WO2020106107A1 - Composé de métal de transition et composition de catalyseur le comprenant - Google Patents

Composé de métal de transition et composition de catalyseur le comprenant

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Publication number
WO2020106107A1
WO2020106107A1 PCT/KR2019/016167 KR2019016167W WO2020106107A1 WO 2020106107 A1 WO2020106107 A1 WO 2020106107A1 KR 2019016167 W KR2019016167 W KR 2019016167W WO 2020106107 A1 WO2020106107 A1 WO 2020106107A1
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WIPO (PCT)
Prior art keywords
carbon atoms
carbons
alkyl
formula
transition metal
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Application number
PCT/KR2019/016167
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English (en)
Korean (ko)
Inventor
장재권
김승효
정승환
김아림
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.)
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Publication date
Priority claimed from KR1020190149757A external-priority patent/KR102531561B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US17/294,522 priority Critical patent/US20220024951A1/en
Priority to CN201980075794.9A priority patent/CN113039190B/zh
Priority to EP19887735.9A priority patent/EP3868770B1/fr
Publication of WO2020106107A1 publication Critical patent/WO2020106107A1/fr

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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
    • 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
    • C07F17/00—Metallocenes
    • 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
    • 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
    • C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
    • 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 specification relates to a novel structured transition metal compound and a catalyst composition comprising the same.
  • olefin polymers such as ethylene copolymers are useful polymer materials used as materials for blow molded articles, extrusion molded articles, films, sheets, etc., and have been produced in the presence of a Ziegler-Natta catalyst system.
  • the Ziegler-Natta catalyst is a heterogeneous catalyst and is a catalyst used in a system in which the phase of the reactant and the phase of the catalyst are not the same, for example, a liquid reactant-solid catalyst.
  • the Ziegler-Natta catalyst is composed of two components, and is typically a transition metal such as titanium (Ti), vanadium (V), chromium (Cr), molybdenum (Mo), halogen compounds such as zirconium (Zr), for example , TiCl 4 ), alkyl lithium and alkyl aluminum.
  • the Ziegler-Natta catalyst has a disadvantage in that the concentration of the active species is in the range of several to several tens of percent relative to the transition metal atom, and most transition metal atoms do not exert their functions and thus do not overcome the limitation as a heterogeneous catalyst.
  • metallocene compounds are homogeneous catalysts containing Group 4 metals and are known to exhibit desirable polymerization activity in olefin polymerization.
  • CGC Constrained-Geometry Catalyst
  • US Patent No. 5,064,802 ethylene
  • CGC Constrained-Geometry Catalyst
  • ethylene ethylene
  • the superior aspect of the CGC compared to the metallocene catalysts known in the past can be broadly summarized as follows: (1) High molecular weight while exhibiting high activity even at high polymerization temperature. It produces polymers, and (2) copolymerization of alpha-olefins with large steric hindrances such as 1-hexene and 1-octene is also excellent.
  • various characteristics of CGC are gradually known, and efforts to synthesize and use derivatives thereof as polymerization catalysts have been actively conducted in academia and industry.
  • metallocene catalysts used in polymerization are composed of a group 4 metal element such as titanium, zirconium, and hafnium (Hf) and a supporting ligand as their precursors, and are composed of two aromatic pentacyclic rings and two halogen compounds which are leaving groups.
  • the supporting ligands coordinated to the center metal are generally aromatic cyclopentadienyl groups.
  • the metallocene catalyst has various applications, such as an olefin polymerization process, but has shown some limitations in catalytic activity (especially in a solution process at a temperature of 100 ° C. or higher), for example, beta-hydride elimination. It is known that olefin polymers having a low molecular weight (Mn) having a molecular weight (Mn) of 20,000 or less at a temperature of 100 ° C. or higher can be produced due to a relatively fast termination reaction (or chain chain reaction) such as reaction). In addition, it is known that the active species of the metallocene catalyst tend to be deactivated at a temperature of 100 ° C or higher. Therefore, in order to increase the applicability of the metallocene catalyst, a situation is needed to overcome the limitations as described above.
  • the first technical problem to be solved of the present invention is to provide a novel transition metal compound.
  • the second technical problem to be solved of the present invention is to provide a catalyst composition comprising the transition metal compound.
  • the present invention provides a transition metal compound represented by the following formula (1):
  • R 1 to R 13 are each independently hydrogen; halogen; Alkyl having 1 to 20 carbons; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Silyl; Or silyl having 1 to 3 substituents selected from the group consisting of alkyl having 1 to 12 carbons and alkoxy having 1 to 12 carbons, and two or more adjacent ones of R 1 to R 12 are connected to each other to form a ring.
  • X and X ' are each independently O, S or a linking group
  • A is alkylene having 1 to 6 carbon atoms
  • Y is C or Si
  • M is a Group 4 transition metal
  • Q is hydrogen; halogen; Alkyl having 1 to 20 carbons; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamino having 1 to 20 carbon atoms; Or arylamino having 6 to 20 carbon atoms.
  • the present invention provides a catalyst composition comprising the transition metal compound of the formula (1).
  • the transition metal compound of the present invention can be usefully used as a catalyst for a polymerization reaction in the production of an olefin-based polymer having a high molecular weight in a low-density region, an olefin-based polymer having a low melt index (MI) at high temperature conditions and a high molecular weight It can be usefully used in the manufacture of.
  • MI melt index
  • 'halogen means fluorine, chlorine, bromine or iodine, unless stated otherwise.
  • alkyl' as used herein, unless stated otherwise, means a straight-chain, cyclic or branched hydrocarbon residue, but is not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , t-butyl, n-pentyl, isopentyl and hexyl.
  • 'cycloalkyl' refers to a non-aromatic cyclic hydrocarbon radical composed of carbon atoms, unless stated otherwise.
  • 'Cycloalkyl' includes, by way of non-limiting example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
  • 'aryl' refers to an optionally substituted benzene ring, unless stated otherwise, or to a ring system that may be formed by fusing one or more optional substituents.
  • Exemplary optional substituents have substituted C 1-3 alkyl, substituted C 2-3 alkenyl, substituted C 2-3 alkynyl, heteroaryl, heterocyclic, aryl, optionally having 1 to 3 fluorine substituents Alkoxy, aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, sulfanyl, sulfinyl, sulfonyl, aminosulfonyl, sulfonylamino, carboxycamide, amino Carbonyl, carboxy, oxo, hydroxy, mercapto, amino, nitro, cyano, halogen or ureido.
  • Such a ring or ring system can optionally be fused to an aryl ring (eg, a benzene ring), a carbocyclic ring or a heterocyclic ring, optionally having one or more substituents.
  • aryl ring eg, a benzene ring
  • carbocyclic ring or a heterocyclic ring optionally having one or more substituents.
  • 'aryl' groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracyl or phenanthryl, and substituted derivatives thereof.
  • 'alkenyl' refers to a straight or branched chain hydrocarbon radical having one or more carbon-carbon double bonds. Examples of 'alkenyl' as used herein include, but are not limited to, ethenyl and propenyl.
  • 'alkoxy' refers to the group -OR a , where R a is alkyl as defined above.
  • 'Alkoxy' includes, but is not limited to, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and t-butoxy.
  • 'silyl' means an unsubstituted silyl or a silyl group substituted with one or more substituents.
  • 'Silyl' includes, but is not limited to, silyl, trimethylsilyl, triethylsilyl, isopropyldimethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, hexyldimethylsilyl, methoxymethylsilyl, (2-methoxyethoxy ) Methylsilyl, trimethoxysilyl, triethoxysilyl,
  • the transition metal compound of the present invention is represented by Formula 1 below.
  • R 1 to R 13 are each independently hydrogen; halogen; Alkyl having 1 to 20 carbons; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Silyl; Or silyl having 1 to 3 substituents selected from the group consisting of alkyl having 1 to 12 carbons and alkoxy having 1 to 12 carbons, and two or more adjacent ones of R 1 to R 12 are connected to each other to form a ring.
  • X and X ' are each independently O, S or a linking group
  • A is alkylene having 1 to 6 carbon atoms
  • Y is C or Si
  • M is a Group 4 transition metal
  • Q is hydrogen; halogen; Alkyl having 1 to 20 carbons; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamino having 1 to 20 carbon atoms; Or arylamino having 6 to 20 carbon atoms.
  • polyolefins having characteristics such as high molecular weight When applied to olefin polymerization using the transition metal compound as a catalyst, polyolefins having characteristics such as high molecular weight can be produced by exhibiting high activity even at high polymerization temperatures and exhibiting high copolymerizability.
  • linear low density polyethylene having a density of 0.860 g / cc to 0.930 g / cc at a high molecular weight due to the structural characteristics of the catalyst.
  • R 1 to R 12 are each independently hydrogen; halogen; Alkyl having 1 to 20 carbons; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Silyl; Or it may be a silyl having 1 to 3 substituents selected from the group consisting of alkyl having 1 to 12 carbons and alkoxy having 1 to 12 carbons, and two or more adjacent ones of R 1 to R 12 are connected to each other to form a ring.
  • R 13 is hydrogen; halogen; Alkyl having 1 to 12 carbons; Cycloalkyl having 3 to 12 carbon atoms; Aryl having 6 to 12 carbons; Alkylaryl having 7 to 12 carbon atoms; Or arylalkyl having 7 to 12 carbon atoms,
  • X and X ' may each independently be O, S or a linking group
  • A is alkylene having 1 to 6 carbon atoms
  • Y may be C or Si
  • the M may be Ti, Zr or Hf,
  • Q is hydrogen; halogen; Alkyl having 1 to 20 carbons; Cycloalkyl having 3 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.
  • R 1 to R 12 are each independently hydrogen; Alkyl having 1 to 12 carbons; Cycloalkyl having 3 to 12 carbon atoms; Silyl; Or it may be a silyl having 1 to 3 substituents selected from the group consisting of alkyl having 1 to 12 carbons and alkoxy having 1 to 12 carbons, and two or more adjacent ones of R 1 to R 12 are connected to each other to form a ring.
  • R 1 to R 12 are each independently hydrogen; Alkyl having 1 to 12 carbons; Cycloalkyl having 3 to 12 carbon atoms; Silyl; Or it may be a silyl having 1 to 3 substituents selected from the group consisting of alkyl having 1 to 12 carbons and alkoxy having 1 to 12 carbons, and two or more adjacent ones of R 1 to R 12 are connected to each other to form a ring.
  • R 13 is hydrogen; Alkyl having 1 to 12 carbons; Aryl having 6 to 12 carbons; Or an alkylaryl having 7 to 12 carbon atoms; Or arylalkyl having 7 to 12 carbon atoms,
  • X and X ' may each independently be O, S or a linking group
  • A may be an alkylene having 1 to 6 carbon atoms
  • Y may be C or Si
  • the M may be Ti, Zr or Hf,
  • Q is hydrogen; halogen; Alkyl having 1 to 12 carbons; It may be a cycloalkyl having 3 to 12 carbon atoms.
  • the transition metal compound of Formula 1 may be a transition metal compound represented by the following Formula 1a.
  • R 1 to R 13 , X, X ', M, Y, and Q are each as defined in Formula 1, and n is an integer of 1, 2, or 3.
  • the transition metal compound of Chemical Formula 1 may be a compound represented by Chemical Formula 2 below.
  • R 1 to R 4 , R 5 , R 8 , R 9 and R 12 may each independently be hydrogen or alkyl having 1 to 12 carbons,
  • R 13 is hydrogen, alkyl having 1 to 12 carbons, aryl having 6 to 12 carbons; Or an alkylaryl having 7 to 12 carbon atoms,
  • R 14 to R 21 may each independently be hydrogen or alkyl having 1 to 6 carbons,
  • X and X ' may each independently be O, S or a linking group
  • A may be alkylene having 1 to 6 carbon atoms
  • Y can be C or Si
  • M may be Hf
  • Q may be halogen or alkyl having 1 to 12 carbons
  • n can be 1, 2, or 3.
  • R 1 to R 4 , R 5 , R 8 , R 9 and R 12 may be hydrogen
  • R 13 may be aryl having 6 to 12 carbon atoms
  • X and X ' may each independently be O, S or a linking group
  • A may be ethylene
  • Y may be C
  • the M may be Hf,
  • the Q may be alkyl having 1 to 6 carbon atoms
  • the n may be 1.
  • the transition metal compound of Formula 2 may be a transition metal compound represented by the following Formula 2a.
  • R 1 to R 13 , X, X ', M, Y, and Q are each as defined in Formula 1, and n is an integer of 1, 2, or 3. Also, n may be 1.
  • the compound represented by Formula 1 may be a compound represented by any one of the following Formulas 1-1 and 1-2.
  • the transition metal compound of Chemical Formula 1 may be specifically used to prepare a catalyst for polymerization of an olefin monomer, but is not limited thereto, and is applicable to all other fields in which the transition metal compound can be used.
  • the present invention also provides a catalyst composition comprising the compound of Formula 1 above.
  • the catalyst composition may further include a cocatalyst.
  • a cocatalyst one known in the art can be used.
  • the catalyst composition may further include at least one of the following Chemical Formulas 3 to 5 as a cocatalyst.
  • R 22 are each independently a halogen radical; A hydrocarbyl radical having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;
  • D is aluminum or boron;
  • R 22 are each independently a halogen radical;
  • a is an integer of 2 or more;
  • L is a neutral or cationic Lewis base
  • H is a hydrogen atom
  • Z is a group 13 element
  • A is each independently aryl having 6 to 20 carbons or alkyl having 1 to 20 carbons, in which one or more hydrogen atoms may be substituted with substituents
  • the substituent is halogen, hydrocarbyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, or aryloxy having 6 to 20 carbons.
  • a method for preparing the catalyst composition comprising: first obtaining a mixture by contacting a transition metal compound represented by Formula 1 with a compound represented by Formula 3 or Formula 4; And adding the compound represented by Chemical Formula 5 to the mixture.
  • the molar ratio of the compound represented by Formula 3 or Formula 4 to the transition metal compound of Formula 1 may be 1: 2 to 1: 5,000, respectively. It may be: 10 to 1: 1,000, and more specifically 1:20 to 1: 500.
  • the molar ratio of the compound represented by Formula 5 to the transition metal compound of Formula 1 may be 1: 1 to 1:25, specifically 1: 1 to 1:10, and more specifically 1: 1 To 1: 5.
  • the amount of the alkylating agent is very small, and there is a problem that the alkylation of the metal compound is not completely progressed, and it is more than 1: 5,000.
  • the alkylation of the metal compound is performed, but there is a problem that the activation of the alkylated metal compound is not completely achieved due to a side reaction between the remaining excess alkylating agent and the activator of Chemical Formula 5.
  • the ratio of the compound represented by the formula (5) is less than 1: 1 compared to the transition metal compound of the formula (1), the amount of the activator is relatively small, so that the activation of the metal compound is not completely achieved and thus the activity of the catalyst composition generated There is a problem of falling, and when it is more than 1:25, the metal compound is completely activated, but there is a problem that the unit cost of the catalyst composition is not economically economical or the purity of the resulting polymer is lowered with the remaining excess activator.
  • the molar ratio of the compound represented by Formula 5 to the transition metal compound of Formula 1 may be 1: 1 to 1: 500, specifically 1: 1 to 1: It may be 50, and more specifically 1: 2 to 1:25.
  • the molar ratio is less than 1: 1, the amount of the activator is relatively small, and thus the activation of the metal compound is not completely achieved, resulting in a decrease in the activity of the resulting catalyst composition, and when it is greater than 1: 500, the activation of the metal compound Although completely made, there is a problem that the unit price of the catalyst composition is not economically feasible or the purity of the resulting polymer is inferior with the remaining excess activator.
  • a hydrocarbon-based solvent such as pentane, hexane, heptane, or the like, or an aromatic-based solvent such as benzene or toluene may be used, but not limited thereto, and all solvents usable in the art may be used. Can be.
  • transition metal compound of Formula 1 and the cocatalyst may be used in a form supported on a carrier.
  • Silica or alumina may be used as the carrier.
  • the compound represented by Chemical Formula 3 is not particularly limited as long as it is an alkylaluminoxane. Specific examples include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and more specifically methyl aluminoxane.
  • the compound represented by Chemical Formula 4 is not particularly limited, but specific examples include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, and tri-s-butyl aluminum.
  • Examples of the compound represented by Chemical Formula 5 include triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra (p-tolyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, trimethylammoniumtetra (p-trifluoromethylphenyl) boron, tributylammoniumtetrapentafluorophenylboron, N, N -Diethylanilidiumtetrafetylboron, N, N-diethylanilidiumtetraphenylboron, N, N-diethylaniliniumtetrapentafluoropheny
  • Transition metal compound of Formula 1 It is possible to prepare a polyolefin homopolymer or copolymer by contacting a catalyst composition comprising at least one compound selected from compounds represented by Formulas 3 to 5 with one or more olefin monomers.
  • the specific manufacturing process using the catalyst composition is a solution process, and when the composition is used together with an inorganic carrier such as silica, it can be applied to a slurry or gas phase process.
  • the activated catalyst composition is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloro It can be injected by dissolving or diluting a hydrocarbon solvent substituted with a chlorine atom such as methane or chlorobenzene.
  • the solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkyl aluminum, and it is also possible to further use a cocatalyst.
  • 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-icocene, 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 catalyst composition has a high molecular weight while having a high molecular weight in the copolymerization reaction of a monomer having a high steric hindrance such as ethylene and 1-octene at a high reaction temperature of 90 ° C or higher, specifically, a high reaction temperature of 150 ° C or higher. It has a feature that it is possible to produce an ultra-low density copolymer of 0.890 g / cc or less.
  • the polymer produced by the production method of the present invention has a density of 0.890 g / cc or less.
  • the polymer produced by the production method of the present invention has a density of 0.880 g / cc or less.
  • the peak of Tm melting temperature
  • the peak of Tm melting temperature
  • Tm can be obtained using a Differential Scanning Calorimeter 6000 (DSC) manufactured by PerkinElmer. After increasing the polymer temperature to 100 ° C, it is maintained at that temperature for 1 minute and then lowered to -100 ° C. , Again, increase the temperature to measure the melting point (melting temperature) of the top of the DSC curve.
  • DSC Differential Scanning Calorimeter 6000
  • the polymer produced by the production method of the present invention has a Tm of 100 ° C or less.
  • the polymer prepared by the production method of the present invention may have a Tm of one or two peaks.
  • the polymer produced by the production method of the present invention may have a weight average molecular weight of 200,000 g / mol or more.
  • the polymer produced by the production method of the present invention may have a weight average molecular weight of 250,000 g / mol or more, and the polymer produced by the production method of the present invention has a weight average molecular weight of 600,000 It may be g / mol or less, and specifically 500,000 g / mol or less.
  • the weight average molecular weight (Mw) is a conversion value for standard polystyrene measured using gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the weight average molecular weight is not limited to this and can be measured by other methods known in the art.
  • the polymer prepared by the production method of the present invention has a MI 10 value of 3 g / 10 min or less.
  • Have have a specifically 0.01 g / 10min to about 2 g / 10min MI of 10 values, and more specifically 0.1 g / 10min to 0.5 g / 10min MI of 10 values.
  • the MI 10 value is a melt index under a load of 10 kg and 190 ° C., which is a value reflecting the number of long chain branches (LCB) in the main chain of the polymer, and the polymer prepared by the production method of the present invention is The fact that it has a value of MI 10 in the range suggests that the catalyst composition containing the transition metal compound of the present invention can control the production of long-chain in the polyolefin-based polymer main chain to be produced.
  • LCB long chain branches
  • the polymer prepared by the production method of the present invention has a MI 2.16 value of 0.005 g / 10min to 0.5 g / 10min.
  • the MI 2.16 value represents the melt index under a load of 2.16 kg and 190 ° C.
  • the polymer produced by the production method of the present invention has a melt flow rate ratio (MFRR) of 1 to 20, specifically 5 to 15, more specifically 7 to 12 MFRR).
  • the melt flow rate ratio (MFRR) means the ratio of MI 10 (10 kg load and melt index under 190 ° C) divided by MI 2.16 (melt index under load 2.16 kg and 190 ° C), and the long-chain (LCB) of the polymer As the number decreases, the MFRR may exhibit a low value, and mechanical properties of the polymer may be improved.
  • Example 1 Preparation of a ligand compound and a transition metal compound
  • Step 1 Preparation of ((ethane-1,2-diylbis (oxy)) bis (4,1-phenylene)) bis (phenylmethanone)
  • Step 2 Preparation of 1,2-bis (4- (cyclopenta-2,4-diene-1-ylidene (phenyl) methyl) phenoxy) ethane)
  • Step 3 1,2-bis (4- (cyclopenta-2,4-diene-1-yl (1,1,4,4,7,7,10,10-octamethyl-2,3,4, Preparation of 7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluoren-12-yl) (phenyl) methyl) phenoxy) ethane
  • Step 4 1,2-bis (4- (cyclopenta-2,4-diene-1-yl (1,1,4,4,7,7,10,10-octamethyl-2,3,4, Preparation of 7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluoren-12-yl) (phenyl) methyl) phenoxy) ethane-hafnium chloride
  • Step 1 Preparation of ethane-1,2-diylbis (4,1-phenylene)) bis (phenylmethanone)
  • Step 2 Preparation of 1,2-bis (4- (cyclopenta-2,4-diene-1-ylidene (phenyl) methyl) phenyl) ethane
  • Step 3 1,2-bis (4- (cyclopenta-2,4-diene-1-yl (1,1,4,4,7,7,10,10-octamethyl-2,3,4, Preparation of 7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluoren-12-yl) (phenyl) methyl) phenyl) ethane
  • Step 4 1,2-bis (4- (cyclopenta-2,4-diene-1-yl (1,1,4,4,7,7,10,10-octamethyl-2,3,4, Preparation of 7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluoren-12-yl) (phenyl) methyl) phenyl) ethane-hafnium chloride
  • 1,2,3,4-tetrahydroquinoline 13.08 g, 98.24 mmol
  • diethyl ether 150 mL
  • the Schlenk flask was immersed in a low temperature bath at -78 ° C made of dry ice and acetone and stirred for 30 minutes.
  • n-BuLi 39.3 mL, 2.5 M, 98.24 mmol
  • the temperature of the flask was raised to room temperature while removing the produced butane gas.
  • the flask was again immersed in a low-temperature bath at -78 ° C to lower the temperature, and then CO 2 gas was added. As the carbon dioxide gas was added, the slurry disappeared, resulting in a transparent solution.
  • the flask was connected to a bubbler to remove the carbon dioxide gas, and the temperature was raised to room temperature. Thereafter, excess CO 2 gas and solvent were removed under vacuum.
  • pentane was added, vigorously stirred, and filtered to obtain lithium carbamate, a white solid compound.
  • the white solid compound is coordinated with diethyl ether. At this time, the yield is 100%.
  • the lithium carbamate compound (8.47 g, 42.60 mmol) prepared in step (i) was placed in a Schlenk flask. Subsequently, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were added sequentially.
  • the Schlenk flask was immersed in a low-temperature bath at -20 ° C made of acetone and a small amount of dry ice, stirred for 30 minutes, and then t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture turned red. Stirring was continued for 6 hours while maintaining -20 ° C.
  • the reactor temperature was preheated to 150 ° C.
  • the pressure of the reactor was pre-filled with ethylene (35 bar).
  • a corresponding amount of the catalyst and a catalyst of 10 eq of dimethylanilinium tetrakis (pentafluorophenyl) borate (AB) of the catalyst were sequentially added to the reactor under high pressure argon pressure.
  • the copolymerization reaction was performed for 8 minutes.
  • the remaining ethylene gas was removed, and a polymer solution was added to excess ethanol to induce precipitation.
  • the properties were measured after drying in a vacuum oven at 90 ° C. for at least 12 hours.
  • Density of the polymer was measured on a Mettler scale after a sample was prepared with a press mold of 190 ° C. and a sheet having a thickness of 3 mm and a radius of 2 cm was annealed at room temperature for 24 hours.
  • the crystallization temperature (Tc) of the polymer and the melting temperature (Tm) of the polymer can be obtained using a differential scanning calorimeter (DSC) manufactured by PerkinElmer, and specifically, a copolymer under a nitrogen atmosphere using DSC. The temperature was increased to 200 ° C. and maintained for 5 minutes, then cooled to 30 ° C., and the temperature was increased again to observe the DSC curve. At this time, the heating rate and the cooling rate were respectively 10 ° C / min. In the measured DSC curve, the crystallization temperature was defined as the maximum point of the exothermic peak upon cooling, and the melting temperature was determined as the maximum point of the endothermic peak during the second heating.
  • DSC differential scanning calorimeter
  • the catalyst composition comprising the compounds of Examples 1 and 2 of the present invention as a catalyst showed higher catalytic activity, and a higher molecular weight polymer at a similar density was obtained. It can be confirmed that it can be produced.

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  • 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 nouveau composé de métal de transition et une composition de catalyseur le comprenant, qui peut être utilisé de manière efficace en tant que catalyseur dans une réaction de polymérisation dans la préparation d'un polymère à base d'oléfine ayant un poids moléculaire élevé dans une région de faible densité, et peut être utilisé de manière efficace pour préparer un polymère à base d'oléfine de poids moléculaire élevé ayant un faible indice de fusion (MI) dans des conditions de température élevée.
PCT/KR2019/016167 2018-11-22 2019-11-22 Composé de métal de transition et composition de catalyseur le comprenant WO2020106107A1 (fr)

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US17/294,522 US20220024951A1 (en) 2018-11-22 2019-11-22 Transition Metal Compound and Catalyst Composition Comprising Same
CN201980075794.9A CN113039190B (zh) 2018-11-22 2019-11-22 过渡金属化合物和包含其的催化剂组合物
EP19887735.9A EP3868770B1 (fr) 2018-11-22 2019-11-22 Composé de métal de transition et composition de catalyseur le comprenant

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
US20050285284A1 (en) * 2004-06-25 2005-12-29 Thorn Matthew G Synthesis of ansa-metallocenes and their parent ligands in high yield
KR20100098670A (ko) * 2007-12-28 2010-09-08 셰브론 필립스 케미컬 컴퍼니 엘피 나노-결합된 메탈로센 촉매조성물 및 이들의 중합체 생성물
US20120059134A1 (en) * 2010-09-07 2012-03-08 Chevron Phillips Chemical Company Lp Novel Catalyst Systems and Methods of Making and Using Same
KR20120028269A (ko) * 2010-09-14 2012-03-22 주식회사 엘지화학 이핵 메탈로센 화합물 및 이를 이용한 폴리올레핀의 제조방법
WO2014120548A1 (fr) * 2013-01-29 2014-08-07 Chevron Phillips Chemical Company Lp Compositions de catalyseur et leurs procédés de fabrication et d'utilisation
CN108530492A (zh) * 2018-05-17 2018-09-14 中国石油天然气股份有限公司 一种桥联双核茂金属化合物及其制备方法与应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
US20050285284A1 (en) * 2004-06-25 2005-12-29 Thorn Matthew G Synthesis of ansa-metallocenes and their parent ligands in high yield
KR20100098670A (ko) * 2007-12-28 2010-09-08 셰브론 필립스 케미컬 컴퍼니 엘피 나노-결합된 메탈로센 촉매조성물 및 이들의 중합체 생성물
US20120059134A1 (en) * 2010-09-07 2012-03-08 Chevron Phillips Chemical Company Lp Novel Catalyst Systems and Methods of Making and Using Same
KR20120028269A (ko) * 2010-09-14 2012-03-22 주식회사 엘지화학 이핵 메탈로센 화합물 및 이를 이용한 폴리올레핀의 제조방법
WO2014120548A1 (fr) * 2013-01-29 2014-08-07 Chevron Phillips Chemical Company Lp Compositions de catalyseur et leurs procédés de fabrication et d'utilisation
CN108530492A (zh) * 2018-05-17 2018-09-14 中国石油天然气股份有限公司 一种桥联双核茂金属化合物及其制备方法与应用

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