WO2016056744A1 - Composé de ligand, composé de métallocène et procédé de préparation d'un polymère oléfinique faisant appel à eux - Google Patents

Composé de ligand, composé de métallocène et procédé de préparation d'un polymère oléfinique faisant appel à eux Download PDF

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WO2016056744A1
WO2016056744A1 PCT/KR2015/008771 KR2015008771W WO2016056744A1 WO 2016056744 A1 WO2016056744 A1 WO 2016056744A1 KR 2015008771 W KR2015008771 W KR 2015008771W WO 2016056744 A1 WO2016056744 A1 WO 2016056744A1
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group
carbon atoms
formula
compound
halogen
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PCT/KR2015/008771
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English (en)
Korean (ko)
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홍복기
이용호
한창완
최이영
이기수
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주식회사 엘지화학
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Priority claimed from KR1020150117300A external-priority patent/KR101784463B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2016516546A priority Critical patent/JP6570517B2/ja
Priority to EP15841031.6A priority patent/EP3064504B1/fr
Priority to CN201580002342.XA priority patent/CN105705506B/zh
Priority to US15/026,119 priority patent/US9850326B2/en
Publication of WO2016056744A1 publication Critical patent/WO2016056744A1/fr

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    • 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
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • 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
    • 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 novel ligand compound, a metallocene compound, and a method for preparing an olefinic polymer using the same.
  • CGC Constrained-Geometry Catalyst
  • US Pat. No. 5,064,802 ethylene and alpha-
  • CGC Constrained-Geometry Catalyst
  • US Pat. No. 5,064,802 ethylene and alpha-
  • the superiority of CGC in the copolymerization reaction of olefins compared to the metallocene catalysts known to the prior art can be summarized into two main categories: (1) The production of high molecular weight polymers with high activity even at high polymerization temperatures. And (2) the copolymerization of alpha-olefins with large steric hindrances such as 1-nuxene and 1-octene is also excellent.
  • various characteristics of CGC were gradually known in the case of addition reaction, and the derivatives thereof were actively synthesized in ' academia' and 'industrial industry ' to use as a polymerization catalyst.
  • a Group 4 metallocene compound having one or two cyclopentadienyl groups as a ligand can be activated as methylaluminoxane or boron compound to be used as a catalyst for leupin polymerization.
  • Such catalysts exhibit unique properties that conventional Ziegler-Natta catalysts cannot realize.
  • the polymer obtained using such a catalyst has a narrow molecular weight distribution, better response to a second monomer such as alpha olefin or cyclic olefin, and a uniform distribution of the second monomer of the polymer.
  • bridged catalysts have good reaction properties with respect to the second monomer.
  • the bridged catalysts studied so far can be classified into three types depending on the type of bridge.
  • the present invention has a wide molecular weight distribution because of the excellent polymerization activity, and excellent comonomer insertion ability, and thus a metallocene compound capable of producing a leupine-based polymer having excellent processability. And, to provide a method for producing an olefin-based polymer using the same. [Measures of problem]
  • Ri to R 16 are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, wherein R! Two or more adjacent to each other to R 16 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, provided that R and R 16 are all hydrogen;
  • L is a direct bond or an alkylene group having 1 to 10 carbon atoms
  • R is a substituted or unsubstituted phenyl group, naphthyl group, a cycloalkyl group having 3 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms;
  • Ql and Q 2 are the same as or different from each other, and are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon atoms
  • the present invention provides a metallocene compound represented by the following formula (2).
  • M is a Group 4 transition metal
  • Xi and 3 ⁇ 4 are the same as or different from each other, and each independently halogen, alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, nitro group, amido group, alkyl of 1 to 20 carbon atoms A silyl group, an alkoxy group having 1 to 20 carbon atoms, or a sulfonate group having 1 to 20 carbon atoms;
  • R) to R 16 are the same as or different from each other, and each independently hydrogen, halogen, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, and cycloalkylalkyl group having 4 to 20 carbon atoms , 1 carbon To 20 alkoxy group, an aryl group having 6 to 20 carbon atoms of the aryl group, having 5 to 20 heteroaryl group, a C7 to C20 alkylaryl group, or a carbon number of 7 to 20 of, adjacent to each other of the to R 16 Two or more may be linked to each other to form a substituted or unsubstituted aliphatic or aromatic ring, except where all of R to 16 are hydrogen;
  • L is a direct bond or an alkylene group having 1 to 10 carbon atoms
  • R is a substituted or unsubstituted phenyl group, naphthyl group, a cycloalkyl group having 3 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms;
  • Q t and Q 2 are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkylaryl group having 7 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms.
  • the present invention provides a method for producing an olefin-based polymer comprising the step of polymerizing a relefin-based monomer in the presence of a catalyst composition comprising the metallocene compound.
  • the metallocene compound having the new ligand can easily control the electronic and three-dimensional environment around the metal by introducing various substituents to the ligand to which the indeno indole derivative and the fluorene derivative are linked, and ultimately, the structure of the polyolefin produced.
  • the physical properties can be adjusted.
  • the metallocene compound according to the present invention or the catalyst composition including the same can be used in the preparation of the olepin-based polymer, and especially exhibits high activity even in the co-polymerization using a comonomer, can improve the comonomer insertion ability, It is possible to manufacture an leupin-based polymer having a molecular weight distribution and excellent in processability.
  • first and second are used to describe various components, which terms constitute one component to another component. It is only used to distinguish it from the element.
  • each layer or element when each layer or element is referred to as being formed “on” or “on” of each layer or element, it means that each layer or element is directly formed on each layer or element, or the other It is meant that a layer or element can additionally be formed between each layer, on the object, the substrate.
  • Ligand compound according to the invention is characterized in that represented by the formula (1).
  • Rt to R 16 are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms of the aryl group, having 5 to 20 heteroaryl group, a C7 to C20 alkylaryl group, or a carbon number of 7 to 20 of the, each of said through R 16
  • Two or more adjacent groups may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, except that the above R 16 are all hydrogen;
  • L is a direct bond or an alkylene group having 1 to 10 carbon atoms
  • R is a substituted or unsubstituted phenyl group, naphthyl group, a cycloalkyl group having 3 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms;
  • Qi and Q 2 are the same as or different from each other, and are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon atoms An alkylaryl group having 7 to 20 or an arylalkyl group having 7 to 20 carbon atoms. When described in more detail with respect to the main substituents in the formula (1).
  • the alkyl group having 1 to 20 carbon atoms includes a linear or branched alkyl group, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nuclear group, heptyl group And an octyl group etc. are mentioned, but it is not limited to this.
  • the alkenyl group having 2 to 20 carbon atoms includes a straight or branched alkenyl group, and specifically includes an allyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and the like, but is not limited thereto. .
  • the aryl group having 6 to 20 carbon atoms includes a monocyclic or condensed aryl group, and specifically includes a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like, but is not limited thereto.
  • the heteroaryl group having 5 to 20 carbon atoms includes a monocyclic or condensed heteroaryl group, and includes a carbazolyl group, a pyridyl group, a quinoline group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, a thiazolyl Groups, triazine groups, tetrahydropyranyl groups, tetrahydrofuranyl groups, and the like, but are not limited thereto.
  • alkoxy group having 1 to 20 carbon atoms examples include mesophilic, ethoxy, phenyloxy, and cyclonucleooxy groups, but are not limited thereto.
  • the cycloalkyl group having 3 to 20 carbon atoms may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclonuxyl group, and the like, but is not limited thereto.
  • Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms include a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group : a cyclopentylethyl group, a cyclonuxylmethyl group, and a cyclonuxylethyl group. It is not limited.
  • R in Formula 1 is a phenyl group, a cyclopentyl group, a cyclonuxyl group, a fluorophenyl group, or a pentafluorophenyl group egg.
  • the functional groups can be introduced into the fluorene derivative of the ligand compound of the embodiment to control the molecular weight and molecular weight distribution of the produced olefin polymer, in particular, using a phenyl group, cyclohexyl group, fluorophenyl group, pentafluorophenyl group, etc.
  • the formula (1) can adjust the angle of the bite angle leading to the ligand, the central metal, and the ligand, depending on the substituent introduced into R, the above-described substituents to increase the bite angle of the compound of the chemical formula 1, comonomer It is easy to introduce and has the effect of improving copolymerizability.
  • R 2 and R 5 in Formula 1 may be the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.
  • the compound represented by Chemical Formula 1 may be synthesized by the same method as in Scheme 1 below.
  • the ligand compound of Formula 1 may prepare a metallocene compound described later through metallization with a transition metal.
  • a metallocene compound represented by the following Chemical Formula 2 is provided.
  • M is a Group 4 transition metal
  • X. and 3 ⁇ 4 are the same as or different from each other, and each independently a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a nitro group, an amido group, a carbon group having 1 to 20 carbon atoms An alkylsilyl group, an alkoxy group having 1 to 20 carbon atoms, or a sulfonate group having 1 to 20 carbon atoms;
  • Ri to R 16 are the same as or different from each other, and each independently hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 1 to 20 carbon atoms, wherein Ri to R 16 Two or more adjacent to each other may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, provided that R ! Except when R 16 are all hydrogen;
  • L is a direct bond or an alkylene group having 1 to 10 carbon atoms
  • R is a substituted or unsubstituted phenyl group, naphthyl group, 3 to 20 carbon atoms A cycloalkyl group or an alkoxy group having 1 to 20 carbon atoms;
  • Qi and Q 2 are the same as or different from each other, and are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon atoms An alkylaryl group having 7 to 20 or an arylalkyl group having 7 to 20 carbon atoms.
  • Group 4 transition metal examples include titanium, zirconium, and hafnium, but are not limited thereto.
  • R in Formula 2 may be a phenyl group, a cyclopentyl group, a cyclonuxyl group, a fluorophenyl group, or a pentafluorophenyl group.
  • the functional groups may be introduced into the fluorene derivative of the metallocene compound of the embodiment to control the molecular weight and molecular weight distribution of the olefin polymer to be produced, in particular, a phenyl group, a cyclonuclear group, a fluorophenyl group, a pentafluorophenyl group, or the like.
  • the formula (1) can adjust the angle of the bite angle leading to the ligand, the central metal, and the ligand, depending on the substituents introduced into R, the above-mentioned substituents to increase the bite angle of the formula and the compound, It is easy to introduce
  • R 2 and R 5 in Formula 2 may be the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.
  • examples of the metallocene compound represented by Formula 2 include the following compounds, but are not limited thereto.
  • the metallocene compound of Chemical Formula 2 has an indeno indole derivative and a fluorene (fl uorene ) derivative as a basic skeleton, and these two derivatives form asymmetrically crosslinked structure by a silicon bridge.
  • a non-covalent electron pair capable of acting as a Lewis base in the ligand structure it is supported on the surface having the Lewis acid characteristic of the carrier and shows high polymerization activity even when supported.
  • the electronically rich indeno indole group and the fluorene group includes a high activity, due to the proper steric hindrance and the electronic effect of the ligand is not only low hydrogen response, but also maintains high activity in the presence of hydrogen.
  • the beta-hydrogen of the polymer chain in which the nitrogen atom of the indeno indole derivative is grown is stabilized by hydrogen bonding, thereby inhibiting beta-hydrogen elimination, thereby polymerizing ultra high molecular weight olepin-based polymer.
  • the metallocene compound of the embodiment may introduce various substituents to the fluorene group, thereby controlling the molecular weight and molecular weight distribution of the leupine copolymer prepared according to the type and bulky degree of the introduced substituents.
  • R in Formula 2 is a substituted or unsubstituted phenyl group, naphthyl group, a C3-C20 cycloalkyl group, or C1-C1
  • the alkoxy group of 20 is used, copolymerization ability can be improved and the comonomer insertion ability can be improved, thereby producing an olefinic polymer having a wide molecular weight distribution and a high molecular weight.
  • the metallocene compound of the present invention can realize excellent activity and high copolymerizability, and can prepare a polyolefin having a high molecular weight and a wide molecular weight distribution, thereby ultimately controlling the structure and physical properties of the resulting polyolefin. It is possible. .
  • the metallocene compound of Chemical Formula 2 according to the present invention may be used as a catalyst for polymerization of olefin monomers.
  • the metallocene compound represented by Chemical Formula 2 may be prepared by reacting the ligand compound represented by Chemical Formula 1 with a metal source according to the following reaction formula 2 and metallization thereof.
  • a catalyst composition comprising a metallocene compound of Formula 2
  • it provides a method for producing an olefinic polymer comprising the step of polymerizing the olefinic monomers /
  • the catalyst composition may further include at least one cocatalyst compound selected from the group consisting of a compound of Formula 3 , a compound of Formula 4, and a compound of Formula 5, in addition to the metallocene compound of Formula 2.
  • R 17 is 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, ⁇ is 2 Is an integer greater than or equal to
  • D is aluminum or boron
  • R 18 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen
  • L is a neutral or divalent Lewis base
  • ⁇ is a hydrogen atom
  • Z is a Group 13 element
  • E may be the same or different from each other, and each independently one or more hydrogen atoms is halogen, a hydrocarbon having 1 to 20 carbon atoms, alkoxy or Or an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with phenoxy.
  • the compound of Formula 3 and the compound of Formula 4 may alternatively be represented by an alkylating agent, and the compound of Formula 5 may be represented by an activator.
  • the compound represented by Chemical Formula 3 is not particularly limited as long as it is an alkyl aluminoxane, but preferred examples thereof include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and preferably methyl aluminoxane.
  • the alkyl metal compound represented by Formula 4 is not particularly limited. However, preferred examples include trimethylaluminum, triethylaluminum triisobutylaluminum, tripropylaluminum, tributylaluminum dimethylchloroaluminum, triisopropylaluminum, tri-S-butylaluminium tricyclopentylaluminum, tripentylaluminum and triiso Pentyl aluminum trinuclear aluminum, trioctyl aluminum, ethyl dimethyl aluminum methyl diethyl aluminum, triphenyl aluminum, tri-P-allyl aluminum dimethyl aluminum mesoxide, dimethyl aluminum ethoxy i, trimethyl boron triethyl boron, triisobutyl boron, Tripropyl boron tributyl boron, and the like, and preferably trimethyl aluminum, triethyl aluminum, triisobutyl aluminum and the like can be used.
  • Examples of the compound represented by Formula 5 include triethylammonium tetra (phenyl) boron, tributyl ammonium tetra (phenyl) boron, trimethyl ammonium tetra (phenyl) boron, tripropyl ammonium tetra (phenyl) boron, trimethyl Ammonium Tetra (P-lryl) boron, Trimethylammonium Tetra ( ⁇ , ⁇ -dimethylphenyl) boron, Tributylammonium Tetra ( ⁇ -trifluoromethylphenyl) boron, Trimethylammonium Tetra ( ⁇ -trifluoromethylphenyl )
  • Triphenylphosphoniumtetra (phenyl) aluminum Triphenylphosphoniumtetra (phenyl) aluminum, -trimethylphosphoniumtetra (phenyl) aluminum,
  • Triphenyl phosphonium tetra (phenyl) boron triphenyl carbonium tetra ( ⁇ - tripulomethylphenyl) boron, triphenyl carbonium tetra (pentapolourophenyl) boron, trityl tetra (pentafluorophenyl) Boron, etc., but is not limited thereto.
  • the catalyst composition may be used for olefin homopolymerization or copolymerization.
  • the following method can be used.
  • the metallocene compound of Formula 2 and the above formula A method of preparing the catalyst composition by contacting the compound of 3 may be used.
  • a method of preparing a catalyst composition by contacting the metallocene compound of Formula 2 and the compound of Formula 5 may be used.
  • the molar ratio of the compound of Formula 3 and the compound of Formula 4 to the metallocene compound of Formula 2 may be 1: 2 to 1: 5,000, preferably Preferably 1:10 to 1: 1,000, more preferably 1:20 to 1: 500.
  • the molar ratio of the metallocene compound of Formula 2 to the compound of Formula 5 may be 1: 1 to 1:25, preferably 1: 1 to 1:10, and more preferably 1: 2 to 1: 5.
  • the amount of the compound of Formula 3 and the compound of Formula 4 is less than 2 moles relative to 1 mole of the metallocene compound of Formula 2, the amount of the alkylating agent is very small so that alkylation of the metal compound may not proceed completely.
  • the amount of the compound of Formula 3 and the compound of Formula 4 is more than 5,000 moles relative to 1 mole of the metallocene compound of Formula 2, alkylation of the metal compound is performed, but the remaining alkylating agent
  • the amount of the compound of the formula (5) to 1 mole of the metallocene compound of the formula (2) may be less than 1 mole.
  • the amount of the activator is relatively small, resulting in incomplete activation of the metal compound. If the activity of the catalyst composition is inferior, and the amount of the compound of Formula 5 is more than 25 moles with respect to 1 mole of the metallocene compound of Formula 2, the activation of the metal compound is completely performed, There is a problem that the cost of the catalyst composition as an activator is not economical or the purity of the resulting polymer is poor.
  • the molar ratio of the metallocene compound of Formula 2 to the compound of Formula 3 may be 1:10 to 1: 10,000, preferably 1: 100 to 1: 5,000, more preferably 1: 500 to 1: 2,000.
  • the amount of the compound of Formula 3 is less than 10 moles with respect to 1 mole of the metallocene compound of Formula 2, Since the amount of the activator is relatively small, there is a problem in that the activity of the catalyst composition generated due to the incomplete activation of the metal compound is insufficient. If the molar excess exceeds the activation of the metal compound, there is a problem that the cost of the catalyst composition is not economically reduced or the purity of the resulting polymer is reduced due to the excess activator remaining.
  • the molar ratio of the metallocene compound of Chemical Formula 2 to the compound of Chemical Formula 5 may be 1: 1 to 1:25, and preferably 1: 1 to 1 : 10, More preferably, it is 1: 2-1: 5.
  • a hydrocarbon solvent such as pentane, nucleic acid, heptane, or an aromatic solvent such as benzene, toluene, or the like may be used as the reaction solvent, but the solvent is not necessarily limited thereto. Can be used.
  • the process of the olefinic polymer according to the invention can be carried out by contacting the catalyst composition with a monomer.
  • a monomer According to the method for producing the olefin polymer of the present invention, an olefin homopolymer or an olefin copolymer can be provided.
  • the polymerization method of the present invention may be carried out by a solution polymerization process, a slurry process or a gas phase process.
  • the catalyst composition eulre pin polymerization process having a carbon number of 5-12 aliphatic hydrocarbon solvents suitable for, for example, pentane, hexane, heptane, nonane, decane, and the, the and isomers thereof
  • Aromatic hydrocarbon solvents such as luene and benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene may be dissolved or diluted and injected.
  • the solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkylaluminum, and may be carried out by further using a promoter.
  • olefin monomer examples include ethylene, alpha-olefin, cyclic olefin, and the like.
  • the diene olefin monomer or triene olefin monomer etc. which have two or more bonds can also superpose
  • 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-dode Sen, 1-tetradecene, 1-nuxadecene, 1-aitocene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, etc., These monomers may be mixed and copolymerized two or more kinds.
  • the olefin polymer is a copolymer of ethylene and other comonomers
  • the monomer constituting the copolymer is selected from the group consisting of propylene, 1-butene, 1-nuxene, and 4-methyl-1-pentene, and 1-octene It is preferred that it is at least one comonomer selected.
  • the catalyst composition is also capable of copolymerization reaction of ethylene and monomers having high steric hindrance, such as 1-nuxene or 1-octene, and various substituents on the basic skeleton of the fluorene derivative.
  • the weight average molecular weight (Mw) of the olefinic polymer may be about 100,000 to 1,000,000 g / mol.
  • the weight average molecular weight of the olepin-based polymer may vary depending on whether the metallocene compound used or the catalyst composition comprising the same is supported and polymerization conditions.
  • the olephine-based polymer prepared using the supported catalyst may be 800,000. It may have a very high weight average molecular weight of at least g / mol, preferably at least 850,000 g / mol.
  • the molecular weight distribution (PDI) of the olefin polymer may be about 1 to 20, preferably about 1 to 10.
  • the reaction group used in the process for producing the polymer according to the invention is continuous It is preferred that it is a stirred reactor (CSTR) or a continuous flow reactor (PFR).
  • the reactor is preferably arranged in two or more in series or in parallel.
  • the production method preferably further includes a separator for continuously separating the solvent and the unfung monomer from the reaction mixture.
  • the method of preparing the polymer according to the present invention is carried out in a continuous solution polymerization process, it may be composed of a catalytic process, a polymerization process, a solvent separation process, a rare water process step, more specifically as follows.
  • the catalyst composition according to the present invention may be injected by dissolving or diluting an aliphatic or aromatic solvent having 5 to 12 carbon atoms or unsubstituted with a halogen suitable for an olefin polymerization process.
  • aliphatic hydrocarbon solvents such as pentane, nucleic acid, heptane, nonane, decane, and isomers thereof, aromatic hydrocarbon solvents such as toluene, xylene, benzene, and hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, chlorobenzene And the like can be used.
  • the solvent used here is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating with a small amount of alkylaluminum or the like, and can also be carried out using an excessive amount of a promoter.
  • the polymerization process is carried out by introduction of at least one olefin monomer and a catalyst composition comprising the organometallic compound of Formula 2 and a promoter in a reactor.
  • a solvent is injected onto the reactor.
  • a mixture of a solvent, a catalyst composition, and a monomer is present in the reaction vessel.
  • the molar ratio of monomer to solvent suitable for the reaction should be a ratio suitable for dissolving the raw material before the reaction and the polymer produced after the reaction.
  • a 20: a molar ratio of monomer to solvent is 10: 1 to 1: 10,000, preferably from 5: 1 to 1: 100, more preferably ⁇ : 1 to 1.
  • the molar ratio of the solvent is less than 10: 1, the amount of the solvent is too small to increase the viscosity of the fluid, which causes a problem in transferring the produced polymer.
  • the molar ratio of the solvent exceeds 1: 10,000, Since the amount is more than necessary, the equipment increase according to the recirculation of solvent purification and There are problems such as increased energy costs.
  • the solvent is preferably introduced into the reactor at a temperature of -40 to 150 ° C using a heater or a pulsator, whereby the polymerization reaction is started with the monomer and the catalyst composition.
  • the temperature of the solvent is -4 (less than C, there will be some differences depending on the reaction amount, but in general, the temperature of the solvent is too low, so the reaction temperature is also difficult to drop, and the temperature control is difficult, exceeding 150 ° C. In this case, the solvent temperature is too high, there is a problem that the heat removal of the reaction semi-heat due to reaction.
  • a high capacity pump raises the pressure above 50 bar to supply the feeds (solvent, monomer, catalyst composition, etc.), thereby providing a mixture of the feeds without additional pumping between the reaction vessel, pressure drop device and separator. Can be passed.
  • the internal temperature of the reaction vessel suitable for the present invention ie the polymerization reaction temperature, is -15 to 300 ° C, preferably 30 to 200 ° C, more preferably 70 to 200 ° C. If the internal temperature is less than -151, there is a problem that the productivity is low because the reaction rate is low, and if it exceeds 300 ° C, problems such as discoloration, such as generation of impurities and carbonization of the polymer due to side reactions may occur. .
  • the internal pressure of the reactor suitable in the present invention is 1 to 300 bar, preferably 10 to 200 bar, more preferably about 30 to 100 bar. If the internal pressure is less than lbar, the reaction rate is low to lower productivity : there is a problem due to evaporation of the solvent used, and if it exceeds 300 bar, there is a problem of an increase in equipment costs such as device cost according to high pressure.
  • the polymer produced in the reaction vessel is maintained at a concentration of less than 20 wt% in the solvent and is preferably transferred to the first solvent separation process for solvent removal after a short residence time.
  • the residence time in the reaction mixture of the resulting polymer is 1 minute to 10 hours, preferably 3 minutes to 1 hour, more preferably 5 minutes to 30 minutes. If the residence time is less than 3 minutes, there is a problem such as productivity loss and catalyst loss due to a short residence time, and increase in the manufacturing cost accordingly, if more than 1 hour, depending on the reaction over the appropriate active period of the catalyst, The reaction period increases and equipment costs increase accordingly there is a problem.
  • the solvent separation process is performed by varying the solution temperature and pressure to remove the solvent present with the polymer exiting the reactor.
  • the polymer solution transferred from the reactor is heated up to about 200 to 230 ° C through a heater and then the pressure is lowered through a pressure drop device to vaporize the raw materials and solvent in the first separator.
  • the pressure in the separator is suitably 1 to 30 bar, preferably 1 to 10 bar, more preferably 3 to 8 bar.
  • the temperature in the separator is suitably 150 to 250 ° C., preferably 170 to 230 ° C., more preferably 180 to 230 ° C.
  • the pressure in the separator is less than 1 bar, the content of the polymer is increased, there is a problem in the transfer, if it exceeds 30 bar there is a problem that the separation of the solvent used in the polymerization process is difficult.
  • the temperature in the separator is less than 150 ° C., the viscosity of the copolymer and its mixture is increased, and there is a problem in transporting.
  • the temperature is less than 250 ° C., there is a problem of discoloration due to carbonization of the polymer due to high temperature.
  • the solvent vaporized in the separator can be recycled to the reaction counter condensed in the overhead system.
  • the first step of solvent separation yields a polymer solution concentrated up to 65%, which is transferred to the second separator by a transfer pump through a heater, where the separation of residual solvent occurs.
  • a heat stabilizer is added and a reaction inhibitor is injected into the heater together with the heat stabilizer to suppress reaction of the polymer due to the residual activity of the activator present in the polymer solution.
  • the residual solvent in the polymer solution injected into the second separator is finally completely removed by a vacuum pump, and the granular polymer can be obtained by passing through the angle and the cutter.
  • the solvent and other unreacted monomers vaporized in the second separation process can be sent to a recovery process for purification and reuse.
  • the organic solvent added with the raw material to the polymerization process may be recycled to the polymerization process together with the non-banung raw material in the primary solvent separation process.
  • the solvent recovered in the secondary solvent separation process contains a large amount of water that acts as a catalyst poison in the solvent due to contamination by the reaction of an anti-inhibitor to stop the catalytic activity and steam supply from the vacuum pump, and is reused after purification in the recovery process. It is preferable.
  • Silica (SYLOPOL 948, manufactured by Grace Davison) was dehydrated under vacuum at 400 ° C. for 12 hours to prepare a silica carrier.
  • the supported catalyst was prepared in the same manner as in Preparation Example 4, except that the metallocene compound prepared in Preparation Example 2 (5. 5 mmd) was used. Prepared.
  • Preparation Example 6 Preparation of Supported Catalyst
  • the supported catalyst was prepared in the same manner as in Preparation Example 4, except that 0.5 mmd of the metallocene compound prepared in Preparation Example 3 was used.
  • Preparation Comparative Example 3 Preparation of Supported Catalyst
  • the supported catalyst was prepared in the same manner as in Preparation Example 4, except that 0.5 mm of the metallocene compound prepared in Preparation Comparative Example 1 was used.
  • Preparation Comparative Example 4 Preparation of Supported Catalyst
  • the supported catalyst was prepared in the same manner as in Preparation Example 4, except that 0.5 mm of the metallocene compound prepared in Preparation Comparative Example 2 was used.
  • a 100 mL Andrew bottle was prepared, assembled with an impeller part, and replaced with argon in a glove box. 70 mL of toluene containing a small amount of TMA was added into the Andrew bottle, and 10 mL of MAO (10 wt% in toluene) solution was added thereto.
  • the metallocene compound catalyst of Preparation Example 1 5 mL (5 ⁇ of catalyst) of 1 mM catalyst / luene solution dissolved in toluene was injected into an Andrew bottle.
  • the Andrew bottle was immersed in an oil bath heated to 90 ° C and the top of the bottle was fixed to the mechanical stirrer and stirred for 5 minutes until the reaction solution reached 90 ° C.
  • Example 3 Solution Polymerization
  • Example 5 Supported Catalytic Polymerization Except that the metallocene compound catalyst of Preparation Example 5 was used, ethylene-1-nuxene copolymerization was performed in the same manner as in Example 4, and the obtained polymer was analyzed.
  • Example 6 Supported Catalytic Polymerization
  • the olefin copolymerization was carried out in the same manner as in Example 4, except that 5 ⁇ of the metallocene compound of Preparation Comparative Example 2 was used.
  • the catalytic activity of Examples 1 to 6 and Comparative Examples 1 to 4 is determined by the ratio of the weight of the polymer produced per mass of catalyst used per unit time (h) and the content of metallocene compound in the catalyst. Calculated as the ratio of the weight of the resulting polymer.
  • the weight average molecular weight and molecular weight distribution of the polymers of Examples 1 to 6 and Comparative Examples 1 to 4 were measured by using a solid silver GPC apparatus, and the results are shown in Table 1 below.
  • the metallocene compound of the Preparation Example or the catalyst composition comprising the same shows high activity in copolymerization using a comonomer, and can improve the comonomer insertion ability. It is possible to prepare a polyolefin copolymer having a high molecular weight while having a high content of nucleene.

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Abstract

La présente invention concerne un nouveau composé de ligand, un composé de métallocène et un procédé de préparation d'un composé oléfinique faisant appel à eux. Selon la présente invention, le composé de métallocène et une composition de catalyseur contenant ce dernier présentent une excellente capacité d'insertion de comonomères, de même qu'une excellente activité de polymérisation, et ont, ainsi, une distribution de poids moléculaire étendue. Par conséquent, un composé oléfinique présentant une excellente aptitude au traitement peut ainsi être préparé.
PCT/KR2015/008771 2014-10-06 2015-08-21 Composé de ligand, composé de métallocène et procédé de préparation d'un polymère oléfinique faisant appel à eux WO2016056744A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2016516546A JP6570517B2 (ja) 2014-10-06 2015-08-21 リガンド化合物、メタロセン化合物およびこれを用いるオレフィン系重合体の製造方法
EP15841031.6A EP3064504B1 (fr) 2014-10-06 2015-08-21 Composé de ligand, composé de métallocène et procédé de préparation d'un polymère oléfinique faisant appel à eux
CN201580002342.XA CN105705506B (zh) 2014-10-06 2015-08-21 配体化合物、茂金属化合物和使用其制备基于烯烃的聚合物的方法
US15/026,119 US9850326B2 (en) 2014-10-06 2015-08-21 Ligand compound, metallocene compound, and method for preparation of olefin-based polymer using the same

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KR10-2014-0134342 2014-10-06
KR20140134342 2014-10-06
KR1020150117300A KR101784463B1 (ko) 2014-10-06 2015-08-20 리간드 화합물, 메탈로센 화합물 및 이를 이용하는 올레핀계 중합체의 제조방법
KR10-2015-0117300 2015-08-20

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Citations (5)

* 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
US20030195306A1 (en) * 2002-04-16 2003-10-16 Tsuie Barbara M. Method for making polyolefins
US20030229188A1 (en) * 2002-05-31 2003-12-11 Sandor Nagy High-temperature solution process for polyolefin manufacture
KR20120087706A (ko) * 2011-01-28 2012-08-07 주식회사 엘지화학 메탈로센 화합물 및 이를 이용하여 제조되는 올레핀계 중합체
KR20150015789A (ko) * 2013-08-01 2015-02-11 주식회사 엘지화학 메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용하는 올레핀계 중합체의 제조방법

Patent Citations (5)

* 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
US20030195306A1 (en) * 2002-04-16 2003-10-16 Tsuie Barbara M. Method for making polyolefins
US20030229188A1 (en) * 2002-05-31 2003-12-11 Sandor Nagy High-temperature solution process for polyolefin manufacture
KR20120087706A (ko) * 2011-01-28 2012-08-07 주식회사 엘지화학 메탈로센 화합물 및 이를 이용하여 제조되는 올레핀계 중합체
KR20150015789A (ko) * 2013-08-01 2015-02-11 주식회사 엘지화학 메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용하는 올레핀계 중합체의 제조방법

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