-24 | Exxon Chemical Patents Inc | Method for polymerization of olefines,diolefins and acetylene unsaturated compounds |
JPH0742301B2 (en) | 1987-02-14 | 1995-05-10 | 三井石油化学工業株式会社 | Particulate aluminoxane, its manufacturing method and its use |
JP2538588B2 (en) | 1987-04-03 | 1996-09-25 | 三井石油化学工業株式会社 | Method for producing solid catalyst for olefin polymerization |
US5206199A (en) | 1987-04-20 | 1993-04-27 | Mitsui Petrochemical Industries, Ltd. | Catalyst for polymerizing an olefin and process for polymerizing an olefin |
US4981927A (en) | 1987-05-20 | 1991-01-01 | National Distillers And Chemical Corporation | Chromium catalyst compositions and polymerization utilizing same |
FR2634212B1 (en) | 1988-07-15 | 1991-04-19 | Bp Chimie Sa | APPARATUS AND METHOD FOR POLYMERIZATION OF GASEOUS OLEFINS IN A FLUIDIZED BED REACTOR |
US5091352A (en) | 1988-09-14 | 1992-02-25 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization catalyst component, olefin polymerization catalyst and process for the polymerization of olefins |
US4908463A (en) | 1988-12-05 | 1990-03-13 | Ethyl Corporation | Aluminoxane process |
US5103031A (en) * | 1989-02-21 | 1992-04-07 | Ethyl Corporation | Falling film aluminoxane process |
US4968827A (en) | 1989-06-06 | 1990-11-06 | Ethyl Corporation | Alkylaluminoxane process |
US4924018A (en) | 1989-06-26 | 1990-05-08 | Ethyl Corporation | Alkylaluminoxane process |
US5064802A (en) | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
US5066741A (en) | 1990-03-22 | 1991-11-19 | The Dow Chemical Company | Process for preparation of syndiotactic vinyl aromatic polymers |
US5763549A (en) | 1989-10-10 | 1998-06-09 | Fina Technology, Inc. | Cationic metallocene catalysts based on organoaluminum anions |
ES2071086T5 (en) | 1989-10-30 | 2002-01-16 | Fina Technology | PREPARATION OF METALOCENICAL CATALYSTS FOR OLEFINE POLYMERIZATION. |
US5387568A (en) | 1989-10-30 | 1995-02-07 | Fina Technology, Inc. | Preparation of metallocene catalysts for polymerization of olefins |
FR2656314B1 (en) | 1989-12-22 | 1992-04-17 | Bp Chemicals Snc | ZIRCONIUM CATALYST SUPPORTED ON MAGNESIUM CHLORIDE, PROCESS FOR THE PREPARATION AND USE OF THE CATALYST IN OLEFIN POLYMERIZATION. |
US5032562A (en) | 1989-12-27 | 1991-07-16 | Mobil Oil Corporation | Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution |
US5272236A (en) | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
JP2545006B2 (en) | 1990-07-03 | 1996-10-16 | ザ ダウ ケミカル カンパニー | Addition polymerization catalyst |
CA2066247C (en) | 1990-07-24 | 1998-09-15 | Ryuichi Sugimoto | Polymerization catalyst for .alpha.-olefin and method for preparing poly-.alpha.-olefin by using it |
US5189192A (en) | 1991-01-16 | 1993-02-23 | The Dow Chemical Company | Process for preparing addition polymerization catalysts via metal center oxidation |
US5296443A (en) * | 1991-03-01 | 1994-03-22 | Dai Nippon Printing Co., Ltd. | Thermal transfer image receiving sheet |
US5206197A (en) | 1991-03-04 | 1993-04-27 | The Dow Chemical Company | Catalyst composition for preparation of syndiotactic vinyl aromatic polymers |
US5721185A (en) | 1991-06-24 | 1998-02-24 | The Dow Chemical Company | Homogeneous olefin polymerization catalyst by abstraction with lewis acids |
US5157137A (en) * | 1991-07-26 | 1992-10-20 | Ethyl Corporation | Method of making gel free alkylaluminoxane solutions |
US5235081A (en) | 1992-03-18 | 1993-08-10 | Ethyl Corporation | Method of removing gel forming materials from methylaluminoxanes |
US5308815A (en) | 1991-07-26 | 1994-05-03 | Ethyl Corporation | Heterogeneous methylaluminoxane catalyst system |
US5674342A (en) * | 1991-10-15 | 1997-10-07 | The Dow Chemical Company | High drawdown extrusion composition and process |
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 |
KR100262023B1 (en) | 1992-01-06 | 2000-07-15 | 그레이스 스티븐 에스. | Improved catalyst composition |
US5329032A (en) | 1992-03-18 | 1994-07-12 | Akzo Chemicals Inc. | Polymethylaluminoxane of enhanced solution stability |
US5352749A (en) | 1992-03-19 | 1994-10-04 | Exxon Chemical Patents, Inc. | Process for polymerizing monomers in fluidized beds |
US5436304A (en) | 1992-03-19 | 1995-07-25 | Exxon Chemical Patents Inc. | Process for polymerizing monomers in fluidized beds |
US5296433A (en) | 1992-04-14 | 1994-03-22 | Minnesota Mining And Manufacturing Company | Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom |
US5288933A (en) * | 1992-04-16 | 1994-02-22 | Union Carbide Chemicals & Plastics Technology Corporation | Process for the production of polyethylene |
US5350723A (en) | 1992-05-15 | 1994-09-27 | The Dow Chemical Company | Process for preparation of monocyclopentadienyl metal complex compounds and method of use |
US5434115A (en) | 1992-05-22 | 1995-07-18 | Tosoh Corporation | Process for producing olefin polymer |
BE1005957A5 (en) | 1992-06-05 | 1994-04-05 | Solvay | Preparation method of catalyst system, process (co) polymerization of olefins and (co) polymer at least one olefine. |
EP0648230B1 (en) | 1992-07-01 | 1999-09-15 | Exxon Chemical Patents Inc. | Transition metal olefin polymerization catalysts |
US5248801A (en) | 1992-08-27 | 1993-09-28 | Ethyl Corporation | Preparation of methylaluminoxanes |
CA2145635A1 (en) | 1992-09-29 | 1994-04-14 | Patrick Brant | Long chain branched polymers and a process to make long chain branched polymers |
CA2146012A1 (en) | 1992-10-02 | 1994-04-14 | Brian W. S. Kolthammer | Supported homogenous catalyst complexes for olefin polymerization |
DE4322884A1 (en) | 1992-10-09 | 1994-04-14 | Bayer Ag | Biologically active polymers |
US5391793A (en) | 1992-11-02 | 1995-02-21 | Akzo Nobel N.V. | Aryloxyaluminoxanes |
US5939346A (en) | 1992-11-02 | 1999-08-17 | Akzo Nobel N.V. | Catalyst system comprising an aryloxyaluminoxane containing an electron withdrawing group |
US5608019A (en) | 1992-12-28 | 1997-03-04 | Mobil Oil Corporation | Temperature control of MW in olefin polymerization using supported metallocene catalyst |
US5420220A (en) * | 1993-03-25 | 1995-05-30 | Mobil Oil Corporation | LLDPE films |
US5332706A (en) | 1992-12-28 | 1994-07-26 | Mobil Oil Corporation | Process and a catalyst for preventing reactor fouling |
US5391529A (en) | 1993-02-01 | 1995-02-21 | Albemarle Corporation | Siloxy-aluminoxane compositions, and catalysts which include such compositions with a metallocene |
TW298593B (en) | 1993-02-12 | 1997-02-21 | Hoechst Ag | |
US6313240B1 (en) | 1993-02-22 | 2001-11-06 | Tosoh Corporation | Process for producing ethylene/α-olefin copolymer |
KR100311244B1 (en) | 1993-02-22 | 2001-12-15 | 가지와라 야스시 | Process for producing ethylene / α-olefin copolymer |
CA2161419C (en) | 1993-04-26 | 1999-05-04 | Marc Louis Dechellis | Process for polymerizing monomers in fluidized beds |
US5462999A (en) | 1993-04-26 | 1995-10-31 | Exxon Chemical Patents Inc. | Process for polymerizing monomers in fluidized beds |
KR100326775B1 (en) * | 1993-04-28 | 2002-10-25 | 더 다우 케미칼 캄파니 | Molded articles made from ethylene polymer blends |
BE1007148A3 (en) | 1993-05-17 | 1995-04-11 | Solvay | Support for catalyst, method for producing gel precursor media for catalyst, method for preparing a catalyst support, catalyst for olefin polymerization and method for olefin polymerization using the catalyst . |
FR2705252B1 (en) | 1993-05-19 | 1995-07-21 | Bp Chemicals Snc | Process for introducing a solid into a reactor and apparatus. |
ZA943399B (en) | 1993-05-20 | 1995-11-17 | Bp Chem Int Ltd | Polymerisation process |
PL175846B1 (en) | 1993-06-24 | 1999-02-26 | Dow Chemical Co | Complexes of titanium (ii) and zirconium (ii) and additive polymerisation catalysts made of them |
US5372682A (en) | 1993-06-24 | 1994-12-13 | The Dow Chemical Company | Electrochemical preparation of addition polymerization catalysts |
WO1995014044A1 (en) | 1993-11-19 | 1995-05-26 | Exxon Chemical Patents Inc. | Polymerization catalyst systems, their production and use |
JPH07144455A (en) * | 1993-11-25 | 1995-06-06 | Canon Inc | Ink jet recording apparatus |
US5648310A (en) | 1993-12-23 | 1997-07-15 | Union Carbide Chemicals & Plastics Technology Corporation | Spray dried, filled metallocene catalyst composition for use in polyolefin manufacture |
US5674795A (en) | 1993-12-23 | 1997-10-07 | Union Carbide Chemicals & Plastics Technology Corporation | Spray dried, filled metallocene catalyst composition for use in polyolefin manufacture |
US5461123A (en) | 1994-07-14 | 1995-10-24 | Union Carbide Chemicals & Plastics Technology Corporation | Gas phase fluidized bed polyolefin polymerization process using sound waves |
US5453471B1 (en) | 1994-08-02 | 1999-02-09 | Carbide Chemicals & Plastics T | Gas phase polymerization process |
US5625087A (en) | 1994-09-12 | 1997-04-29 | The Dow Chemical Company | Silylium cationic polymerization activators for metallocene complexes |
DE4436392C2 (en) | 1994-10-12 | 2002-10-31 | Fraunhofer Ges Forschung | Metal niobates and / or tantalates, processes for their preparation and their further processing into perovskites |
US5616661A (en) | 1995-03-31 | 1997-04-01 | Union Carbide Chemicals & Plastics Technology Corporation | Process for controlling particle growth during production of sticky polymers |
UA47394C2 (en) | 1995-05-16 | 2002-07-15 | Юнівейшн Текнолоджіз, Ллс | Ethylene polymer with improved processability and an article containing the ethylene polymer |
US5869723A (en) | 1995-06-08 | 1999-02-09 | Showa Denko K.K. | Ionic compound and olefin polymerization catalyst containing the 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 |
US5767208A (en) | 1995-10-20 | 1998-06-16 | Exxon Chemical Patents Inc. | High temperature olefin polymerization process |
US5693838A (en) | 1995-11-13 | 1997-12-02 | Albemarle Corporation | Aluminoxane process and product |
US5814714A (en) * | 1995-11-30 | 1998-09-29 | The Dow Chemical Company | Mono-olefin/polyene interpolymers, method of preparation, compositions containing the same, and articles made thereof |
EP0786466B1 (en) | 1996-01-25 | 2003-04-16 | Tosoh Corporation | Olefin polymerisation process which comprises a transition metal catalyst. |
CA2244999C (en) * | 1996-03-05 | 2007-03-27 | The Dow Chemical Company | Rheology-modified polyolefins |
BR9708232A (en) | 1996-03-27 | 1999-08-03 | Dow Chemical Co | Catalyst activator catalyst system for polymerization of alpha-olefins and polymerization process |
CN1214698A (en) | 1996-03-27 | 1999-04-21 | 陶氏化学公司 | Solution polymerization process with dispersed catalyst activator |
US5977251A (en) | 1996-04-01 | 1999-11-02 | The Dow Chemical Company | Non-adiabatic olefin solution polymerization |
US5731451A (en) | 1996-07-12 | 1998-03-24 | Akzo Nobel Nv | Modified polyalkylauminoxane composition formed using reagent containing aluminum trialkyl siloxide |
US5854166A (en) | 1996-08-19 | 1998-12-29 | Northwestern University | Synthesis and use of (perfluoroaryl) fluoro-aluminate anion |
EP0927201B1 (en) | 1996-09-06 | 2004-04-14 | Hyundai Petrochemical Co., Ltd. | Catalyst system for (co)polymerization of olefins and process for the preparation of olefin (co)polymers using the catalyst system |
US5744656A (en) | 1996-10-25 | 1998-04-28 | Boulder Scientific Company | Conversion of hexafluorobenzene to bromopentafluorobenzene |
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 |
FI970349A (en) | 1997-01-28 | 1998-07-29 | Borealis As | New activator systems for metallocene compounds |
WO1998043983A1 (en) | 1997-04-03 | 1998-10-08 | Colorado State University Research Foundation | Polyhalogenated monoheteroborane anion compositions |
US6420507B1 (en) * | 1997-05-01 | 2002-07-16 | The Dow Chemical Company | Olefin polymers prepared with substituted indenyl containing metal complexes |
US6103657A (en) | 1997-07-02 | 2000-08-15 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
US6319989B1 (en) | 1997-07-21 | 2001-11-20 | The Dow Chemical Company | Broad MWD, compositionally uniform ethylene interpolymer compositions, process for making the same and article made therefrom |
CN1270595A (en) | 1997-09-19 | 2000-10-18 | 陶氏化学公司 | Modified alumoxane catalyst activator |
DE69821511T2 (en) | 1997-09-19 | 2004-07-08 | The Dow Chemical Co., Midland | ETHYLENE-COPOLYMER MIXTURES WITH NARROW MOLECULAR WEIGHT DISTRIBUTION AND OPTIMIZED COMPOSITION, METHOD FOR THEIR PRODUCTION AND THEIR USE |
US6696379B1 (en) | 1997-09-19 | 2004-02-24 | The Dow Chemical Company | Supported modified alumoxane catalyst activator |
DE19744102A1 (en) | 1997-10-06 | 1999-04-15 | Targor Gmbh | Metallocene catalyst system useful in (co)polyolefin production |
JP4722287B2 (en) * | 1998-02-20 | 2011-07-13 | ダウ グローバル テクノロジーズ インコーポレーテッド | Catalyst activators containing expanded anions |
AU2801899A (en) | 1998-03-04 | 1999-09-20 | Exxon Chemical Patents Inc. | Noncoordinating anions for olefin polymerization |
US6827976B2 (en) | 1998-04-29 | 2004-12-07 | Unaxis Trading Ag | Method to increase wear resistance of a tool or other machine component |
US6140521A (en) | 1998-08-11 | 2000-10-31 | The Dow Chemical Company | Ansa group 4 metal bis (μ-substituted) aluminum complexes |
CA2337380C (en) | 1998-08-11 | 2010-11-09 | The Dow Chemical Company | Catalyst activator composition |
KR100568839B1 (en) | 1998-10-23 | 2006-04-10 | 엑손 케미칼 패턴츠, 아이엔씨. | Bridged metallocenes for olefin copolymerization |
JP2000129045A (en) * | 1998-10-27 | 2000-05-09 | Asahi Chem Ind Co Ltd | Clean vessel made of polyethylene |
WO2000026268A1 (en) * | 1998-11-02 | 2000-05-11 | Du Pont Dow Elastomers L.L.C. | SHEAR THINNING ETHYLENE/α-OLEFIN INTERPOLYMERS AND THEIR PREPARATION |
US6500135B2 (en) * | 1998-12-31 | 2002-12-31 | Homedics, Inc. | Percussive massager |
CN1334817A (en) | 1999-02-19 | 2002-02-06 | 陶氏化学公司 | Process for preparing trifluoroarylaluminum etherates |
US6420298B1 (en) * | 1999-08-31 | 2002-07-16 | Exxonmobil Oil Corporation | Metallocene catalyst compositions, processes for making polyolefin resins using such catalyst compositions, and products produced thereby |
JP2001098028A (en) * | 1999-09-29 | 2001-04-10 | Japan Polychem Corp | Polyethylene resin for medical and medical container |
US6750302B1 (en) * | 1999-12-16 | 2004-06-15 | Phillips Petroleum Company | Organometal catalyst compositions |
WO2002046249A2 (en) | 2000-11-07 | 2002-06-13 | Symyx Technologies, Inc. | Methods of copolymerizing ethylene and isobutylene and polymers made thereby |
SK6682003A3 (en) * | 2000-12-04 | 2004-02-03 | Univation Tech Llc | Polymerization process |
JP3549868B2 (en) * | 2001-02-08 | 2004-08-04 | 三井化学株式会社 | Ethylene polymer, method for producing the same, and molded article using the same |
MY137183A (en) | 2001-03-16 | 2009-01-30 | Dow Global Technologies Inc | Method of making interpolymers and products made therefrom |
WO2003010171A1 (en) | 2001-07-23 | 2003-02-06 | Dow Global Technologies, Inc. | Salt of lewis acid/acid adducts and catalyst activators therefrom |
US6960635B2 (en) | 2001-11-06 | 2005-11-01 | Dow Global Technologies Inc. | Isotactic propylene copolymers, their preparation and use |
US6908972B2 (en) * | 2002-04-16 | 2005-06-21 | Equistar Chemicals, Lp | Method for making polyolefins |
US6756455B2 (en) | 2002-05-31 | 2004-06-29 | Equistar Chemicals, Lp | High-temperature solution process for polyolefin manufacture |
US6794908B2 (en) * | 2002-05-31 | 2004-09-21 | Honeywell International Inc. | Radiation-hard circuit |
US6953764B2 (en) | 2003-05-02 | 2005-10-11 | Dow Global Technologies Inc. | High activity olefin polymerization catalyst and process |
CN1954005B (en) * | 2004-03-17 | 2012-10-10 | 陶氏环球技术有限责任公司 | Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation |
WO2005095475A1 (en) | 2004-03-24 | 2005-10-13 | Exxonmobil Chemical Patents Inc. | Process for making ethylene interpolymers and interpolymers made thereby; compositions and electrical devices containing such interpolymers |
US20050288461A1 (en) | 2004-06-25 | 2005-12-29 | Jensen Michael D | Polymerization catalysts for producing polymers with low levels of long chain branching |
CA2479704C (en) * | 2004-08-31 | 2013-08-13 | Nova Chemicals Corporation | High density homopolymer blends |
US7645893B2 (en) * | 2004-11-05 | 2010-01-12 | Dow Global Technologies, Inc. | Highly soluble ferrocenyl compounds |
KR100639696B1 (en) * | 2005-07-01 | 2006-10-30 | 에스케이 주식회사 | ARYLPHENOXY CATALYST SYSTEM FOR PRODUCING ETHYLENE HOMOPOLYMERS OR ETHYLENE COPOLYMERS WITH alpha;-OLEFINS |
KR101384380B1 (en) * | 2006-05-17 | 2014-04-10 | 다우 글로벌 테크놀로지스 엘엘씨 | Polypropylene solution polymerization process |
-
2007
- 2007-04-24 KR KR1020087030593A patent/KR101384380B1/en active IP Right Grant
- 2007-04-24 KR KR1020087030632A patent/KR101397337B1/en active IP Right Grant
- 2007-04-24 MX MX2008014668A patent/MX2008014668A/en unknown
- 2007-04-24 BR BRPI0711819-8A patent/BRPI0711819A2/en not_active IP Right Cessation
- 2007-04-24 ES ES12169643.9T patent/ES2634440T3/en active Active
- 2007-04-24 RU RU2008149709/04A patent/RU2450026C2/en not_active IP Right Cessation
- 2007-04-24 MX MX2008014669A patent/MX2008014669A/en unknown
- 2007-04-24 EP EP20140174865 patent/EP2787013A1/en not_active Withdrawn
- 2007-04-24 RU RU2008149711/04A patent/RU2463311C2/en not_active IP Right Cessation
- 2007-04-24 BR BRPI0711018A patent/BRPI0711018A8/en not_active IP Right Cessation
- 2007-04-24 CA CA002652551A patent/CA2652551A1/en not_active Abandoned
- 2007-04-24 WO PCT/US2007/009843 patent/WO2007136495A2/en active Application Filing
- 2007-04-24 JP JP2009510956A patent/JP5666129B2/en active Active
- 2007-04-24 KR KR1020087030640A patent/KR101352674B1/en active IP Right Grant
- 2007-04-24 RU RU2008149714/04A patent/RU2008149714A/en not_active Application Discontinuation
- 2007-04-24 AR ARP070101769A patent/AR060641A1/en not_active Application Discontinuation
- 2007-04-24 CN CN2007800259052A patent/CN101490094B/en active Active
- 2007-04-24 EP EP07755919A patent/EP2024400B1/en active Active
- 2007-04-24 EP EP07755917.7A patent/EP2021378B1/en active Active
- 2007-04-24 ES ES07755918.5T patent/ES2475159T3/en active Active
- 2007-04-24 WO PCT/US2007/009845 patent/WO2007136497A2/en active Application Filing
- 2007-04-24 CN CN2007800233160A patent/CN101472952B/en active Active
- 2007-04-24 CA CA002652460A patent/CA2652460A1/en not_active Abandoned
- 2007-04-24 CN CN2007800256425A patent/CN101484475B/en active Active
- 2007-04-24 BR BRPI0711029-4A patent/BRPI0711029A2/en not_active IP Right Cessation
- 2007-04-24 CN CN200780023101.9A patent/CN101472951B/en active Active
- 2007-04-24 CA CA002653534A patent/CA2653534A1/en not_active Abandoned
- 2007-04-24 AR ARP070101767A patent/AR060639A1/en not_active Application Discontinuation
- 2007-04-24 ES ES07776022T patent/ES2651590T5/en active Active
- 2007-04-24 ES ES07755919T patent/ES2394225T3/en active Active
- 2007-04-24 US US12/300,861 patent/US8101696B2/en active Active
- 2007-04-24 CA CA002652456A patent/CA2652456A1/en not_active Abandoned
- 2007-04-24 EP EP07776212.8A patent/EP2024403B1/en active Active
- 2007-04-24 MX MX2008014671A patent/MX2008014671A/en unknown
- 2007-04-24 WO PCT/US2007/009842 patent/WO2007136494A2/en active Application Filing
- 2007-04-24 AR ARP070101768A patent/AR060640A1/en not_active Application Discontinuation
- 2007-04-24 KR KR1020087030639A patent/KR101395970B1/en active IP Right Grant
- 2007-04-24 ES ES07776212.8T patent/ES2524779T3/en active Active
- 2007-04-24 US US12/300,863 patent/US8299189B2/en active Active
- 2007-04-24 EP EP07776022.1A patent/EP2024402B2/en active Active
- 2007-04-24 JP JP2009510952A patent/JP5623738B2/en active Active
- 2007-04-24 CN CN201510094535.4A patent/CN104725535A/en active Pending
- 2007-04-24 CN CN2007800266677A patent/CN101490096B/en active Active
- 2007-04-24 WO PCT/US2007/009844 patent/WO2007136496A2/en active Application Filing
- 2007-04-24 AR ARP070101771A patent/AR060643A1/en unknown
- 2007-04-24 JP JP2009510950A patent/JP5603595B2/en active Active
- 2007-04-24 CN CN201210266123.0A patent/CN102786619B/en active Active
- 2007-04-24 AR ARP070101766A patent/AR060638A1/en not_active Application Discontinuation
- 2007-04-24 US US12/300,859 patent/US8202953B2/en active Active
- 2007-04-24 MX MX2008014667A patent/MX2008014667A/en unknown
- 2007-04-24 KR KR1020087030627A patent/KR101396058B1/en active IP Right Grant
- 2007-04-24 JP JP2009510951A patent/JP5583402B2/en active Active
- 2007-04-24 EP EP12169643.9A patent/EP2492287B1/en active Active
- 2007-04-24 ES ES07755917.7T patent/ES2567140T3/en active Active
- 2007-04-24 WO PCT/US2007/010070 patent/WO2007136506A2/en active Application Filing
- 2007-04-24 ES ES07776021.3T patent/ES2534469T3/en active Active
- 2007-04-24 SG SG200908023-5A patent/SG158102A1/en unknown
- 2007-04-24 CA CA002652465A patent/CA2652465A1/en not_active Abandoned
- 2007-04-24 AR ARP070101770A patent/AR060642A1/en not_active Application Discontinuation
- 2007-04-24 AU AU2007254428A patent/AU2007254428A1/en not_active Abandoned
- 2007-04-24 US US12/302,050 patent/US8354484B2/en active Active
- 2007-04-24 US US12/300,857 patent/US8450438B2/en active Active
- 2007-04-24 EP EP07755918.5A patent/EP2024399B1/en active Active
- 2007-04-24 WO PCT/US2007/009841 patent/WO2007136493A2/en active Application Filing
- 2007-04-24 EP EP07776021.3A patent/EP2024401B1/en active Active
- 2007-04-24 KR KR1020087030629A patent/KR101401785B1/en active IP Right Grant
- 2007-04-24 US US12/300,515 patent/US8058373B2/en active Active
- 2007-04-24 JP JP2009510949A patent/JP5645400B2/en active Active
- 2007-04-24 RU RU2008149712/04A patent/RU2008149712A/en not_active Application Discontinuation
- 2007-04-24 CN CNA2007800259531A patent/CN101490095A/en active Pending
-
2011
- 2011-12-19 US US13/329,486 patent/US8349984B2/en active Active
-
2014
- 2014-12-10 JP JP2014249797A patent/JP6001042B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6686490B1 (en) * | 2000-11-06 | 2004-02-03 | Ramot University Authority For Applied Research & Industrial Development Ltd. | Active non-metallocene pre-catalyst and method for tactic catalytic polymerization of alpha-olefin monomers |
US20050164872A1 (en) * | 2002-04-24 | 2005-07-28 | Symyx Technologies, Inc. | Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom |
WO2006020624A1 (en) * | 2004-08-09 | 2006-02-23 | Dow Global Technologies Inc. | Supported bis(hydroxyarylaryloxy) catalysts for manufacture of polymers |
Cited By (103)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8222361B2 (en) | 2009-01-06 | 2012-07-17 | Sk Innovation Co., Ltd. | Ethylene-propylene-diene copolymer production method |
WO2010079906A3 (en) * | 2009-01-06 | 2010-08-26 | 에스케이에너지 주식회사 | Ethylene-propylene-diene copolymer production method |
WO2011025784A1 (en) | 2009-08-31 | 2011-03-03 | Dow Global Technologies Inc. | Catalyst and process for polymerizing an olefin and polyolefin prepared thereby |
US8784996B2 (en) | 2009-11-24 | 2014-07-22 | Dow Global Technologies Llc | Extrusion coating composition |
WO2011066469A1 (en) | 2009-11-24 | 2011-06-03 | Dow Global Technologies Inc. | Extrusion coating composition |
US8679639B2 (en) | 2009-11-24 | 2014-03-25 | Dow Global Technologies Llc | Extrusion coating composition |
WO2011079207A1 (en) | 2009-12-24 | 2011-06-30 | Dow Global Technologies Llc | Polymer compositions, methods of making the same, and articles prepared from the same |
EP2523983B1 (en) * | 2010-01-14 | 2018-03-21 | ExxonMobil Chemical Patents Inc. | Processes and apparatus for continuous solution polymerization |
JP2013521382A (en) * | 2010-03-02 | 2013-06-10 | ダウ グローバル テクノロジーズ エルエルシー | Ethylene polymer composition |
WO2011146291A1 (en) | 2010-05-17 | 2011-11-24 | Dow Global Technologies Llc | Process for selectively polymerizing ethylene and catalyst therefor |
US8609794B2 (en) | 2010-05-17 | 2013-12-17 | Dow Global Technologies, Llc. | Process for selectively polymerizing ethylene and catalyst therefor |
JP2013528689A (en) * | 2010-06-14 | 2013-07-11 | ダウ グローバル テクノロジーズ エルエルシー | Ethylene-based polymer composition for use as a blend component in shrink film applications |
WO2012064630A2 (en) | 2010-11-08 | 2012-05-18 | Dow Global Technologies Llc | Solution polymerization process and procatalyst carrier systems useful therein |
US20130253126A1 (en) * | 2010-12-03 | 2013-09-26 | Dow Global Technologies Llc | Processes to prepare ethylene-based polymer compositions |
EP2813545A1 (en) | 2010-12-03 | 2014-12-17 | Dow Global Technologies LLC | Processes to prepare ethylene-based polymer compositions |
US9045628B2 (en) | 2010-12-03 | 2015-06-02 | Dow Global Technologies Llc | Processes to prepare ethylene-based polymer compositions |
WO2012074812A1 (en) | 2010-12-03 | 2012-06-07 | Dow Global Technologies Llc | Processes to prepare ethylene-based polymer compositions |
WO2012088217A1 (en) | 2010-12-21 | 2012-06-28 | Dow Global Technologies Llc | Polymerization process and raman analysis for olefin-based polymers |
CN103391948A (en) * | 2010-12-21 | 2013-11-13 | 陶氏环球技术有限责任公司 | Polymerization process and Raman analysis for olefin-based polymers |
EP3091038B1 (en) | 2010-12-21 | 2019-09-18 | Dow Global Technologies LLC | Olefin-based polymers and dispersion polymerizations |
EP3091038A1 (en) | 2010-12-21 | 2016-11-09 | Dow Global Technologies LLC | Olefin-based polymers and dispersion polymerizations |
WO2012088235A2 (en) | 2010-12-21 | 2012-06-28 | Dow Global Technologies Llc | Olefin-based polymers and dispersion polymerizations |
WO2012092491A2 (en) | 2010-12-30 | 2012-07-05 | Dow Global Technologies Llc | Compositions, methods of making the same, and articles prepared from the same |
WO2013039739A1 (en) | 2011-09-07 | 2013-03-21 | Dow Global Technologies Llc | Polymer compositions and articles prepared from the same |
US9133327B2 (en) | 2011-09-12 | 2015-09-15 | Dow Global Technologies Llc | Compositions and articles formed from the same |
WO2013039850A1 (en) | 2011-09-12 | 2013-03-21 | Dow Global Technologies Llc | Compositions and articles formed from the same |
US9580533B2 (en) | 2011-09-23 | 2017-02-28 | Exxonmobil Chemical Patents Inc. | Modified polyethylene compositions |
US11180644B2 (en) | 2011-09-23 | 2021-11-23 | Exxonmobil Chemical Patents Inc. | Modified polyethylene compositions with enhanced melt strength |
WO2013043796A3 (en) * | 2011-09-23 | 2013-07-04 | Exxonmobil Chemical Patents Inc. | Modified polyethylene compositions |
WO2013043796A2 (en) * | 2011-09-23 | 2013-03-28 | Exxonmobil Chemical Patents Inc. | Modified polyethylene compositions |
WO2013055642A1 (en) | 2011-10-10 | 2013-04-18 | Dow Global Technologies Llc | Polymer compositions with improved retention of properties under mechanical and thermal stresses |
WO2013059391A1 (en) | 2011-10-20 | 2013-04-25 | Dow Global Technologies Llc | Ethylene-based polymer compositions and articles prepared therefrom |
WO2013096418A1 (en) | 2011-12-19 | 2013-06-27 | Dow Global Technologies Llc | Ethylene-based polymers prepared by dispersion polymerization |
US9422383B2 (en) * | 2011-12-20 | 2016-08-23 | Dow Global Technologies Llc | Ethylene/alpha-olefin/nonconjugated polyene interpolymers and processes to form the same |
WO2013096573A1 (en) | 2011-12-20 | 2013-06-27 | Dow Global Technologies Llc | Ethylene/alpha-olefin/nonconjugated polyene interpolymers and processes to form the same |
US10836853B2 (en) | 2012-09-20 | 2020-11-17 | Exxonmobil Chemical Patents Inc. | Crack-resistant polyethylene compositions |
US10822479B2 (en) | 2012-09-20 | 2020-11-03 | Exxonmobil Chemical Patents Inc. | Foamed polyethylene compositions |
WO2014084893A1 (en) | 2012-11-30 | 2014-06-05 | Dow Global Technologies Llc | Ethylene/alpha-olefin/polyene based compositions |
US10160819B2 (en) | 2012-11-30 | 2018-12-25 | Dow Global Technologies Llc | Ethylene/alpha-olefin/polyene based compositions |
US10214602B2 (en) | 2012-12-27 | 2019-02-26 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US10059787B2 (en) | 2012-12-27 | 2018-08-28 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US10214622B2 (en) | 2012-12-27 | 2019-02-26 | Dow Global Technologies Llc | Catalyst systems for olefin polymerization |
US9534070B2 (en) | 2013-01-18 | 2017-01-03 | Dow Global Technologies Llc | Polymerization processes for high molecular weight polymers |
WO2014113046A1 (en) | 2013-01-18 | 2014-07-24 | Dow Global Technologies Llc | Polymerization processes for high molecular weight polyolefins |
EP3925989A1 (en) | 2013-06-28 | 2021-12-22 | Dow Global Technologies LLC | Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts |
US9605098B2 (en) | 2013-06-28 | 2017-03-28 | Dow Global Technologies Llc | Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts |
US10144791B2 (en) | 2013-06-28 | 2018-12-04 | Dow Global Technologies Llc | Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts |
CN104628920A (en) * | 2013-11-08 | 2015-05-20 | 中国石油天然气股份有限公司 | Preparation method of solution polymerized ethylene propylene (EP) rubber |
WO2015116381A1 (en) * | 2014-01-30 | 2015-08-06 | Exxonmobil Chemical Patents Inc. | Crack-resistant polyethylene composiitions |
WO2015116382A1 (en) * | 2014-01-30 | 2015-08-06 | Exxonmobil Chemical Patents Inc. | Foamed polyethylene compositions |
EP3578578A1 (en) | 2014-07-24 | 2019-12-11 | Dow Global Technologies Llc | Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers |
US9975975B2 (en) | 2014-07-24 | 2018-05-22 | Dow Global Technologies Llc | Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers |
WO2016014749A1 (en) | 2014-07-24 | 2016-01-28 | Dow Global Technologies Llc | Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers |
US10336846B2 (en) | 2015-05-28 | 2019-07-02 | Dow Global Technologies Llc | Process to form ethylene/α-olefin interpolymers |
CN107735414A (en) * | 2015-06-22 | 2018-02-23 | 陶氏环球技术有限责任公司 | The method that the polymer based on ethene is prepared using carbon carbon radicals initiator |
WO2016209807A1 (en) | 2015-06-22 | 2016-12-29 | Dow Global Technologies Llc | Process for making ethylene-based polymers using carbon-carbon free radical initiators |
US10647789B2 (en) | 2015-06-22 | 2020-05-12 | Dow Global Technologies Llc | Process for making ethylene-based polymers using carbon-carbon free radical initiators |
US11041027B2 (en) | 2015-06-30 | 2021-06-22 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US10597473B2 (en) | 2015-06-30 | 2020-03-24 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US11155693B2 (en) | 2015-09-02 | 2021-10-26 | Dow Global Technologies Llc | Flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation |
US10490319B2 (en) | 2015-09-02 | 2019-11-26 | Dow Global Technologies Llc | Flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation |
US10870713B2 (en) | 2015-09-30 | 2020-12-22 | Dow Global Technologies Llc | Procatalyst and polymerization process using the same |
US10647797B2 (en) | 2015-09-30 | 2020-05-12 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US10487200B2 (en) | 2015-10-29 | 2019-11-26 | Dow Global Technologies Llc | Crosslinkable polymeric compositions for flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation |
WO2017210201A1 (en) | 2016-05-30 | 2017-12-07 | Dow Global Technologies Llc | Ethylene/alpha-olefin/diene interpolymers compositions |
WO2017210195A1 (en) | 2016-05-30 | 2017-12-07 | Dow Global Technologies Llc | Ethylene/alpha-olefin/diene interpolymer |
WO2018005789A1 (en) | 2016-06-30 | 2018-01-04 | Dow Global Technologies Llc | Procatalyst compositions useful for low comonomer incorporation and process for preparing the same |
WO2018005922A1 (en) | 2016-06-30 | 2018-01-04 | Dow Global Technologies Llc | Ethylene/alpha-olefin/polyene interpolymers and compositions containing the same |
EP4029886A2 (en) | 2016-06-30 | 2022-07-20 | Dow Global Technologies LLC | Ethylene/alpha-olefin/polyene interpolymers and compositions containing the same |
EP3805277A1 (en) | 2016-06-30 | 2021-04-14 | Dow Global Technologies LLC | Procatalyst compositions useful for low comonomer incorporation and process for preparing the same |
WO2018005852A1 (en) | 2016-06-30 | 2018-01-04 | Dow Global Technologies Llc | Ethylene/alpha-olefin/polyene based compositions |
WO2018013283A2 (en) | 2016-07-13 | 2018-01-18 | Exxonmobil Chemical Patents Inc. | Dual metallocene catalyst copolymer compositions |
WO2018013284A2 (en) | 2016-07-13 | 2018-01-18 | Exxonmobil Chemical Patents Inc. | Dual metallocene catalyst copolymer compositions |
WO2018013286A1 (en) | 2016-07-14 | 2018-01-18 | Exxonmobil Chemical Patents Inc. | Lubricating oil compositions comprising dual metallocene-catalyzed bimodal copolymer compositions useful as viscosity modifiers |
WO2018013285A1 (en) | 2016-07-14 | 2018-01-18 | Exxonmobil Chemical Patents Inc. | Dual metallocene-catalyzed bimodal copolymer compositions |
US11008412B2 (en) | 2016-09-29 | 2021-05-18 | Dow Global Technologies Llc | Method of polymerizing an olefin |
US11091572B2 (en) | 2016-09-29 | 2021-08-17 | Dow Global Technologies Llc | Modified Ziegler-Natta (pro) catalysts and system |
US11649307B2 (en) | 2016-09-29 | 2023-05-16 | Dow Global Technologies Llc | Modified Ziegler-Natta (pro) catalysts and system |
US11649306B2 (en) | 2016-09-29 | 2023-05-16 | Dow Global Technologies Llc | Modified Ziegler-Natta (pro) catalysts and system |
WO2018063898A1 (en) | 2016-09-29 | 2018-04-05 | Dow Global Technologies Llc | Modified ziegler-natta (pro)catalyst and system |
WO2018063900A1 (en) | 2016-09-29 | 2018-04-05 | Dow Global Technologies Llc | Method of polymerizing an olefin |
US11123726B2 (en) | 2016-10-27 | 2021-09-21 | Univation Technologies, Lle | Method of preparing a molecular catalyst |
WO2018080690A1 (en) | 2016-10-27 | 2018-05-03 | Univation Technologies, Llc | Method of preparing a molecular catalyst |
WO2018231224A1 (en) | 2017-06-14 | 2018-12-20 | Exxonmobil Chemical Patents Inc. | Ethylene copolymer blends for cross-linking applications |
WO2019040845A1 (en) | 2017-08-24 | 2019-02-28 | Dow Global Technologies Llc | Ethylene/c5-c10 alpha-olefin/ polyene interpolymers |
US11066428B2 (en) | 2017-09-29 | 2021-07-20 | Dow Global Technologies Llc | Bis-phenyl-phenoxy polyolefin catalysts having a methylenetrialkylsilicon ligand on the metal for improved solubility |
US11066489B2 (en) | 2017-09-29 | 2021-07-20 | Dow Global Technologies Llc | Bis-phenyl-phenoxy polyolefin catalysts having two methylenetrialkylsilicon ligands on the metal for improved solubility |
US11242415B2 (en) | 2017-09-29 | 2022-02-08 | Dow Global Technologies Llc | Bis-phenyl-phenoxy polyolefin catalysts having an alkoxy- or amido-ligand on the metal for improved solubility |
US11970602B2 (en) | 2018-02-14 | 2024-04-30 | Dow Global Technologies Llc | Ethylene/alpha-olefin interpolymer compositions with improved long term heat aging performance |
WO2019157687A1 (en) | 2018-02-14 | 2019-08-22 | Dow Global Technologies Llc | Ethylene/alpha-olefin interpolymer compositions with improved long term heat aging performance |
US11787880B2 (en) | 2018-03-30 | 2023-10-17 | Dow Global Technologies Llc | Highly soluble alkyl substituted carbenium borate as co-catalysts for olefin polymerizations |
US11542350B2 (en) | 2018-03-30 | 2023-01-03 | Dow Global Technologies Llc | Binuclear olefin polymerization activators |
US11447586B2 (en) | 2018-03-30 | 2022-09-20 | Dow Global Technologies Llc | Olefin polymerization activators |
US11447584B2 (en) | 2018-03-30 | 2022-09-20 | Dow Global Technologies Llc | Olefin polymerization activators |
WO2020046597A1 (en) | 2018-08-29 | 2020-03-05 | Exxonmobil Chemical Patents Inc. | Methods of making polymer compositions with enhanced elasticity by employing vtp and hmp catalyst systems in parallel processes |
WO2021022014A1 (en) | 2019-07-31 | 2021-02-04 | Dow Global Technologies Llc | Polymerization of ethylene in solution processes using a ziegler-natta catalyst and a hydrogenation procatalyst |
WO2021041562A1 (en) | 2019-08-30 | 2021-03-04 | Dow Global Technologies Llc | Polyolefin compositions having improved electrical properties |
WO2021061577A1 (en) | 2019-09-24 | 2021-04-01 | Dow Global Technologies Llc | Ethylene/alpha-olefin/polyene interpolymer compositions |
WO2021061580A1 (en) | 2019-09-24 | 2021-04-01 | Dow Global Technologies Llc | Polymer compositions for extruded profiles |
WO2021202091A1 (en) | 2020-03-30 | 2021-10-07 | Exxonmobil Chemical Patents Inc. | Comb-block copolymers and methods thereof |
WO2022015369A1 (en) | 2020-07-17 | 2022-01-20 | Dow Global Technologies Llc | Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes |
WO2022015370A1 (en) | 2020-07-17 | 2022-01-20 | Dow Global Technologies Llc | Hydrocarbyl-modified methylaluminoxane cocatalyst for bis-phenylphenoxy metal-ligand complexes |
WO2022015368A1 (en) | 2020-07-17 | 2022-01-20 | Dow Global Technologies Llc | Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8299189B2 (en) | Ethylene/α-olefin/diene solution polymerization process and polymer |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200780023316.0 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07755918 Country of ref document: EP Kind code of ref document: A2 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2007755918 Country of ref document: EP Ref document number: MX/A/2008/014668 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2652456 Country of ref document: CA Ref document number: 2009510950 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007254428 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020087030629 Country of ref document: KR |
|
ENP | Entry into the national phase |
Ref document number: 2007254428 Country of ref document: AU Date of ref document: 20070424 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12300863 Country of ref document: US |