WO2017034142A1 - Composé de métal de transition, composition catalytique le comprenant, et procédé de production d'un polymère oléfinique l'utilisant - Google Patents

Composé de métal de transition, composition catalytique le comprenant, et procédé de production d'un polymère oléfinique l'utilisant Download PDF

Info

Publication number
WO2017034142A1
WO2017034142A1 PCT/KR2016/006910 KR2016006910W WO2017034142A1 WO 2017034142 A1 WO2017034142 A1 WO 2017034142A1 KR 2016006910 W KR2016006910 W KR 2016006910W WO 2017034142 A1 WO2017034142 A1 WO 2017034142A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon atoms
group
transition metal
metal compound
catalyst composition
Prior art date
Application number
PCT/KR2016/006910
Other languages
English (en)
Korean (ko)
Inventor
김병석
박희광
노경섭
안상은
이인선
이혜경
전상진
최라윤
Original Assignee
주식회사 엘지화학
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
Priority claimed from KR1020160007128A external-priority patent/KR101790672B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP16839432.8A priority Critical patent/EP3252061B1/fr
Priority to US15/557,328 priority patent/US10280238B2/en
Priority to CN201680015630.3A priority patent/CN107406475B/zh
Publication of WO2017034142A1 publication Critical patent/WO2017034142A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • 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
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • Transition metal compound, catalyst composition comprising the same, and method for producing olefin polymer using same
  • the present invention relates to a transition metal compound, a catalyst composition comprising the transition metal compound, and a method for producing an olefin polymer using the catalyst composition.
  • Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used in the commercial production process of polyolefins.
  • the Ziegler-Natta catalysts have high activity, but because they are multi-site catalysts, the molecular weight distribution of the resulting polymers is broad and Since the composition distribution of the monomer was not uniform, there was a limit to securing desired physical properties.
  • metallocene catalysts in which a transition metal such as titanium, zirconium, hafnium and the like and a ligand including a cyclopentadiene functional group have been developed have been widely used.
  • Metallocene compounds are generally used by activating aluminoxane, borane, borate or other activators.
  • a metallocene compound having a ligand containing a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator.
  • These metallocene catalysts are characterized by a narrow molecular weight distribution of the resulting polymer as a single active site catalyst having one type of active site.
  • the polyolefin polymerized with a metallocene catalyst has a narrow molecular weight distribution, and when used in some products, there is a problem that it is difficult to apply the field such as productivity decreases significantly due to the extruded load.
  • the present invention provides a transition metal compound capable of providing an olefin polymer having excellent energy saving effect during processing or molding.
  • the present invention also provides a catalyst composition comprising the transition metal compound and a method for producing an olefin polymer using the catalyst composition.
  • a transition metal compound represented by the following formula (1).
  • M 1 is any one of a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide transition metal and an actanide transition metal,
  • X 1 and X 2 are the same as or different from each other, and each independently one of halogen and alkyl having 1 to 20 carbon atoms,
  • A is any one of Group 14 elements, n is an integer between 1 and 20, R 1 is alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, and having 7 to 7 carbon atoms. Any one of arylalkyl of 30 and aryl of 6 to 30 carbon atoms,
  • R 2 is hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkylaryl of 7 to 30 carbon atoms, arylalkyl of 7 to 30 carbon atoms and 6 carbon atoms Aryl of any one of from 30 to 30,
  • R 3 and R 4 are each independently hydrogen or alkyl having 1 to 20 carbon atoms. Specifically, in Formula 1, R 3 and R 4 may be each independently hydrogen and straight chain alkyl having 1 to 5 carbon atoms. In the general formula 1 R 1 is either a branched alkyl having 3 to 6, n can be an integer between 4-8. In Formula 1, R 2 may be any one of linear alkyl alkyl having 1 to 6 carbon atoms.
  • M 1 may be either a Group 4 transition metal.
  • a catalyst composition comprising a transition metal compound represented by the formula (1).
  • the catalyst composition may include one or more cocatalysts selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4.
  • R 5 , R 6 and R 7 are each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
  • n is an integer of 2 or more
  • D is aluminum or boron
  • Each R 8 is independently a halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
  • L is a neutral or cationic Lewis base
  • W is a Group 13 element
  • J is each independently a hydrocarbyl group having 1 to 20 carbon atoms; Hydrocarbyloxy group having 1 to 20 carbon atoms; And one or more hydrogen atoms of these substituents are substituted with one or more substituents of halogen, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms.
  • the catalyst composition may further include a carrier supporting the transition metal compound.
  • a carrier supporting the transition metal compound.
  • silica, alumina, magnesia or a mixture thereof may be used.
  • the catalyst composition when the catalyst composition further includes a carrier supporting the transition metal compound, the catalyst composition may include the transition metal compound and the promoter in a molar ratio of 10: 1 to 1: 1.
  • the catalyst composition can be used in a propylene polymerization reaction to provide a polypropylene exhibiting a low melt temperature and a high melt flow rate.
  • a method for producing an olephine polymer comprising the step of polymerizing the olephine monomer in the presence of the catalyst composition.
  • the method for producing the olepin polymer can provide polypropylene that exhibits low melt temperature and high melt flow rate using propylene as an olepin monomer.
  • the melting temperature of the polypropylene may be about .13 CTC to 146 ° C, measured under a load of temperature of 230 ° C 2. 16 kg for polypropylene having a weight average molecular weight of less than 150, 000 g / mol
  • the melt flow may be 70 g / 10 min or more.
  • the present invention not only can exhibit high activity in the olefin polymerization reaction, but also a transition metal compound capable of easily controlling the physical properties of the olefin polymer to be synthesized, a catalyst composition comprising the same, and the preparation of inolepine polymer using the catalyst composition.
  • a method may be provided.
  • olefins with excellent energy saving effect during processing or molding Polymers may be provided.
  • transition metal compound according to a specific embodiment of the present invention, a catalyst composition including the same, and a method for preparing an olefin polymer using the same will be described.
  • a transition metal compound represented by the following formula (1).
  • M 1 is a transition metal of Group 3, "Group 4 transition metal, a Group 5 transition metal, lanthanide series transition metals, transition metal of any one of a series of akta arsenide, and
  • X 1 and X 2 are the same as or different from each other, and each independently one of halogen and alkyl having 1 to 20 carbon atoms,
  • A is any one of elemental elements of group 14, n is an integer between 1 and 20,
  • R 1 is any one of alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkylaryl of 7 to 30 carbon atoms, arylalkyl of 7 to 30 carbon atoms, and aryl of 6 to 30 carbon atoms,
  • R 2 is any one of hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, arylalkyl having 7 to 30 carbon atoms, and aryl having 6 to 30 carbon atoms,
  • R 3 and R 4 are each independently hydrogen and alkyl of 1 to 20 carbon atoms Which one.
  • Halogen may be fluorine (F), chlorine (C1), bromine (Br) or iodine (I).
  • Alkyl having 1 to 20 carbon atoms may be linear, branched or cyclic alkyl. Specifically, alkyl having 1 to 20 carbon atoms is straight chain alkyl having 1 to 20 carbon atoms; Straight chain alkyl having 1 to 10 carbon atoms; Straight chain alkyl of 1 to 5 carbon atoms; Branched or cyclic alkyl having 3 to 20 carbon atoms; Branched or cyclic alkyl having 3 to 15 carbon atoms; Or branched or cyclic alkyl having 3 to 10 carbon atoms.
  • alkyl having 1 to 20 carbon atoms is methyl group, ethyl group, n-propyl group, i so-propyl group, n-butyl group, i so-butyl group, tert-butyl group, n—pentyl group, i so- Penyl group or cyclonuclear group.
  • Alkenyl having 2 to 20 carbon atoms may be straight-chain branched or cyclic alkenyl.
  • alkenyl having 2 to 20 carbon atoms includes straight-chain alkenyl having 2 to 20 carbon atoms, straight-chain alkenyl having 2 to 10 carbon atoms, straight-chain alkenyl having 2 to 5 carbon atoms, branched alkenyl having 3 to 20 carbon atoms, and 3 carbon atoms.
  • alkenyl having 2 to 20 carbon atoms may be ethenyl, propenyl, butenyl, pentenyl or cyclonuxenyl.
  • Aryl having 6 to 30 carbon atoms may mean monocyclic, bicyclic or tricyclic aromatic hydrocarbons. Specifically, the aryl having 6 to 30 carbon atoms may be a phenyl group, a naphthyl group, an anthracenyl group, or the like.
  • Alkylaryl having 7 to 30 carbon atoms may mean a substituent in which at least one hydrogen of aryl is substituted by alkyl.
  • the alkylaryl having 7 to 30 carbon atoms may be methylphenyl, ethylphenyl, n-propylphenyl, i so-propylphenyl, n-butylphenyl, i so-butylphenyl, tert-butylphenyl or cyclonucleophenyl.
  • Arylalkyl having 7 to 30 carbon atoms has at least one hydrogen of alkyl It may mean a substituent substituted by.
  • arylalkyl having 7 to 30 carbon atoms may be a benzyl group, phenylpropyl, or phenylnuclear chamber.
  • the transition metal compound represented by Formula 1 includes two benzoindenyl groups as ligands, and serves as a Lewis base as an oxygen-donor to a bridge group connecting the two ligands. It has a structure that includes a working container capable of doing so. For example, when a transition metal compound having such a specific structure is activated in an appropriate manner and used as a polymerization catalyst for an olefin monomer, an olefin polymer having a low melting temperature and a high melt flow rate can be produced with excellent energy saving effect during processing or molding. Can be. In particular, as described below, this effect can be maximized during the propylene addition.
  • the benzoindenyl ligand may be substituted with an unsubstituted or less sterically hindered substituent.
  • the olefin polymer of the desired three-dimensional structure can be manufactured easily, showing favorable catalytic activity.
  • R 3 and R 4 of Formula 1 may each independently be any one of hydrogen and linear alkyl having 1 to 5 carbon atoms.
  • R 1 of Formula 1 may be any one of branched alkyl having 3 to 6 carbon atoms, and n may be an integer of 4 to 8 for improved supporting efficiency.
  • R 2 of Formula 1 may be any one of linear alkyl having 1 to 6 carbon atoms.
  • the results of the inventors of the present invention can exhibit an excellent energy saving effect during molding or processing.
  • the olefin polymer which can be prepared, can be prepared only through a transition metal compound in which the ligand of the above-described structure is connected to the bridge group of the above-described structure, as shown in Formula 1, and even if the ligand of the above-described structure It was found that it could not be made via a transition metal compound that was not linked to a bridge group.
  • any one of Group 4 transition metals any one of Ti, Zr, and Hf may be used to improve the storage stability of the metal complex.
  • X 1 and X 2 are the same as or different from each other, and each Independently halogen or any one of alkyl of 1 to 20 carbon atoms; Or each independently halogen or alkyl having 1 to 10 carbon atoms; Or each independently halogen.
  • the transition metal compound represented by Chemical Formula 1 may be synthesized by using known reactions, and a detailed synthesis method may be referred to Preparation Example 1, which will be described later.
  • a catalyst composition comprising a transition metal compound represented by the formula (1).
  • the catalyst composition may further comprise a cocatalyst that was able to activate the transition metal compound.
  • a promoter any one conventionally used in the art to which the present invention pertains may be used without particular limitation.
  • the promoter may be at least one compound selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4.
  • R 5 , R 6 and R 7 are each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
  • n is an integer of 2 or more
  • D is aluminum or boron
  • Each R 8 is independently a halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
  • L is a neutral or cationic Lewis base
  • ⁇ is a Group 13 element, and each J independently represents a hydrocarbyl group having 1 to 20 carbon atoms; Hydrocarbyloxy group having 1 to 20 carbon atoms; And one or more hydrogen atoms of these substituents are substituted with one or more substituents of halogen, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms.
  • Hydrocarbyl groups are monovalent functional groups in which hydrogen atoms are removed from hydrocarbons, and are alkyl, alkenal, alkynyl, aryl, aralkyl, aralkenyl, aralkynyl, alkylaryl, alkenylaryl and alkoxy groups. And a arylaryl 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 methyl group, ethyl group, n-propyl group, i so-propyl group, n-butyl group, i so-butyl group, t ert-butyl group, n_pentyl group, n — Straight chain, branched or cyclic alkyl groups such as —nuclear group, n-heptyl group and cyclonuclear group; Or an aryl group such as a phenyl group, naphthyl group, or anthracenyl group.
  • Hydrocarbyloxy group is a functional group which the hydrocarbyl group couple
  • 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. More specifically, the hydrocarbyloxy group having 1 to 20 carbon atoms has a methoxy group, ethoxy group, n-propoxy group, i so-propoxy group, n-butoxy group, i so-subspecial group, t er t-butoxy group, linear, branched, or cyclic alkoxy groups such as n _ phenoxy group, n _ nucleo group, n _ heptoxy group, and cyclonucleooxy group; Or an aryloxy group such as a phenoxy group or a naphthaleneoxy group.
  • Hydrocarbyl (oxy) silyl groups are functional groups in which one to three hydrogens of -Si3 ⁇ 4 are substituted with one to three 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 include alkylsilyl groups such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group and dimethylpropylsilyl group; Alkoxy silyl groups, such as a mesoxy silyl group, a dimethoxy silyl group, a trimethoxy silyl group, and a dimethoxy ethoxy silyl group; Alkoxy alkyl silyl groups, such as a methoxy dimethyl silyl group, a dieoxy methyl silyl group, and a dimethoxy propyl silyl group, etc. can be sufficient.
  • Non-limiting examples of the compound represented by the formula (2) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane or tert- butyl aluminoxane.
  • Non-limiting examples of the compound represented by Formula 3 include trimethylaluminum, triethylaluminum triisobutylaluminum, tripropylaluminum, tributylaluminum dimethylchloroaluminum, triisopropylaluminum, tri- sec -butylaluminum tricyclopentyl Aluminum, tripentylaluminum, triisopentylaluminum trinuclear silaluminum, trioctylaluminum, ethyldimethylaluminum methyldiethylaluminum, triphenylaluminum, tri-P-lrylaluminum dimethylaluminum mesoxide or dimethylaluminum have.
  • non-limiting examples of the compound represented by the formula (4) include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis ' (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (Pentafluorophenyl) borate, ⁇ , ⁇ -dimethylanilinium ⁇ -butyltris (pentafluorophenyl) borate, ⁇ , ⁇ -dimethylanilinium benzyltris (pentafluorophenyl) borate, ⁇ , ⁇ -dimethylaniyl Linium tetrakis (4- ( t -butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, ⁇ , ⁇ -dimethylanilinium pentakis (4- (triisopropylsilyl) -2
  • the catalyst composition may be a supported catalyst having the above-described transition metal compound supported on a carrier.
  • the transition metal compound represented by Chemical Formula 1 may be stably supported on a carrier having the above-described structural characteristics.
  • the supported catalyst on which the transition metal compound is supported exhibits high activity in olefin polymerization and can easily provide a low molecular weight olefin polymer.
  • a carrier containing a hydroxyl group or a siloxane group may be used.
  • the carrier may be a carrier containing a hydroxyl group or a siloxane group having high reaction properties by drying at a high temperature to remove moisture on the surface.
  • the carrier may be used, such as silica, alumina, magnesia or a mixture thereof.
  • the carrier may be dried at high temperature, and they may typically include oxides, carbonates, sulfates, nitrates, such as Na 2 O, K 2 CO 3, BaS0 4, and Mg (N0 3 ) 2 .
  • a small amount of promoter may activate the transition metal compound according to the embodiment.
  • the catalyst composition further includes a carrier supporting the transition metal compound
  • the transition metal compound and the promoter may be used in a molar ratio of 10: 1 to 1: 1.
  • the catalyst composition described above is used in the polymerization reaction of the olefin monomer, exhibits high catalytic activity, and can easily provide a low molecular weight olefin polymer.
  • the catalyst composition is used in the propylene polymerization reaction, and exhibits a much lower melting temperature and higher melt flow rate than the polymer of the same molecular weight, thereby providing a polypropylene excellent energy saving effect during processing or molding.
  • a method for producing an olefin polymer comprising the step of polymerizing the olefin monomer in the presence of the catalyst composition.
  • the additive catalyst composition is a conventional structure due to the specific structure Compared to the polyolefin polymerized using a metallocene catalyst, it is easy to provide a low molecular weight olefin polymer, and may exhibit higher activity in the polymerization of the olefin monomer.
  • olefin monomer examples include ethylene, alpha-olefin, cyclic olefin, and the like, and diene olefin monomers or triene olefin resin monomers having two or more double bonds can also be polymerized.
  • the monomer examples include ethylene, propylene, 1-butene, 1-pentene, 4-methyl- 1-pentene, 1-nuxene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodec Sen, 1-tetradecene, 1-nuxadecene, 1-aitocene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1, 4-butadiene, 1, 5-pentadiene, 1, 6-nuxadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethyl styrene, etc., These monomers may be mixed and copolymerized two or more kinds.
  • the catalyst composition may provide an olefin polymer having high hydrophobicity and a narrow molecular weight distribution under excellent hydrogen reactivity even under the same amount of hydrogen feeding conditions.
  • the leupin polymer prepared by the manufacturing method according to another embodiment may have a narrow molecular weight distribution of about 1.5 to 3 black or about 1.5 to 2.5.
  • Such olepin polymer is excellent in impact resistance, strength, elasticity, etc. and is expected to be used in various products.
  • the catalyst composition may be used in the propylene polymerization reaction due to the specific structure of the transition metal compound of Formula 1 described above to provide a polypropylene having a low melting temperature.
  • These polypropylenes can be processed or molded at relatively low temperatures due to their low melting temperature, providing a variety of plastic products with less energy.
  • the melting temperature of the polypropylene produced using the catalyst composition is about 20 ° C lower than that of the polypropylene produced using a known Ziegler-Natta catalyst, using a known metallocene catalyst It was found to appear about 6 ° C. lower than the polypropylene produced. More specifically, using the catalyst composition The polypropylene produced may have a melting temperature of about 130 ° C. to 146 ° C. Therefore, the catalyst composition may be particularly useful for the production method of the propylene polymer.
  • the catalyst composition may be used in a propylene polymerization reaction to provide a polypropylene having a high melt flow rate due to the specific structure of the transition metal compound of Formula 1 described above.
  • These polypropylenes have excellent flowability and processability due to the high melt flow rate, which can significantly increase the productivity of various plastic products.
  • the melt flow rate measured under a load of temperature of 230 ' C 2. 16 kg for polypropylene having a weight average molecular weight of 150, 000 g / mol or less, 70g / 10min or more, 80g 10 g or more, 90 g / 10 min or more Black can provide polypropylene of 100 g / 10 min or more.
  • the upper limit of the melt flow rate is not particularly limited and may be adjusted, for example, to about 150 g / 10 min or less.
  • polymerization reaction of olefin monomers such as continuous solution polymerization, bulk polymerization, suspension polymerization, slurry polymerization or emulsion polymerization, can be employed for the polymerization reaction of the olefin resin.
  • the polymerization reaction is about 50 . To 110 ° C. or about 60 to KXrC and a pressure of about 1 to 100 kgf / cm 2 .
  • the catalyst composition in the polymerization reaction, may be used in a dissolved or diluted state in a solvent such as pentane, nucleic acid, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene and the like.
  • a solvent such as pentane, nucleic acid, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene and the like.
  • the olefin polymer prepared by the above method is manufactured using the catalyst composition described above, the olefin polymer may have a low melting temperature and thus exhibit an excellent energy saving effect during molding or processing.
  • reaction mixture containing the compound D was dried to remove the solvent. Then, the remaining solute was added to 10 mL of dichloromethane, and cooled to 0 ° C.
  • 5.2 g of aluminum chloride was dispersed in 40 mL of dichloromethane and slowly added to the reaction mixture. Then obtained The reaction mixture was refluxed for 30 minutes, and the compound E was obtained by extracting an organic layer using HC1 aqueous solution and dichloromethane.
  • Step 3 Preparation of bis (2-methyl-1H ⁇ benzoinden-1-yl) (6- (t-subspecial) nucleus) (methyl) silane
  • Step 4 Preparation of bis (2-methyl-1H-benzoinden-1-yl) (6 ′ (t-subsidiary) nucleus) (methyl) silane zirconium dichloride
  • reaction mixture was added to a reaction vessel containing 2.09 g of bis (tetrahydrofuran) zirconium tetrachloride [ZrCl 4 (C 4 H 5 0) 2 ] and stirred at room temperature for one day. Then, after drying the reaction mixture to remove the solvent Dichloromethane was injected. Then, the obtained mixed solution was filtered to dry the filtrate. And the solid obtained by drying was recrystallized in -3 (C using toluene, and the transition metal compound was obtained in 17% yield.
  • Methyl aluminoxane (MA0) 30 ⁇ ol was added to a shrink flask containing 3 g of silica and reacted at 90 ° C for 24 hours. After the completion of the reaction, when the reaction product was settled, the upper layer solution was removed and the remaining precipitate was washed once with toluene. Then, 180 ⁇ l of the transition metal compound prepared above was dissolved in toluene, and the flask was reacted at 70 ° C. for 5 hours. After the reaction was completed, when the reaction product subsided, the upper layer solution was removed and the remaining precipitate was washed once with toluene.
  • reaction mixture was added to a reaction vessel containing 1.78 g of hafnium tetrachloride (HfCl 4 ), followed by stirring at room temperature for one day. Thereafter, the reaction mixture was dried to remove the solvent, followed by dichloromethane. And then obtained The combined solution was filtered to dry the filtrate. Then, the solid obtained by drying was recrystallized at -30 ° C with toluene to obtain a transition metal compound in a yield of 1.
  • hafnium tetrachloride HfCl 4
  • the 2L stainless reaction vessel was dried in vacuo at 65 ° C., chopped, and 3 mL of triethylaluminum was added at room temperature, and 770 g of propylene was added thereto.
  • 45 mg of the supported catalyst prepared in Preparation Example 1 was dispersed in 20 mL of nucleic acid, prepared in a slurry form, and charged into a reactor using nitrogen pressure. At this time, about 331 ppm hydrogen gas was added together with the catalyst. Thereafter, the temperature of the reactor was gradually raised to 70 ° C. and then polymerized for 1 hour. After the reaction was completed, unreacted propylene was vented.
  • Example 2 Polymerization of Olefin Monomer
  • the 2 L stainless reactor was dried in vacuo at 65 ° C., then cooled, and 3 mL of triethylaluminum was added at room temperature, and 770 g of propylene was added thereto.
  • 45 mg of the supported catalyst prepared in Preparation Example 2 was dispersed in 20 mL of nucleic acid, prepared in a slurry form, and charged into a reactor using nitrogen pressure. At this time, about 331 ppm hydrogen gas was added together with the catalyst. After the reaction temperature was slowly raised to 70 ° C. and then polymerized for 1 hour. Unreacted propylene was vented after completion of the reaction.
  • Example 3 Polymerization of Illepin Monomer First, the 2L stainless reaction vessel was dried in vacuo at 65 ° C., chopped, and 3 mL of triethylaluminum was added at room temperature, and 770 g of propylene and 12, 000 cc of ethylene were added thereto. After stirring for 10 minutes, 30 mg of the supported catalyst prepared in Preparation Example 1 was dispersed in 20 mL of nucleic acid, prepared in a slurry form, and charged into a reactor using nitrogen pressure. At this time, about 331 ppm hydrogen gas was added together with the catalyst. The reactor temperature was then slowly raised to 7 rc and then polymerized for 1 hour. After completion of the reaction, unmixed propylene and ethylene were vented.
  • Example 4 Polymerization of an Olefin Monomer
  • a supported catalyst was prepared in the same manner as in step 5 of Preparation Example 1 using the transition metal compound represented by Formula P1.
  • the olefin monomer was polymerized using a supported catalyst containing the transition metal compound of Formula P1.
  • the optimum conditions for the polymerization of the olefin monomers are different depending on the type of catalyst, so that the olefin monomers are polymerized under conditions optimized for the supported catalyst including the transition metal compound represented by the above formula (P1).
  • the olefin monomer was polymerized using a transition metal compound represented by the following formula (P2).
  • P2 a transition metal compound represented by the following formula (P2)
  • the supporting stability was low and was activated by an excessive promoter as follows.
  • melt flow rate MFR: mel tf low rate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne un composé de métal de transition, une composition catalytique le contenant, et un procédé de production d'un polymère d'oléfine utilisant la composition catalytique, le composé de métal de transition étant capable de présenter une activité élevée dans une réaction de polymérisation d'oléfines, et étant également capable de réguler facilement les propriétés physiques d'un polymère d'oléfine. Lorsque le composé de métal de transition est utilisé, il est possible de fournir un polymère d'oléfine ayant un excellent effet d'économie d'énergie au moment de la transformation ou du moulage.
PCT/KR2016/006910 2015-08-24 2016-06-28 Composé de métal de transition, composition catalytique le comprenant, et procédé de production d'un polymère oléfinique l'utilisant WO2017034142A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP16839432.8A EP3252061B1 (fr) 2015-08-24 2016-06-28 Composé de métal de transition, composition catalytique le comprenant, et procédé de production d'un polymère oléfinique l'utilisant
US15/557,328 US10280238B2 (en) 2015-08-24 2016-06-28 Transition metal compound, catalyst composition comprising same, and method for producing olefin polymer using same
CN201680015630.3A CN107406475B (zh) 2015-08-24 2016-06-28 过渡金属化合物、包含其的催化剂组合物和使用该催化剂组合物制备烯烃聚合物的方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2015-0118902 2015-08-24
KR20150118902 2015-08-24
KR10-2016-0007128 2016-01-20
KR1020160007128A KR101790672B1 (ko) 2015-08-24 2016-01-20 전이 금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조 방법

Publications (1)

Publication Number Publication Date
WO2017034142A1 true WO2017034142A1 (fr) 2017-03-02

Family

ID=58100452

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2016/006910 WO2017034142A1 (fr) 2015-08-24 2016-06-28 Composé de métal de transition, composition catalytique le comprenant, et procédé de production d'un polymère oléfinique l'utilisant

Country Status (1)

Country Link
WO (1) WO2017034142A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10204112A (ja) * 1997-01-17 1998-08-04 Mitsui Chem Inc オレフィン重合用触媒、オレフィン重合体の製造方法およびオレフィン重合体
EP0953581A1 (fr) * 1998-04-27 1999-11-03 Repsol Quimica S.A. Sytèmes catalytiques pour la polymérisation et la copolymérisation d'alpha-oléfines
US6534665B1 (en) * 1999-10-26 2003-03-18 Repsol Quimica S.A. Single-carbon bridges bys cyclopentadienyl compounds and metallocene complexes thereof
KR20150037652A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 폴리프로필렌의 제조방법 및 이로부터 수득되는 폴리프로필렌
KR20150058054A (ko) * 2013-11-18 2015-05-28 주식회사 엘지화학 메탈로센 담지 촉매 및 이를 이용하는 폴리올레핀의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10204112A (ja) * 1997-01-17 1998-08-04 Mitsui Chem Inc オレフィン重合用触媒、オレフィン重合体の製造方法およびオレフィン重合体
EP0953581A1 (fr) * 1998-04-27 1999-11-03 Repsol Quimica S.A. Sytèmes catalytiques pour la polymérisation et la copolymérisation d'alpha-oléfines
US6534665B1 (en) * 1999-10-26 2003-03-18 Repsol Quimica S.A. Single-carbon bridges bys cyclopentadienyl compounds and metallocene complexes thereof
KR20150037652A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 폴리프로필렌의 제조방법 및 이로부터 수득되는 폴리프로필렌
KR20150058054A (ko) * 2013-11-18 2015-05-28 주식회사 엘지화학 메탈로센 담지 촉매 및 이를 이용하는 폴리올레핀의 제조방법

Similar Documents

Publication Publication Date Title
CN105473601B (zh) 茂金属化合物、包含其的催化剂组合物及使用其制备烯烃聚合物的方法
US11767377B2 (en) Metallocene-supported catalyst and method of preparing polyolefin using the same
JP6440832B2 (ja) メタロセン化合物、メタロセン担持触媒およびこれを用いるポリオレフィンの製造方法
WO2015047030A1 (fr) Procédé de préparation de copolymère de propylène-1-butène et copolymère de propylène-1-butène ainsi obtenu
EP3312201A2 (fr) Catalyseur supporté hybride et procédé de préparation d'un polymère d'oléfine à l'aide de celui-ci
KR101790672B1 (ko) 전이 금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조 방법
JP6511061B2 (ja) メタロセン化合物、これを含む触媒組成物およびこれを用いるオレフィン系重合体の製造方法
JP2022528411A (ja) プロピレン－エチレンランダム共重合体
US10550204B2 (en) Transition metal compound and catalyst composition including the same
KR20170073385A (ko) 가공성이 우수한 폴리올레핀
KR102080640B1 (ko) 혼성 담지 촉매 및 이를 이용하는 올레핀계 중합체의 제조방법
KR102117650B1 (ko) 올레핀 중합체 및 이의 제조 방법
KR101092572B1 (ko) 담지촉매를 이용한 폴리올레핀의 제조방법
KR102089057B1 (ko) 전이 금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조 방법
JP2022517077A (ja) 遷移金属化合物、触媒組成物およびそれを用いたポリプロピレンの製造方法
US10550207B2 (en) Method for preparing supported hybrid metallocene catalyst, and supported hybrid metallocene catalyst using the same
WO2017034142A1 (fr) Composé de métal de transition, composition catalytique le comprenant, et procédé de production d'un polymère oléfinique l'utilisant
KR102029447B1 (ko) 전이 금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조 방법
KR20180055601A (ko) 전이 금속 화합물, 이를 포함하는 메탈로센 담지 촉매 및 이를 이용한 올레핀 중합체의 제조 방법
KR101828930B1 (ko) 전이 금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조 방법
KR102157784B1 (ko) 전이 금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조 방법
WO2017159994A1 (fr) Polypropylène

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16839432

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2016839432

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 15557328

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE