WO2020149643A1 - Catalyseur hybride sur support et procédé de préparation d'un polymère d'oléfine à l'aide de celui-ci - Google Patents

Catalyseur hybride sur support et procédé de préparation d'un polymère d'oléfine à l'aide de celui-ci Download PDF

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WO2020149643A1
WO2020149643A1 PCT/KR2020/000748 KR2020000748W WO2020149643A1 WO 2020149643 A1 WO2020149643 A1 WO 2020149643A1 KR 2020000748 W KR2020000748 W KR 2020000748W WO 2020149643 A1 WO2020149643 A1 WO 2020149643A1
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group
formula
metallocene catalyst
olefin polymer
catalyst
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PCT/KR2020/000748
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English (en)
Korean (ko)
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이예진
송은경
홍대식
이혜경
김중수
신은영
곽진영
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주식회사 엘지화학
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Priority claimed from KR1020190172478A external-priority patent/KR102432898B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US17/043,194 priority Critical patent/US11384183B2/en
Priority to EP20742086.0A priority patent/EP3760654A4/fr
Priority to CN202080002414.1A priority patent/CN112020522B/zh
Publication of WO2020149643A1 publication Critical patent/WO2020149643A1/fr

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    • 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
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • 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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F210/02—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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the present invention relates to a hybrid supported metallocene catalyst having high activity and high polymerizability and a method for producing an olefin polymer using the same.
  • Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used in the commercial manufacturing process of the existing olefin polymers. Although the Ziegler-Natta catalysts have high activity, the molecular weight distribution of the resulting polymer is wide due to the high activity catalyst. Since the composition distribution of the monomers is not uniform, there is a limit to securing desired physical properties.
  • metallocene catalyst in which a transition metal such as titanium, zirconium or hafnium and a ligand including a cyclopentadiene functional group are combined has been developed and widely used.
  • Metallocene compounds are generally activated by using aluminoxane, borane, borate or other activators.
  • a metallocene compound having a ligand including a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator.
  • the metallocene catalyst is a single active point catalyst having one kind of active point, and the molecular weight distribution of the resulting polymer is narrow, and the molecular weight, stereoregularity, crystallinity, and especially the reactivity of the comonomer can be adjusted depending on the structure of the catalyst and ligand.
  • an olefin polymer polymerized with a metallocene catalyst has a low melting point and a narrow molecular weight distribution, and thus, when applied to some products, there is a problem in that it is difficult to apply in the field, such as a significant drop in productivity due to the effect of extrusion load.
  • PE-RT Polyethylene-Raised Temperature
  • FNCT stress cracking resistance
  • the present invention compensates for shortcomings in product processing by improving the Broad Orthogonal Comonomer Distribution (BOCD) and melt flow rate ratio (MFRR), and can manufacture olefin polymers for pipes with excellent physical properties. It is to provide a method for producing a hybrid supported metallocene catalyst and an olefin polymer using the same.
  • BOCD Broad Orthogonal Comonomer Distribution
  • MFRR melt flow rate ratio
  • the first metallocene compound represented by Formula 1 below provides a hybrid supported metallocene catalyst comprising a.
  • X 1 and X 2 are each independently halogen
  • R 1 and R 5 are each independently C 6-20 aryl substituted with C 1-20 alkyl
  • R 2 to R 4 and R 6 to R 8 are each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkylsilyl, C 1-20 silylalkyl, C 1-20 Alkoxysilyl, C 1-20 ether, C 1-20 silyl ether, C 1-20 alkoxy, C 6-20 aryl, C 7-20 alkylaryl, or C 7-20 arylalkyl,
  • A is carbon, silicon or germanium
  • R 9 and R 10 are each independently C 1-2 straight chain alkyl; Or C 3-10 straight chain alkyl substituted with C 1-10 alkoxy, at least one of R 9 and R 10 is C 3-10 straight chain alkyl substituted with C 1-10 alkoxy,
  • X 3 and X 4 are each independently halogen
  • R 11 to R 20 are each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkylsilyl, C 1-20 silylalkyl, C 1-20 alkoxysilyl, C 1- 20 ether, C 1-20 silyl ether, C 1-20 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 7-20 alkylaryl, or C 7-20 arylalkyl,
  • At least one of R 11 and R 12 is C 2-20 alkoxyalkyl
  • At least one of R 17 to R 20 is C 1-20 alkyl.
  • a method for producing an olefin polymer comprising the step of polymerizing an olefin monomer is provided.
  • the melt flow rate ratio (MFRR; Melt flow rate ratio) is 22 to 50
  • stress cracking resistance (FNCT; Full Notch Creep Test)
  • FNCT Full Notch Creep Test
  • the present invention as well as exhibiting high activity and polymerizability in the production of olefin polymers, it is possible to secure excellent processability and long-term properties by broadening the molecular weight distribution of synthesized olefin polymers, and contributing to reducing catalyst costs.
  • a supported metallocene catalyst and a method for producing an olefin polymer using the hybrid supported metallocene catalyst may be provided. Therefore, the olefin polymer prepared according to the method of the present invention is suitable for use in pipes because of its excellent processability and long-term physical properties.
  • a first metallocene compound represented by the following Chemical Formula 1 a second metallocene compound represented by the following Chemical Formula 2, and a carrier supporting the first and second metallocene compounds
  • a hybrid supported metallocene catalyst is provided.
  • X 1 and X 2 are each independently halogen
  • R 1 and R 5 are each independently C 6-20 aryl substituted with C 1-20 alkyl
  • R 2 to R 4 and R 6 to R 8 are each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkylsilyl, C 1-20 silylalkyl, C 1-20 Alkoxysilyl, C 1-20 ether, C 1-20 silyl ether, C 1-20 alkoxy, C 6-20 aryl, C 7-20 alkylaryl, or C 7-20 arylalkyl,
  • A is carbon, silicon or germanium
  • R 9 and R 10 are each independently C 1-2 straight chain alkyl; Or C 3-10 straight chain alkyl substituted with C 1-10 alkoxy, at least one of R 9 and R 10 is C 3-10 straight chain alkyl substituted with C 1-10 alkoxy,
  • X 3 and X 4 are each independently halogen
  • R 11 to R 20 are each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkylsilyl, C 1-20 silylalkyl, C 1-20 alkoxysilyl, C 1- 20 ether, C 1-20 silyl ether, C 1-20 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 7-20 alkylaryl, or C 7-20 arylalkyl,
  • At least one of R 11 and R 12 is C 2-20 alkoxyalkyl
  • At least one of R 17 to R 20 is C 1-20 alkyl.
  • Halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
  • C 1-20 alkyl may be straight chain, branched chain or cyclic alkyl. Specifically, C 1-20 alkyl is C 1-20 straight chain alkyl; C 1-10 straight chain alkyl; C 1-5 straight chain alkyl; C 3-20 branched chain or cyclic alkyl; C 3-15 branched or cyclic alkyl; Or C 3-10 branched chain or cyclic alkyl.
  • C 1-20 alkyl is a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group or cyclo Hexyl group and the like.
  • C 2-20 The alkenyl can be straight chain, branched chain or cyclic alkenyl.
  • C 2-20 alkenyl is C 2-20 straight chain alkenyl, C 2-10 straight chain alkenyl, C 2-5 straight chain alkenyl, C 3-20 branched chain alkenyl, C 3-15 branched chain alkenyl Kenyl, C 3-10 branched chain alkenyl, C 5-20 cyclic alkenyl or C 5-10 cyclic alkenyl. More specifically, C 2-20 alkenyl may be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl, and the like.
  • C 6-20 aryl may mean a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. Specifically, C 6-20 aryl may be a phenyl group, a naphthyl group or anthracenyl group.
  • C 7-20 Alkylaryl may mean a substituent in which one or more hydrogens of aryl are substituted by alkyl.
  • C 7-20 alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, or cyclohexylphenyl.
  • Arylalkyl may mean a substituent in which one or more hydrogens of alkyl are substituted by aryl.
  • the arylalkyl may be a benzyl group, phenylpropyl or phenylhexyl.
  • alkoxy examples include methoxy group, ethoxy group, phenyloxy group, cyclohexyloxy group, and tert-butoxyhexyl group.
  • substituents are optionally composed of hydroxy, halogen, alkyl, heterocycloalkyl, alkoxy, alkenyl, silyl, sulfonate, sulfone, aryl and heteroaryl within the range of exerting the same or similar effect as the desired effect. It may be substituted with one or more substituents selected from.
  • the hybrid supported metallocene catalyst according to the embodiment may exhibit high activity and polymerizability by using together the first metallocene compound represented by Chemical Formula 1 and the second metallocene compound represented by Chemical Formula 2
  • the molecular weight distribution of the synthesized olefin polymer is somewhat widened to improve bio-CD (BOCD) and melt flow rate ratio (MFRR) to ensure excellent processability.
  • long-term physical properties such as stress cracking resistance (FNCT) of the olefin polymer to be synthesized can be secured.
  • the olefin polymer may be suitable for use in pipes.
  • the two positions of the two indenyl groups which are ligands are substituted with methyl, and the positions of four (R 1 and R 5 ) are each substituted with alkyl phenyl.
  • R 1 and R 5 By being substituted with, it can exhibit better catalytic activity by an inductive effect capable of supplying sufficient electrons.
  • the first metallocene compound contains zirconium (Zr) as a central metal, and thus has more orbitals capable of accepting electrons compared to other group 14 elements such as hafnium (Hf). It can exhibit a characteristic that can be easily combined with a monomer with a higher affinity, thereby exhibiting a better catalytic activity improvement effect.
  • Zr zirconium
  • Hf hafnium
  • R 1 and R 5 may each independently be C 6-12 aryl substituted with C 1-10 alkyl or phenyl substituted with C 3-6 branched chain alkyl, and more specifically May be tert-butyl phenyl.
  • the substitution position of the alkyl group with respect to the phenyl group may be the 4th position corresponding to the R 1 or R 5 position and the para position bonded to the indenyl group.
  • R 2 to R 4 and R 6 to R 8 may be hydrogen, and X 1 and X 2 may be chloro.
  • A may be silicon
  • substituents R 9 and R 10 of A are each independently methyl; Or C 5-9 straight chain alkyl substituted with tert-butoxy, but may be C 5-9 straight chain alkyl substituted with at least tert-butoxy among R 9 and R 10 . More specifically, R 9 is methyl, and R 10 may be normal-hexyl substituted with tert-butoxy.
  • a representative example of the first metallocene compound represented by Chemical Formula 1 may be Chemical Formula 1-1.
  • the first metallocene compound represented by Chemical Formula 1 may be synthesized by applying known reactions, and detailed examples of synthesis may be referred to Examples.
  • the second metallocene compound represented by Chemical Formula 2 has a structure in which an indenyl group and a cyclopentadienyl group are non-crosslinked, and can easily control the electronic/stereoscopic environment around the transition metal zirconium (Zr).
  • Zr transition metal zirconium
  • the second metallocene compound contains zirconium (Zr) as the central metal, and thus has more orbitals capable of accepting electrons compared to other group 14 elements such as hafnium (Hf). It can exhibit a characteristic that can be easily combined with a monomer with a higher affinity, thereby exhibiting a better catalytic activity improvement effect.
  • Zr zirconium
  • Hf hafnium
  • C 2-20 alkoxyalkyl may be substituted at least one position (one of R 11 to R 16 ) of the indenyl group, and specifically, to R 11 or R 12 C 2-20 alkoxyalkyl may be substituted, and more specifically, R 11 or R 12 may be substituted with C 5-9 straight chain alkyl substituted with tert-butoxy or hexyl substituted with tert-butoxy.
  • C 2-20 alkoxyalkyl is substituted on at least one of the indenyl groups, thereby affecting the copolymerization of an alpha olefin comonomer such as 1-butene or 1-hexene.
  • the C 2-20 alkoxyalkyl substituted with the indenyl group can form a covalent bond through close interaction with the silanol group on the silica surface used as a support, thereby enabling stable supported polymerization.
  • C 1-20 alkyl may be substituted at at least one position (one of R 17 to R 20 ) of the cyclopentadienyl group, specifically, one of R 18 and R 19 may be C 1-20 alkyl It may be substituted, and more specifically, one of R 18 and R 19 may be substituted with normal-butyl.
  • R 11 , R 13 to R 17 , R 19 and R 20 may be hydrogen, and X 3 and X 4 may be chloro.
  • a representative example of the second metallocene compound represented by Chemical Formula 2 may be Chemical Formula 2-1.
  • the second metallocene compound represented by Chemical Formula 2 may be synthesized by applying known reactions, and detailed examples of synthesis may be referred to Examples.
  • the first and second metallocene compounds have the above structural characteristics and can be stably supported on a carrier.
  • a carrier containing a hydroxy group or a siloxane group on the surface may be used.
  • a carrier containing a hydroxy group or a siloxane group having high reactivity may be used by drying at a high temperature to remove moisture on the surface.
  • silica, alumina, magnesia or a mixture thereof can be used.
  • the carrier may be dried at a high temperature, and these may typically include oxides, carbonates, sulfates, and nitrate components such as Na 2 O, K 2 CO 3 , BaSO 4 and Mg(NO 3 ) 2 .
  • the drying temperature of the carrier is preferably 200 to 800°C, more preferably 300 to 600°C, and most preferably 300 to 400°C.
  • the drying temperature of the carrier is less than 200°C, there is too much moisture so that the surface moisture and the co-catalyst react, and when it exceeds 800°C, the surface area decreases as the pores of the carrier surface are combined, and there are many hydroxyl groups on the surface. It is not preferable because the reaction site with the co-catalyst decreases because it disappears and only the siloxane group remains.
  • the amount of hydroxy groups on the surface of the carrier is preferably 0.1 to 10 mmol/g, and more preferably 0.5 to 5 mmol/g.
  • the amount of hydroxy groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or drying conditions, such as temperature, time, vacuum or spray drying.
  • the amount of the hydroxy group is less than 0.1 mmol/g, there are few reaction sites with the cocatalyst, and if it exceeds 10 mmol/g, it is not preferable because it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. not.
  • the hybrid supported metallocene catalyst according to the above embodiment may further include a cocatalyst to activate the metallocene compound as a catalyst precursor.
  • the cocatalyst is an organometallic compound containing a Group 13 metal, and is not particularly limited as long as it can be used when polymerizing an olefin under a general metallocene catalyst.
  • the cocatalyst may be one or more compounds selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5.
  • R 21 , R 22 and R 23 are each independently hydrogen, halogen, C 1-20 hydrocarbyl group, or C 1-20 hydrocarbyl group substituted with halogen,
  • n is an integer of 2 or more
  • D is aluminum or boron
  • R 24 are each independently halogen, C 1-20 hydro-car invoking, C 1-20 hydro-car bilok group, or substituted C 1-20 hydro-car invoking by halogen,
  • L is a neutral or cationic Lewis base
  • H is a hydrogen atom
  • W is a group 13 element
  • A is each independently a C 1-20 hydrocarbyl group; C 1-20 hydrocarbyloxy group; And one or more substituents in which one or more hydrogen atoms of these substituents are substituted with one or more substituents among halogen, C 1-20 hydrocarbyloxy group and C 1-20 hydrocarbyl(oxy)silyl group.
  • the hydrocarbyl group is a monovalent functional group in which hydrogen atoms are removed from the hydrocarbon, and an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkylaryl group, an alkenylaryl group, and an alkyl group And a nilaryl group.
  • the hydrocarbyl group having 1 to 20 carbon atoms may be a hydrocarbyl group having 1 to 15 carbon atoms or 1 to 10 carbon atoms.
  • the hydrocarbyl group having 1 to 20 carbon atoms is a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group , n-heptyl group, cyclohexyl group, such as a straight chain, branched chain or cyclic alkyl group; Or it may be an aryl group such as a phenyl group, naphthyl group, or anthracenyl group.
  • the hydrocarbyloxy group is a functional group in which the hydrocarbyl group is bonded to oxygen.
  • the hydrocarbyloxy group having 1 to 20 carbon atoms may be a hydrocarbyloxy group having 1 to 15 carbon atoms or 1 to 10 carbon atoms.
  • the hydrocarbyloxy group having 1 to 20 carbon atoms is a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a tert-butoxy group, an n-pentoxy group , straight-chain, branched-chain or cyclic alkoxy groups such as n-hexoxy group, n-heptoxy group and cyclohexoxy group; Or it may be an aryloxy group such as a phenoxy group or a naphthalenoxy group.
  • the hydrocarbyl (oxy) silyl group is a functional group in which 1-3 hydrogens of -SiH 3 are substituted with 1 to 3 hydrocarbyl groups or hydrocarbyloxy groups.
  • the hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms may be a hydrocarbyl (oxy) silyl group having 1 to 15 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms.
  • hydrocarbyl (oxy) silyl groups having 1 to 20 carbon atoms include alkyls such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group and dimethylpropylsilyl group.
  • alkyls such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group and dimethylpropylsilyl group.
  • Silyl group Alkoxysilyl groups such as methoxysilyl group, dimethoxysilyl group, trimethoxysilyl group and dimethoxyethoxysilyl group
  • alkoxyalkylsilyl groups such as methoxydimethylsilyl group, diethoxymethylsilyl group, and dimethoxypropylsilyl group.
  • Non-limiting examples of the compound represented by Chemical Formula 3 may include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, or tert-butyl aluminoxane.
  • non-limiting examples of the compound represented by Chemical Formula 4 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-sec-butyl aluminum, To tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide or dimethyl aluminum And thoxide.
  • non-limiting examples of the compound represented by Formula 5 include trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis( Pentafluorophenyl)borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate, N,N-dimethylanilinium Tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2,3 ,5,6-tetrafluorophenyl)
  • the use content of the co-catalyst can be appropriately adjusted according to the properties or effects of the desired hybrid supported metallocene catalyst.
  • the hybrid supported metallocene catalyst according to the above embodiment is prepared, for example, by supporting a cocatalyst on a carrier and supporting a first and second metallocene compound as a catalyst precursor on a cocatalyst carrier.
  • a cocatalyst on a carrier
  • a first and second metallocene compound as a catalyst precursor on a cocatalyst carrier.
  • the co-catalyst supported carrier can be prepared by adding the co-catalyst to the carrier dried at high temperature and stirring it at a temperature of about 20 to 120°C.
  • the first and second metallocene compounds are added to the co-catalyst carrier obtained in the step of supporting the co-catalyst on the carrier, which is again about 20 to 120°C. It can be prepared by stirring at a temperature of the supported catalyst.
  • the first and second metallocene compounds are added to the cocatalyst carrier and stirred, and then a cocatalyst is further added to prepare a supported catalyst.
  • the content of the carrier, cocatalyst, cocatalyst carrier, and transition metal compound used in the hybrid supported metallocene catalyst according to the above embodiment may be appropriately adjusted according to the properties or effects of the desired supported catalyst.
  • the molar ratio of the first metallocene compound and the second metallocene compound may be 1:1 to 15:1.
  • the first and second metallocene compounds in the mixing molar ratio described above, it is possible to provide a hybrid supported metallocene catalyst having high activity and high polymerizability compared to the prior art.
  • the molecular weight distribution can be widened to improve long-term physical properties such as stress cracking resistance (FNCT), and bioCD (BOCD) and melt flow rate ratio. The workability can be improved by improving (MFRR).
  • the molar ratio of the first metallocene compound and the second metallocene compound is less than 1:1, copolymerizability and processability may be deteriorated, and when the molar ratio exceeds 15:1, activity and physical properties may be deteriorated. .
  • the weight ratio of the total metallocene compound and the carrier including the first and second metallocene compounds is 1:10 to 1:1,000 or 1: 10 to 1:500.
  • the carrier and the metallocene compound are included in the above-described range of rangrang ratio, an optimum shape may be exhibited.
  • the weight ratio of the cocatalyst and the carrier may be 1:1 to 1:100 or 1:1 to 1:50.
  • the cocatalyst and carrier are included in the above weight ratio, it is possible to optimize the active and polymer microstructure.
  • hydrocarbon solvents such as pentane, hexane, and heptane
  • an aromatic solvent such as benzene or toluene may be used.
  • the manufacturing method of the supported catalyst is not limited to the contents described in the present specification, and the manufacturing method may further employ a step conventionally employed in the technical field to which the present invention pertains, and the step of the manufacturing method ( The field(s) can be modified by the step(s), which are usually changeable.
  • a method for producing an olefin polymer comprising the step of polymerizing an olefin monomer is provided.
  • the hybrid supported metallocene catalyst has a broad molecular weight distribution compared to an olefin polymer polymerized using a conventional metallocene compound catalyst due to a specific structure, thereby providing excellent processability and long-term physical properties. Can provide.
  • olefin monomer polymerizable with the hybrid supported catalyst examples include ethylene, alpha-olefin, cyclic olefin, and the like, and diene olefin monomer or triene olefin monomer having two or more double bonds may also be polymerized.
  • the monomers are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-hexadecene, 1-atocene, norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like, and may be copolymerized by mixing two or more of these monomers.
  • the comonomer is one or more comonomers selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. It is preferred.
  • polymerization reactions of olefin monomers such as a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process, or an emulsion polymerization process, may be employed, and more specifically ,
  • the polymerization reaction can be carried out in a semi-batch reactor.
  • the polymerization reaction may be performed under a temperature of about 50 to 110°C or about 60 to 100°C and a pressure of about 1 to 100kgf/cm 2 or about 1 to 50 kgf/cm 2 .
  • the hybrid supported catalyst in the polymerization reaction, may be used in a dissolved or diluted state in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, and the like.
  • a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, and the like.
  • the olefin polymer prepared by the above method has a somewhat wider molecular weight distribution as it is prepared using the above-mentioned hybrid supported metallocene catalyst, and improves bio-CD (BOCD) and melt flow rate ratio (MFRR) to ensure excellent processability It is also possible to secure long-term physical properties such as stress cracking resistance (FNCT) of the olefin polymer to be synthesized.
  • BOCD bio-CD
  • MFRR melt flow rate ratio
  • FNCT stress cracking resistance
  • the olefin polymer has a melt flow rate ratio (MFRR) of 22 to 50 or 25 to 32, and a stress cracking resistance (FNCT; Full Notch Creep Test) of 1000 to 3000 hr or 1000 to 2000 hr,
  • MFRR melt flow rate ratio
  • FNCT stress cracking resistance
  • FNCT Full Notch Creep Test
  • the Bio Orthogonal Comonomer Distribution (BOCD) index may be 0.8 to 3.0 or 0.9 to 1.4.
  • the polymer to be polymerized using the above-mentioned hybrid supported catalyst is, for example, an ethylene-alpha olefin copolymer, preferably an ethylene-1-butene polymer, the above physical properties can be more appropriately met.
  • Step 1 Preparation of ((6-(t-butoxy)hexyl)methylsilane-diyl)-bis((2-methyl-4-t-butyl-phenylindenyl)silane
  • 2-Methyl-4-t-butyl-phenylindene (10.0 g, compound 1) was dissolved in 76.2 mL of diethyl ether (Et 2 O) and cooled to -25 °C. Then, 16.0 mL of n-butyllithium solution (2.5 M, hexane solvent) was slowly added dropwise, and then stirred at room temperature for 4 hours. Thereafter, the mixture was cooled to -25°C, 1 mol% of copper cyanide (CuCN) was added, and 2.92 mL of (6-(t-butoxy)hexyl)methyldichlorosilane was dissolved in 38 mL of diethyl ether and slowly added dropwise.
  • Et 2 O diethyl ether
  • CuCN copper cyanide
  • Step 2 Preparation of [((6-(t-butoxy)hexyl)methylsilane-diyl)-bis((2-methyl-4-t-butyl-phenylindenyl)]zirconium dichloride
  • Step 2 Preparation of 3-(6-(t-butoxy)hexyl)-1H-inden-1-yl)(3-butylcyclopenta-2,4-dien-1-yl) zirconium dichloride
  • Example 1 Preparation of hybrid supported catalyst and olefin polymer using the same
  • Silica (SYLOPOL 948 manufactured by Grace Davison) was dehydrated at a temperature of 200° C. for 15 hours under vacuum. 10 g of dried silica was placed in a glass reactor, and 100 mL of toluene was further added and stirred. 50 mL of a 10% by weight methylaluminoxane (MAO)/toluene solution was added, and the temperature was raised to 60° C., followed by reaction for 12 hours with stirring. After the temperature of the reactor was lowered to 40° C., stirring was stopped, and after being set for 10 minutes, the reaction solution was decanted.
  • MAO methylaluminoxane
  • Toluene was filled up to 100 mL of the reactor, and 0.01 mmol of the first metallocene compound (A) of Preparation Example 1 was dissolved in 10 ml of toluene and added together, followed by reaction for 1 hour. After the reaction was over, 0.01 mmol of the second metallocene compound (B) of Preparation Example 2 was dissolved in 10 ml of toluene and added together, followed by further reacting for 1 hour.
  • TEAL 2ml (1.0M hexane), 1-butene 10g was added to a 2L autoclave high-pressure reactor, and 0.8kg of hexane was added, followed by stirring at 500rpm and raising the temperature to 80°C.
  • Example 1 a hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that the first metallocene compound (A) of Preparation Example 1 was used as 0.05 mmol.
  • Example 1 a hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that the first metallocene compound (A) of Preparation Example 1 was used in 0.1 mmol.
  • Example 1 a hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that 0.15 mmol of the first metallocene compound (A) of Preparation Example 1 was used.
  • Example 1 instead of the first and second metallocene compound composition (A/B), the second metallocene compound (B) of Preparation Example 2 was set to be the molar ratio (1/1) of Table 1 below.
  • a hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that 0.01 mmol and 0.01 mmol of the metallocene compound (C) represented by Formula C below were used.
  • An olefin polymer was prepared in the same manner as in Example 1, except that the Ziegler-Natta catalyst of Preparation Example 3 (Z/N catalyst) was used as 0.1 mmol.
  • Example 1 a hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that only the first metallocene compound (A) of Preparation Example 1 was used in 0.1 mmol.
  • Example 1 a hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that only the second metallocene compound (B) of Preparation Example 2 was used in 0.1 mmol.
  • Example 1 instead of the first and second metallocene compound composition (A/B), the second metallocene compound (B) of Preparation Example 2 was set to be the molar ratio (1/1) of Table 1 below.
  • a hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that 0.01 mmol and 0.01 mmol of the metallocene compound (D) represented by the following Chemical Formula D were used.
  • the metallocene compound (E) 0.01 represented by the following Chemical Formula E is set to be the molar ratio (1/1) of Table 1 below.
  • a hybrid supported catalyst and an olefin polymer were prepared in the same manner as in Example 1, except that mmol and 0.01 mmol of the metallocene compound (F) represented by Formula F below were used.
  • Test Example Evaluation of activity of hybrid supported catalyst and physical properties of olefin polymer
  • melt index MI2.16
  • g weight of the polymer melted for 10 minutes.
  • the polymers of Examples 1 to 4 of the present application show high activity using a supported catalyst using a combination of specific precursors.
  • the polymers of Examples 1 to 4 are all excellent in MFRR, BOCD, and FNCT compared to the comparative example, and thus can provide a polymer for pipes with improved processability and long-term physical properties.

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Abstract

Selon la présente invention, l'invention concerne une composition de catalyseur et un procédé de préparation d'un polymère d'oléfine à l'aide de la composition de catalyseur, la composition de catalyseur pouvant contribuer à une économie de coût pour le catalyseur du fait qu'elle présente une activité élevée dans une réaction de polymérisation d'oléfine, et qu'elle est capable de présenter une excellente aptitude au traitement et des propriétés à long terme en présentant une capacité de copolymérisation élevée, ce qui la rend appropriée pour fournir un polymère pour des tuyaux.
PCT/KR2020/000748 2019-01-17 2020-01-15 Catalyseur hybride sur support et procédé de préparation d'un polymère d'oléfine à l'aide de celui-ci WO2020149643A1 (fr)

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US17/043,194 US11384183B2 (en) 2019-01-17 2020-01-15 Hybrid supported metallocene catalyst and method for preparing olefin polymer using the same
EP20742086.0A EP3760654A4 (fr) 2019-01-17 2020-01-15 Catalyseur hybride sur support et procédé de préparation d'un polymère d'oléfine à l'aide de celui-ci
CN202080002414.1A CN112020522B (zh) 2019-01-17 2020-01-15 混杂负载型茂金属催化剂及使用其制备烯烃聚合物的方法

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KR20190006226 2019-01-17
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KR20160057930A (ko) * 2014-11-14 2016-05-24 주식회사 엘지화학 혼성 담지 촉매 및 이를 이용하는 올레핀계 중합체의 제조방법
KR20170055149A (ko) * 2015-11-11 2017-05-19 한화토탈 주식회사 가공성이 우수한 에틸렌 공중합체
KR20170075533A (ko) * 2015-12-23 2017-07-03 주식회사 엘지화학 혼성 담지 촉매 및 이를 이용하는 올레핀계 중합체의 제조방법
KR20180054443A (ko) * 2016-11-15 2018-05-24 주식회사 엘지화학 내환경 응력 균열성이 우수한 에틸렌/알파-올레핀 공중합체
KR20180099269A (ko) * 2017-02-28 2018-09-05 주식회사 엘지화학 올레핀 공중합체 합성용 촉매 조성물 및 올레핀 공중합체의 제조 방법
KR20190074959A (ko) * 2017-12-20 2019-06-28 주식회사 엘지화학 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조 방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160057930A (ko) * 2014-11-14 2016-05-24 주식회사 엘지화학 혼성 담지 촉매 및 이를 이용하는 올레핀계 중합체의 제조방법
KR20170055149A (ko) * 2015-11-11 2017-05-19 한화토탈 주식회사 가공성이 우수한 에틸렌 공중합체
KR20170075533A (ko) * 2015-12-23 2017-07-03 주식회사 엘지화학 혼성 담지 촉매 및 이를 이용하는 올레핀계 중합체의 제조방법
KR20180054443A (ko) * 2016-11-15 2018-05-24 주식회사 엘지화학 내환경 응력 균열성이 우수한 에틸렌/알파-올레핀 공중합체
KR20180099269A (ko) * 2017-02-28 2018-09-05 주식회사 엘지화학 올레핀 공중합체 합성용 촉매 조성물 및 올레핀 공중합체의 제조 방법
KR20190074959A (ko) * 2017-12-20 2019-06-28 주식회사 엘지화학 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조 방법

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