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WO1996013532A1 - Deshydroxylation in situ de supports et preparation de catalyseurs polyolefiniques a alliage organometallique sur support - Google Patents

Deshydroxylation in situ de supports et preparation de catalyseurs polyolefiniques a alliage organometallique sur support Download PDF

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Publication number
WO1996013532A1
WO1996013532A1 PCT/US1995/014363 US9514363W WO9613532A1 WO 1996013532 A1 WO1996013532 A1 WO 1996013532A1 US 9514363 W US9514363 W US 9514363W WO 9613532 A1 WO9613532 A1 WO 9613532A1
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WO
WIPO (PCT)
Prior art keywords
mixtures
group
cyclopentadienyl
dichloride
aluminum
Prior art date
Application number
PCT/US1995/014363
Other languages
English (en)
Inventor
David George Ward
Patrick Brems
Original Assignee
W.R. Grace & Co.-Conn.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by W.R. Grace & Co.-Conn. filed Critical W.R. Grace & Co.-Conn.
Priority to AU41468/96A priority Critical patent/AU4146896A/en
Publication of WO1996013532A1 publication Critical patent/WO1996013532A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • transition metals as catalysts for polymerization and copolymerization of olefins.
  • metallocene catalyst systems provides the ability to produce uniform polymers and copolymers of
  • M D narrow molecular weight distribution
  • a drawback to the use of supported metallocene catalysts is that many oxide supports contain active _
  • hydroxyl groups are reactive and tend to deactivate the active, expensive metallocene specie. Accordingly, it is often desirable to deactivate the hydroxyl groups .
  • oxide supports e.g., silica gel
  • thermal treatments often result in an undesirable loss of pore volume
  • invention is to provide a catalyst which is capable of producing polymer with a broad molecular weight.
  • the invention further provides unique catalyst compositions suitable for forming polymers having broad molecular weight distribution and good flow properties
  • the polymers produced in accordance with the present invention also have reduced presence of polymer degrading and equipment corroding materials, such as
  • the present invention provides a method to prepare, in-situ, a supported metallocene catalyst precursor on a dehydroxylated support.
  • the method comprises the
  • (i) is a compound that is a transition metal compound, optionally containing a five-member carbon s ring, a heterosubstituted five-member carbon ring,
  • a bridged (ansa) ligand defined as multi- cyclic moieties capable of coordinating to the transition or rare earth metals
  • metal component of the reagent is selected from the group consisting of tin, silicon, germanium and mixtures
  • the remaining component of the reagent is selected from the group of halogen elements, organics,
  • amides and mixtures thereof and optionally, containing an additional organic component that contains a five- member carbon ring, a heterosubstituted five-member carbon ring, or be a bridged (ansa) ligand defined as mulit-cyclic moieties capable of coordinating to the transition or rare earth metals; and
  • (iii) is a hydroxyl group containing support material
  • Catalyst precursors of the present invention are useful in the polymerization of any olefin in which separate polymerization with a homogeneous catalyst or with a heterogeneous catalyst is possible.
  • catalysts of the present invention are useful in the polymerization, copolymerization and terpolmerization of
  • olefinic monomers preferably, ⁇ -olefins, and most
  • the Support can be any sufficiently porous inorganic, inorganic oxides and organic materials
  • Suitable inorganic materials include magnesium compounds or their complex salts such as MgCl(OH) and Mg(OH) 2
  • Inorganic oxide supports include talcs, clays, and metal oxides from Groups 2-14, actinide, lanthanide Series metals from the Periodic Table; suitable metal oxides are typically Si0 2 , Al 2 0 3 ,
  • silica-alumina for example, silica-alumina, silica-titania, silica-titania-alumina, zeolite, ferrite, glass fibers,
  • magnesia, titania, zirconia, aluminum phosphate gel magnesia, titania, zirconia, aluminum phosphate gel
  • Organic Supports include resinous material such as polyvinylaicoho1, starches and mixtures thereof.
  • the supports are compositions
  • the degree of porosity in the carrier may be any level that is conventionally used as catalyst support materials.
  • the degree of porosity in the carrier may be any level that is
  • the carrier particles of the present invention have a pore
  • the carrier particles have a surface area of about 1-1000 m 2 /g; more preferably in the range of from
  • this invention is from 1 to 300 microns, preferably from 5 to 200 microns and more preferably from 25 to 150
  • Pore volume and surface area can be measured from volume of nitrogen gas adsorbed in
  • C represents a ligand defined as one five-member
  • the ansa bridge can be selected from the group
  • R comprising carbon, silicon, phosphorus, sulfur, oxygen, nitrogen, germanium, species such as R" 2 C, R" 2 Si, R" 2 Ge, R" 2 CR" 2 C, R" 2 SiR" 2 Si, R" 2 GeR” : Ge, R" 2 CR" 2 Si, R" 2 CR" 2 Ge, R" 2 CR" 2 CR” 2 C, R" 2 SiR" 2 Si, diradicals where R is independently selected from the group containing hydride,
  • the ansa bridge has a length of two atoms or less as in methylene, ethylene, diphenysilyl, dimethylsilyl, and
  • M' represents a metal selected from the group comprising silicon, tin, germanium and mixtures thereof.
  • M represents a metal selected from the group consisting of Groups 3 through 10, lanthanides, actinides
  • metals of the Periodic Table and mixtures thereof preferably titanium, zirconium, hafnium, chromium, vanadium, samarium, neodymium and mixtures thereof; most preferably Ti, Zr, and Hf, and mixtures thereof.
  • MZ is intended to include any existing Ziegler-Natta catalytic precursors.
  • X and Z represents elements from the halogen group (preferably chlorine, fluorine, bromine and mixtures thereof) ; and substituted and nonsubstituted alkoxys (preferably C1-C20 alkoxys, such as methoxy, ethoxy, isopropyloxy, butoxy and phenoxy) ; alkyls (preferably Cl- C20 alkyls such as ethyl, butyl, octyl, ethylhexyl) ;
  • aryls preferably C6-C20 aryls such as phenyl, p-tolyl,
  • alkenyls preferably C1-C20 alkenyls, such as ethenyl, propenyl, butenyl, pentenyl
  • amides preferably NR a R b , wherein the R a and R b can be the same or different and
  • alkyls independently selected from alkyls, alkenyls, aryls, or silanes; preferably C1-C20 alkyls and alkenyls and C6-C20
  • aryls including substitued aryls, such as ethyl, butyl, octyl, ethylhexyl) , phenyl, p-tolyl, benzyl, 4-t-
  • groups in the NR 2 R b are C1-C5 alkyls, C2-C5 alkenyls, phenyl and napthyl and mixtures thereof.
  • Preferred amides are dimethylamide, diethylamide, hexamethyldisilazide and mixtures of two or more of the foregoing.
  • CM'X is preferably selected from the group comprising (chlorodimethylsilyl) (3-trimethylsilyl) cyclopentadiene, cyclopentadienyltrimethylsilane, indenyltrimethylsilane, indenyltributylstannane, indenyltrimethylgermanium, cyclopentadienyl trimethylgermanium, and mixtures thereof. / /
  • A may be optionally used to further modify the catalyst and/or support, and can be selected from the
  • acid halides e.g. , HCl, HBr and HI
  • metal halides preferably, Al, Si, Sn, Ti, Mg, Cr and mixtures thereof, wherein the halide are Cl, Br, I and
  • R" are the same or different and independently selected from mono or multi-cyclic, halosubstituted and non-
  • R groups and mixtures thereof. More preferred R groups are Cl-5 alkyls, C2-5 alkenyls phenyl and napthyl and
  • A can also be C1-C20 alkylaluminums (preferably C1-C10 alkyl aluminums, and most preferably triethyl aluminum, trimethylaluminum, tributylaluminum and
  • C1-C20 alkyl lithium preferably, Cl- C6 alkyl lithiums, and most preferably n-butyllithium, methyllithium, ethyllithium and mixtures thereof
  • Grignard reagents generally represented by the formula
  • RMgX where X is selected from the members of the halogen group from the Periodic Table, R is selected from the
  • preferred Grignard reagents are methyl magnesium chloride, ethyl magnesium chloride, and isopropyl magnesium bromide and mixtures thereof.
  • Additional suitable "A” compounds for use in this invention is selected from the halogen gases and C1-C5 alkyl alumoxanes such as methylalumoxane, isobutylalumoxane and mixtures thereof.
  • Preferred A's include CH.C1, tetraydrafuran, t- butylchloride, dialkyl phthalates, ethanol, phenol, ethyl-aluminumdichloride, silicon tetrachloride,
  • the reaction can be carried over a broad range of temperatures, typically from approximately -78°C to 200°C,
  • the reaction product will typically have the
  • CMZ is approximately 0.1% to 50%; preferably 0.1 - 10; most preferably 0.1-5.0;
  • M'X is approximately 0.1% to 99.8%; preferably 5.0-
  • the solvent is a non-polar organic solvent
  • aliphatic hydrocarbons typically C3 to C12 , such as butane, isobutane, pentane, isopentane, hexane, octane, decane, dodecane, hexadecane, octadecane, and the like
  • alicyclic hydrocarbons typically C5-C20, such as cyclopentane, methylcyclopentane, cyclohexane, decalin cycloctane, norbornane, ethyleyelohexane and the
  • aromatic hydrocarbons including substituted aromatics such as benzene, chlorobenzene, xylene, toluene and the like
  • petroleum fractions such as gasoline, kerosene, light oils, and the like. It may also be desirable to use tetrahydrofuran or another ether. Mixtures of two or more solvents may also be used, e.g. ,
  • the starting materials can be selected as defined
  • CMZ or CMX metallocene catalytic precursors are defined as
  • organometallic compounds having a transition metal having a transition metal
  • rare earth metals M as defined previously, in coordination with members of at least one five-member carbon ring, heterosubstituted five-member carbon ring, or a bridged (ansa) ligand defined as multi cyclic
  • the ansa bridge can be selected from the group comprising carbon, silicon, phosphorus, sulfur, oxygen,
  • R 2 SiR 3 2 Si diradicals where R 3 is independently selected from the- group containing hydride, halogen radicals, and Cl-20 hydrocarbyl radicals including ethyl and propyl; preferred ansa bridges are Me 2 Si (dimethylsilyl) , Ph 2 Si (diphenylsilyl) , Me 2 C (isopropylidene) , Ph 2 P
  • the ansa bridge has a length of two atoms or less as in methylene, ethylene, lb diphenysilyl, dimethylsilyl, propylidene and methylphenylsilyl .
  • the transition metal component of the metallocene is the transition metal component of the metallocene
  • product is selected from Groups 3 through 10, lanthanides and actinides of the Periodic Table and mixtures thereof;
  • chromium vanadium, samarium and neodymium and mixtures thereof. Of these Ti, Zr, and Hf and mixtures thereof are most preferable.
  • CMZ metallocene catalyst precursor product is represented by the general
  • m+n+p equals the oxidation state of M.
  • Me is a Group 3-6, lanthanide, actinide series metal from-the Periodic Table and mixtures thereof;
  • C 5 R 6 m is a substituted cyclopentadienyl each R 6 , which can be the same or different is hydrogen, alkenyl, aryl, or arylalkyl radical having from 1 to 20 carbon atoms or two carbon atoms joined together to form a part
  • R 7 is one or more of or a combination
  • each K which can be the same or different is an aryl alkyl, alkenyl, alkaryl, or arylalkyl radical having from 1-20 carbon atoms or halogen, K' is an alkylidene radical
  • s having from 1 to 20 carbon atoms, s is 0 to 1 and when s
  • preferred metallocenes are derivatives of a cyclopentadiene (Cp) , including
  • cyclopentadienyl indenyl, fluorenyl, tetrahydroindenyl, and l ⁇ l-disubstituted silacyclopentadienes, phosphocyclopentadienes, l-metallocyclopenta-2, 4-dienes, bis (indenyl) ethane and mixtures thereof.
  • metallocenes represented by the above definition are dialkyl metallocenes such as bis (cyclopentadienyl) titanium I ⁇
  • tadienyl) titanium methyl chloride bis (cyclopentadienyl) ti tanium ethyl chloride, bis (cyclopentadienyl) titanium phenyl chloride, bis (cyclopentadienyl) zirconium methyl chloride, bis (cyclopentadienyl) zirconium ethyl chloride, bis(cyclope
  • titanium methyl bromide the trialkyl metallocenes such as cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium triphenyl, and cyclopentadienyl zirconium trineopentyl, cyclopentadienyl zirconium trimethyl,
  • cyclopentadienyl hafnium triphenyl cyclopentadienyl hafnium trineopentyl, and cyclopentadienyl hafnium
  • monocyclopentadienyls titanocenes such as, pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride;
  • dimethylcyclopentadienyl) -titanium diphenyl or dichloride bis (1, 2-diethylcyclopentadienyl) titanium diphenyl or dichloride; silicon, phosphine, amine or carbon bridged cyclopentadiene complexes, such as dimethyl silyldicyclope
  • dienyl) (fluorenyl) zirconium dichloride isopropyl (eye1open tadienyl) (octahydrofluorenyl) zirconium dichloride diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diisopropylmethylene (cyclopentadienyl) (fluore nyl) zirconium dichloride, diisobutylmethylene(cyclopentadi enyl) (fluorenyl) zirconium
  • cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diisopropylmethylene (2,5- dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl)hafnium dichloride, diisopropylmethylene(cyclop entadienyl) (fluorenyl)hafnium dichloride, diisobutylmethy lene(cyclopentadienyl) (fluorenyl)hafnium dichloride, ditertbutylmethylene (cyclopentadienyl) (fluorenyl)hafnium dichloride, ditertbutylmethylene (cyclopentadienyl
  • pentadienyl) (fluorenyl) titanium dichloride diisobutylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ditertbutylmethylene(cyclopentadienyl) (fluorenyl) titanium dichloride, cyclohexylidene(cyclopenta dienyl) (fluorenyl) titanium dichloride,
  • CMXs or CMZs are bis (cyclopenta ⁇
  • dienyl) titanium diehloro bis (cyclopentadienyl) zirconium, isopropyl (cyclopentaienyl) fluroenyl)zirconium diehloro, bis (1-indenyl) zirconium (IV) diehloro, (4,5,6,7-
  • dimethylzireonoeene dimethylzireonoeene, dichloroethylenebisindenylzirconium, and dichloroethylene bis (tetrahydroindenyl) zirconium.
  • the catalytic precursors prepared according to the method of the present invention may be activated by any number of catalytic activators and used to polymerize olefinic materials.
  • the catalytic activator includes organometallic compounds.
  • the metals are selected from the
  • Such catalyst are known for their use in polymerization reactions, especially the polymerization of olefins.
  • organo aluminum compounds such as lithium, aluminum, magnesium, zinc and boron.
  • each alkyl or alkoxy group contains 1-16 carbons.
  • examples of such compounds include trimethylaluminum, triethylaluminum, diethyl aluminumhydride, triisobutylaluminum, trideeyl aluminum, tridodecylaluminum, diethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, diethyl aluminum chloride, ethyl aluminum dichloride, methyl diethoxy aluminum and methyaluminoxane.
  • trimethylaluminum triethylaluminum, diethyl aluminumhydride, triisobutylaluminum, trideeyl aluminum, tridodecylaluminum, diethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, diethyl aluminum chloride, ethyl aluminum dichloride, methyl diethoxy aluminum and methyalum
  • compound is as an alkyl aluminoxane, the alkyl group having 1 to 10 carbon atoms, especially methyl
  • [C * ] is an activating cation, which may be a Bronsted acid capable of donating a proton to the transition metal ionic catalytic precursor resulting in a transition metal
  • Bronsted acids include but are not limited to ammoniums, oxoniums, phosphoniums and mixtures thereof; preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-
  • [C * ] may be an abstracting moiety that is capable of reacting with a transition metal catalytic 0 precursor resulting in the transition metal cation.
  • Acceptable abstracting moiety include but are not limited to silver, carbocations, tropylium, carbeniums, ⁇ • ferroceniums and mixtures thereof; preferably carboniums
  • the [C * ] may also include mixtures of the Bronsted acids and the abstracting moiety
  • [N] is selected from the group consisting of boron
  • the [N] is boron, aluminum and mixtures thereof.
  • [_ ! -_ solo ! _ are independent, wherein Q j -Q. ⁇ are RX is defined wherein X is a halogen group element and is typically fluorine, chlorine, and bromine and mixtures thereof; preferred halogens are fluorine, chlorine, iodine and mixtures thereof; and most preferred is
  • R is mono or multi-cyclic, halosubstituted and non-substituted aryls, alkyls, and alkenyl groups and
  • R groups are Cl-5 alkyls, C2-5 alkenyls phenyl and napthy1 and
  • pentasubstituted such as p-fluorophenyl, 3,5- difluorophenyl, pentafluorophenyl, 3 , 4, 5-trifluorophenyl, and 3 , 5-bis (trifluoromethyl)phenyl groups
  • pentafluorophenyl mono to pentasubstituted (such as p-fluorophenyl, 3,5- difluorophenyl, pentafluorophenyl, 3 , 4, 5-trifluorophenyl, and 3 , 5-bis (trifluoromethyl)phenyl groups) and mixtures thereof; of these the most preferred is pentafluorophenyl.
  • the Q ⁇ to Q n may be hydride radicals, bridged or unbridged dialkylamido radicals, alkoxide and aryloxide radicals, substituted hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals and hydrocarbyl- and halocarbyl-substituted organometalloid radicals.
  • the Q x to Q n can simply be the X alone; for example as in " BX 4 .
  • neutral N"(Q n) can be used in place of the[C * 3 " [ “(Q 1 -Q Iwl )], for example B(C 6 F 5 ) 3 .
  • Preferred " [t. (C ⁇ -Q ⁇ ) ] are selected from the group consisting of " BPhenyl,, " B(C 6 H 2 (CF 3 ) 3 ) 4 , ⁇ B(C S H 5 ) 4 ,
  • Preferred _T(Q n ) from the neutral species of the preferred list above of " [N"(Q 1 -Q n+1 ) ] .
  • the preferred catalytic activators when not a Lewis acid such as MgCl 2 is present, are the alkylalumoxanes and
  • borate activators in combination with an alkyating agent such as TEAL.
  • Catalytic systems incorporating the present invention are useful to polymerize olefinic materials
  • Polymerization includes copolymerization and terpolymerization and the terms olefins and olefinic monomer includes olefins,
  • alphaolefins alphaolefins, diolefins, strained cyclic olefins, styrenic monomers, acetylenically unsaturated monomers, cyclic olefins aline or in combination with other unsaturated monomers. While the catalyst system of the present invention is active for this broad range of olefinic monomer feedstock, alpha-olefin polymerizations ⁇
  • polymerization according to the present invention can be solution polymerization, slurry polymerization or gas
  • the catalyst according to the present invention can be used in similar amounts and under similar conditions to known olefin polymerization catalyst.
  • the temperature is from approximately 0 degrees C to just below the
  • the temperature is from approximately 0 degrees C to just below the melting point of the polymer.
  • the temperature is typically the temperature from which the polymer is soluble in the reaction medium
  • the pressure used can be selected from a relatively wide range of suitable pressures, e.g., from
  • the process is from atmospheric to about 6.9 Mpa, or 0.05-10 Mpa, especially 0.14-5.5 Mpa.
  • the process is suitably performed with a liquid
  • inert diluent such as a saturated aliphatic hydrocarbon.
  • hydrocarbon is a C4 to CIO hydorcarbon,
  • the catalyst of the present invention are:
  • compositions according to the present invention are used in amounts sufficient to cause polymerization in the feedstocks. Typically, the amount used will be the
  • Example B Silica oxide with MgCl 2 , having a particle size of
  • the solid was dried in vacuo .
  • Example A 50 mg was blown into the reactor under argon pressure. Polymerization was
  • a 2 L Zipperclave * reactor was charged with heptanes (500 mL) and MAO (5 mmol) .
  • the reactor was pressurized with ethylene to 180 psig and the temperature
  • Example B 50 mg was blown into the reactor under argon pressure. Polymerization was carried out for 1 hour and was quenched by rapid venting
  • Example B 50 mg was blown into the reactor under argon pressure.
  • This example illustrates that the metallocene according can be activated without MAO in the presence of a Lewis acid support material, e.g. MgCl 2 .
  • APG aluminum phosphate gel
  • PVA polyvinylalcohol

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Abstract

La présente invention se rapporte à un procédé de préparation in situ, d'un précurseur de catalyseur à alliage organométallique placé sur un support déshydroxylé. Le procédé consiste: (A) à faire réagir des agents réactifs (i), (ii) et (iii) en présence ou en l'absence d'un solvant, dans lequel (i) est un composé de métaux de transition ou de terres rares (ii) est un réactif contenant du métal, le constituant métallique du réactif étant sélectionné dans le groupe comprenant l'étain, le silicium, le germanium et des mélanges de ceux-ci, et le réactif contenant un noyau de carbone à cinq éléments à hétérosubstitution ou un ligand ponté (ansa) défini en tant que fractions multicycliques capables d'une coordination avec les métaux de transition ou avec les métaux des terres rares; et (iii) est un groupe hydroxyle contenant des matériau support; (B) à récupérer le précurseur de catalyseur sur support obtenu.
PCT/US1995/014363 1994-10-31 1995-10-25 Deshydroxylation in situ de supports et preparation de catalyseurs polyolefiniques a alliage organometallique sur support WO1996013532A1 (fr)

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Application Number Priority Date Filing Date Title
AU41468/96A AU4146896A (en) 1994-10-31 1995-10-25 In situ dehydroxylation of supports and preparation of supported metallocene polyolefin catalysts

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US33143994A 1994-10-31 1994-10-31
US08/331,439 1994-10-31
US54544795A 1995-10-19 1995-10-19
US08/545,447 1995-10-19

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998030602A1 (fr) * 1997-01-14 1998-07-16 Dsm N.V. Procede pour polymeriser les olefines
US6218487B1 (en) 1997-01-14 2001-04-17 Dsm N.V. Process for polymerizing olefins
WO2001046270A1 (fr) * 1999-12-22 2001-06-28 Nova Chemicals (International) S.A. Catalyseur mao doux
US6399531B1 (en) 1999-12-28 2002-06-04 Union Carbide Chemicals & Plastics Technology Corporation Hybrid ziegler-natta and cycloalkadienyl catalysts for the production of polyolefins
US6444605B1 (en) 1999-12-28 2002-09-03 Union Carbide Chemicals & Plastics Technology Corporation Mixed metal alkoxide and cycloalkadienyl catalysts for the production of polyolefins
US7166553B2 (en) 2002-05-06 2007-01-23 Union Carbide Chemicals & Plastics Technology Corporation Mixed catalyst compositions for the production of polyolefins
US7629481B2 (en) 2004-09-25 2009-12-08 Lg Chem, Ltd. Ansa-metallocene compound, process of preparing the same, and process of preparing polyolefin using the same
WO2013147539A1 (fr) 2012-03-30 2013-10-03 대림산업 주식회사 Résine de polyoléfine multimodale et produit moulé préparé à partir de celle-ci
WO2014088287A1 (fr) 2012-12-03 2014-06-12 대림산업 주식회사 Composition catalytique pour la préparation de résine polyoléfinique multimodale présentant d'excellentes propriétés d'aptitude au moulage et mécaniques et procédé de polymérisation l'utilisant
EP3239196A1 (fr) 2016-04-26 2017-11-01 Daelim Industrial Co., Ltd Résine de polyoléfine multimodale ayant une résistance élevée à la fusion et produit moulé préparé avec celle-ci
WO2023051575A1 (fr) * 2021-09-30 2023-04-06 中国石油化工股份有限公司 Composition de catalyseur et application associée

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JPH0485306A (ja) * 1990-07-26 1992-03-18 Mitsubishi Petrochem Co Ltd オレフィン重合用触媒およびその製造法ならびにオレフィン重合体の製造法
EP0546690A1 (fr) * 1991-11-12 1993-06-16 Nippon Oil Co. Ltd. Composants de catalyseur pour polymérisation d'oléfines
EP0585512A1 (fr) * 1992-08-31 1994-03-09 Fina Research S.A. Procédé de préparation d'un composant de catalyseur pour polymérisation d'oléfines

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Publication number Priority date Publication date Assignee Title
JPH0485306A (ja) * 1990-07-26 1992-03-18 Mitsubishi Petrochem Co Ltd オレフィン重合用触媒およびその製造法ならびにオレフィン重合体の製造法
EP0546690A1 (fr) * 1991-11-12 1993-06-16 Nippon Oil Co. Ltd. Composants de catalyseur pour polymérisation d'oléfines
EP0585512A1 (fr) * 1992-08-31 1994-03-09 Fina Research S.A. Procédé de préparation d'un composant de catalyseur pour polymérisation d'oléfines

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998030602A1 (fr) * 1997-01-14 1998-07-16 Dsm N.V. Procede pour polymeriser les olefines
US6218487B1 (en) 1997-01-14 2001-04-17 Dsm N.V. Process for polymerizing olefins
WO2001046270A1 (fr) * 1999-12-22 2001-06-28 Nova Chemicals (International) S.A. Catalyseur mao doux
US6399531B1 (en) 1999-12-28 2002-06-04 Union Carbide Chemicals & Plastics Technology Corporation Hybrid ziegler-natta and cycloalkadienyl catalysts for the production of polyolefins
US6444605B1 (en) 1999-12-28 2002-09-03 Union Carbide Chemicals & Plastics Technology Corporation Mixed metal alkoxide and cycloalkadienyl catalysts for the production of polyolefins
US7166553B2 (en) 2002-05-06 2007-01-23 Union Carbide Chemicals & Plastics Technology Corporation Mixed catalyst compositions for the production of polyolefins
US7629481B2 (en) 2004-09-25 2009-12-08 Lg Chem, Ltd. Ansa-metallocene compound, process of preparing the same, and process of preparing polyolefin using the same
WO2013147539A1 (fr) 2012-03-30 2013-10-03 대림산업 주식회사 Résine de polyoléfine multimodale et produit moulé préparé à partir de celle-ci
US10040883B2 (en) 2012-03-30 2018-08-07 Daelim Industrial Co., Ltd. Multimodal polyolefin resin and molded product prepared therefrom
WO2014088287A1 (fr) 2012-12-03 2014-06-12 대림산업 주식회사 Composition catalytique pour la préparation de résine polyoléfinique multimodale présentant d'excellentes propriétés d'aptitude au moulage et mécaniques et procédé de polymérisation l'utilisant
EP3239196A1 (fr) 2016-04-26 2017-11-01 Daelim Industrial Co., Ltd Résine de polyoléfine multimodale ayant une résistance élevée à la fusion et produit moulé préparé avec celle-ci
US9975977B2 (en) 2016-04-26 2018-05-22 Daelim Industrial Co., Ltd. Multimodal polyolefin resin having high melt strength and molded product prepared with the same
WO2023051575A1 (fr) * 2021-09-30 2023-04-06 中国石油化工股份有限公司 Composition de catalyseur et application associée

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