WO2015102251A1 - Method for preparing alpha-olefin oligomer using ansa-metallocene catalyst - Google Patents

Method for preparing alpha-olefin oligomer using ansa-metallocene catalyst Download PDF

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WO2015102251A1
WO2015102251A1 PCT/KR2014/012056 KR2014012056W WO2015102251A1 WO 2015102251 A1 WO2015102251 A1 WO 2015102251A1 KR 2014012056 W KR2014012056 W KR 2014012056W WO 2015102251 A1 WO2015102251 A1 WO 2015102251A1
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carbon atoms
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ansa
independently
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이분열
박지혜
전종엽
장영은
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아주대학교산학협력단
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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
    • C07F17/00—Metallocenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • 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 System
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the present invention relates to a method for preparing an alpha-olefin oligomer using an ansa-metallocene catalyst. More specifically, the present invention relates to a method for producing an alpha-olefin oligomer for lubricating oil using an ansa-metallocene catalyst.
  • Alpha-olefin oligomers obtained through oligomerization reactions having 6 or more carbon atoms can be used as higher lubricants.
  • the alpha-olefin oligomer is a viscous material, has a high viscosity coefficient, low pour point and volatility, high thermal stability, high oxidation stability, and high hydrolytic stability, such as engine oil, transmission oil, gear oil, etc. It is known to be applicable as a top-tier product (high grade lubricant). At present, about 500,000 tons of global market is formed and annual growth is estimated at 7%.
  • the alpha-olefin oligomer is usually prepared through cationic polymerization, but cationic polymerization has a disadvantage in that polymerization degree and chain shape control are not easy. Recently, a manufacturing process using a metallocene catalyst has been developed as a tool that can overcome these disadvantages.
  • U.S. Pat.Nos. 7,989,670 and 6,548,724 disclose alpha-olefin polymerization processes using metallocene catalysts ((Cp) (Cp *) MX 2 , Cp and Cp *: substituted or unsubstituted cyclopentadienyl ligands). Started.
  • ansa-metallocene compound a compound in which Cp and Cp * are covalently linked to an appropriate group (bridge) is called an ansa-metallocene compound.
  • rac-Me 2 Si (C 5 H 3 -3-t-Bu) 2 ZrCl 2
  • rac-Me 2 Si (C 5 H 3 -3-Me) 2 ZrCl 2
  • meso-Me 2 Si (When an ansa-metallocene catalyst such as C 5 H-2,3,5-Me 3 ) 2 ZrCl 2 , Me 2 C (Cp) (flu) ZrCl 2 is used, a polyolefin having a number average molecular weight of 10,000 g / mol or more It is manufactured and not suitable for use as a lubricant.
  • An object of the present invention is to provide a method for preparing an alpha-olefin oligomer capable of producing an alpha-olefin oligomer having a degree of polymerization suitable for use as a lubricating oil, using an ansa-metallocene catalyst showing high activity.
  • Another object of the present invention is to provide an ansa-metallocene catalyst having a novel structure capable of mass production.
  • Still another object of the present invention is to provide a method for preparing the ansa-metallocene catalyst.
  • One aspect of the invention relates to a process for the preparation of alpha-olefin oligomers.
  • the preparation method is characterized in that the catalyst composition comprising an ansa-metallocene compound represented by the following formula (1), and a cocatalyst compound is contacted with an alpha-olefin monomer having 6 to 20 carbon atoms:
  • M is a Group 4 transition metal of the periodic table, each R is independently a hydrocarbon group of 1 to 20 carbon atoms, B is an alkylene group of 1 to 20 carbon atoms, an arylene group of 6 to 20 carbon atoms, 1 to C carbon 20 is a dialkylsilicone, a dialkylgerium having 1 to 20 carbon atoms, an alkylphosphine group having 1 to 20 carbon atoms, or an alkylamine group having 1 to 20 carbon atoms, and Q is a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 2 to 20 carbon atoms.
  • the cocatalyst compound is characterized by comprising at least one of a compound represented by the following formula (2), a compound represented by the following formula (3), and a compound represented by the following formula (4) or (5).
  • R 21 is each independently a hydrocarbon atom substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen group having 1 to 20 carbon atoms, and a is an integer of 2 or more;
  • D is aluminum or boron
  • R 31 is each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • L is a neutral or cationic Lewis acid
  • Z is a Group 13 element of the Periodic Table of the Elements
  • A is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted each independently It is a C1-C20 alkyl group.
  • ansa-metallocene compound is represented by the following formula (6):
  • R 1 is each independently a phenyl group or a tert-butyl group
  • R 2 and R 3 are each independently an alkyl group having 1 to 5 carbon atoms
  • Q 1 and Q 2 are each independently a halogen atom and 1 carbon atom.
  • Another aspect of the present invention relates to a method for preparing the ansa-metallocene compound of Chemical Formula 6.
  • the preparation method includes reacting a compound represented by Formula 7 and ZrCl 2 coordinated with dimethoxyethane:
  • R 1 , R 2 and R 3 are as defined in Formula 6.
  • the present invention provides a method for preparing an alpha-olefin oligomer capable of producing an alpha-olefin oligomer having a degree of polymerization suitable for use as a lubricating oil, using an ansa-metallocene catalyst showing a high activity. It has the effect of the invention to provide a strong catalyst and its preparation method.
  • the alpha-olefin oligomerization reaction is performed using the ansa-metallocene catalyst represented by the formula (1) having a substituent only at the alpha-position of the cyclopentadienyl ligand of the present invention, the catalyst activity is excellent, and as a lubricant Highly usable alpha-olefin oligomers can be produced.
  • the ansa-metallocene catalyst represented by the formula (6) is easy to mass-produce the synthetic method compared to the existing known method, it is suitable for commercialization.
  • FIG. 1 is an X-ray diffraction crystal structure of the metallocene catalyst represented by Chemical Formula 6a prepared in Example 1.
  • FIG. 1 is an X-ray diffraction crystal structure of the metallocene catalyst represented by Chemical Formula 6a prepared in Example 1.
  • FIG. 2 is an X-ray diffraction crystal structure of the metallocene catalyst represented by Chemical Formula 6b prepared in Example 2.
  • FIG. 2 is an X-ray diffraction crystal structure of the metallocene catalyst represented by Chemical Formula 6b prepared in Example 2.
  • Figure 4 is the result of sidmis (stimulated distillation) GC analysis of the olefin oligomer prepared in Example 4.
  • the method for preparing an alpha-olefin oligomer according to the present invention is characterized by contacting an alpha-olefin monomer having 6 to 20 carbon atoms with a catalyst composition comprising an ansa-metallocene compound represented by Formula 1 below, and a promoter compound. do.
  • M is a Group 4 transition metal of the periodic table of the elements, such as Zr (zirconium), Ti (titanium), Hf (hafnium),
  • R is a hydrocarbon group having 1 to 20 carbon atoms, for example, 1 to 20 carbon atoms It may be an alkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms.
  • B is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, dialkylsilicone having 1 to 20 carbon atoms, dialkylgerium having 1 to 20 carbon atoms, alkylphosphine group having 1 to 20 carbon atoms or having 1 to 20 carbon atoms. It is a bridge which binds two cyclopentadienyl ligands, such as an alkylamine group, by covalent bond.
  • Q is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, and having 7 to 40 carbon atoms It is an arylalkyl group, a C1-C20 alkyl amido group, a C6-C20 aryl amido group, or a C1-C20 alkylidene group.
  • Ansa-metallocene catalyst represented by Formula 1 may be prepared, for example, based on Scheme 1 below.
  • the preparation method of Scheme 1 has been reported by the present inventors (Korean Patent No. 10-0398740; J. Organomet. Chem. 2002, 660, 161).
  • an anza-metallocene compound represented by Formula 1, wherein B is -CH 2 CH 2 -and R is -CH 3 was synthesized, and based on this, cyclopetadienyl (Cp) Claims are made with respect to the ansa-metallocene compound (catalyst) represented by the general formula (1) having substituents only at the alpha-position of the ligand.
  • ansa-metallocene compound represented by Formula 1 has been reported to study ethylene polymerization reactivity such as ethylene / 1-hexene copolymerization and ethylene / norbornene copolymerization.
  • ethylene polymerization reactivity such as ethylene / 1-hexene copolymerization and ethylene / norbornene copolymerization.
  • no alpha-olefin oligomerization reaction having 8 to 20 carbon atoms claimed in the present invention has been reported at all.
  • the alpha-olefin oligomer production method of the present invention is a catalyst composition based on the ansa-metallocene compound represented by the formula (1) as exemplified in the following example, and has 6 carbon atoms such as 1-decene and 1-octene. It is based on the newly found that when the alpha-olefin monomers of 20 to 20 are polymerized, oligomers having a degree of polymerization suitable for use as lubricating oils are obtained with high activity.
  • ansa-metallocene compound represented by Chemical Formula 1 it may be preferable to use an ansa-metallocene compound represented by the following Chemical Formula 6 (catalyst).
  • the ansa-metallocene compound represented by the following formula (6) has a simple manufacturing method, unlike Scheme 1, which allows mass production and is suitable for commercialization.
  • Ansa-metallocene compound (catalyst) represented by the following formula (6) is a novel structure.
  • R 1 is each independently a phenyl group or a tert-butyl group
  • R 2 and R 3 are each independently an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, and the like, specifically, Methyl group.
  • Q 1 and Q 2 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl having 7 to 40 carbon atoms.
  • a group, a C7-40 arylalkyl group, a C1-C20 alkylamido group, a C6-C20 arylamido group, or a C1-C20 alkylidene group for example, a chlorine atom (Cl), a fluorine atom Halogen atoms, such as (F), a methyl group, a phenyl group, a benzyl group, a toryl group, a dimethyl amido group, etc., are specifically a chlorine atom (Cl) or a methyl group.
  • examples of the ansa-metallocene catalyst represented by Chemical Formula 6 may include a compound represented by Chemical Formula 6a, a compound represented by Chemical Formula 6b, a mixture thereof, and the like, but are not limited thereto.
  • the cocatalyst compound may include a compound represented by Formula 2, a compound represented by Formula 3, a compound represented by Formula 4 or 5, a mixture thereof, and the like.
  • R 21 is each independently a hydrocarbon atom substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen group having 1 to 20 carbon atoms, and a is an integer of 2 or more;
  • D is aluminum or boron
  • R 31 is each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • L is a neutral or cationic Lewis acid
  • Z is a Group 13 element of the Periodic Table of the Elements
  • A is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted each independently It is a C1-C20 alkyl group.
  • the compound represented by the formula (2) is an aluminoxane, and is not particularly limited as long as it is a normal alkylaluminoxane.
  • methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like can be used, and specifically, methyl aluminoxane can be used.
  • the alkylaluminoxane may be prepared by a conventional method such as adding an appropriate amount of water to trialkylaluminum, or reacting a trialkylaluminum with a hydrocarbon compound or an inorganic hydrate salt containing water, and is generally linear and cyclic. Aluminoxanes are obtained in mixed form.
  • a conventional alkyl metal compound may be used.
  • trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, Trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron , Tributyl boron, tripentafluorophenylboron and the like can be used, and more specifically, trimethylaluminum, triisobutylaluminum, tripentafluorophenylboron and the like can be used, and more specifically, trimethylalum
  • Examples of the compound represented by the formula (4) or (5) include methyl dioctateyl ammonium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (phenyl) borate, triethylammonium tetrakis (phenyl) borate, tripropylammonium tetra Kis (phenyl) borate, tributylammonium tetrakis (phenyl) borate, trimethylammonium tetrakis (p-tolyl) borate, tripropylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o, p-dimethylphenyl Borate, triethylammonium tetrakis (o, p-dimethylphenyl) borate, trimethylammonium tetrakis (p-trifluoromethylphenyl) borate
  • the catalyst composition of the present invention may be prepared by mixing (contacting) the ansa-metallocene compound and the cocatalyst compound.
  • the mixing may be carried out in the presence of a hydrocarbon organic solvent such as toluene, hexane, cyclohexane, methylcyclohexane, usually under an inert atmosphere of nitrogen or argon.
  • the temperature upon mixing is about 0 to about 150 ° C., for example room temperature (about 15 to about 30 ° C.).
  • the catalyst composition in a solution state uniformly dissolved in the organic solvent or the like may be used as it is, or may be used in a solid powder state in which the solvent is removed.
  • the catalyst composition may also be used in a form supported on a carrier such as silica, alumina, or a mixture thereof.
  • the molar ratio of the ansa-metallocene compound and the center metal of the cocatalyst compound is about 1: about 10 to about 1: when the cocatalyst compound is an Al compound (M (Zr, etc.): Al). About 5,000, for example about 1: about 10 to about 1: about 1,000, specifically about 1: about 20 to about 1: about 200. In addition, when the cocatalyst compound is a boron compound (M (Zr, etc.): boron), about 1: about 1 to about 1: about 10, for example about 1: about 1 to about 1: about 4, specifically about 1: about 1 to about 1: about 2.
  • the aluminoxane compound of Formula 2 and the alkylaluminum compound of Formula 3 may be mixed with each other, or the borate compound of Formula 4 or 5 may be used instead of the compound of Formulas 2 to 5 alone.
  • the borate compound of Formula 4 or 5 may be used instead of the compound of Formulas 2 to 5 alone.
  • the catalyst composition dissolves the ansa-metallocene compound in the hydrocarbon organic solvent, in which the compound represented by Formula 4 or 5 and the alkyl aluminum compound represented by Formula 3 are added and contacted It can manufacture by mixing.
  • the molar ratio of the center metal of the ansa-metallocene compound, the borate compound represented by the formula (4) or (5), and the alkylaluminum compound represented by the formula (3) is about 1: about 1 to about 10: about 10 to about 1000, For example, about 1: about 1 to about 5: about 10 to about 500, specifically, the molar ratio may be about 1: about 1 to about 2: about 100 to about 200. It is excellent in the activity of the catalyst composition in the above range, it may be preferable in terms of economics.
  • the method for preparing alpha-olefin oligomer of the present invention can be carried out in a liquid phase or a bulk phase.
  • Each polymerization reaction condition may be variously modified depending on the desired polymerization result such as the state of the catalyst composition used (uniform or heterogeneous phase (support type)) and the polymerization method. The degree of modification thereof can be easily carried out by those skilled in the art.
  • solvents include propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, dichloromethane, Chloroethane, dichloroethane, chlorobenzene, etc. can be illustrated, These solvent can also be mixed and used in fixed ratio.
  • examples of the alpha 6-olefin monomer having 6 to 20 carbon atoms include 1-hexene, 1-octene, 1-decene, 1-dodecene dodecene), mixtures thereof, and the like.
  • suitable monomers for the preparation of higher lubricating oils are 1-octene, 1-decene, 1-dodecene and the like.
  • the amount of the catalyst composition is not particularly limited, for example, the concentration of the center metal (Zr) of the ansa-metallocene catalyst represented by the formula (1) in the reaction system to be polymerized. May be about 1 * 10 ⁇ 5 to about 1 * 10 ⁇ 4 mol / L.
  • the temperature and pressure during the polymerization is not particularly limited because it may vary depending on the reaction material, reaction conditions, etc., the polymerization temperature may be about 0 to about 200 °C, for example about 50 to about 150 °C.
  • the polymerization can be carried out batchwise, semicontinuously or continuously.
  • the polymerization can also be carried out in two or more stages with different reaction conditions, and the degree of polymerization of the final oligomer can be controlled by varying the polymerization temperature or by injecting hydrogen into the reactor.
  • the alpha-olefin oligomer prepared according to the alpha-olefin oligomerization method of the present invention has a low dimer (dimer) fraction of about 10 to about 20%, and a trimer to penmer (3-5 trimer) fraction of about 30 To about 50%, hexamer to nonamer (6-9 monomer) fractions of about 20 to about 30%, with trimers to nonomers (3-9 monomer) accounting for most of the oligomer (about 60 to about 80%).
  • the fraction of the polymerization degree of about 10 or more (more than 10 dimers) is low to about 30% or less. Therefore, the alpha-olefin oligomer produced by the production method of the present invention is preferably suitable for application of the degree of polymerization to top-tier products (high grade lubricating oil) such as engine oil, transmission oil and gear oil.
  • Another aspect of the present invention relates to a method for producing an ansa-metallocene compound (catalyst) represented by the formula (6).
  • the ansa-metallocene compound (catalyst) represented by the formula (6) of the new structure can be prepared by, for example, reacting a compound represented by the following formula (7) and ZrCl 2 coordinated with dimethoxyethane.
  • R 1 , R 2, and R 3 are the same as defined in Formula 6.
  • Zr (II) Cl 2 is prepared by reacting an equivalent amount of ZrCl 4 with 2 equivalents of n-BuLi in a solvent of toluene or tetrahydrofuran (THF), and then, the 1,4,6-position of Chemical Formula 7
  • the yield is less than 15% when the synthesis of the ansa-metallocene compound of Chemical Formula 6 is attempted by reacting with a fulvene compound having a substituent.
  • the metallocene catalyst of the present invention in particular, the metallocene catalyst represented by the above formula (6) wherein Q 1 and Q 2 are chlorine atoms, is ZrCl 2 (ZrCl 2 coordinated with dimethoxyethane in an organic solvent. It can be prepared by reacting DME) with about 2 equivalents of n-butyllithium (n-BuLi), and adding and stirring the compound represented by the formula (7).
  • reaction of converting the chlorine atom (ligand) of the metallocene catalyst to Q 1 and Q 2 of Chemical Formula 1, except for the chlorine atom is a conventional method, that is, through a nucleophilic attack reaction on a compound having a chlorine atom. Easily possible.
  • Non-limiting examples of the compound represented by Formula 7 may include a compound represented by Formula 7a, a compound represented by Formula 7b, a mixture thereof, and the like.
  • the organic solvent used to prepare the metallocene catalyst may be an aliphatic or aromatic hydrocarbon having 5 to 10 carbon atoms, a hydrocarbon solvent having 1 to 10 carbon atoms substituted with a halogen atom, and mixtures thereof, such as pentane and hexane.
  • pentane and hexane such as pentane and hexane.
  • Heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, dichloroethane, chlorobenzene and the like can be used.
  • the reaction of the compound represented by Formula 2 and the ZrCl 2 coordinated with the dimethoxyethane is at a temperature of about 60 to about 150 ° C., for example about 80 to about 120 ° C., for example, The stirring may be performed for 1 to about 30 hours.
  • Ansa-metallocene catalyst can be obtained in a high yield in the said range.
  • high-purity eye massage through a conventional post-treatment process, for example, removing a solvent, an unreacted substance using a vacuum pump, etc., and extracting, washing, and drying with a hydrocarbon solvent.
  • Metallocene catalysts can be obtained.
  • olefin oligomer 214 g was obtained in the same manner as in Example 3, except that 1-octene was used instead of 1-decene (activity: 21,400 Kg / mol.cat.hr, conversion: 60%).
  • Simdis-GC analysis of the prepared olefin oligomer is shown in Figure 4 and Table 1. As a result, it was confirmed that 2-9 monomers were evenly formed, and the proportion of 3-5 monomers in the entire oligomer was 35.9%, the mainstream, and 23.4% or more were less than 10 monomers.
  • 141 g of 141 g was obtained by the same method as Example 3, except that (nBuC 5 H 4 ) 2 ZrCl 2 (manufacturer: Strem), which was an unbridged catalyst, was used instead of the ansa-metallocene catalyst represented by Chemical Formula 6a.
  • An olefin oligomer was obtained (activity: 14,100 Kg / mol. Cat.hr, conversion: 38%).
  • Simdis-GC analysis of the prepared olefin oligomer is shown in Figure 7 and Table 1. As a result of the analysis, the dimer was 33.3%, the trimer was 36.8%, and it was confirmed that the polymer was produced mainly with a very low degree of polymerization.
  • Example 3 13.3 14.3 11.3 9.5 7.8 7.2 6.2 5.2 25.2
  • Example 4 13.1 14.1 11.8 10.0 8.7 7.5 5.9 5.5 23.4
  • Example 5 17.0 18.4 13.9 11.1 9.0 7.1 5.4 4.6 13.5
  • Comparative Example 1 54.8 26.2 10.5 4.6 2.1 0.8 1.0 0 0 Comparative Example 2 33.3 26.8 16.1 8.9 5.0 3.7 2.2 1.3 2.7 Comparative Example 3 2.0 5.3 4.0 5.4 5.6 5.6 5.1 4.7 62.3 Comparative Example 4 9.6 7.0 4.0 2.6 2.3 3.3 3.0 3.7 64.5
  • Activity (unit: Kg (alpha-olefin oligomer) /mol.catal (Zr) .hr): The value obtained by dividing the amount of the obtained alpha-olefin oligomer by the amount of catalyst added.

Abstract

A method for preparing an alpha-olefin oligomer of the present invention is characterized by bringing a catalyst composition into contact with an alpha-olefin monomer having 6 to 20 carbon atoms, the catalyst composition being composed of an ansa-metallocene compound (chemical formula 1) having a substituent at only the alpha-position and a cocatalyst compound. The preparing method is useful to prepare an alpha-olefin oligomer for a lubricant.

Description

안사-메탈로센 촉매를 이용한 알파-올레핀 올리고머의 제조방법Method for preparing alpha-olefin oligomer using ansa-metallocene catalyst
본 발명은 안사-메탈로센 촉매를 이용한 알파-올레핀 올리고머의 제조방법에 관한 것이다. 보다 구체적으로 본 발명은 안사-메탈로센 촉매를 이용한 윤활유용 알파-올레핀 올리고머의 제조방법에 관한 것이다.The present invention relates to a method for preparing an alpha-olefin oligomer using an ansa-metallocene catalyst. More specifically, the present invention relates to a method for producing an alpha-olefin oligomer for lubricating oil using an ansa-metallocene catalyst.
탄소수 6 이상의 알파-올레핀, 예를 들면, 1-헥센, 1-옥텐, 1-데센, 1-도데센, 이들의 혼합물 등의 올리고머화 반응을 통하여 얻어진 알파-올레핀 올리고머는 고급 윤활유로 사용될 수 있어, 연구 개발 관심의 대상이다. 상기 알파-올레핀 올리고머는 점액성 물질로서 점도 계수가 높으며, 유동점(pour point) 및 휘발성(volatility)이 낮고, 열 안정성, 산화 안정성 및 가수분해 안정성이 높아, 엔진 오일, 트랜스미션 오일, 기어 오일 등의 탑-티어(top-tier) 제품(고급 윤활유)로 적용 가능하다고 알려져 있다. 현재 약 50만 톤의 세계 시장이 형성되어 있고 연 7% 성장이 추정된다.Alpha-olefin oligomers obtained through oligomerization reactions having 6 or more carbon atoms, such as 1-hexene, 1-octene, 1-decene, 1-dodecene, and mixtures thereof, can be used as higher lubricants. , Research and development is of interest. The alpha-olefin oligomer is a viscous material, has a high viscosity coefficient, low pour point and volatility, high thermal stability, high oxidation stability, and high hydrolytic stability, such as engine oil, transmission oil, gear oil, etc. It is known to be applicable as a top-tier product (high grade lubricant). At present, about 500,000 tons of global market is formed and annual growth is estimated at 7%.
상기 알파-올레핀 올리고머는 통상적으로 양이온 중합을 통하여 제조되었으나, 양이온 중합은 중합도 및 사슬 모양 조절이 용이하지 않은 단점이 있다. 최근에 이러한 단점을 극복할 수 있는 도구로 메탈로센 촉매를 이용한 제조 공정이 개발되고 있다. 미국 특허 US 7,989,670호 및 US 6,548,724호에는 메탈로센 촉매[(Cp)(Cp*)MX2, Cp 및 Cp*: 치환 또는 치환되지 않은 사이클로펜타다이에닐 리간드]를 이용한 알파-올레핀 중합 공정이 개시되었다. 그러나, 상기 (Cp)(Cp*)MX2 촉매에서 Cp 또는 Cp* 리간드에 치환체가 전혀 붙어 있지 않거나, 알킬기가 하나 붙어 있으면 알파-올레핀 올리고머화 반응에서 중합도가 낮은 다이머, 트리머가 주요 성분으로 생성될 수 있다. 다이머 및 트리머가 주성분인 중합도가 낮은 알파-올레핀 올리고머는 윤활유로 사용하기에 부적절할 수 있다.The alpha-olefin oligomer is usually prepared through cationic polymerization, but cationic polymerization has a disadvantage in that polymerization degree and chain shape control are not easy. Recently, a manufacturing process using a metallocene catalyst has been developed as a tool that can overcome these disadvantages. U.S. Pat.Nos. 7,989,670 and 6,548,724 disclose alpha-olefin polymerization processes using metallocene catalysts ((Cp) (Cp *) MX 2 , Cp and Cp *: substituted or unsubstituted cyclopentadienyl ligands). Started. However, in the (Cp) (Cp *) MX 2 catalyst, when no substituent is attached to the Cp or Cp * ligand or one alkyl group is attached, a dimer and trimer having a low degree of polymerization in the alpha-olefin oligomerization reaction is generated as a main component. Can be. Low degree of polymerization of alpha-olefin oligomers, which are predominantly dimers and trimers, may be inappropriate for use as lubricating oils.
상기 메탈로센 화합물에서 Cp와 Cp*가 적당한 그룹(브리지)과 공유결합에 의하여 연결된 화합물을 안사-메탈로센(ansa-metallocene) 화합물이라 칭한다. 안사-메탈로센(ansa-metallocene) 화합물을 촉매로 사용한 1-헥센의 중합 결과가 Macromolecules에 발표되었다(Macromolecules 2000, 33, 4602 등). 예를 들어, rac-Me2Si(C5H3-3-t-Bu)2ZrCl2, rac-Me2Si(C5H3-3-Me)2ZrCl2, meso-Me2Si(C5H-2,3,5-Me3)2ZrCl2, Me2C(Cp)(flu)ZrCl2 등의 안사-메탈로센 촉매를 사용할 경우, 수평균 분자량이 10,000 g/mol 이상인 폴리올레핀이 제조되어 윤활유로는 사용하기에 부적절하다. Me2Si(C5H4)2ZrCl2을 사용한 경우, 수평균분자량이 약 1,500 g/mol인 오일을 얻을 수 있으나, 이 경우, 다른 촉매에 비해서 활성이 1/5 이하로 현격히 낮다. 또한, 미국 특허 US 2012/0040878에 이중으로 Me2Si에 의하여 브리지된 안사-메탈로센 화합물(1,1'-dimethylsilylene)(2,2'-dimethylsilylene)-bis(Cp)ZrCl2)을 이용한 윤활유용 알파-올레핀 올리고머화 반응 공정이 개시되었다. 그러나, 상기 이중으로 Me2Si에 의하여 브리지된 안사-메탈로센 화합물은 합성이 까다롭고 수율이 매우 낮아 상업공정 투입에 한계가 있다(리간드 제조 수율: 약 12%, 메탈레이션 수율: 약 7%).In the metallocene compound, a compound in which Cp and Cp * are covalently linked to an appropriate group (bridge) is called an ansa-metallocene compound. Results of polymerization of 1-hexene using ansa-metallocene compounds as catalysts have been published in Macromolecules (Macromolecules 2000, 33, 4602, etc.). For example, rac-Me 2 Si (C 5 H 3 -3-t-Bu) 2 ZrCl 2 , rac-Me 2 Si (C 5 H 3 -3-Me) 2 ZrCl 2 , meso-Me 2 Si ( When an ansa-metallocene catalyst such as C 5 H-2,3,5-Me 3 ) 2 ZrCl 2 , Me 2 C (Cp) (flu) ZrCl 2 is used, a polyolefin having a number average molecular weight of 10,000 g / mol or more It is manufactured and not suitable for use as a lubricant. When Me 2 Si (C 5 H 4 ) 2 ZrCl 2 is used, an oil having a number average molecular weight of about 1,500 g / mol can be obtained. In this case, the activity is significantly lower than 1/5 of other catalysts. In addition, US Pat. No. 2012/0040878, an ansa-metallocene compound (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) -bis (Cp) ZrCl 2 , bridged by Me 2 Si in double An alpha-olefin oligomerization process for lubricating oils has been disclosed. However, the ansa-metallocene compound bridged by Me 2 Si is difficult to synthesize and has a very low yield, thus limiting commercial process input (ligand production yield: about 12%, metallization yield: about 7%). ).
본 발명의 목적은 높은 활성을 보이는 안사-메탈로센 촉매를 이용하여, 윤활유로 활용하기에 적합한 중합도를 갖는 알파-올레핀 올리고머를 제조할 수 있는 알파-올레핀 올리고머의 제조방법을 제공하기 위한 것이다.An object of the present invention is to provide a method for preparing an alpha-olefin oligomer capable of producing an alpha-olefin oligomer having a degree of polymerization suitable for use as a lubricating oil, using an ansa-metallocene catalyst showing high activity.
본 발명의 다른 목적은 양산이 가능한 신규한 구조의 안사-메탈로센 촉매를 제공하기 위한 것이다.Another object of the present invention is to provide an ansa-metallocene catalyst having a novel structure capable of mass production.
본 발명의 또 다른 목적은 상기 안사-메탈로센 촉매의 제조방법을 제공하기 위한 것이다.Still another object of the present invention is to provide a method for preparing the ansa-metallocene catalyst.
본 발명의 상기 및 기타의 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
본 발명의 하나의 관점은 알파-올레핀 올리고머의 제조방법에 관한 것이다. 상기 제조방법은 하기 화학식 1로 표시되는 안사-메탈로센 화합물, 및 조촉매 화합물을 포함하는 촉매 조성물과 탄소수 6 내지 20의 알파-올레핀 단량체를 접촉시키는 것을 특징으로 한다:One aspect of the invention relates to a process for the preparation of alpha-olefin oligomers. The preparation method is characterized in that the catalyst composition comprising an ansa-metallocene compound represented by the following formula (1), and a cocatalyst compound is contacted with an alpha-olefin monomer having 6 to 20 carbon atoms:
[화학식 1][Formula 1]
Figure PCTKR2014012056-appb-I000001
Figure PCTKR2014012056-appb-I000001
상기 화학식 1에서, M은 주기율표의 4족 전이금속이고, R은 각각 독립적으로 탄소수 1 내지 20의 탄화수소기이고, B는 탄소수 1 내지 20의 알킬렌기, 탄소수 6 내지 20의 아릴렌기, 탄소수 1 내지 20의 디알킬실리콘, 탄소수 1 내지 20의 디알킬게르마늄, 탄소수 1 내지 20의 알킬포스핀기 또는 탄소수 1 내지 20의 알킬아민기이고, Q는 할로겐 원자, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 2 내지 20의 알키닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 40의 알킬아릴기, 탄소수 7 내지 40의 아릴알킬기, 탄소수 1 내지 20의 알킬아미도기, 탄소수 6 내지 20의 아릴아미도기, 또는 탄소수 1 내지 20의 알킬리덴기이다.In Formula 1, M is a Group 4 transition metal of the periodic table, each R is independently a hydrocarbon group of 1 to 20 carbon atoms, B is an alkylene group of 1 to 20 carbon atoms, an arylene group of 6 to 20 carbon atoms, 1 to C carbon 20 is a dialkylsilicone, a dialkylgerium having 1 to 20 carbon atoms, an alkylphosphine group having 1 to 20 carbon atoms, or an alkylamine group having 1 to 20 carbon atoms, and Q is a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 2 to 20 carbon atoms. Alkenyl group, alkynyl group of 2 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, alkylaryl group of 7 to 40 carbon atoms, arylalkyl group of 7 to 40 carbon atoms, alkyl amido group of 1 to 20 carbon atoms, 6 to 20 carbon atoms Or an arylamido group or an alkylidene group having 1 to 20 carbon atoms.
구체예에서, 상기 조촉매 화합물은 하기 화학식 2로 표시되는 화합물, 하기 화학식 3으로 표시되는 화합물, 및 하기 화학식 4 또는 5로 표시되는 화합물 중 1종 이상을 포함하는 것을 특징으로 한다.In embodiments, the cocatalyst compound is characterized by comprising at least one of a compound represented by the following formula (2), a compound represented by the following formula (3), and a compound represented by the following formula (4) or (5).
[화학식 2][Formula 2]
Figure PCTKR2014012056-appb-I000002
Figure PCTKR2014012056-appb-I000002
상기 화학식 2에서, R21은 각각 독립적으로 할로겐 원자, 탄소수 1 내지 20의 탄화수소기, 또는 탄소수 1 내지 20의 할로겐으로 치환된 탄화수소기이며, a는 2 이상의 정수이다;In Formula 2, R 21 is each independently a hydrocarbon atom substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen group having 1 to 20 carbon atoms, and a is an integer of 2 or more;
[화학식 3][Formula 3]
D(R31)3 D (R 31 ) 3
상기 화학식 3에서, D는 알루미늄 또는 보론이며, R31은 각각 독립적으로 할로겐 원자, 탄소수 1 내지 20의 탄화수소기, 탄소수 1 내지 20의 할로겐으로 치환된 탄화수소기, 또는 탄소수 1 내지 20의 알콕시기이다;In Formula 3, D is aluminum or boron, and R 31 is each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. ;
[화학식 4][Formula 4]
[L-H]+[Z(A)4]- [LH] + [Z (A) 4 ] -
[화학식 5][Formula 5]
[L]+[Z(A)4]- [L] + [Z (A) 4 ] -
상기 화학식 4 및 5에서, L은 중성 또는 양이온성 루이스 산이고, Z는 원소 주기율표의 13족 원소이고, A는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기 또는 치환 또는 비치환된 탄소수 1 내지 20의 알킬기이다.In Formulas 4 and 5, L is a neutral or cationic Lewis acid, Z is a Group 13 element of the Periodic Table of the Elements, A is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted each independently It is a C1-C20 alkyl group.
본 발명의 다른 관점은 안사-메탈로센 화합물에 관한 것이다. 상기 안사-메탈로센 화합물 하기 화학식 6으로 표시되는 것을 특징으로 한다:Another aspect of the invention relates to an ansa-metallocene compound. The ansa-metallocene compound is represented by the following formula (6):
[화학식 6][Formula 6]
Figure PCTKR2014012056-appb-I000003
Figure PCTKR2014012056-appb-I000003
상기 화학식 6에서, R1은 각각 독립적으로 페닐기 또는 tert-부틸기이고, R2 및 R3는 각각 독립적으로 탄소수 1 내지 5의 알킬기이며, Q1 및 Q2는 각각 독립적으로 할로겐 원자, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 2 내지 20의 알키닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 40의 알킬아릴기, 탄소수 7 내지 40의 아릴알킬기, 탄소수 1 내지 20의 알킬아미도기, 탄소수 6 내지 20의 아릴아미도기, 또는 탄소수 1 내지 20의 알킬리덴기이다.In Chemical Formula 6, R 1 is each independently a phenyl group or a tert-butyl group, R 2 and R 3 are each independently an alkyl group having 1 to 5 carbon atoms, and Q 1 and Q 2 are each independently a halogen atom and 1 carbon atom. An alkyl group of 20 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms, an arylalkyl group of 7 to 40 carbon atoms, and 1 to 20 carbon atoms An alkylamido group, an arylamido group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms.
본 발명의 또 다른 관점은 상기 화학식 6의 안사-메탈로센 화합물 제조방법에 관한 것이다. 상기 제조방법은 하기 화학식 7로 표시되는 화합물, 및 디메톡시에탄이 배위된 ZrCl2를 반응시키는 단계를 포함한다:Another aspect of the present invention relates to a method for preparing the ansa-metallocene compound of Chemical Formula 6. The preparation method includes reacting a compound represented by Formula 7 and ZrCl 2 coordinated with dimethoxyethane:
[화학식 7][Formula 7]
Figure PCTKR2014012056-appb-I000004
Figure PCTKR2014012056-appb-I000004
상기 화학식 4에서, R1, R2 및 R3는 상기 화학식 6에서 정의한 바와 같다.In Formula 4, R 1 , R 2 and R 3 are as defined in Formula 6.
본 발명은 높은 활성을 보이는 안사-메탈로센 촉매를 이용하여, 윤활유로 활용하기에 적합한 중합도를 갖는 알파-올레핀 올리고머를 제조할 수 있는 알파-올레핀 올리고머의 제조방법, 독특한 구조의 안사-메탈로센 촉매 및 이의 제조방법을 제공하는 발명의 효과를 가진다. 본 발명의 사이클로펜타디에닐 리간드의 알파-위치에만 치환체가 있는 상기 화학식 1로 표시되는 안사-메탈로센 촉매를 이용하여 알파-올레핀 올리고머화 반응을 수행할 경우, 촉매 활성이 우수하고, 윤활유로 활용 가능성이 높은 알파-올레핀 올리고머가 생성될 수 있다. 특히, 상기 화학식 6으로 표시되는 안사-메탈로센 촉매는 합성 방법이 기존 공지된 방법 대비 수월하여 양산이 가능하며, 상업화하기에 적당하다.The present invention provides a method for preparing an alpha-olefin oligomer capable of producing an alpha-olefin oligomer having a degree of polymerization suitable for use as a lubricating oil, using an ansa-metallocene catalyst showing a high activity. It has the effect of the invention to provide a strong catalyst and its preparation method. When the alpha-olefin oligomerization reaction is performed using the ansa-metallocene catalyst represented by the formula (1) having a substituent only at the alpha-position of the cyclopentadienyl ligand of the present invention, the catalyst activity is excellent, and as a lubricant Highly usable alpha-olefin oligomers can be produced. In particular, the ansa-metallocene catalyst represented by the formula (6) is easy to mass-produce the synthetic method compared to the existing known method, it is suitable for commercialization.
도 1은 실시예 1에서 제조된 화학식 6a로 표시되는 메탈로센 촉매의 X선 회절 결정 구조이다.1 is an X-ray diffraction crystal structure of the metallocene catalyst represented by Chemical Formula 6a prepared in Example 1. FIG.
도 2는 실시예 2에서 제조된 화학식 6b로 표시되는 메탈로센 촉매의 X선 회절 결정 구조이다.2 is an X-ray diffraction crystal structure of the metallocene catalyst represented by Chemical Formula 6b prepared in Example 2. FIG.
도 3은 실시예 3에서 제조된 올레핀 올리고머의 sidmis(stimulated distillation) GC 분석 결과이다.3 is a result of sidmis (stimulated distillation) GC analysis of the olefin oligomer prepared in Example 3.
도 4는 실시예 4에서 제조된 올레핀 올리고머의 sidmis(stimulated distillation) GC 분석 결과이다.Figure 4 is the result of sidmis (stimulated distillation) GC analysis of the olefin oligomer prepared in Example 4.
도 5는 실시예 5에서 제조된 올레핀 올리고머의 sidmis(stimulated distillation) GC 분석 결과이다.5 is a result of sidmis (stimulated distillation) GC analysis of the olefin oligomer prepared in Example 5.
도 6은 비교예 1에서 제조된 올레핀 올리고머의 sidmis(stimulated distillation) GC 분석 결과이다.6 is a sidmis (stimulated distillation) GC analysis of the olefin oligomer prepared in Comparative Example 1.
도 7은 비교예 2에서 제조된 올레핀 올리고머의 sidmis(stimulated distillation) GC 분석 결과이다.7 is a result of sidmis (stimulated distillation) GC analysis of the olefin oligomer prepared in Comparative Example 2.
도 8은 비교예 3에서 제조된 올레핀 올리고머의 sidmis(stimulated distillation) GC 분석 결과이다.8 is a result of sidmis (stimulated distillation) GC analysis of the olefin oligomer prepared in Comparative Example 3.
도 9은 비교예 4에서 제조된 올레핀 올리고머의 sidmis(stimulated distillation) GC 분석 결과이다.9 is a result of sidmis (stimulated distillation) GC analysis of the olefin oligomer prepared in Comparative Example 4.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 알파-올레핀 올리고머의 제조방법은 하기 화학식 1로 표시되는 안사-메탈로센 화합물, 및 조촉매 화합물을 포함하는 촉매 조성물과 탄소수 6 내지 20의 알파-올레핀 단량체를 접촉시키는 것을 특징으로 한다.The method for preparing an alpha-olefin oligomer according to the present invention is characterized by contacting an alpha-olefin monomer having 6 to 20 carbon atoms with a catalyst composition comprising an ansa-metallocene compound represented by Formula 1 below, and a promoter compound. do.
[화학식 1][Formula 1]
Figure PCTKR2014012056-appb-I000005
Figure PCTKR2014012056-appb-I000005
상기 화학식 1에서, M은 Zr(지르코늄), Ti(티타늄), Hf(하프늄) 등의 원소 주기율표의 4족 전이금속이고, R은 탄소수 1 내지 20의 탄화수소기, 예를 들면, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 2 내지 20의 알키닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 40의 알킬아릴기, 탄소수 7 내지 40의 아릴알킬기일 수 있다. B는 탄소수 1 내지 20의 알킬렌기, 탄소수 6 내지 20의 아릴렌기, 탄소수 1 내지 20의 디알킬실리콘, 탄소수 1 내지 20의 디알킬게르마늄, 탄소수 1 내지 20의 알킬포스핀기 또는 탄소수 1 내지 20의 알킬아민기 등의 두 개의 사이클로펜타디에닐 리간드를 공유 결합으로 묶어주는 브리지이다. Q는 할로겐 원자, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 2 내지 20의 알키닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 40의 알킬아릴기, 탄소수 7 내지 40의 아릴알킬기, 탄소수 1 내지 20의 알킬아미도기, 탄소수 6 내지 20의 아릴아미도기, 또는 탄소수 1 내지 20의 알킬리덴기이다.In Formula 1, M is a Group 4 transition metal of the periodic table of the elements, such as Zr (zirconium), Ti (titanium), Hf (hafnium), R is a hydrocarbon group having 1 to 20 carbon atoms, for example, 1 to 20 carbon atoms It may be an alkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms. B is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, dialkylsilicone having 1 to 20 carbon atoms, dialkylgerium having 1 to 20 carbon atoms, alkylphosphine group having 1 to 20 carbon atoms or having 1 to 20 carbon atoms. It is a bridge which binds two cyclopentadienyl ligands, such as an alkylamine group, by covalent bond. Q is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, and having 7 to 40 carbon atoms It is an arylalkyl group, a C1-C20 alkyl amido group, a C6-C20 aryl amido group, or a C1-C20 alkylidene group.
상기 화학식 1로 표시되는 안사-메탈로센 촉매는 예를 들면, 하기 반응식 1에 의거하여 제조될 수 있다. 상기 반응식 1의 제조방법은 본 발명자에 의하여 보고되었다(대한민국 등록특허(소멸) 10-0398740호; J. Organomet. Chem. 2002, 660, 161). 상기 특허에서, 상기 반응식 1과 같이, B가 -CH2CH2-이고 R이 -CH3인 화학식 1로 표시되는 안사-메탈로센 화합물을 합성하였으며, 이를 근간으로 사이클로페타디에닐(Cp) 리간드의 알파-위치에만 치환체를 갖는 넓은 범위의 상기 화학식 1로 표시되는 안사-메탈로센 화합물(촉매)에 관한 권리를 청구하였다.Ansa-metallocene catalyst represented by Formula 1 may be prepared, for example, based on Scheme 1 below. The preparation method of Scheme 1 has been reported by the present inventors (Korean Patent No. 10-0398740; J. Organomet. Chem. 2002, 660, 161). In this patent, as in Scheme 1, an anza-metallocene compound represented by Formula 1, wherein B is -CH 2 CH 2 -and R is -CH 3 , was synthesized, and based on this, cyclopetadienyl (Cp) Claims are made with respect to the ansa-metallocene compound (catalyst) represented by the general formula (1) having substituents only at the alpha-position of the ligand.
[반응식 1]Scheme 1
Figure PCTKR2014012056-appb-I000006
Figure PCTKR2014012056-appb-I000006
현재까지, 상기 화학식 1로 표시되는 안사-메탈로센 화합물은 에틸렌/1-헥센 공중합 및 에틸렌/노보넨 공중합과 같이 에틸렌 중합 반응성이 연구되어 보고되었다. 그러나, 본 발명이 주장하는 탄소수 8 내지 20의 알파-올레핀 올리고머화 반응은 전혀 보고되지 않았다.To date, the ansa-metallocene compound represented by Formula 1 has been reported to study ethylene polymerization reactivity such as ethylene / 1-hexene copolymerization and ethylene / norbornene copolymerization. However, no alpha-olefin oligomerization reaction having 8 to 20 carbon atoms claimed in the present invention has been reported at all.
본 발명의 알파-올레핀 올리고머 제조방법은, 하기 실시예에서 예시한 바와 같이, 상기 화학식 1로 표시되는 안사-메탈로센 화합물을 근간으로 한 촉매 조성물로 1-데센, 1-옥텐 등의 탄소수 6 내지 20의 알파-올레핀 단량체를 중합하였을 때, 윤활유로 사용하기에 적당한 중합도를 가진 올리고머가 높은 활성으로 얻어지는 것을 새롭게 발견하였음을 근간으로 한다.The alpha-olefin oligomer production method of the present invention is a catalyst composition based on the ansa-metallocene compound represented by the formula (1) as exemplified in the following example, and has 6 carbon atoms such as 1-decene and 1-octene. It is based on the newly found that when the alpha-olefin monomers of 20 to 20 are polymerized, oligomers having a degree of polymerization suitable for use as lubricating oils are obtained with high activity.
구체예에서, 상기 화학식 1로 표시되는 안사-메탈로센 화합물로서, 하기 화학식 6으로 표시되는 안사-메탈로센 화합물(촉매)을 사용하는 것이 바람직할 수 있다. 하기 화학식 6으로 표시되는 안사-메탈로센 화합물은 하기 기술하는 바와 같이, 제조방법이 상기 반응식 1과 달리, 단계가 단순하여, 양산이 가능하며, 상업화에 적합하다. 하기 화학식 6으로 표시되는 안사-메탈로센 화합물(촉매)은 신규 구조이다.In an embodiment, as the ansa-metallocene compound represented by Chemical Formula 1, it may be preferable to use an ansa-metallocene compound represented by the following Chemical Formula 6 (catalyst). As described below, the ansa-metallocene compound represented by the following formula (6) has a simple manufacturing method, unlike Scheme 1, which allows mass production and is suitable for commercialization. Ansa-metallocene compound (catalyst) represented by the following formula (6) is a novel structure.
[화학식 6][Formula 6]
Figure PCTKR2014012056-appb-I000007
Figure PCTKR2014012056-appb-I000007
상기 화학식 6에서, R1은 각각 독립적으로 페닐기 또는 tert-부틸기이고, R2 및 R3는 각각 독립적으로 탄소수 1 내지 5의 알킬기, 예를 들면, 메틸기, 에틸기, 프로필기 등이고, 구체적으로, 메틸기이다. Q1 및 Q2는 각각 독립적으로 할로겐 원자, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 2 내지 20의 알키닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 40의 알킬아릴기, 탄소수 7 내지 40의 아릴알킬기, 탄소수 1 내지 20의 알킬아미도기, 탄소수 6 내지 20의 아릴아미도기, 또는 탄소수 1 내지 20의 알킬리덴기, 예를 들면, 염소 원자(Cl), 불소 원자(F) 등의 할로겐 원자, 메틸기, 페닐기, 벤질기, 토릴기, 디메틸아미도기 등이고, 구체적으로, 염소 원자(Cl) 또는 메틸기이다.In Formula 6, R 1 is each independently a phenyl group or a tert-butyl group, R 2 and R 3 are each independently an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, and the like, specifically, Methyl group. Q 1 and Q 2 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl having 7 to 40 carbon atoms. A group, a C7-40 arylalkyl group, a C1-C20 alkylamido group, a C6-C20 arylamido group, or a C1-C20 alkylidene group, for example, a chlorine atom (Cl), a fluorine atom Halogen atoms, such as (F), a methyl group, a phenyl group, a benzyl group, a toryl group, a dimethyl amido group, etc., are specifically a chlorine atom (Cl) or a methyl group.
구체예에서, 상기 화학식 6으로 표시되는 안사-메탈로센 촉매의 예로는 하기 화학식 6a로 표시되는 화합물, 하기 화학식 6b로 표시되는 화합물, 이들의 혼합물 등을 예시할 수 있으나, 이에 제한되지 않는다.In an embodiment, examples of the ansa-metallocene catalyst represented by Chemical Formula 6 may include a compound represented by Chemical Formula 6a, a compound represented by Chemical Formula 6b, a mixture thereof, and the like, but are not limited thereto.
[화학식 6a][Formula 6a]
Figure PCTKR2014012056-appb-I000008
Figure PCTKR2014012056-appb-I000008
[화학식 6b][Formula 6b]
Figure PCTKR2014012056-appb-I000009
Figure PCTKR2014012056-appb-I000009
상기 화학식 6a 및 6b에서, Q1 및 Q2는 상기 화학식 1에서 정의한 바와 같다.In Chemical Formulas 6a and 6b, Q 1 and Q 2 are the same as defined in Chemical Formula 1.
구체예에서, 상기 조촉매 화합물은 하기 화학식 2로 표시되는 화합물, 하기 화학식 3으로 표시되는 화합물, 하기 화학식 4 또는 5로 표시되는 화합물, 이들을 혼합물 등을 포함할 수 있다.In embodiments, the cocatalyst compound may include a compound represented by Formula 2, a compound represented by Formula 3, a compound represented by Formula 4 or 5, a mixture thereof, and the like.
[화학식 2][Formula 2]
Figure PCTKR2014012056-appb-I000010
Figure PCTKR2014012056-appb-I000010
상기 화학식 2에서, R21은 각각 독립적으로 할로겐 원자, 탄소수 1 내지 20의 탄화수소기, 또는 탄소수 1 내지 20의 할로겐으로 치환된 탄화수소기이며, a는 2 이상의 정수이다;In Formula 2, R 21 is each independently a hydrocarbon atom substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen group having 1 to 20 carbon atoms, and a is an integer of 2 or more;
[화학식 3] [Formula 3]
D(R31)3 D (R 31 ) 3
상기 화학식 3에서, D는 알루미늄 또는 보론이며, R31은 각각 독립적으로 할로겐 원자, 탄소수 1 내지 20의 탄화수소기, 탄소수 1 내지 20의 할로겐으로 치환된 탄화수소기, 또는 탄소수 1 내지 20의 알콕시기이다;In Formula 3, D is aluminum or boron, and R 31 is each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. ;
[화학식 4][Formula 4]
[L-H]+[Z(A)4]- [LH] + [Z (A) 4 ] -
[화학식 5][Formula 5]
[L]+[Z(A)4]- [L] + [Z (A) 4 ] -
상기 화학식 4 및 5에서, L은 중성 또는 양이온성 루이스 산이고, Z는 원소 주기율표의 13족 원소이고, A는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기 또는 치환 또는 비치환된 탄소수 1 내지 20의 알킬기이다.In Formulas 4 and 5, L is a neutral or cationic Lewis acid, Z is a Group 13 element of the Periodic Table of the Elements, A is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted each independently It is a C1-C20 alkyl group.
상기 화학식 2로 표시되는 화합물은 알루미녹산이며, 통상의 알킬알루미녹산이라면 특별히 한정되지 않는다. 예를 들면, 메틸알루미녹산, 에틸알루미녹산, 이소부틸알루미녹산, 부틸알루미녹산 등을 사용할 수 있으며, 구체적으로 메틸알루미녹산을 사용할 수 있다. 상기 알킬알루미녹산은 트리알킬알루미늄에 적량의 물을 첨가하거나, 물을 포함하는 탄화수소 화합물 또는 무기 수화물 염과 트리알킬알루미늄을 반응시키는 등의 통상의 방법으로 제조할 수 있으며, 일반적으로 선상과 환상의 알루미녹산이 혼합된 형태로 얻어진다.The compound represented by the formula (2) is an aluminoxane, and is not particularly limited as long as it is a normal alkylaluminoxane. For example, methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like can be used, and specifically, methyl aluminoxane can be used. The alkylaluminoxane may be prepared by a conventional method such as adding an appropriate amount of water to trialkylaluminum, or reacting a trialkylaluminum with a hydrocarbon compound or an inorganic hydrate salt containing water, and is generally linear and cyclic. Aluminoxanes are obtained in mixed form.
상기 화학식 3으로 표시되는 화합물로는 예를 들면, 통상의 알킬 금속 화합물을 사용할 수 있다. 구체적으로, 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 디메틸클로로알루미늄, 트리이소프로필알루미늄, 트리시클로펜틸알루미늄, 트리펜틸알루미늄, 트리이소펜틸알루미늄, 트리헥실알루미늄, 트리옥틸알루미늄, 에틸디메틸알루미늄, 메틸디에틸알루미늄, 트리페닐알루미늄, 트리-p-톨릴알루미늄, 디메틸알루미늄메톡시드, 디메틸알루미늄에톡시드, 트리메틸보론, 트리에틸보론, 트리이소부틸보론, 트리프로필보론, 트리부틸보론, 트리펜타플루오로페닐보론 등을 사용할 수 있고, 더욱 구체적으로 트리메틸알루미늄, 트리이소부틸알루미늄, 트리펜타플루오로페닐보론 등을 사용할 수 있다.As the compound represented by Formula 3, for example, a conventional alkyl metal compound may be used. Specifically, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, Trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron , Tributyl boron, tripentafluorophenylboron and the like can be used, and more specifically, trimethylaluminum, triisobutylaluminum, tripentafluorophenylboron and the like can be used.
상기 화학식 4 또는 5로 표시되는 화합물의 예로는 메틸디옥타테실암모늄 테트라키스(펜타플루오로페닐)보레이트, 트리메틸암모늄 테트라키스(페닐)보레이트, 트리에틸암모늄 테트라키스(페닐)보레이트, 트리프로필암모늄 테트라키스(페닐)보레이트, 트리부틸암모늄 테트라키스(페닐)보레이트, 트리메틸암모늄 테트라키스(p-톨릴)보레이트, 트리프로필암모늄 테트라키스(p-톨릴)보레이트, 트리메틸암모늄 테트라키스(o,p-디메틸페닐)보레이트, 트리에틸암모늄 테트라키스(o,p-디메틸페닐)보레이트, 트리메틸암모늄 테트라키스(p-트리플루오로메틸페닐)보레이트, 트리부틸암모늄 테트라키스(p-트리플루오로메틸페닐)보레이트, 트리부틸암모늄 테트라키스(펜타플루오로페닐)보레이트, 디에틸암모늄 테트라키스(펜타플루오로페닐)보레이트, 트리페닐포스포늄 테트라키스(페닐)보레이트, 트리메틸포스포늄 테트라키스(페닐)보레이트, N,N-디에틸아닐리늄 테트라키스(페닐)보레이트, N,N-디메틸아닐리늄 테트라키스(펜타플루오로페닐)보레이트, N,N-디에틸아닐리늄 테트라키스(펜타플루오로페닐)보레이트, 트리페닐카보늄 테트라키스(p-트리플루오로메틸페닐)보레이트, 트리페닐카보늄 테트라키스(펜타플루오로페닐)보레이트([(C6H5)3C]+[B(C6F5)4]-), 트리메틸암모늄 테트라키스(페닐)알루미네이트, 트리에틸암모늄 테트라키스(페닐)알루미네이트, 트리프로필암모늄 테트라키스(페닐)알루미네이트, 트리부틸암모늄 테트라키스(페닐)알루미네이트, 트리메틸암모늄 테트라키스(p-톨릴)알루미네이트, 트리프로필암모늄 테트라키스(p-톨릴)알루미네이트, 트리에틸암모늄 테트라키스(o,p-디메틸페닐)알루미네이트, 트리부틸암모늄 테트라키스(p-트리플루오로메틸페닐)알루미네이트, 트리메틸암모늄 테트라키스(p-트리플루오로메틸페닐)알루미네이트, 트리부틸암모늄 테트라키스(펜타플루오로페닐)알루미네이트, N,N-디에틸아닐리늄 테트라키스(페닐)알루미네이트, N,N-디에틸아닐리늄 테트라키스(페닐)알루미네이트, N,N-디에틸아닐리늄 테트라키스(펜타플루오로페닐)알루미네이트, 디에틸암모늄 테트라키스(펜타플루오로페닐)알루미네이트, 트리페닐포스포늄 테트라키스(페닐)알루미네이트, 트리메틸포스포늄 테트라키스(페닐)알루미네이트, 트리에틸암모늄 테트라키스(페닐)알루미네이트, 트리부틸암모늄 테트라키스(페닐)알루미네이트 등을 예시할 수 있으나, 이에 제한되지 않는다. 구체적으로, 메틸디옥타테실암모늄 테트라키스(펜타플루오로페닐)보레이트, N,N-디메틸아닐리늄 테트라키스(펜타플루오로페닐)보레이트, 트리페닐카보늄 테트라키스(펜타플루오로페닐)보레이트([(C6H5)3C]+[B(C6F5)4]-) 등이다.Examples of the compound represented by the formula (4) or (5) include methyl dioctateyl ammonium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (phenyl) borate, triethylammonium tetrakis (phenyl) borate, tripropylammonium tetra Kis (phenyl) borate, tributylammonium tetrakis (phenyl) borate, trimethylammonium tetrakis (p-tolyl) borate, tripropylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o, p-dimethylphenyl Borate, triethylammonium tetrakis (o, p-dimethylphenyl) borate, trimethylammonium tetrakis (p-trifluoromethylphenyl) borate, tributylammonium tetrakis (p-trifluoromethylphenyl) borate, tributylammonium Tetrakis (pentafluorophenyl) borate, diethylammonium tetrakis (pentafluorophenyl) borate, triphenylforce Phosphium tetrakis (phenyl) borate, trimethylphosphonium tetrakis (phenyl) borate, N, N-diethylanilinium tetrakis (phenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (p-trifluoromethylphenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate ([( C 6 H 5 ) 3 C] + [B (C 6 F 5 ) 4 ] - ), trimethylammonium tetrakis (phenyl) aluminate, triethylammonium tetrakis (phenyl) aluminate, tripropylammonium tetrakis (phenyl Aluminate, tributylammonium tetrakis (phenyl) aluminate, trimethylammonium tetrakis (p-tolyl) aluminate, tripropylammonium tetrakis (p-tolyl) aluminate, triethylammonium tetrakis (o, p- Dimethylphenyl) Aluminum Nitrate, tributylammonium tetrakis (p-trifluoromethylphenyl) aluminate, trimethylammonium tetrakis (p-trifluoromethylphenyl) aluminate, tributylammonium tetrakis (pentafluorophenyl) aluminate, N, N -Diethylanilinium tetrakis (phenyl) aluminate, N, N-diethylanilinium tetrakis (phenyl) aluminate, N, N-diethylanilinium tetrakis (pentafluorophenyl) aluminate, diethyl Ammonium Tetrakis (pentafluorophenyl) aluminate, Triphenylphosphonium Tetrakis (phenyl) aluminate, Trimethylphosphonium Tetrakis (phenyl) aluminate, Triethylammonium Tetrakis (phenyl) aluminate, Tributylammonium Tetra Keys (phenyl) aluminate and the like can be exemplified, but is not limited thereto. Specifically, methyl dioctateyl ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate ([ (C 6 H 5 ) 3 C] + [B (C 6 F 5 ) 4 ] - ), and the like.
본 발명의 촉매 조성물은 상기 안사-메탈로센 화합물 및 상기 조촉매 화합물을 혼합(접촉)하여 제조할 수 있다. 상기 혼합은, 통상적으로 질소 또는 아르곤의 불활성 분위기 하에서, 톨루엔, 헥산, 사이클로헥산, 메틸사이클로헥산과 같은 하이드로카본 유기용매 존재 하에 수행될 수 있다. 구체예에서, 상기 혼합 시 온도는 약 0 내지 약 150℃, 예를 들면 상온(약 15 내지 약 30℃)이다. 예를 들면, 상기 유기용매 등에 균일하게 용해된 용액 상태의 촉매 조성물을 그대로 사용되거나, 용매를 제거시킨 고체 분말 상태로 사용될 수 있다. 또한, 상기 촉매 조성물을 실리카, 알루미나, 이들의 혼합물 등의 담체에 담지된 형태로 사용할 수도 있다.The catalyst composition of the present invention may be prepared by mixing (contacting) the ansa-metallocene compound and the cocatalyst compound. The mixing may be carried out in the presence of a hydrocarbon organic solvent such as toluene, hexane, cyclohexane, methylcyclohexane, usually under an inert atmosphere of nitrogen or argon. In an embodiment, the temperature upon mixing is about 0 to about 150 ° C., for example room temperature (about 15 to about 30 ° C.). For example, the catalyst composition in a solution state uniformly dissolved in the organic solvent or the like may be used as it is, or may be used in a solid powder state in which the solvent is removed. The catalyst composition may also be used in a form supported on a carrier such as silica, alumina, or a mixture thereof.
구체예에서, 상기 안사-메탈로센 화합물 및 상기 조촉매 화합물의 중심 금속의 몰비는, 조촉매 화합물이 Al 화합물인 경우(M(Zr 등):Al), 약 1 : 약 10 내지 약 1 : 약 5,000, 예를 들면 약 1 : 약 10 내지 약 1 : 약 1,000, 구체적으로 약 1 : 약 20 내지 약 1 : 약 200일 수 있다. 또한, 조촉매 화합물이 보론 화합물인 경우(M(Zr 등):보론), 약 1 : 약 1 내지 약 1 : 약 10, 예를 들면 약 1 : 약 1 내지 약 1 : 약 4, 구체적으로 약 1 : 약 1 내지 약 1 : 약 2일 수 있다. 특히, 조촉매 화합물로 화학식 2 내지 5의 화합물을 단독으로 사용하는 것보다 화학식 2의 알루미녹산 화합물과 화학식 3의 알킬알루늄 화합물을 혼합하여 사용하거나, 화학식 4 또는 5의 보레이트 화합물을 화학식 3의 알킬알루늄 화합물과 혼합하여 사용할 때 활성이 우수하여 바람직할 수 있다.In embodiments, the molar ratio of the ansa-metallocene compound and the center metal of the cocatalyst compound is about 1: about 10 to about 1: when the cocatalyst compound is an Al compound (M (Zr, etc.): Al). About 5,000, for example about 1: about 10 to about 1: about 1,000, specifically about 1: about 20 to about 1: about 200. In addition, when the cocatalyst compound is a boron compound (M (Zr, etc.): boron), about 1: about 1 to about 1: about 10, for example about 1: about 1 to about 1: about 4, specifically about 1: about 1 to about 1: about 2. In particular, the aluminoxane compound of Formula 2 and the alkylaluminum compound of Formula 3 may be mixed with each other, or the borate compound of Formula 4 or 5 may be used instead of the compound of Formulas 2 to 5 alone. When used in admixture with alkylaluminium compounds, it may be preferred because of its excellent activity.
일 구체예에서, 상기 촉매 조성물은 상기 안사-메탈로센 화합물을 상기 하이드로카본 유기용매에 녹이고, 여기에 상기 화학식 4 또는 5로 표시되는 화합물과 상기 화학식 3으로 표시되는 알킬알루미늄 화합물을 투입 및 접촉(혼합)시켜 제조할 수 있다. 이때, 상기 안사-메탈로센 화합물, 화학식 4 또는 5로 표시되는 보레이트 화합물, 및 화학식 3으로 표시되는 알킬알루미늄 화합물의 중심 금속의 몰비는 약 1 : 약 1 ~ 약 10 : 약 10 ~ 약 1000, 예를 들면 약 1 : 약 1 ~ 약 5 : 약 10 ~ 약 500, 구체적으로 상기 몰비가 약 1 : 약 1 ~ 약 2 : 약 100 ~ 약 200일 수 있다. 상기 범위에서 촉매 조성물의 활성이 우수하고, 경제성 면에서 바람직할 수 있다.In one embodiment, the catalyst composition dissolves the ansa-metallocene compound in the hydrocarbon organic solvent, in which the compound represented by Formula 4 or 5 and the alkyl aluminum compound represented by Formula 3 are added and contacted It can manufacture by mixing. At this time, the molar ratio of the center metal of the ansa-metallocene compound, the borate compound represented by the formula (4) or (5), and the alkylaluminum compound represented by the formula (3) is about 1: about 1 to about 10: about 10 to about 1000, For example, about 1: about 1 to about 5: about 10 to about 500, specifically, the molar ratio may be about 1: about 1 to about 2: about 100 to about 200. It is excellent in the activity of the catalyst composition in the above range, it may be preferable in terms of economics.
본 발명의 알파-올레핀 올리고머 제조방법(알파-올레핀의 올리고머화 반응)은 액상 또는 괴상(bulk phase)으로 수행할 수 있다. 각각의 중합 반응 조건은, 사용되는 촉매 조성물의 상태(균일상 또는 불균일상(담지형)) 및 중합 방법 등 목적하는 중합결과에 따라 다양하게 변형될 수 있다. 그의 변형 정도는 당업자에 의해 용이하게 수행될 수 있다. 상기 중합이 액상에서 실시되는 경우 용매로는 프로판, 부탄, 펜탄, 헥산, 옥탄, 데칸, 도데칸, 시클로펜탄, 메틸시클로펜탄, 시클로헥산, 메틸시클로헥산, 벤젠, 톨루엔, 자일렌, 디클로로메탄, 클로로에탄, 디클로로에탄, 클로로벤젠 등을 예시할 수 있으며, 이들 용매를 일정한 비율로 섞어 사용할 수도 있다.The method for preparing alpha-olefin oligomer of the present invention (oligomerization reaction of alpha-olefin) can be carried out in a liquid phase or a bulk phase. Each polymerization reaction condition may be variously modified depending on the desired polymerization result such as the state of the catalyst composition used (uniform or heterogeneous phase (support type)) and the polymerization method. The degree of modification thereof can be easily carried out by those skilled in the art. When the polymerization is carried out in a liquid phase, solvents include propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, dichloromethane, Chloroethane, dichloroethane, chlorobenzene, etc. can be illustrated, These solvent can also be mixed and used in fixed ratio.
구체예에서, 상기 탄소수 6 내지 20의 알파(α)-올레핀 단량체의 예로는, 1-헥센, 1-옥텐(1-octene), 1-데센(1-decene), 1-도데센(1-dodecene), 이들의 혼합물 등을 예시할 수 있다. 특히, 고급 윤활유 제조에 적합한 단량체는 1-옥텐(1-octene), 1-데센(1-decene), 1-도데센(1-dodecene) 등이다.In an embodiment, examples of the alpha 6-olefin monomer having 6 to 20 carbon atoms include 1-hexene, 1-octene, 1-decene, 1-dodecene dodecene), mixtures thereof, and the like. In particular, suitable monomers for the preparation of higher lubricating oils are 1-octene, 1-decene, 1-dodecene and the like.
상기 알파-올레핀의 올리고머화 반응에서 있어서, 상기 촉매 조성물의 사용량은 특별히 한정되지 않으나, 예를 들면, 중합되는 반응계 내에서 상기 화학식 1로 표시되는 안사-메탈로센 촉매의 중심 금속(Zr) 농도가 약 1*10-5 내지 약 1*10-4 mol/L일 수 있다. 또한, 중합 시 온도 및 압력은 반응 물질, 반응 조건 등에 따라 변할 수 있기 때문에 특별히 한정되지 않지만, 중합 온도는, 약 0 내지 약 200℃, 예를 들면 약 50 내지 약 150℃일 수 있다. 상기 중합은 배치식, 반연속식 또는 연속식으로 수행될 수 있다. 상기 중합은 상이한 반응 조건을 갖는 둘 이상의 단계로도 수행될 수 있으며, 최종 올리고머의 중합도는 중합 온도를 변화시키거나, 반응기 내에 수소를 주입하는 방법으로 조절할 수 있다.In the oligomerization reaction of the alpha-olefin, the amount of the catalyst composition is not particularly limited, for example, the concentration of the center metal (Zr) of the ansa-metallocene catalyst represented by the formula (1) in the reaction system to be polymerized. May be about 1 * 10 −5 to about 1 * 10 −4 mol / L. In addition, the temperature and pressure during the polymerization is not particularly limited because it may vary depending on the reaction material, reaction conditions, etc., the polymerization temperature may be about 0 to about 200 ℃, for example about 50 to about 150 ℃. The polymerization can be carried out batchwise, semicontinuously or continuously. The polymerization can also be carried out in two or more stages with different reaction conditions, and the degree of polymerization of the final oligomer can be controlled by varying the polymerization temperature or by injecting hydrogen into the reactor.
본 발명의 알파-올레핀 올리고머화 방법에 따라 제조된 알파-올레핀 올리고머는 다이머(2량체)의 분율이 약 10 내지 약 20% 수준으로 낮고, 트리머 내지 펜머(3-5량체)의 분율이 약 30 내지 약 50%, 헥사머 내지 노나머(6-9량체) 분율이 약 20 내지 약 30%로서, 트리머 내지 노나머(3-9량체)가 올리고머의 대부분(약 60 내지 약 80%)을 차지하며, 중합도가 약 10 이상인 것(10량체 이상)의 분율이 약 30% 이하 수준으로 낮다. 따라서, 본 발명의 제조방법으로 제조된 알파-올레핀 올리고머는 중합도 분포가 엔진 오일, 트랜스미션 오일, 기어 오일 등의 탑-티어(top-tier) 제품(고급 윤활유)로 적용하기에 바람직하다.The alpha-olefin oligomer prepared according to the alpha-olefin oligomerization method of the present invention has a low dimer (dimer) fraction of about 10 to about 20%, and a trimer to penmer (3-5 trimer) fraction of about 30 To about 50%, hexamer to nonamer (6-9 monomer) fractions of about 20 to about 30%, with trimers to nonomers (3-9 monomer) accounting for most of the oligomer (about 60 to about 80%). The fraction of the polymerization degree of about 10 or more (more than 10 dimers) is low to about 30% or less. Therefore, the alpha-olefin oligomer produced by the production method of the present invention is preferably suitable for application of the degree of polymerization to top-tier products (high grade lubricating oil) such as engine oil, transmission oil and gear oil.
본 발명의 또 다른 관점은 상기 화학식 6으로 표시되는 안사-메탈로센 화합물(촉매)의 제조방법에 관한 것이다. 새로운 구조의 상기 화학식 6으로 표시되는 안사-메탈로센 화합물(촉매)은, 예를 들면, 하기 화학식 7로 표시되는 화합물, 및 디메톡시에탄이 배위된 ZrCl2를 반응시킴으로써 제조할 수 있다.Another aspect of the present invention relates to a method for producing an ansa-metallocene compound (catalyst) represented by the formula (6). The ansa-metallocene compound (catalyst) represented by the formula (6) of the new structure can be prepared by, for example, reacting a compound represented by the following formula (7) and ZrCl 2 coordinated with dimethoxyethane.
[화학식 7][Formula 7]
Figure PCTKR2014012056-appb-I000011
Figure PCTKR2014012056-appb-I000011
상기 화학식 7에서, R1, R2 및 R3는 상기 화학식 6에서 정의한 바와 같다.In Formula 7, R 1 , R 2, and R 3 are the same as defined in Formula 6.
상기 화학식 7로 표시되는 화합물은 1,4,6-위치에만 치환체를 가지고 있는 풀벤 화합물로서, 본 발명자에 의하여, 수십-g 스케일의 제조방법이 개시되었다(Synthesis, 2004, 1052; 대한민국 등록특허(소멸) 10-0515585호; 대한민국 등록특허(소멸) 10-0551137호: 상기 논문 및 특허는 본 발명의 개시의 일부를 구성한다).Compound represented by the formula (7) is a fulbene compound having a substituent only in 1,4,6-position, by the present inventors, a method for producing dozens-g scale has been disclosed (Synthesis, 2004, 1052; Republic of Korea Patent ( Extinction) 10-0515585; Republic of Korea Patent (Extinction) 10-0551137: The papers and patents form part of the disclosure of the present invention).
참고로, 6,6-디메틸풀벤 및 6-페닐풀벤과 같은 6-위치에만 치환체를 갖는 풀벤 화합물을 in-situ로 제조된 ZrCl2를 반응시켜 안사-메탈로센 화합물을 합성하는 방법이 보고되었다(Organometallics 1998, 17, 5219; Polyhedron 2005, 24, 1325). 그러나, 상기 문헌의 방법을 그대로 차용하여 1,4,6-위치에 치환체를 갖는 풀벤 화합물로부터 상기 화학식 6의 화합물 제조를 시도하였을 때 수율이 매우 낮았다. 즉, 톨루엔 또는 테트라하이드로퓨란(THF)의 용매 중에서 당량의 ZrCl4을 2 당량의 n-BuLi과 반응시켜 Zr(II)Cl2를 제조한 후, 이를 상기 화학식 7의 1,4,6-위치에 치환체를 갖는 풀벤 화합물과 반응시켜 상기 화학식 6의 안사-메탈로센 화합물의 합성을 시도하였을 때 수율이 15% 미만이다.For reference, a method for synthesizing ansa-metallocene compound by reacting a ZuCl 2 prepared in-situ with a Fulven compound having a substituent only at the 6-position, such as 6,6-dimethylpulben and 6-phenylpulben, has been reported. (Organometallics 1998, 17, 5219; Polyhedron 2005, 24, 1325). However, the yield was very low when the compound of Formula 6 was attempted from the Fulbene compound having a substituent at the 1,4,6-position using the method of the document as it is. That is, Zr (II) Cl 2 is prepared by reacting an equivalent amount of ZrCl 4 with 2 equivalents of n-BuLi in a solvent of toluene or tetrahydrofuran (THF), and then, the 1,4,6-position of Chemical Formula 7 The yield is less than 15% when the synthesis of the ansa-metallocene compound of Chemical Formula 6 is attempted by reacting with a fulvene compound having a substituent.
본 발명에서는 디메톡시에탄이 배위된 Zr(II)Cl2를 제조한 후, 이를 상기 화학식 7의 1,4,6-위치에 치환체를 갖는 풀벤 화합물과 반응시켜 상기 화학식 6의 안사-메탈로센 화합물을 약 60% 이상의 수율로 제조하였다. 또한, 기존의 제조방법과 달리 약 2 당량의 지르코늄을 사용해야 풀벤 화합물이 모두 전환되어 수율이 높아짐을 확인하였다.In the present invention, after preparing Zr (II) Cl 2 coordinated with dimethoxyethane, and reacted with a pullbene compound having a substituent in the 1,4,6-position of the formula (7) Ansa-metallocene of the formula (6) The compound was prepared in a yield of at least about 60%. In addition, it was confirmed that unlike the conventional manufacturing method, about 2 equivalents of zirconium should be used to convert all of the pullene compounds to increase the yield.
참고로, 치환체 R1이 페닐기 또는 tert-부틸기가 아닌, 메틸기, 이소프로필기, 또는 펜틸기일 경우, 각각 하기 화학식 6c, 6d 또는 6e의 구조를 갖는 안사-메탈로센 화합물과 함께 하기 구조의 브릿지되지 않은 화합물(화학식 6f, 6g, 또는 6h)이 부산물로 얻어지는 것을 확인하였다. 상기 안사-메탈로센 화합물과 부산물은 분리하기가 쉽지 않으며, 합성 수율도 낮아, 상업적 촉매로 사용하기에 부적절하다.For reference, when the substituent R 1 is not a phenyl group or tert-butyl group, but is a methyl group, isopropyl group, or a pentyl group, the bridge of the following structure together with an ansa-metallocene compound having a structure of the following Chemical Formula 6c, 6d or 6e, respectively It was confirmed that an uncompounded compound (Formula 6f, 6g, or 6h) was obtained as a by-product. The ansa-metallocene compound and by-products are not easy to separate, and the synthesis yield is low, which is inappropriate for use as a commercial catalyst.
[화학식 6c][Formula 6c]
Figure PCTKR2014012056-appb-I000012
Figure PCTKR2014012056-appb-I000012
[화학식 6d][Formula 6d]
Figure PCTKR2014012056-appb-I000013
Figure PCTKR2014012056-appb-I000013
[화학식 6e][Formula 6e]
Figure PCTKR2014012056-appb-I000014
Figure PCTKR2014012056-appb-I000014
[화학식 6f][Formula 6f]
Figure PCTKR2014012056-appb-I000015
Figure PCTKR2014012056-appb-I000015
[화학식 6g][Formula 6g]
Figure PCTKR2014012056-appb-I000016
Figure PCTKR2014012056-appb-I000016
[화학식 6h][Formula 6h]
Figure PCTKR2014012056-appb-I000017
Figure PCTKR2014012056-appb-I000017
상기 화학식 6c 내지 6h에서, Q1 및 Q2는 상기 화학식 6에서 정의한 바와 같다.In Chemical Formulas 6c to 6h, Q 1 and Q 2 are the same as defined in Chemical Formula 6.
구체예에서, 본 발명의 메탈로센 촉매, 특히, Q1 및 Q2가 염소 원자인 상기 화학식 6로 표시되는 메탈로센 촉매는, 유기용매 중에서, 디메톡시에탄이 배위된 ZrCl2(ZrCl2·DME)을 n-부틸리튬(n-BuLi) 약 2 당량과 반응시키고, 여기에 상기 화학식 7로 표시되는 화합물을 투입 및 교반함으로써, 제조할 수 있다.In an embodiment, the metallocene catalyst of the present invention, in particular, the metallocene catalyst represented by the above formula (6) wherein Q 1 and Q 2 are chlorine atoms, is ZrCl 2 (ZrCl 2 coordinated with dimethoxyethane in an organic solvent. It can be prepared by reacting DME) with about 2 equivalents of n-butyllithium (n-BuLi), and adding and stirring the compound represented by the formula (7).
또한, 상기 메탈로센 촉매의 염소 원자(리간드)를 염소 원자를 제외한 상기 화학식 1의 Q1 및 Q2로 변환하는 반응은 통상적인 방법, 즉, 염소 원자를 가지고 있는 화합물에 친핵체 공격 반응을 통하여 쉽게 가능하다.In addition, the reaction of converting the chlorine atom (ligand) of the metallocene catalyst to Q 1 and Q 2 of Chemical Formula 1, except for the chlorine atom, is a conventional method, that is, through a nucleophilic attack reaction on a compound having a chlorine atom. Easily possible.
상기 화학식 7로 표시되는 화합물의 비한정적인 예로는 하기 화학식 7a로 표시되는 화합물, 하기 화학식 7b로 표시되는 화합물, 이들의 혼합물 등을 예시할 수 있다.Non-limiting examples of the compound represented by Formula 7 may include a compound represented by Formula 7a, a compound represented by Formula 7b, a mixture thereof, and the like.
[화학식 7a][Formula 7a]
Figure PCTKR2014012056-appb-I000018
Figure PCTKR2014012056-appb-I000018
[화학식 7b][Formula 7b]
Figure PCTKR2014012056-appb-I000019
Figure PCTKR2014012056-appb-I000019
구체예에서, 상기 메탈로센 촉매 제조에 사용되는 유기용매로는 탄소수 5 내지 10의 지방족 또는 방향족 탄화수소, 할로겐 원자로 치환된 탄소수 1 내지 10의 탄화수소 용매, 이들의 혼합물, 예를 들면, 펜탄, 헥산, 헵탄, 시클로헥산, 메틸사이클로헥산, 벤젠, 톨루엔, 자일렌, 디클로로메탄, 클로로에탄, 디클로로에탄, 클로로벤젠 등을 사용할 수 있다.In an embodiment, the organic solvent used to prepare the metallocene catalyst may be an aliphatic or aromatic hydrocarbon having 5 to 10 carbon atoms, a hydrocarbon solvent having 1 to 10 carbon atoms substituted with a halogen atom, and mixtures thereof, such as pentane and hexane. , Heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, dichloroethane, chlorobenzene and the like can be used.
구체예에서, 상기 화학식 2로 표시되는 화합물 및 상기 디메톡시에탄이 배위된 ZrCl2의 반응은, 약 60 내지 약 150℃, 예를 들면 약 80 내지 약 120℃의 온도에서, 예를 들면, 약 1 내지 약 30 시간 동안 교반하며 수행될 수 있다. 상기 범위에서 고수율로 안사-메탈로센 촉매를 얻을 수 있다.In embodiments, the reaction of the compound represented by Formula 2 and the ZrCl 2 coordinated with the dimethoxyethane is at a temperature of about 60 to about 150 ° C., for example about 80 to about 120 ° C., for example, The stirring may be performed for 1 to about 30 hours. Ansa-metallocene catalyst can be obtained in a high yield in the said range.
구체예에서, 상기 반응이 완료되면, 통상적인 후처리 공정, 예를 들면, 진공 펌프 등을 사용하여 용매, 미반응물 등을 제거하고, 하이드로카본 용매로 추출 및 세척, 건조하는 공정을 통하여 고순도 안사-메탈로센 촉매를 얻을 수 있다.In an embodiment, when the reaction is completed, high-purity eye massage through a conventional post-treatment process, for example, removing a solvent, an unreacted substance using a vacuum pump, etc., and extracting, washing, and drying with a hydrocarbon solvent. Metallocene catalysts can be obtained.
이하, 본 발명의 바람직한 실시예를 통해 본 발명의 구성 및 작용을 더욱 상세히 설명하기로 한다. 다만, 이는 본 발명의 바람직한 예시로 제시된 것이며 어떠한 의미로도 이에 의해 본 발명이 제한되는 것으로 해석될 수는 없다.Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.
실시예Example
실시예 1: 화학식 6a로 표시되는 안사-메탈로센 촉매의 제조 Example 1 Preparation of Ansa-Metallocene Catalysts of Formula 6a
디메톡시에탄이 배위된 ZrCl2(ZrCl2·DME) 1.6 g(4.95 mmol)을 톨루엔(32 mL)에 녹인 후 용액의 온도를 -78℃로 낮추었다. n-부틸리튬 용액(1.6 M 헥산 용액) 4.21 g(9.90 mmol)을 질소 분위기 하에 천천히 주입하였다. 상온에서 6시간 교반한 후, 진공펌프를 이용하여 일부 용매를 제거하여 용액의 부피를 약 16 mL가 되게 하였다. 100 ℃에서 4시간 부탄 및 1-부텐가스를 버블러를 통해 제거하면서 교반하였다. 화학식 7a로 표시되는 화합물 902 mg(4.95 mmol)을 톨루엔(3.60 mL)에 녹인 후 상온에서 주입하고, 100℃에서 18시간 동안 교반하였다. 여과를 통하여 얻어진 용액을 진공펌프로 용매를 제거하여 용매의 양이 약 6 mL가 되게 한 후 차콜(1.14 g)을 투입 후 12시간 교반하였다. 여과 후 용매를 제거하여 옅은 갈색 분말 형태의 하기 화학식 6a로 표시되는 안사-메탈로센 촉매(Q1 및 Q2: Cl) 991 mg을 얻었다 (수율: 76 %). 제조된 안사-메탈로센 촉매의 X선 회절 결정 구조를 도 1에 나타내었다. 1H NMR 분석 결과 racemic 아이조머(isomer)와 meso 아이조머가 1.6:1.0 비율로 얻어졌음을 확인할 수 있었다{1H NMR (C6D6): δ 7.03-6.98 (m, 5H, meso-Ph), 6.94-6.86 (m, 3H, racemic-ortho, para-Ph), 6.86-6.80 (m, 2H, racemic-meso-Ph), 6.53 (d, J = 3.6 Hz, 1.2H, racemic-Cp), 6.46 (d, J = 3.2 Hz, 1.2H, racemic-Cp), 6.44 (d, J = 3.2 Hz, 0.8H, meso-Cp), 6.33 (d, J = 3.2 Hz, 0.8H, meso-Cp), 5.64 (s, 1.2H, racemic-CpCH), 5.39 (s, 0.8H, meso-CpCH), 2.17 (s, 2.4H, meso-CH3), 1.98 (s, 3.6H, racemic-CH3), 1.80 (s, 3.6H, racemic-CH3), 1.73 (s, 2.4H, meso-CH3) ppm}.1.6 g (4.95 mmol) of ZrCl 2 (ZrCl 2 · DME) coordinated with dimethoxyethane was dissolved in toluene (32 mL), and the temperature of the solution was lowered to -78 ° C. 4.21 g (9.90 mmol) of n-butyllithium solution (1.6 M hexane solution) was injected slowly under a nitrogen atmosphere. After stirring for 6 hours at room temperature, a portion of the solvent was removed by using a vacuum pump to a volume of about 16 mL. It was stirred while removing butane and 1-butene gas at 100 ° C. for 4 hours through a bubbler. 902 mg (4.95 mmol) of the compound represented by Chemical Formula 7a were dissolved in toluene (3.60 mL), injected at room temperature, and stirred at 100 ° C. for 18 hours. The solution obtained through the filtration was removed with a vacuum pump so that the solvent was about 6 mL, and then charcoal (1.14 g) was added thereto, followed by stirring for 12 hours. After filtration, the solvent was removed to obtain 991 mg of ansa-metallocene catalyst (Q 1 and Q 2 : Cl) represented by the following Chemical Formula 6a in the form of a light brown powder (yield: 76%). X-ray diffraction crystal structure of the prepared Ansa-metallocene catalyst is shown in FIG. 1 H NMR analysis showed that racemic and meso isomers were obtained at a ratio of 1.6: 1.0 { 1 H NMR (C 6 D 6 ): δ 7.03-6.98 (m, 5H, meso-Ph ), 6.94-6.86 (m, 3H, racemic- ortho, para- Ph), 6.86-6.80 (m, 2H, racemic- meso- Ph), 6.53 (d, J = 3.6 Hz, 1.2H, racemic-Cp) , 6.46 (d, J = 3.2 Hz, 1.2H, racemic-Cp), 6.44 (d, J = 3.2 Hz, 0.8H, meso-Cp), 6.33 (d, J = 3.2 Hz, 0.8H, meso-Cp ), 5.64 (s, 1.2H, racemic-CpC H ), 5.39 (s, 0.8H, meso-CpC H ), 2.17 (s, 2.4H, meso-CH 3 ), 1.98 (s, 3.6H, racemic- CH 3 ), 1.80 (s, 3.6H, racemic-CH 3 ), 1.73 (s, 2.4H, meso-CH 3 ) ppm}.
[화학식 6a][Formula 6a]
Figure PCTKR2014012056-appb-I000020
Figure PCTKR2014012056-appb-I000020
[화학식 7a][Formula 7a]
Figure PCTKR2014012056-appb-I000021
Figure PCTKR2014012056-appb-I000021
실시예 2: 화학식 6b로 표시되는 안사-메탈로센 촉매의 제조 Example 2 Preparation of Anza-Metallocene Catalysts of Formula 6b
상기 화학식 6a로 표시되는 화합물 대신에 하기 화학식 6b로 표시되는 화합물을 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 합성하여 얻어낸 생성물을 헥산으로 트리추레이션하여 하기 화학식 6b로 표시되는 안사-메탈로센 촉매(Q1 및 Q2: Cl)를 얻었다(수율: 39 %). 제조된 안사-메탈로센 촉매의 X선 회절 결정 구조를 도 2에 나타내었다. 1H NMR 분석 결과 racemic 아이조머와 meso 아이조머가 1.5:1 비율로 얻어졌다{1H NMR (C6D6): δ 6.54 (d, J = 3.6 Hz, 1.2H, racemic-Cp), 6.49 (d, J = 3.6 Hz, 0.8H, meso-Cp), 6.43 (d, J = 3.6 Hz, 0.8H, meso-Cp), 6.35 (d, J = 3.6 Hz, 1.2H, racemic-Cp), 3.93 (s, 0.8H, meso-CpCH), 3.53 (s, 1.2H, racemic-CpCH), 2.17 (s, 2.4H, meso-CH3), 1.97 (s, 3.6H, racemic-CH3), 1.92 (s, 2.4H, meso-CH3), 1.89 (s, 3.6H, racemic-CH3), 1.05 (s, 7.2H, meso-C(CH 3)3), 0.91 (s, 10.8H, racemic-C(CH 3)3) ppm}.Ansasa represented by the following formula (6b) by triturating the product obtained by synthesis in the same manner as in Example 1 with hexane, except that the compound represented by the following formula (6b) was used instead of the compound represented by the formula (6a). Metallocene catalysts (Q 1 and Q 2 : Cl) were obtained (yield 39%). X-ray diffraction crystal structure of the prepared Ansa-metallocene catalyst is shown in FIG. 1 H NMR analysis showed racemic and meso isomers at a ratio of 1.5: 1 { 1 H NMR (C 6 D 6 ): δ 6.54 (d, J = 3.6 Hz, 1.2H, racemic-Cp), 6.49 (d, J = 3.6 Hz, 0.8H, meso-Cp), 6.43 (d, J = 3.6 Hz, 0.8H, meso-Cp), 6.35 (d, J = 3.6 Hz, 1.2H, racemic-Cp), 3.93 (s, 0.8H, meso-CpC H ), 3.53 (s, 1.2H, racemic-CpC H ), 2.17 (s, 2.4H, meso-CH 3 ), 1.97 (s, 3.6H, racemic-CH 3 ), 1.92 (s, 2.4H, meso-CH 3 ), 1.89 (s, 3.6H, racemic-CH 3 ), 1.05 (s, 7.2H, meso-C (C H 3 ) 3 ), 0.91 (s, 10.8H, racemic-C (C H 3 ) 3 ) ppm}.
[화학식 6b][Formula 6b]
Figure PCTKR2014012056-appb-I000022
Figure PCTKR2014012056-appb-I000022
[화학식 7b][Formula 7b]
Figure PCTKR2014012056-appb-I000023
Figure PCTKR2014012056-appb-I000023
실시예 3: 화학식 6a 화합물을 이용한 1-데센의 중합 Example 3: Polymerization of 1-decene Using Compound of Formula 6a
고압 반응기에 1-데센 500 mL(370 g)와 트리이소부틸알루미늄 1.5 mmol을 투입하고 온도를 120℃로 올렸다. 상기 화학식 6a로 표시되는 안사-메탈로센 촉매 0.010 mmol, 트리페닐카보늄 테트라키스(펜타플루오로페닐)보레이트([(C6H5)3C]+[B(C6F5)4]-) 0.020 mmol 및 트리이소부틸알루미늄 0.50 mmol을 톨루엔 5 mL에서 혼합하여, 활성화된 촉매를 제조하고, 이를 주사기에 취해 상기 반응기에 투입하였다. 1시간 동안 반응시킨 후, 물 5 mL를 투입하여 반응을 종결시켰다. 미반응 1-데센을 진공 증류하여 제거한 후, 얻어진 점액성 액체(올레핀 올리고머)의 질량을 측정하여 활성을 계산하였다(212 g, 활성: 21,200 Kg/mol.cat·hr, 전환율: 57%). 제조된 올레핀 올리고머의 분포를 sidmis(stimulated distillation) GC 분석을 통하여 알아내었다(도 3, 표 1). 분석 결과, 2-9량체가 골고루 생성되었고, 전체 중 중 3-5량체가 차지하는 비율이 35.1%로 주류를 차지하고 10량체 이상이 25.2%임을 확인하였다.500 mL (370 g) of 1-decene and 1.5 mmol of triisobutylaluminum were added to a high pressure reactor, and the temperature was raised to 120 ° C. 0.010 mmol of ansa-metallocene catalyst represented by Formula 6a, triphenylcarbonium tetrakis (pentafluorophenyl) borate ([(C 6 H 5 ) 3 C] + [B (C 6 F 5 ) 4 ] - ) 0.020 mmol and 0.50 mmol of triisobutylaluminum were mixed in 5 mL of toluene to prepare an activated catalyst, which was taken in a syringe and put into the reactor. After reacting for 1 hour, 5 mL of water was added to terminate the reaction. After unreacted 1-decene was removed by vacuum distillation, the mass of the obtained viscous liquid (olefin oligomer) was measured to calculate the activity (212 g, activity: 21,200 Kg / mol.cat.hr, conversion: 57%). Distribution of the prepared olefin oligomer was found through sidmis (stimulated distillation) GC analysis (FIG. 3, Table 1). As a result, 2-9 monomers were evenly produced, and the proportion of 3-5 monomers was 35.1%, and the mainstream was 25.2% or more.
실시예 4: 화학식 6a 화합물을 이용한 1-옥텐의 중합 Example 4 Polymerization of 1-Octene Using Compound of Formula 6a
상기 1-데센 대신에 1-옥텐을 사용한 것을 제외하고는, 상기 실시예 3과 동일한 방법으로 214 g의 올레핀 올리고머를 얻었다(활성: 21,400 Kg/mol.cat·hr, 전환율: 60%). 제조된 올레핀 올리고머의 simdis-GC 분석 결과를 도 4 및 표 1에 나타내었다. 분석 결과, 2-9량체가 골고루 생성되었고, 전체 올리고머 중 3-5량체가 차지하는 비율이 35.9%로 주류를 차지하고 있고 10량체 이상이 23.4%로 적음을 확인하였다.214 g of olefin oligomer was obtained in the same manner as in Example 3, except that 1-octene was used instead of 1-decene (activity: 21,400 Kg / mol.cat.hr, conversion: 60%). Simdis-GC analysis of the prepared olefin oligomer is shown in Figure 4 and Table 1. As a result, it was confirmed that 2-9 monomers were evenly formed, and the proportion of 3-5 monomers in the entire oligomer was 35.9%, the mainstream, and 23.4% or more were less than 10 monomers.
실시예 5: 화학식 6b 화합물을 이용한 1-데센의 중합 Example 5 Polymerization of 1-decene Using Compound of Formula 6b
상기 화학식 6a로 표시되는 안사-메탈로센 촉매 대신에 상기 화학식 6b로 표시되는 안사-메탈로센 촉매를 사용한 것을 제외하고는, 상기 실시예 3과 동일한 방법으로 127 g의 올리고머를 얻었다(활성: 12700 Kg/mol·cat·hr, 전환율: 34.2%). 제조된 올레핀 올리고머의 simdis-GC 분석 결과를 도 5 및 표 1에 나타내었다. 분석 결과, 2-9량체가 골고루 생성되었고, 전체 올리고머 중 3-5량체가 차지 하는 비율이 43.4%로 주류를 차지하고 있으며, 10량체 이상이 13.5%로 적음을 확인하였다.127 g of an oligomer was obtained in the same manner as in Example 3, except that the ansa-metallocene catalyst represented by Formula 6b was used instead of the ansa-metallocene catalyst represented by Formula 6a. 12700 Kg / mol.cat.hr, conversion: 34.2%). Simdis-GC analysis of the prepared olefin oligomer is shown in Figure 5 and Table 1. As a result, 2-9 monomers were evenly produced, and the proportion of 3-5 monomers in total oligomers occupied the mainstream at 43.4%, and less than 10 monomers were 13.5%.
비교예 1: (Me4C5H)2ZrCl2 화합물을 이용한 1-데센 중합 Comparative Example 1: 1-decene polymerization using (Me 4 C 5 H) 2 ZrCl 2 compound
상기 화학식 6a로 표시되는 안사-메탈로센 촉매 대신에 브릿지되지 않은 촉매인 (Me4C5H)2ZrCl2(제조사: Strem사)을 사용한 것을 제외하고는, 실시예 3과 동일한 방법으로 130 g의 올레핀 올리고머를 얻었다(활성: 13,000 Kg/mol.cat·hr, 전환율: 35%). 제조된 올레핀 올리고머의 simdis-GC 분석 결과를 도 6 및 표 1에 나타내었다. 분석 결과, 2량체가 54.8%이고, 3량체가 26.2%로, 중합도가 매우 낮은 화합물 위주로 생성됨을 확인하였다.130 in the same manner as in Example 3, except that (Me 4 C 5 H) 2 ZrCl 2 (manufacturer: Strem), which was an unbridged catalyst, was used instead of the ansa-metallocene catalyst represented by Chemical Formula 6a. g olefin oligomer was obtained (activity: 13,000 Kg / mol.cat.hr, conversion: 35%). Simdis-GC analysis of the prepared olefin oligomer is shown in Figure 6 and Table 1. As a result of the analysis, it was confirmed that the dimer was 54.8% and the trimer was 26.2%.
비교예 2: (nBuC5H4)2ZrCl2를 이용한 1-데센 중합 Comparative Example 2: 1-decene polymerization with (nBuC 5 H 4 ) 2 ZrCl 2
상기 화학식 6a로 표시되는 안사-메탈로센 촉매 대신에 브릿지되지 않은 촉매인 (nBuC5H4)2ZrCl2(제조사: Strem)을 사용한 것을 제외하고는, 실시예 3과 동일한 방법으로 141 g의 올레핀 올리고머를 얻었다(활성: 14,100 Kg/mol.cat·hr, 전환율: 38%). 제조된 올레핀 올리고머의 simdis-GC 분석 결과를 도 7 및 표 1에 나타내었다. 분석 결과, 2량체가 33.3%이고, 3량체가 36.8%로, 중합도가 매우 낮은 화합물 위주로 생성됨을 확인하였다.141 g of 141 g was obtained by the same method as Example 3, except that (nBuC 5 H 4 ) 2 ZrCl 2 (manufacturer: Strem), which was an unbridged catalyst, was used instead of the ansa-metallocene catalyst represented by Chemical Formula 6a. An olefin oligomer was obtained (activity: 14,100 Kg / mol. Cat.hr, conversion: 38%). Simdis-GC analysis of the prepared olefin oligomer is shown in Figure 7 and Table 1. As a result of the analysis, the dimer was 33.3%, the trimer was 36.8%, and it was confirmed that the polymer was produced mainly with a very low degree of polymerization.
비교예 3: (EBI)ZrCl2를 이용한 1-데센 중합 Comparative Example 3: 1-decene polymerization with (EBI) ZrCl 2
상기 화학식 6a로 표시되는 안사-메탈로센 촉매 대신에 브릿지되지 않은 촉매인 (EBI)ZrCl2(EBI: ethylenebisindenyl, 제조사: Strem)을 사용한 것을 제외하고는, 실시예 3과 동일한 방법으로 299 g의 올레핀 올리고머를 얻었다(활성: 29,900 Kg/mol.cat·hr, 전환율: 81%). 제조된 올레핀 올리고머의 simdis-GC 분석 결과를 도 8 및 표 1에 나타내었다. 분석 결과, 10량체 이상이 62.3%인 중합도가 매우 높은 화합물 위주로 생성됨을 확인하였다.299 g of the same method as in Example 3, except that an unbridged catalyst (EBI) ZrCl 2 (EBI: ethylenebisindenyl, manufactured by Strem) was used instead of the ansa-metallocene catalyst represented by Chemical Formula 6a. An olefin oligomer was obtained (activity: 29,900 Kg / mol. Cat.hr, conversion: 81%). Simdis-GC analysis of the prepared olefin oligomer is shown in Figure 8 and Table 1. As a result of the analysis, it was confirmed that at least 10-mers were mainly produced with a high degree of polymerization of 62.3%.
비교예 4: 화학식 8로 표시되는 화합물을 이용한 1-옥텐 중합 Comparative Example 4: 1-octene polymerization using the compound represented by the formula (8)
하기 화학식 8로 표시되는 화합물은 문헌(Polyhedron 2005, 24, 1325)에 보고된 방법을 따라 합성하였다. 상기 화학식 6a로 표시되는 안사-메탈로센 촉매 대신에 하기 화학식 8로 표시되는 안사-메탈로센 촉매를 사용한 것을 제외하고는, 실시예 4와 동일한 방법으로 66.5 g의 올리고머를 얻었다(활성: 6,638 Kg/mol.cat·hr, 전환율: 18.6%). 제조된 올레핀 올리고머의 simdis-GC 분석 결과를 도 9 및 표 1에 나타내었다. 분석 결과, simdis-GC 분석 결과 10량체 이상이 64.5%인 중합도가 매우 높은 화합물 위주로 생성됨을 확인하였다.Compound represented by the following formula (8) was synthesized according to the method reported in the literature (Polyhedron 2005, 24, 1325). 66.5 g of an oligomer was obtained in the same manner as in Example 4, except that the ansa-metallocene catalyst represented by the following Formula 8 was used instead of the ansa-metallocene catalyst represented by the above Formula 6a (activity: 6,638 Kg / mol. Cat hr, conversion: 18.6%). Simdis-GC analysis of the prepared olefin oligomer is shown in Figure 9 and Table 1. As a result of the analysis, simdis-GC analysis showed that the above-mentioned dimers were produced mainly with a very high degree of polymerization of 64.5%.
[화학식 8][Formula 8]
Figure PCTKR2014012056-appb-I000024
Figure PCTKR2014012056-appb-I000024
표 1
2량체 (%) 3량체 (%) 4량체 (%) 5량체 (%) 6량체 (%) 7량체 (%) 8량체 (%) 9량체 (%) 10량체 이상 (%)
실시예 3 13.3 14.3 11.3 9.5 7.8 7.2 6.2 5.2 25.2
실시예 4 13.1 14.1 11.8 10.0 8.7 7.5 5.9 5.5 23.4
실시예 5 17.0 18.4 13.9 11.1 9.0 7.1 5.4 4.6 13.5
비교예 1 54.8 26.2 10.5 4.6 2.1 0.8 1.0 0 0
비교예 2 33.3 26.8 16.1 8.9 5.0 3.7 2.2 1.3 2.7
비교예 3 2.0 5.3 4.0 5.4 5.6 5.6 5.1 4.7 62.3
비교예 4 9.6 7.0 4.0 2.6 2.3 3.3 3.0 3.7 64.5
Table 1
Dimer (%) Terpolymer (%) Tetramer (%) Pentamer (%) Hexamer (%) Tetramer (%) Octomer (%) N-mer (%) More than 10 dimers (%)
Example 3 13.3 14.3 11.3 9.5 7.8 7.2 6.2 5.2 25.2
Example 4 13.1 14.1 11.8 10.0 8.7 7.5 5.9 5.5 23.4
Example 5 17.0 18.4 13.9 11.1 9.0 7.1 5.4 4.6 13.5
Comparative Example 1 54.8 26.2 10.5 4.6 2.1 0.8 1.0 0 0
Comparative Example 2 33.3 26.8 16.1 8.9 5.0 3.7 2.2 1.3 2.7
Comparative Example 3 2.0 5.3 4.0 5.4 5.6 5.6 5.1 4.7 62.3
Comparative Example 4 9.6 7.0 4.0 2.6 2.3 3.3 3.0 3.7 64.5
물성 평가 방법Property evaluation method
(1) 활성(단위: Kg(알파-올레핀 올리고머)/mol.catal(Zr)·hr): 얻어진 알파-올레핀 올리고머의 질량을 측정하여 투입한 촉매 양으로 나눈 값. (1) Activity (unit: Kg (alpha-olefin oligomer) /mol.catal (Zr) .hr): The value obtained by dividing the amount of the obtained alpha-olefin oligomer by the amount of catalyst added.
(2) 전환율(단위: %): 얻어진 알파-올레핀 올리고머의 질량/투입한 알파-올레핀 질량(2) Conversion rate (unit:%): mass of alpha-olefin oligomer obtained / mass of alpha-olefin injected
(3) 올리고머 분포 데이터: sidmis(stimulated distillation) GC(gas chromatography)를 사용하여 측정.(3) Oligomer distribution data: measured using sidmis (stimulated distillation) GC (gas chromatography).
상기 표 1의 결과로부터, 1-데센 또는 1-옥텐과 같은 알파-올레핀 중합 시, 본 발명에 따른 화학식 1 구조의 메탈로센 촉매를 사용할 경우, 윤활유 용도에 적합한 중합도를 갖는 3-5량체 위주의 올리고머가 주요 성분으로 형성됨을 알 수 있다.From the results of Table 1, when the alpha-olefin polymerization such as 1-decene or 1-octene, when the metallocene catalyst of the formula (1) according to the present invention is used, it is mainly a 3-5-mer having a degree of polymerization suitable for lubricating oil applications It can be seen that the oligomer of is formed as a main component.
반면, 브릿지 안된 촉매(비교예 1 및 2)을 사용할 경우, 2-3당량체 위주의 중합도가 매우 낮은 올리고머가 얻어지고, ansa-메탈로센 화합물의 대표격인 (EBI)ZrCl2(비교예 3)을 사용할 경우, 10량체 이상이 주요 성분인 중합도가 높은 화합물이 생성되어, 윤활유 용도로 사용하기에 적합하지 않음을 알 수 있다. 또한, 촉매의 구조가 상기 화학식 6i와 같이 알파-위치에 치환체를 갖지 않을 경우(비교예 4), 활성이 낮아(화학식 6a 촉매의 1/3 수준) 상업 공정 투입에 적당하지 않음을 알 수 있다. On the other hand, when unbridged catalysts (Comparative Examples 1 and 2) were used, oligomers having a very low degree of polymerization of 2-3 equivalents were obtained, and (EBI) ZrCl 2 (Comparative Example 3), which is representative of ansa-metallocene compound, was obtained. In the case of using, it is understood that a compound having a high degree of polymerization, in which more than 10 dimers is a main component, is produced and is not suitable for use in lubricating oil applications. In addition, when the structure of the catalyst does not have a substituent in the alpha-position as shown in Formula 6i (Comparative Example 4), it can be seen that the activity is low (about 1/3 of the formula 6a catalyst) is not suitable for commercial process input. .
이와 같이, 실시예 및 비교예로부터, 본 발명의 촉매와 같이, 사이클로펜타디에닐 리간드의 알파-위치에만 치환체를 도입하는 것이 중합도 조절 및 고활성 구현에 매우 중요함을 확인하였다.Thus, from the examples and comparative examples, it was confirmed that, like the catalyst of the present invention, introducing a substituent only at the alpha-position of the cyclopentadienyl ligand is very important for the degree of polymerization control and high activity implementation.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (8)

  1. 하기 화학식 1로 표시되는 안사-메탈로센 화합물, 및 조촉매 화합물을 포함하는 촉매 조성물과 탄소수 6 내지 20의 알파-올레핀 단량체를 접촉시키는 것을 특징으로 하는 알파-올레핀 올리고머의 제조방법:A method for preparing an alpha-olefin oligomer, comprising contacting an alpha-olefin monomer having 6 to 20 carbon atoms with a catalyst composition comprising an ansa-metallocene compound represented by Formula 1 and a promoter compound:
    [화학식 1][Formula 1]
    Figure PCTKR2014012056-appb-I000025
    Figure PCTKR2014012056-appb-I000025
    상기 화학식 1에서, M은 주기율표의 4족 전이금속이고, R은 각각 독립적으로 탄소수 1 내지 20의 탄화수소기이고, B는 탄소수 1 내지 20의 알킬렌기, 탄소수 6 내지 20의 아릴렌기, 탄소수 1 내지 20의 디알킬실리콘, 탄소수 1 내지 20의 디알킬게르마늄, 탄소수 1 내지 20의 알킬포스핀기 또는 탄소수 1 내지 20의 알킬아민기이고, Q는 할로겐 원자, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 2 내지 20의 알키닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 40의 알킬아릴기, 탄소수 7 내지 40의 아릴알킬기, 탄소수 1 내지 20의 알킬아미도기, 탄소수 6 내지 20의 아릴아미도기, 또는 탄소수 1 내지 20의 알킬리덴기이다.In Formula 1, M is a Group 4 transition metal of the periodic table, each R is independently a hydrocarbon group of 1 to 20 carbon atoms, B is an alkylene group of 1 to 20 carbon atoms, an arylene group of 6 to 20 carbon atoms, 1 to C carbon 20 is a dialkylsilicone, a dialkylgerium having 1 to 20 carbon atoms, an alkylphosphine group having 1 to 20 carbon atoms, or an alkylamine group having 1 to 20 carbon atoms, and Q is a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 2 to 20 carbon atoms. Alkenyl group, alkynyl group of 2 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, alkylaryl group of 7 to 40 carbon atoms, arylalkyl group of 7 to 40 carbon atoms, alkyl amido group of 1 to 20 carbon atoms, 6 to 20 carbon atoms Or an arylamido group or an alkylidene group having 1 to 20 carbon atoms.
  2. 제1항에 있어서, 상기 조촉매 화합물은 하기 화학식 2로 표시되는 화합물, 하기 화학식 3으로 표시되는 화합물, 및 하기 화학식 4 또는 5로 표시되는 화합물 중 1종 이상을 포함하는 것을 특징으로 하는 알파-올레핀 올리고머의 제조방법:The alpha-catalyst of claim 1, wherein the cocatalyst compound comprises at least one of a compound represented by Formula 2, a compound represented by Formula 3, and a compound represented by Formula 4 or 5 below. Process for preparing olefin oligomers:
    [화학식 2][Formula 2]
    Figure PCTKR2014012056-appb-I000026
    Figure PCTKR2014012056-appb-I000026
    상기 화학식 2에서, R21은 각각 독립적으로 할로겐 원자, 탄소수 1 내지 20의 탄화수소기, 또는 탄소수 1 내지 20의 할로겐으로 치환된 탄화수소기이며, a는 2 이상의 정수이다;In Formula 2, R 21 is each independently a hydrocarbon atom substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen group having 1 to 20 carbon atoms, and a is an integer of 2 or more;
    [화학식 3][Formula 3]
    D(R31)3 D (R 31 ) 3
    상기 화학식 3에서, D는 알루미늄 또는 보론이며, R31은 각각 독립적으로 할로겐 원자, 탄소수 1 내지 20의 탄화수소기, 탄소수 1 내지 20의 할로겐으로 치환된 탄화수소기, 또는 탄소수 1 내지 20의 알콕시기이다;In Formula 3, D is aluminum or boron, and R 31 is each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. ;
    [화학식 4][Formula 4]
    [L-H]+[Z(A)4]- [LH] + [Z (A) 4 ] -
    [화학식 5][Formula 5]
    [L]+[Z(A)4]- [L] + [Z (A) 4 ] -
    상기 화학식 4 및 5에서, L은 중성 또는 양이온성 루이스 산이고, Z는 원소 주기율표의 13족 원소이고, A는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기 또는 치환 또는 비치환된 탄소수 1 내지 20의 알킬기이다.In Formulas 4 and 5, L is a neutral or cationic Lewis acid, Z is a Group 13 element of the Periodic Table of the Elements, A is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted each independently It is a C1-C20 alkyl group.
  3. 제1항에 있어서, 상기 안사-메탈로센 화합물은 하기 화학식 6으로 표시되는 안사-메탈로센 화합물인 것을 특징으로 하는 알파-올레핀 올리고머의 제조방법:The method of claim 1, wherein the ansa-metallocene compound is an ansa-metallocene compound represented by the following Chemical Formula 6.
    [화학식 6][Formula 6]
    Figure PCTKR2014012056-appb-I000027
    Figure PCTKR2014012056-appb-I000027
    상기 화학식 6에서, R1은 각각 독립적으로 페닐기 또는 tert-부틸기이고, R2 및 R3는 각각 독립적으로 탄소수 1 내지 5의 알킬기이며, Q1 및 Q2는 각각 독립적으로 할로겐 원자, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 2 내지 20의 알키닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 40의 알킬아릴기, 탄소수 7 내지 40의 아릴알킬기, 탄소수 1 내지 20의 알킬아미도기, 탄소수 6 내지 20의 아릴아미도기, 또는 탄소수 1 내지 20의 알킬리덴기이다.In Chemical Formula 6, R 1 is each independently a phenyl group or a tert-butyl group, R 2 and R 3 are each independently an alkyl group having 1 to 5 carbon atoms, and Q 1 and Q 2 are each independently a halogen atom and 1 carbon atom. An alkyl group of 20 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms, an arylalkyl group of 7 to 40 carbon atoms, and 1 to 20 carbon atoms An alkylamido group, an arylamido group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms.
  4. 제3항에 있어서, 상기 안사-메탈로센 화합물은 하기 화학식 6a로 표시되는 화합물, 하기 화학식 6b로 표시되는 화합물 중 1종 이상을 포함하는 것을 특징으로 하는 알파-올레핀 올리고머의 제조방법:The method of claim 3, wherein the ansa-metallocene compound comprises at least one of a compound represented by Formula 6a and a compound represented by Formula 6b:
    [화학식 6a][Formula 6a]
    Figure PCTKR2014012056-appb-I000028
    Figure PCTKR2014012056-appb-I000028
    [화학식 6b][Formula 6b]
    Figure PCTKR2014012056-appb-I000029
    Figure PCTKR2014012056-appb-I000029
    상기 화학식 6a 및 6b에서, Q1 및 Q2는 상기 화학식 6에서 정의한 바와 같다.In Chemical Formulas 6a and 6b, Q 1 and Q 2 are the same as defined in Chemical Formula 6.
  5. 제1항에 있어서, 상기 알파-올레핀 단량체는 1-옥텐, 1-데센, 또는 1-도데센인 것을 특징으로 하는 알파-올레핀 올리고머의 제조방법.The method of claim 1, wherein the alpha-olefin monomer is 1-octene, 1-decene, or 1-dodecene.
  6. 하기 화학식 6으로 표시되는 안사-메탈로센 화합물:Ansa-metallocene compound represented by the following formula (6):
    [화학식 6][Formula 6]
    Figure PCTKR2014012056-appb-I000030
    Figure PCTKR2014012056-appb-I000030
    상기 화학식 6에서, R1은 각각 독립적으로 페닐기 또는 tert-부틸기이고, R2 및 R3는 각각 독립적으로 탄소수 1 내지 5의 알킬기이며, Q1 및 Q2는 각각 독립적으로 할로겐 원자, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 2 내지 20의 알키닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 40의 알킬아릴기, 탄소수 7 내지 40의 아릴알킬기, 탄소수 1 내지 20의 알킬아미도기, 탄소수 6 내지 20의 아릴아미도기, 또는 탄소수 1 내지 20의 알킬리덴기이다.In Chemical Formula 6, R 1 is each independently a phenyl group or a tert-butyl group, R 2 and R 3 are each independently an alkyl group having 1 to 5 carbon atoms, and Q 1 and Q 2 are each independently a halogen atom and 1 carbon atom. An alkyl group of 20 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms, an arylalkyl group of 7 to 40 carbon atoms, and 1 to 20 carbon atoms An alkylamido group, an arylamido group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms.
  7. 제6항에 있어서, 상기 안사-메탈로센 화합물은 하기 화학식 6a로 표시되는 화합물 또는 화학식 6b로 표시되는 화합물인 것을 특징으로 하는 안사-메탈로센 화합물:The ansa-metallocene compound according to claim 6, wherein the ansa-metallocene compound is a compound represented by Formula 6a or a compound represented by Formula 6b:
    [화학식 6a][Formula 6a]
    Figure PCTKR2014012056-appb-I000031
    Figure PCTKR2014012056-appb-I000031
    [화학식 6b][Formula 6b]
    Figure PCTKR2014012056-appb-I000032
    Figure PCTKR2014012056-appb-I000032
    상기 화학식 6a 및 6b에서, Q1 및 Q2는 상기 화학식 6에서 정의한 바와 같다.In Chemical Formulas 6a and 6b, Q 1 and Q 2 are the same as defined in Chemical Formula 6.
  8. 하기 화학식 7로 표시되는 화합물, 및 디메톡시에탄이 배위된 ZrCl2를 반응시키는 단계를 포함하는 하기 화학식 6으로 표시되는 안사-메탈로센 촉매의 제조방법:Method for preparing an ansa-metallocene catalyst represented by the following formula (6) comprising the step of reacting a compound represented by the formula (7), and ZrCl 2 coordinated with dimethoxyethane:
    [화학식 6][Formula 6]
    Figure PCTKR2014012056-appb-I000033
    Figure PCTKR2014012056-appb-I000033
    상기 화학식 6에서, R1은 각각 독립적으로 페닐기 또는 tert-부틸기이고, R2 및 R3는 각각 독립적으로 탄소수 1 내지 5의 알킬기이며, Q1 및 Q2는 각각 독립적으로 할로겐 원자, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 2 내지 20의 알키닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 40의 알킬아릴기, 탄소수 7 내지 40의 아릴알킬기, 탄소수 1 내지 20의 알킬아미도기, 탄소수 6 내지 20의 아릴아미도기, 또는 탄소수 1 내지 20의 알킬리덴기이다;In Chemical Formula 6, R 1 is each independently a phenyl group or a tert-butyl group, R 2 and R 3 are each independently an alkyl group having 1 to 5 carbon atoms, and Q 1 and Q 2 are each independently a halogen atom and 1 carbon atom. An alkyl group of 20 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms, an arylalkyl group of 7 to 40 carbon atoms, and 1 to 20 carbon atoms An alkylamido group, an arylamido group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms;
    [화학식 7][Formula 7]
    Figure PCTKR2014012056-appb-I000034
    Figure PCTKR2014012056-appb-I000034
    상기 화학식 4에서, R1, R2 및 R3는 상기 화학식 1에서 정의한 바와 같다.In Formula 4, R 1 , R 2 and R 3 are as defined in Formula 1.
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