WO2015056974A1 - Method for producing hybrid-supported metallocene catalyst - Google Patents

Method for producing hybrid-supported metallocene catalyst Download PDF

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WO2015056974A1
WO2015056974A1 PCT/KR2014/009680 KR2014009680W WO2015056974A1 WO 2015056974 A1 WO2015056974 A1 WO 2015056974A1 KR 2014009680 W KR2014009680 W KR 2014009680W WO 2015056974 A1 WO2015056974 A1 WO 2015056974A1
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group
substituted
aryl
compound
alkyl
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PCT/KR2014/009680
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French (fr)
Korean (ko)
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홍대식
권헌용
송은경
이용호
조경진
이기수
최이영
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주식회사 엘지화학
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Priority claimed from KR1020140138347A external-priority patent/KR101631700B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2016518114A priority Critical patent/JP6247751B2/en
Priority to EP14853376.3A priority patent/EP3040124B1/en
Priority to US15/029,196 priority patent/US9902789B2/en
Publication of WO2015056974A1 publication Critical patent/WO2015056974A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged

Definitions

  • the present invention relates to a method for preparing a common supported metallocene catalyst. More particularly, the present invention relates to a method for preparing a common supported metallocene catalyst which can be used for preparing an olefin polymer.
  • the metallocene catalyst is composed of a combination of a main catalyst composed mainly of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum, and such a catalyst is a single site catalyst as a homogeneous complex catalyst.
  • the polymer has a narrow molecular weight distribution according to the characteristics of a single active site and a homogeneous composition of the comonomer, and the stereoregularity, copolymerization characteristics, molecular weight, It has the property to change the crystallinity.
  • U. S. Patent No. 5,032, 562 describes a process for preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. It is a method of producing a bimodal distribution polymer by supporting a titanium (Ti) -based Ziegler-Natta catalyst generating high molecular weight and a zirconium (Zr) -based metallocene catalyst generating low molecular weight on one support. As a result, the supporting process is complicated, and the morphology of the polymer is deteriorated due to the promoter.
  • Ti titanium
  • Zr zirconium
  • 5,525,678 describes a method of using a catalyst system for olefine polymerization in which a high molecular weight polymer and a low molecular weight polymer can be simultaneously polymerized by simultaneously supporting a metallocene compound and a nonmetallocene compound on a carrier. . It is a metallocene compound and a nonmetallocene . There is a disadvantage in that the compounds must be supported separately, and the carrier must be pretreated with various compounds for supporting reaction.
  • U.S. Patent No. 5,914,289 describes a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount of solvent used and the time required for preparing the supported catalyst are high. The hassle of having to support the metallocene catalyst to be used on the carrier, respectively.
  • Korean Patent Application No. 2003-12308 discloses a method of controlling the molecular weight distribution by supporting a double-nucleated metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing the combination of catalysts in the reactor. have.
  • this method is limited in realizing the characteristics of each catalyst at the same time, and also has a disadvantage in that the metallocene catalyst portion is liberated in the carrier component of the finished catalyst, causing fouling.
  • the present invention is to provide a method for producing a common supported metallocene catalyst that can be produced an olefin polymer having excellent activity, high molecular weight and desired physical properties.
  • the first cocatalyst compound, the first metallocene compound, and the second metallocene It provides a method for preparing a common supported metallocene catalyst comprising the step of supporting a second cocatalyst compound on a carrier on which the compound is supported.
  • the common supported metallocene catalyst obtained according to the production method of the present invention includes two or more different metallocene compounds, and in particular, one metallocene compound is an indeno indole derivative and / or flu
  • one metallocene compound is an indeno indole derivative and / or flu
  • a ligand compound in which an fluorene derivative forms a crosslinked structure by a bridge it exhibits high polymerization activity even when supported, and is excellent in activity, and can be used for polymerization of an ultra high molecular weight olefin polymer.
  • A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 C20 alkoxyalkyl group, C3 to C20 heterocycloalkyl group, or C5 to C20 heteroaryl group;
  • D is -0-, -S-, -N (R)-or -Si (R) (R, wherein R and R 'are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group , An alkenyl group of C2 to C20, or an aryl group of C6 to C20;
  • L is a C1 to C10 straight or branched chain alkylene group
  • B is carbon, silicon. Or germanium
  • Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group;
  • M is a Group 4 transition metal
  • X 1 and X 2 are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
  • C 1 and C 2 are the same as or different from each other, and are each independently represented by one of the following Chemical Formula 2a, Chemical Formula 2b, or Chemical Formula 2c, except that both C 1 and C 2 are Chemical Formula 2c;
  • Rl to R17 and Rl 'to R9' are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group of C1 to C20, an alkenyl group of C2 to C20, and an alkyl of C1 to C20.
  • Silyl group C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, Two or more adjacent to each other of R10 to R17 may be linked to each other to form a substituted or unsubstituted aliphatic or aromatic ring; .
  • M 1 is a Group 4 transition metal
  • Cp 1 and Cp 2 are the same as or different from each other, and each independently Cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1 -indenyl, and fluorenyl radicals, and any one selected from the group consisting of hydrocarbons having 1 to 20 carbon atoms, ;
  • R a and R b are the same as or different from each other, and each independently hydrogen, C 1 to C 20 alkyl, C 1 to C 10 alkoxy, C 2 to C 20 alkoxyalkyl, C 6 to C 20 aryl, C 6 to C 10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
  • Z 1 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , Substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
  • n 1 or 0;
  • M 2 is a Group 4 transition metal
  • Cp 3 and Cp 4 are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals They may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
  • R c and R d are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 To alkenyl of C20, alkylaryl of C7 to C40, arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;
  • Z 2 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene Or a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
  • B 1 is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp 3 R c ring with the Cp 4 R d ring or crosslinks one Cp 4 R d ring with M 2 Or a combination thereof;
  • n 1 or 0;
  • M 3 is a Group 4 transition metal
  • Cp 5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which are substituted with hydrocarbons having 1 to 20 carbon atoms Can be;
  • R e is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl C7-C40 arylalkyl, C8-C40 arylalkenyl, or C2-C10 alkynyl;
  • Z 3 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene A substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
  • B 2 is at least one or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp 5 R e ring and J;
  • J is any one selected from the group consisting of NR f , 0, PR f and S, wherein R f is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl.
  • the C1 to C20 alkyl group includes a linear or branched alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nucleosil group, heptyl group, An octyl group etc. are mentioned, but it is not limited to this.
  • the alkenyl group of Q to C20 includes a straight or branched alkenyl group, and specifically, an allyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like But it is not limited thereto.
  • the C6 to C20 aryl group includes a monocyclic or condensed aryl group, and specifically includes a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like, but is not limited thereto.
  • the C5 to C20 heteroaryl group includes a monocyclic or condensed heteroaryl group, and includes a carbazolyl group, a pyridyl group, a quinoline group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, a thiazolyl group , Triazine group, tetrahydropyranyl group, tetrahydrofuranyl group and the like, but are not limited thereto.
  • alkoxy group for C 1 to C 20 examples include a methoxy group, an hydroxy group, a phenyloxy group, a cyclonuxyloxy group, and the like, but are not limited thereto.
  • Group 4 transition metal examples include titanium, zirconium, and hafnium, but are not limited thereto.
  • R1 to R17 and R1 'to R9' of Formulas 2a, 2b and 2c are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nucleosil group, heptyl group, octyl group, phenyl group, halogen group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl
  • the group, trimethylsilylmethyl group, mesophilic group, or hydroxy group is more preferable, but is not limited thereto.
  • L of Formula 1 is more preferably a straight or branched chain alkylene group of C4 to C8, but is not limited thereto.
  • the alkylene group is C1 to
  • An alkyl group of C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20 may be substituted or unsubstituted.
  • a in Formula 1 is hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, methoxymethyl, tert-butoxymethyl, 1-ethoxyethyl, 1-methyl It is preferable that it is a 1- methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group, but it is not limited to this.
  • B of Formula 1 is preferably silicon, but is not limited thereto.
  • the first metallocene compound of Formula 1 is indeno indole Derivatives and / or fluorene derivatives form a crosslinked structure by the bridge, and have a non-covalent electron pair that can act as a Lewis base in the ligand structure, so that it is supported on the surface having the Lewis acid characteristics of the carrier and is highly supported. It shows polymerization activity.
  • the activity is high, and due to the proper steric hindrance and the electronic effect of the ligand, the hydrogen reaction is low and high activity is maintained even in the presence of hydrogen. .
  • the beta-hydrogen of the polymer chain in which the nitrogen atom of the indeno indole derivative is grown is stabilized by hydrogen bonding, thereby inhibiting beta-hydrogen elimination, thereby polymerizing ultra high molecular weight olepin-based polymer.
  • specific examples of the compound represented by Chemical Formula 2a may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.
  • specific examples of the compound represented by Chemical Formula 2b may include a compound represented by one of the following structural formulas.
  • specific examples of the compound represented by Chemical Formula 2c may include a compound represented by one of the following structural formulas, but the present invention
  • specific examples of the first metallocene compound represented by Chemical Formula 1 may include a compound represented by one of the following structural formulas,
  • the first metallocene compound of Chemical Formula 1 has excellent activity and may polymerize a high molecular weight olefin-based polymer. In particular, even when used on a carrier, it exhibits high polymerization activity, and thus an ultrahigh molecular weight polyolefin polymer can be prepared.
  • the first metallocene compound of the formula according to the present invention exhibits low hydrogen reaction properties. It is still possible to polymerize ultra high molecular weight olepin-based polymers with high activity. Therefore, even when used in combination with a catalyst having different properties, it is possible to prepare an ' ulrepin-based polymer that satisfies the high molecular weight characteristics without degrading the activity, and thus contains an olefinic polymer of the polymer and has a wide molecular weight distribution. System polymers can be easily produced.
  • the first metallocene compound of Chemical Formula 1 may be prepared by connecting an indenoindole derivative and / or fluorene derivative with a bridge compound to prepare a ligand compound, and then performing metallation by introducing a metal precursor compound. Can be. The manufacturing method of the said 1st metallocene compound is demonstrated to an Example mentioned later.
  • the second metallocene compound may be at least one selected from compounds represented by the following Chemical Formulas 3 to 5.
  • M 1 is a Group 4 transition metal
  • Cp l and Cp 2 are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and pulluorenyl radicals One, they may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
  • R a and R b are the same as or different from each other, and each independently hydrogen, C1 to
  • C20 alkyl C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl Arylalkenyl of C8 to C40, or alkynyl of C2 to C10;
  • Z 1 is a halogen atom, C 1 to C 20 alkyl, C 2 to C 10 alkenyl, C 7 to
  • C40 alkylaryl C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene, substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 aryl Alkoxy;
  • n 1 or 0;
  • M 2 is a Group 4 transition metal
  • Cp 3 and Cp 4 are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals They may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
  • R c and R d are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
  • Z 2 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , Substituted or unsubstituted amino group, C2 Alkylalkoxy to C20 or arylalkoxy of C7 to C40;
  • B 1 is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp 3 R c ring and the Cp 4 R d ring or crosslinks one Cp 4 R d ring with M 2 Or a combination thereof;
  • n 1 or 0;
  • M 3 is a Group 4 transition metal
  • Cp 5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6, gtetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms And;
  • R e is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl , C7-C40 arylalkyl, C8.
  • Z 3 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , Substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
  • B 2 is one or more or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp 5 R e ring and J;
  • J is any one selected from the group consisting of NR f , 0, PR f and S, wherein R f is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl.
  • the compound represented by Chemical Formula 3 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.
  • the compound represented by Chemical Formula 4 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.
  • the compound may be represented, but is not limited thereto.
  • the common supported metallocene catalyst may include at least one of the first metallocene compound represented by Formula 1 and at least one of the second metallocene compound selected from the compounds represented by Formulas 3 to 5. It is commonly supported on the carrier together with all cocatalyst compounds.
  • the first metallocene compound represented by Formula 1 of the common supported metallocene catalyst contributes to making a high molecular weight co-polymer having a high SCB (short chain branch) content, and the second metal represented by Formula 3 Sen compound is mainly low
  • the second metallocene compound represented by Formula 4 or 5 may contribute to making a low molecular weight copolymer having a moderate SCB content.
  • the -commonly supported metallocene catalyst may include at least one first metallocene compound of Formula 1 and at least one second metallocene compound of Formula 3.
  • the common supported metallocene catalyst is In addition to at least one first metallocene compound of formula i and at least one second metallocene compound of formula 3, at least one second metallocene compound of formula 4 or formula 5 may be included. .
  • the first metallocene compound forms a ligand structure in which an indeno indole derivative and a fluorene derivative are crosslinked by a bridge compound, and a Lewis base in the ligand structure.
  • a non-covalent electron pair that can act as a support on the surface having the Lewis acid characteristics of the carrier it shows a high polymerization activity even when supported.
  • it is highly active as it contains an electronically rich indeno indole group and / or fluorene group, and due to proper steric hindrance and the electronic effect of the ligand, the hydrogen reactivity is low and the activity is maintained even in the presence of hydrogen.
  • the common supported metallocene catalyst obtained according to the preparation method of the present invention includes a first metallocene compound represented by Chemical Formula 1 and a second metallocene compound represented by Chemical Formulas 3 to 5, and different from each other.
  • a first metallocene compound represented by Chemical Formula 1 and a second metallocene compound represented by Chemical Formulas 3 to 5, and different from each other.
  • the cocatalyst supported on a carrier for activating the metallocene compound is an organometallic compound containing a Group 13 metal, and a general metallocene catalyst. It will not be specifically limited if it can be used when superposing
  • the cocatalyst compound may include at least one of an aluminum-containing first cocatalyst of Formula 6 and a borate-based second cocatalyst of Formula 7 below.
  • each R 1S is independently halogen, halogen substituted or unsubstituted.
  • T + is a + monovalent polyatomic ion
  • B is boron in the +3 oxidation state
  • G is independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryl oxide group, a hydrocar It is selected from the group consisting of bil group, halocarbyl group and halo-substituted hydrocarbyl group, wherein G has 20 carbons or less, but at one or less positions, G is a halide group.
  • the molecular weight distribution of the finally produced polyolefin can be made more uniform, and the polymerization activity can be improved.
  • the first cocatalyst of Chemical Formula 6 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular, or reticular form.
  • Specific examples of the first cocatalyst include methylaluminoxane (MAO) and ethylalumina. Noxic acid, isobutyl aluminoxane, or butyl aluminoxane etc. are mentioned.
  • the second cocatalyst of Formula 7 may be a borate-based compound in the form of a trisubstituted ammonium salt, or a dialkyl ammonium salt, a trisubstituted phosphonium salt.
  • Such a second cocatalyst include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate , Methyltetracyclooctadecylammonium tetraphenylborate , ⁇ , ⁇ -dimethylanile tetraphenylborate, ⁇ , ⁇ -diethylaninynium tetraphenylborate , ⁇ , ⁇ -dimethyl (2,4,6-trimethylaninium Tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis
  • Tripropylammonium tetrakis (pentafluorophenyl) borate tri ( ⁇ -butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate , ⁇ , ⁇ -dimethylaninium tetrakis (pentafluorophenyl) borate, ⁇ , ⁇ - Diethylaninium tetrakis (pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylaninynium) tetrakis (pentafluorophenyl) borate,
  • the common supported metallocene catalyst as described above may include the steps of: supporting a first cocatalyst compound on a carrier; at least one first metallocene compound represented by the following Formula 1 on a carrier on which the first cocatalyst compound is supported: And supporting at least one second metallocene compound selected from compounds represented by Formulas 3 to 5; And supporting the second cocatalyst compound on a carrier on which the first cocatalyst compound, the first metallocene compound, and the sieve 2 metallocene association " are supported.
  • the first cocatalyst compound represented by Chemical Formula 6 is first supported on the prepared carrier.
  • the first metallocene compound and the second metallocene compound are supported on the carrier on which the first cocatalyst compound is supported.
  • the supporting order between the first and second metallocene compounds is not limited, and the first metallocene compound may be first supported or the second metallocene compound may be first supported.
  • all of the first cocatalyst compound, the first metallocene compound, and the second metallocene compound are supported.
  • the carrier carries the second cocatalyst compound represented by the formula (7).
  • the first supported promoter compound is reacted with the hydroxy group on the surface of the carrier in advance.
  • it can help to prepare a uniform catalyst by acting as a scavenger for impurities such as moisture and catalyst foreign matter. Accordingly, the possibility of deactivating the first and second metallocene catalysts supported after the supporting of the first cocatalyst compound can be reduced, thereby preparing a supported catalyst having high activity.
  • the total transition metal to the carrier contained in the first metallocene compound represented by Formula 1 and the second metallocene compound represented by Formulas 3 to 5 The mass ratio may be 1:10 to 1: 1.000.
  • the carrier and the metallocene compound are included in the mass ratio, the optimum shape can be exhibited.
  • the mass ratio of the promoter compound to the carrier may be from 1: 1 to 1: 100.
  • the mass ratio of the first metallocene compound represented by Formula 1 to the second metallocene compound represented by Formulas 3 to 5 is 10: 1 to 1:10, preferably 5: 1 to 1: 5 days. have.
  • a carrier containing a hydroxyl group on the surface may be used, and preferably, a semi-astringent hydride is dried to remove moisture from the surface.
  • the carrier which has a hydroxy group and a siloxane group can be used.
  • silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, which are typically oxides, carbonates, such as Na 2 O, K 2 C0 3 , BaS0 4 , and Mg (N0 3 ) 2 , Sulfate, and nitrate components.
  • the drying temperature of the carrier is preferably 200 to 800 ° C., more preferably 300 to 600 ° C., most preferably 300 to 400 ° C.
  • the drying temperature of the carrier is less than 200 ° C, there is too much moisture to react with the surface moisture and the promoter, and when it exceeds 80 CTC, the surface area decreases as the pores on the surface of the carrier are combined, and more hydroxyl groups are present on the surface. Disappear and only siloxane remains, and with the promoter It is not desirable because the reaction sign is reduced.
  • the amount of hydroxy groups on the surface of the carrier is preferably 0.1 to 10 mmol / g, more preferably 0.5 to 5 mmol / g.
  • the amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions such as silver, time, vacuum or spray drying.
  • the amount of the hydroxy group is less than 0.1 'mmol / g, the reaction space with the promoter is small, and if the amount of the hydroxy group is more than 10 mmol / g, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. Not.
  • the common supported metallocene catalyst obtained according to the preparation method of the present invention can be used by itself for the polymerization of .lefin-based monomers.
  • the common supported metallocene catalyst according to the present invention may be prepared by using a pre-polymerized catalyst in contact with an olefinic monomer.
  • the catalyst may be used separately from ethylene, propylene, 1-butene, 1-hexene, and 1-octene. It may be prepared and used as a prepolymerized catalyst by contacting with an olefinic monomer such as the like.
  • the order of the step of supporting the first metallocene compound and the step of supporting the second metallocene compound may be changed as necessary. That is, the first metallocene compound is first supported on a carrier, and then the second metallocene compound is further supported to prepare a common supported metallocene catalyst, or the second metallocene compound is supported on the carrier. After supporting first, the common metallocene catalyst may be prepared by further supporting the first metallocene compound.
  • the temperature may be performed at a condition of about 0 to about 100 ° C. and a pressure of normal pressure, but is not limited thereto.
  • the olefinic polymer can be prepared by polymerizing the olefinic monomers.
  • the olefinic monomer may be ethylene, alpha-olefin, cyclic olefin, diene olefin or triene olefin having two or more double bonds.
  • olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-nucleadecene, 1-aitosen, norbornene, norbonadiene, ethylidene norbornene, phenylnorbornene, Vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-nuxadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like. You may mix and copolymerize 2 or more types of these monomers.
  • the polymerization reaction may be carried out by homopolymerization with one olefinic monomer or copolymerization with two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.
  • the common supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, nucleic acid, heptane, nonane, decane, and isomers thereof, and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane and chlorobenzene. It may be dissolved or diluted and injected into a hydrocarbon solvent substituted with a chlorine atom such as.
  • the solvent used herein is preferably used by removing a small amount of water or air, which acts as a catalyst poison, by using a small amount of alkyl aluminum, and may be carried out by further using a promoter.
  • a low molecular weight portion has a wide molecular weight distribution of the BOCD structure having a low SCB content and a high SCB content of the high molecular weight portion.
  • Eggplant can produce an olefin-based polymer.
  • the olefin polymer not only has excellent physical properties but also has excellent workability.
  • olefinic polymers prepared using common supported metallocene catalysts obtained in accordance with the process of the present invention have a high content of at least about 300,000 or at least about 350,000. Increased average molecular weight can be indicated.
  • a broad molecular weight distribution (PDI) of about 3.0 to about 8.0, preferably about 4.0 to about 8.0, more preferably 5.0 to about 8.0 can be seen to show excellent processability.
  • PDI molecular weight distribution
  • the solution was changed to violet color at room temperature overnight.
  • the reaction solution was filtered to remove LiCl.
  • the toluene of the filtrate was removed by vacuum drying, and the nucleic acid was added and sonicated for 1 hour.
  • the slurry was filtered to obtain 6 g of a dark violet metallocene compound (Mw 758.02, 7.92 mmol, yield 66 mol%). Two isomers were observed on 1 H-NMR.
  • t-Butyl-0- (CH 2 ) 6 -C 5 H 5 was dissolved in THF at -78 ° C, and normal butyllithium (n-BuLi) was slowly added, followed by heating to room temperature, followed by an 8 hour reaction. I was. The solution was slowly added to a pre-synthesized lithium salt solution at -78 ° C to a suspension solution of ZrCl 4 (THF) 2 (1.70 g, 4.50 mmol) / THF (30 m) at room temperature. Recoiled for 6 hours more.
  • THF ZrCl 4
  • 6-t-butoxynucleic acid (6-t-buthoxyhexane) was confirmed by 1 H-NMR. It can be seen that the Gringanrd reaction progressed well from the 6 ′ t-subspecific nucleic acid. Thus 6-t-buthoxyhexyl magnesium chloride was synthesized.
  • the reaction temperature was adjusted to -20 ° C.
  • 560 g of the synthesized 6-t-subsilicate magnesium chloride was added to the reaction vessel at a rate of 5 mL / min using a feeding pump. After feeding the Grignard reagent, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours, it was confirmed that a white MgCl 2 salt was produced.
  • 4 L of nucleic acid was added to remove the salt through a labdori to obtain a filter solution. After adding the obtained filter solution to the reactor, the nucleic acid was removed at 70 ° C to obtain a pale yellow liquid.
  • the yellow solution obtained was identified as methyl (6-t-butoxynucleosil) (tetramethyl CpH) t-butylaminosilane (Methyl (6-t-buthoxyhexyl) (tetramethylCpH) t-Butylaminosilane) compound by 1 H-NMR. .
  • TiCl 3 (THF) 3 (10 mmol) was rapidly added to the dilithium salt of 8 ° C ligand synthesized from (Dirnethyl (tetramethylCpH) t-Butylaminosilane) in THF solution.
  • the reaction solution was stirred for 12 hours while slowly raising the temperature to -78 ° C.
  • an equivalent amount of PbCl 2 (10 mmol) was added to the semi-aqueous solution in silver, followed by stirring for 12 hours. After stirring for 12 hours, the blue vagina obtained a black solution.
  • nucleic acid was added to filter the product.
  • Silica (SYLOPOL 948, manufactured by Grace Davison) was dehydrated under vacuum at a temperature of 400 ° C. for 15 hours.
  • the supported catalyst was prepared in the same manner as in Example 1, except that 0.25 mmd of the metallocene catalyst of Preparation Example 2 was used instead of 0.25 mmol of the metallocene catalyst of Preparation Example 1 in Example 1.
  • Example 3
  • Example 4 After 1 hour of 0.25 mmol reaction of the metallocene catalyst of Preparation Example 1 in Example 1 was completed, the reaction of 0.25 mmol of the metallocene catalyst of Preparation Example 4 was further performed. Thereafter, the metallocene catalyst 0.25 of Preparation Example 3. The supported catalyst was prepared in the same manner except that the mmol reaction was carried out.
  • Example 4
  • the supported catalyst was prepared in the same manner as in Example 3, except that 0.25 mmol reaction of the metallocene catalyst of Preparation Example 2 was used instead of 0.25 mmol of the metallocene catalyst of Preparation Example 1 initially reacted.
  • Example 5
  • Example 2 instead of 0.25 mmol of the metallocene catalyst of Preparation Example 1, which was initially reacted in Example 3, 0.25 mmol of the metallocene catalyst of Preparation Example 2 was first performed. Thereafter, 0.25 mmol of the metallocene catalyst of Preparation Example 1 was used as the second catalyst, and finally, the supported catalyst was prepared in the same manner except that the metallocene catalyst of Preparation Example 3 was used.
  • Comparative Example 1 10 g of dried silica is placed in a glass reactor, and 100 ml of toluene is added and stirred. 50 mL of 10 wt% methylaluminoxane (MAO) / luene solution was added thereto, followed by slow reaction at 40 ° C.
  • MAO wt% methylaluminoxane
  • the supported catalyst was prepared in the same manner except that 0.25 mmol reaction of the metallocene catalyst of Preparation Example 4 was used instead of 0.25 mmol of the metallocene catalyst of Preparation Example 3, which was initially reacted in Comparative Example 1. Comparative Example 3
  • the supported catalyst was prepared in the same manner as in Comparative Example 3, except that 1.0 mmol of anilinium borate ( ⁇ , ⁇ -dimethylanilinium tetrakis (pentafluorophenyl) borate, AB) was finally added.
  • the polymer obtained therefrom was filtered off to remove most of the polymerization solvent and then dried in an 80 " C vacuum oven for 4 hours.
  • Examples 1 to 5 for the common supported catalyst of the present invention include two or more metallocene compounds, but have a much higher activity than the comparative example including only a single catalyst or a second metallocene compound. It can be seen that a polymer having a high molecular weight and a broad molecular weight distribution can be prepared.

Abstract

The present invention relates to a method for producing a hybrid-supported metallocene catalyst. More specifically, the method for producing a hybrid-supported metallocene catalyst uses two mutually different types of metallocene compounds, the one type of metallocene compound thereamong exhibiting high polymeric activity even when supported, and thus having superb activity and capable of being used to polymerize olefin-based polymer having ultra-high molecular weight. The hybrid-supported metallocene catalyst obtained by means of the production method according to the present invention can produce an olefin-based polymer having a high molecular weight and other desirable properties.

Description

【명세세  [Specifications
【발명의 명칭】  [Name of invention]
흔성 담지 메탈로센 촉매의 제조방법  Process for preparing common supported metallocene catalyst
【기술분야】  Technical Field
본 발명은 흔성 담지 메탈로센 촉매의 제조방법에 관한 것이다. 보다 상세하게는 올레핀계 중합체 제조에 사용될 수 있는 흔성 담지 메탈로센 촉매의 제조방법에 관한 것이다.  The present invention relates to a method for preparing a common supported metallocene catalyst. More particularly, the present invention relates to a method for preparing a common supported metallocene catalyst which can be used for preparing an olefin polymer.
본 출원은 2013년 10월 18일에 한국특허청에 제출된 한국 특허 출원 제 10-2013-0124517호 및 2014년 10월 14일에 한국특허청에 제출된 한슥 특허 출원 제 10-2014-0138347호의 출원일의 이익을 주장하며， 그 내용 전부는 본 명세서에 포함된다.  This application is for the date of filing of Korean Patent Application No. 10-2013-0124517 filed with the Korean Patent Office on October 18, 2013 and Korean Patent Application No. 10-2014-0138347 filed with the Korean Patent Office on October 14, 2014. Claiming benefit, the entire contents of which are incorporated herein.
【배경기술】  Background Art
을레핀 중합 촉매계는 지글러 나타 및 메탈로센 촉매계로 분류할 수 있으며， 이 두 가지의 고활성 촉매계는 각각의 특징에 맞게 발전되어 왔다. 지글러 나타 촉매는 50년대 발명된 이래 기존의 상업 프로세스에 널리 적.용되어 왔으나, 활성점이 여러 개 흔재하는 다활성점 촉매 (multi site catalyst)이기 때문어)， 중합체의 분자량 분포가 넓은 것이 특징이며， 공단량체의 조성 분포가 균일하지 않아 원하는 물성 확보에 한계가 있다는 문제점이 있다. Ellefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed for their respective characteristics. Ziegler-Natta catalysts have been widely used in conventional commercial processes since they were invented in the 50s . Has been used, but the active site is a multi-site catalyst (multi-site catalyst) is common, characterized by a wide molecular weight distribution of the polymer, and because the composition of the comonomer is not uniform distribution, there is a limit in securing the desired physical properties There is a problem.
한편, 메탈로센 촉매는 전이금속 화합물이 주성분인 주촉매와 알루미늄이 주성분인 유기 금속 화합물인 조촉매의 조합으로 이루어지며， 이와 같은 촉매는 균일계 착체 촉매로 단일 활성점 촉매 (single site catalyst)이며, 단일 활성점 특성에 따라 분자량 분포가 좁으며, 공단량체의 조성 분포가 균일한 고분자가 얻어지며， 촉매의 리간드 구조 변형 및 중합 조건의 변경에 따라 고분자의 입체 규칙도, 공중합 특성, 분자량, 결정화도 등을 변화시킬 수 있는 특성을 가지고 있다.  On the other hand, the metallocene catalyst is composed of a combination of a main catalyst composed mainly of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum, and such a catalyst is a single site catalyst as a homogeneous complex catalyst. The polymer has a narrow molecular weight distribution according to the characteristics of a single active site and a homogeneous composition of the comonomer, and the stereoregularity, copolymerization characteristics, molecular weight, It has the property to change the crystallinity.
미국 특허 제 5,032,562호에는 두 개의 상이한 전이금속 촉매를 한 개의 담지 촉매 상에 지지시켜 중합 촉매를 제조하는 방법이 기재되어 있다. 이는 고분자량을 생성하는 티타늄 (Ti) 계열의 지글러 -나타 촉매와 저분자량을 생성하는 지르코늄 (Zr) 계열의 메탈로센 촉매를 하나의 지지체에 담지시켜 이정 분산 (bimodal distribution) 고분자를 생성하는 방법으로써， 담지 과정이 복잡하고, 조촉매로 인해 중합체의 형상 (morphology)이 나빠지는 단점이 있다. 미국 특허 제 5,525,678호에는 메탈로센 화합물과 비메탈로센 화합물을 담체 위에 동시에 담지시켜 고분자량의 중합체와 저분자량의 중합체가 동시에 중합될 수 있는 을레핀 중합용 촉매계를 사용하는 방법을 기재하고 있다. 이는 메탈로센 화합물과 비메탈로센. 화합물들을 각각 따로 담지시켜야 하고, 담지 반웅을 위해 담체를 여러 가지 화합물로 전처리해야 하는 단점이 있다. U. S. Patent No. 5,032, 562 describes a process for preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. It is a method of producing a bimodal distribution polymer by supporting a titanium (Ti) -based Ziegler-Natta catalyst generating high molecular weight and a zirconium (Zr) -based metallocene catalyst generating low molecular weight on one support. As a result, the supporting process is complicated, and the morphology of the polymer is deteriorated due to the promoter. U.S. Patent No. 5,525,678 describes a method of using a catalyst system for olefine polymerization in which a high molecular weight polymer and a low molecular weight polymer can be simultaneously polymerized by simultaneously supporting a metallocene compound and a nonmetallocene compound on a carrier. . It is a metallocene compound and a nonmetallocene . There is a disadvantage in that the compounds must be supported separately, and the carrier must be pretreated with various compounds for supporting reaction.
미국 특허 제 5,914,289호에는 각각의 담체에 담지된 메탈로센 촉매를 이용하여 고분자의 분자량 및 분자량 분포를 제어하는 방법이 기재되어 있으나, 담지촉매 제조시 사용된 용매의 양 및 제조시간이 많이 소요되고, 사용되는 메탈로센 촉매를 담체에 각각 담지시켜야 하는 번거로움이 따랐다.  U.S. Patent No. 5,914,289 describes a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount of solvent used and the time required for preparing the supported catalyst are high. The hassle of having to support the metallocene catalyst to be used on the carrier, respectively.
대한민국 특허 출원 제 2003-12308호에는 담체에 이중핵 메탈로센 촉매와 단일핵 메탈로센 촉매를 활성화제와 함께 담지하여 반응기 내 촉매의 조합을 변화시키며 중합함으로써 분자량 분포를 제어하는 방안을 개시하고 있다. 그러나, 이러한 방법은 각각의 촉매의 특성을 동시에 구현하기에 한계가 있으며, 또한 완성된 촉매의 담체 성분에서 메탈로센 촉매 부분이 유리되어 반웅기에 파울링 (fouling)을 유발하는 단점이 있다.  Korean Patent Application No. 2003-12308 discloses a method of controlling the molecular weight distribution by supporting a double-nucleated metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing the combination of catalysts in the reactor. have. However, this method is limited in realizing the characteristics of each catalyst at the same time, and also has a disadvantage in that the metallocene catalyst portion is liberated in the carrier component of the finished catalyst, causing fouling.
따라서， 상기한 단점들을 해결하기 위해서 간편하게 활성이 우수한 흔성 담지 메탈로센 촉매를 제조하여 원하는 물성의 을레핀계 중합체를 제조하는 방법에 대한 요구가 계속되고 있다.  Therefore, in order to solve the above disadvantages, there is a continuous need for a method for preparing a common supported metallocene catalyst having excellent activity and preparing a olefinic polymer of desired physical properties.
【발명의 내용]  [Contents of the Invention]
【해결하려는 과제 1  【Action to be solved 1
상기 종래기술의 문제를 해결하기 위해, 본 발명은 활성이 우수하고, 고분자량 및 원하는 물성을 가지는 올레핀계 중합체를 제조할 수 있는 흔성 담지 메탈로센 촉매의 제조방법를 제공하고자 한다.  In order to solve the problems of the prior art, the present invention is to provide a method for producing a common supported metallocene catalyst that can be produced an olefin polymer having excellent activity, high molecular weight and desired physical properties.
【과제의 해결수단】  [Measures of problem]
이에 본 발명은，  In the present invention,
담체에 제 1 조촉매 화합물을 담지시키는 단계;  Supporting the first cocatalyst compound on a carrier;
상기 제 1 조촉매 화합물이 담지된 담체에 하기 화학식 1로 표시되는 제 1 메탈로센 화합물 1종 이상， 및 하기 화학식 3 내지 5로 표시되는 화합물 증에서 선택되는 제 2 메탈로센 화합물 1종 이상을 담지시키는 단계; 및  At least one first metallocene compound represented by Formula 1 below, and at least one second metallocene compound selected from Compounds represented by Formulas 3 to 5 above, on the carrier on which the first promoter compound is supported Supporting the step; And
상기 제 1 조촉매 화합물， 제 1 메탈로센 화합물, 및 제 2 메탈로센 화합물이 담지된 담체에 제 2 조촉매 화합물을 담지시키는 단계를 포함하는 흔성 담지 메탈로센 촉매의 제조방법을 제공한다. The first cocatalyst compound, the first metallocene compound, and the second metallocene It provides a method for preparing a common supported metallocene catalyst comprising the step of supporting a second cocatalyst compound on a carrier on which the compound is supported.
[  [
Figure imgf000004_0001
Figure imgf000004_0001
[화학식 3]  [Formula 3]
(Cp1^) nCCp^M'Z1,.,, (Cp 1 ^) n CCp ^ M'Z 1 ,. ,,
[화학식 4]  [Formula 4]
(C^R^mB^C^R^M^^m (C ^ R ^ m B ^ C ^ R ^ M ^^ m
[화학식 5]  [Formula 5]
(Cp5Re)B2(J)M3Z3 2 (Cp 5 R e ) B 2 (J) M 3 Z 3 2
상기 화학식 1, 3, 4 및 5에 대해서는 하기에서 상세히 설명한다.  Formulas 1, 3, 4 and 5 will be described in detail below.
【발명의 효과】  【Effects of the Invention】
본 발명의 제조방법에 따라 수득된 흔성 담지 메탈로센 촉매는 서로 다른 2종 이상의 메탈로센 화합물을 포함하고， 특히 1종의 메탈로센 화합물은 인데노 인돌 (indeno indole) 유도체 및 /또는 플루오렌 (fluorene) 유도체가 브릿지에 의해 가교된 구조를 형성한 리간드 화합물을 이용함으로서 담지 시에도 높은 중합 활성을 나타내어, 활성이 우수하고， 초고분자량의 올레핀계 중합체의 중합에 이용될 수 있다.  The common supported metallocene catalyst obtained according to the production method of the present invention includes two or more different metallocene compounds, and in particular, one metallocene compound is an indeno indole derivative and / or flu By using a ligand compound in which an fluorene derivative forms a crosslinked structure by a bridge, it exhibits high polymerization activity even when supported, and is excellent in activity, and can be used for polymerization of an ultra high molecular weight olefin polymer.
【발명의 실시를 위한 구체적인 내용】  [Specific contents for implementation of the invention]
이하， 발명의 구체적인 구현예에 따른 흔성 담지 메탈로센 촉매의 제조방법에 대해 설명하기로 한다. 본 발명에 따른 흔성 담지 메탈로센 촉매의 제조방법은，  Hereinafter, a method for preparing a common supported metallocene catalyst according to a specific embodiment of the present invention will be described. Method for producing a common supported metallocene catalyst according to the present invention,
담체에 제 1 조촉매 화합물을 담지시키는 단계;  Supporting the first cocatalyst compound on a carrier;
상기 제 1 조촉매 화합물이 담지된 담체에 하기 화학식 1로 표시되는 제 1 메탈로센 화합물 1종 이상, 및 하기 화학식 3 내지 5로 표시되는 화합물 중에서 선택되는 제 2 메탈로센 화합물 1종 이상을 담지시키는 단계; 및 상기 제 1 조촉매 화합물, 제 1 메탈로센 화합물, 및 제 2 메탈로센 화합물이 담지된 담체에 제 2 조촉매 화합물을 담지시키는 단계를 포함한다. At least one first metallocene compound represented by the following Formula 1, and at least one second metallocene compound selected from the compounds represented by the following Formulas 3 to 5 on the carrier having the first cocatalyst compound Supporting; And And supporting the second cocatalyst compound on a carrier on which the first cocatalyst compound, the first metallocene compound, and the second metallocene compound are supported.
[  [
Figure imgf000005_0001
Figure imgf000005_0001
상기 화학식 1에서,  In Chemical Formula 1,
A는 수소， 할로겐， C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기， C6 내지 C20의 아릴기, C7 내지 C20의 알킬아릴기， C7 내지 C20의 아릴알킬기, C1 내지 C20의 알콕시기, C2 내지 C20의 알콕시알킬기， C3 내지 C20의 헤테로시클로알킬기， 또는 C5 내지 C20의 헤테로아릴기이고;  A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 C20 alkoxyalkyl group, C3 to C20 heterocycloalkyl group, or C5 to C20 heteroaryl group;
D는 -0-, -S-, -N(R)- 또는 -Si(R)(R 이고, 여기서 R 및 R'은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 할로겐， C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, 또는 C6 내지 C20의 아릴기이고;  D is -0-, -S-, -N (R)-or -Si (R) (R, wherein R and R 'are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group , An alkenyl group of C2 to C20, or an aryl group of C6 to C20;
L은 C1 내지 C10의 직쇄 또는 분지쇄 알킬렌기이고;  L is a C1 to C10 straight or branched chain alkylene group;
B는 탄소, 실리콘.또는 게르마늄이고;  B is carbon, silicon. Or germanium;
Q는 수소, 할로겐, C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C6 내지 C20의 아릴기， C7 내지 C20의 알킬아릴기, 또는 C7 내지 C20의 아릴알킬기이고;  Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group;
. M은 4족 전이금속이며; . M is a Group 4 transition metal;
X1 및 X2는 서로 동일하거나 상이하고, 각각 독립적으로 할로겐， C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C6 내지 C20의 아릴기, 니트로기, 아미도기， C1 내지 C20의 알킬실릴기, C1 내지 C20의 알콕시기, 또는 C1 내지 C20의 술폰네이트기이고; X 1 and X 2 are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
C1 및 C2는 서로 동일하거나 상이하고， 각각 독립적으로 하기 화학식 2a, 화학식 2b 또는 하기 화학식 2c 중 하나로 표시되고， 단, C1 및 C2가 모두 화학식 2c인 경우는 제외하며; C 1 and C 2 are the same as or different from each other, and are each independently represented by one of the following Chemical Formula 2a, Chemical Formula 2b, or Chemical Formula 2c, except that both C 1 and C 2 are Chemical Formula 2c;
[화학식 2a]
Figure imgf000006_0001
[Formula 2a]
Figure imgf000006_0001
[  [
[ [
Figure imgf000006_0002
Figure imgf000006_0002
상기 화학식 2a, 2b 및 2c에서， Rl 내지 R17 및 Rl' 내지 R9'는 서로 동일하거나 상이하고, 각각 독립적으로 수소, 할로겐, C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C1 내지 C20의 알킬실릴기, C1 내지 C20의 실릴알킬기, C1 내지 C20의 알콕시실릴기, C1 내지 C20의 알콕시기， C6 내지 C20의 아릴기， C7 내지 C20의 알킬아릴기, 또는 C7 내지 C20의 아릴알킬기이며, 상기 R10 내지 R17 중 서로 인접하는 2개 이상이 서로 연결되어 치환 또는 비치환된 지방족 또는 방향족 고리를 형성할 수 있고; .  In Formulas 2a, 2b, and 2c, Rl to R17 and Rl 'to R9' are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group of C1 to C20, an alkenyl group of C2 to C20, and an alkyl of C1 to C20. Silyl group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, Two or more adjacent to each other of R10 to R17 may be linked to each other to form a substituted or unsubstituted aliphatic or aromatic ring; .
[화학식 3] [Formula 3]
Figure imgf000006_0003
Figure imgf000006_0003
상기 화학식 3에서，  In Chemical Formula 3,
M1은 4족 전이금속이고; M 1 is a Group 4 transition metal;
Cp1 및 Cp2는 서로 동일하거나 상이하고, 각각 독립적으로 시클로펜타디엔닐, 인데닐, 4,5,6,7-테트라하이드로 - 1 -인데닐， 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고， 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며; Cp 1 and Cp 2 are the same as or different from each other, and each independently Cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1 -indenyl, and fluorenyl radicals, and any one selected from the group consisting of hydrocarbons having 1 to 20 carbon atoms, ;
Ra 및 Rb는 서로 동일하거나 상이하고, 각각 독립적으로 수소， C 1 내지 C20의 알킬, C1 내지 C10의 알콕시， C2 내지 C20의 알콕시알킬, C6 내지 C20의 아릴， C6 내지 C10의 아릴옥시, C2 내지 C20의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C8 내지 C40의 아릴알케닐, 또는 C2 내지 C10의 알키닐이고; R a and R b are the same as or different from each other, and each independently hydrogen, C 1 to C 20 alkyl, C 1 to C 10 alkoxy, C 2 to C 20 alkoxyalkyl, C 6 to C 20 aryl, C 6 to C 10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z1은 할로겐 원자, C1 내지 C20의 알킬, C2 내지 C10의 알케닐, C7 내지 C40의 알킬아릴， C7 내지 C40의 아릴알킬, C6 내지 C20의 아릴, 치환되거나 치환되지 않은 C1 내지 C20의 알킬리덴, 치환되거나 치환되지 않은 아미노기, C2 내지 C20의 알킬알콕시 , 또는 C7 내지 C40의 아릴알콕시이고; Z 1 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , Substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
n은 1 또는 0 이고;  n is 1 or 0;
[화학식 4]  [Formula 4]
(Cp3Rc) mB'(Cp4Rd)M2Z2 3.m (Cp 3 R c ) m B '(Cp 4 R d ) M 2 Z 2 3 . m
상기 화학식 4에서,  In Chemical Formula 4,
M2는 4족 전이 금속이고; M 2 is a Group 4 transition metal;
Cp3 및 Cp4는 서로 동일하거나 상이하고, 각각 독립적으로 시클로펜타디에닐, 인데닐， 4,5,6,7-테트라하이드로 -1 -인데닐 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고， 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며; Cp 3 and Cp 4 are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals They may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
Rc 및 Rd는 서로 동일하거나 상이하고, 각각 독립적으로 수소, C1 내지 C20의 알킬, C1 내지 C10의 알콕시, C2 내지 C20의 알콕시알킬, C6 내지 C20의 아릴, C6 내지 C10의 아릴옥시, C2 내지 C20의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C8 내지 C40의 아릴알케닐, 또는 C2 내지 C10의 알키닐이고; R c and R d are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 To alkenyl of C20, alkylaryl of C7 to C40, arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;
Z2는 할로겐 원자, C1 내지 C20의 알킬, C2 내지 C10의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬， C6 내지 C20의 아릴, 치환되거나 치환되지 않은 C1 내지 C20의 알킬리덴， 치환되거나 치환되지 않은 아미노기, C2 내지 C20의 알킬알콕시 , 또는 C7 내지 C40의 아릴알콕시이고; B1은 Cp3Rc 고리와 Cp4Rd 고리를 가교 결합시키거나, 하나의 Cp4Rd 고리를 M2에 가교 결합시키는, 탄소, 게르마늄, 규소, 인 또는 질소 원자 함유 라디칼 중 하나 이상 또는 이들의 조합이고; Z 2 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene Or a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy; B 1 is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp 3 R c ring with the Cp 4 R d ring or crosslinks one Cp 4 R d ring with M 2 Or a combination thereof;
m은 1 또는 0 이고;  m is 1 or 0;
[화학식 5]  [Formula 5]
(Cp5Re)B2(J)M3Z32 (Cp 5 R e ) B 2 (J) M 3 Z 3 2
상기 화학식 5에서,  In Chemical Formula 5,
• M3은 4족 전이 금속이고; M 3 is a Group 4 transition metal;
Cp5는 시클로펜타디에닐, 인데닐, 4,5,6,7-테트라하이드로 -1-인데닐 및 플루오레닐 라디칼로 이루어진.군으로부터 선택된 어느 하나이고, 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며; Cp 5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which are substituted with hydrocarbons having 1 to 20 carbon atoms Can be;
Re는 수소, C1 내지 C20의 알킬， C1 내지 C10의 알콕시, C2 내지 C20의 알콕시알킬, C6 내지 C20의 아릴, C6 내지 C10의 아릴옥시, C2 내지 C20의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C8 내지 C40의 아릴알케닐, 또는 C2 내지 C10의 알키닐이고; R e is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl C7-C40 arylalkyl, C8-C40 arylalkenyl, or C2-C10 alkynyl;
Z3은 할로겐 원자， C1 내지 C20의 알킬, C2 내지 C10의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬， C6 내지 C20의 아릴, 치환되거나 치환되지 않은 C1 내지 C20의 알킬리덴, 치환되거나 치환되지 않은 아미노기， C2 내지 C20의 알킬알콕시，또는 C7 내지 C40의 아릴알콕시이고; Z 3 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene A substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
B2는 Cp5Re 고리와 J를 가교 결합시키는 탄소, 게르마늄, 규소， 인 또는 질소 원자 함유 라디칼중 하나 이상 또는 이들의 조합이고; B 2 is at least one or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp 5 R e ring and J;
J는 NRf, 0, PRf 및 S로 이루어진 군에서 선택된 어느 하나이고， 상기 Rf는 C1 내지 C20의 알킬, 아릴， 치환된 알킬 또는 치환된 아릴이다. J is any one selected from the group consisting of NR f , 0, PR f and S, wherein R f is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl.
본 발명에 따른 흔성 담지 메탈로센 촉매에 있어서， 상기 화학식 1, 3, 4 및 5의 치환기들을 보다 구체적으로 설명하면 하기와 같다.  In the common supported metallocene catalyst according to the present invention, the substituents of Chemical Formulas 1, 3, 4 and 5 will be described in more detail.
상기 C1 내지 C20의 알킬기로는 직쇄 또는 분지쇄의 알킬기를 포함하고， 구체적으로 메틸기， 에틸기, 프로필기， 이소프로필기, n-부틸기, tert-부틸기, 펜틸기， 핵실기， 헵틸기, 옥틸기 등을 들 수 있으나, 이에만 한정되는 것은 아니다.  The C1 to C20 alkyl group includes a linear or branched alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nucleosil group, heptyl group, An octyl group etc. are mentioned, but it is not limited to this.
상기 Q 내지 C20의 알케닐기로는 직쇄 또는 분지쇄의 알케닐기를 포함하고, 구체적으로 알릴기， 에테닐기， 프로페닐기, 부테닐기， 펜테닐기 등을 들 수 있으나, 이에만 한정되는 것은 아니다. The alkenyl group of Q to C20 includes a straight or branched alkenyl group, and specifically, an allyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like But it is not limited thereto.
상기 C6 내지 C20의 아릴기로는 단환 또는 축합환의 아릴기를 포함하고， 구체적으로 페닐기, 비페닐기， 나프틸기, 페난트레닐기, 플루오레닐기 등을 들 수 있으나, 이에만 한정되는 것은 아니다.  The C6 to C20 aryl group includes a monocyclic or condensed aryl group, and specifically includes a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like, but is not limited thereto.
상기 C5 내지 C20의 헤테로아릴기로는 단환 또는 축합환의 헤테로아릴기를 포함하고, 카바졸릴기， 피리딜기, 퀴놀린기, 이소퀴놀린기, 티오페닐기， 퓨라닐기, 이미다졸기, 옥사졸릴기， 티아졸릴기, 트리아진기, 테트라하이드로피라닐기, 테트라하이드로퓨라닐기 등을 들 수 있으나, 이에만 한정되는 것은 아니다.  The C5 to C20 heteroaryl group includes a monocyclic or condensed heteroaryl group, and includes a carbazolyl group, a pyridyl group, a quinoline group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, a thiazolyl group , Triazine group, tetrahydropyranyl group, tetrahydrofuranyl group and the like, but are not limited thereto.
상기 C1 내지 C20의 알콕시기로는 메톡시기, 에록시기, 페닐옥시기, 시클로핵실옥시기 등을 들 수 있으나, 이에만 한정되는 것은 아니다.  Examples of the alkoxy group for C 1 to C 20 include a methoxy group, an hydroxy group, a phenyloxy group, a cyclonuxyloxy group, and the like, but are not limited thereto.
상기 4족 전이금속으로는 티타늄, 지르코늄, 하프늄 등을 들 수 있으나， 이에만 한정되는 것은 아니다.  Examples of the Group 4 transition metal include titanium, zirconium, and hafnium, but are not limited thereto.
본 발명에 따른 흔성 담지 메탈로센 촉매의 제조방법에 있어서, 상기 화학식 2a, 2b 및 2c의 R1 내지 R17 및 R1' 내지 R9'는 각각 독립적으로 수소, 메틸기, 에틸기， 프로필기， 이소프로필기, n-부틸기， tert-부틸기, 펜틸기， 핵실기， 헵틸기, 옥틸기, 페닐기， 할로겐기， 트리메틸실릴기, 트리에틸실릴기, 트리프로필실릴기， 트리부틸실릴기, 트리이소프로필실릴기, 트리메틸실릴메틸기， 메특시기， 또는 에록시기인 것이 더욱 바람직하나, 이에만 한정되는 것은 아니다. 상기 화학식 1의 L은 C4 내지 C8의 직쇄 또는 분지쇄 알킬렌기인 것이 더욱 바람직하나, 이에만 한정되는 것은 아니다. 또한， 상기 알킬렌기는 C1 내지 In the method for preparing a common supported metallocene catalyst according to the present invention, R1 to R17 and R1 'to R9' of Formulas 2a, 2b and 2c are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nucleosil group, heptyl group, octyl group, phenyl group, halogen group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl The group, trimethylsilylmethyl group, mesophilic group, or hydroxy group is more preferable, but is not limited thereto. L of Formula 1 is more preferably a straight or branched chain alkylene group of C4 to C8, but is not limited thereto. In addition, the alkylene group is C1 to
C20의 알킬기, C2 내지 C20의 알케닐기, 또는 C6 내지 C20의 아릴기로 치환 또는 비치환될 수 있다. An alkyl group of C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20 may be substituted or unsubstituted.
또한, 상기 화학식 1의 A는 수소， 메틸기, 에틸기, 프로필기， 이소프로필기, n-부틸기, tert-부틸기, 메톡시메틸기, tert-부톡시메틸기, 1-에록시에틸기， 1-메틸 -1- 메록시에틸기， 테트라하이드로피라닐기， 또는 테트라하이드로퓨라닐기인 것이 바람직하나, 이에만 한정되는 것은 아니다.  In addition, A in Formula 1 is hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, methoxymethyl, tert-butoxymethyl, 1-ethoxyethyl, 1-methyl It is preferable that it is a 1- methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group, but it is not limited to this.
또한, 상기 화학식 1의 B는 실리콘인 것이 바람직하나， 이에만 한정되는 것은 아니다.  In addition, B of Formula 1 is preferably silicon, but is not limited thereto.
상기 화학식 1의 제 1 메탈로센 화합물은 인데노 인돌 (indeno indole) 유도체 및 /또는 클루오렌 (fluorene) 유도체가 브릿지에 의해 가교된 구조를 형성하며, 리간드 구조에 루이스 염기로 작용할 수 있는 비공유 전자쌍을 가짐으로써 담체의 루이스 산 특성을 지니는 표면에 담지되어 담지 시에도 높은 중합 활성을 나타낸다. 또한 전자적으로 풍부한 인데노 인돌기 및 /또는 플루오렌기를 포함함에 따라 활성이 높고, 적절한 입체 장애와 리간드의 전자적인 효과로 인해 수소 반웅성이 낮올 뿐 아니라 수소가 존재하는 상황에서도 높은 활성이 유지된다. 또한 인데노 인돌 유도체의 질소 원자가 자라나는 고분자 사슬의 beta-hydrogen을 수소결합에 의해 안정화시켜 beta-hydrogen elimination을 억제하여 초고분자량의 을레핀계 증합체를 중합할 수 있다. The first metallocene compound of Formula 1 is indeno indole Derivatives and / or fluorene derivatives form a crosslinked structure by the bridge, and have a non-covalent electron pair that can act as a Lewis base in the ligand structure, so that it is supported on the surface having the Lewis acid characteristics of the carrier and is highly supported. It shows polymerization activity. In addition, due to the electronically rich indeno indole and / or fluorene group, the activity is high, and due to the proper steric hindrance and the electronic effect of the ligand, the hydrogen reaction is low and high activity is maintained even in the presence of hydrogen. . In addition, the beta-hydrogen of the polymer chain in which the nitrogen atom of the indeno indole derivative is grown is stabilized by hydrogen bonding, thereby inhibiting beta-hydrogen elimination, thereby polymerizing ultra high molecular weight olepin-based polymer.
본 발명의 일 실시예에 따르면, 상기 화학식 2a로 표시되는 화합물의 구체적인 예로는 하기 구조식들 중 하나로 표시되는 화합물을 들 수 있으나, 본 발명이 이에만 한정되는 것은 아니다.  According to one embodiment of the present invention, specific examples of the compound represented by Chemical Formula 2a may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.
Figure imgf000010_0001
Figure imgf000010_0001
Figure imgf000011_0001
Figure imgf000011_0001
본 발명의 일 실시예에 따르면, 상기 화학식 2b로 표시 -되는 화합물의 구체적인 예로는 하기 구조식 들 중 하나로 표시되는 화합물올 들 수 있으나, 본  According to an embodiment of the present invention, specific examples of the compound represented by Chemical Formula 2b may include a compound represented by one of the following structural formulas.
Figure imgf000011_0002
Figure imgf000012_0001
Figure imgf000011_0002
Figure imgf000012_0001
본 발명의 일 실시예에 따르면, 상기 화학식 2c로 표시되는 화합물의 구체적인 예로는 하기 구조식 들 증 하나로 표시되는 화합물을 들 수 있으나， 본 발명이  According to an embodiment of the present invention, specific examples of the compound represented by Chemical Formula 2c may include a compound represented by one of the following structural formulas, but the present invention
Figure imgf000012_0002
Figure imgf000012_0002
본 발명의 일 실시예에 따르면, 상기 화학식 1로 표시되는 제 1 메탈로센 화합물의 구체적인 예로는 하기 구조식들 중 하나로 표시되는 화합물을 들 수 있으나,  According to one embodiment of the present invention, specific examples of the first metallocene compound represented by Chemical Formula 1 may include a compound represented by one of the following structural formulas,
Figure imgf000012_0003
Figure imgf000012_0003
Figure imgf000013_0001
Figure imgf000013_0001
089600/Μ0ΖΗΜ/Χ3<Ι 17.69S0/S10Z OAV
Figure imgf000014_0001
089600 / Μ0ΖΗΜ / Χ3 <Ι 17.69S0 / S10Z OAV
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000015_0001
상기 화학식 1의 제 1 메탈로센 화합물은 활성이 우수하고 고분자량의 올레핀계 증합체를 중합할 수 있다. 특히, 담체에 담지하여 사용할 경우에도 높은 중합 활성을 나타내어, 초고분자량의 폴리을레핀계 중합체를 제조할 수 있다.  The first metallocene compound of Chemical Formula 1 has excellent activity and may polymerize a high molecular weight olefin-based polymer. In particular, even when used on a carrier, it exhibits high polymerization activity, and thus an ultrahigh molecular weight polyolefin polymer can be prepared.
또한， 고분자량과 동시에 넓은 분자량 분포를 갖는 올레핀계 중합체를 제조하기 위해 수소를 포함하여 중합'반웅올 진행하는 경우에도, 본 발명에 따른 화학식 의 제 1 메탈로센 화합물은 낮은 수소 반웅성을 나타내어 여전히 높은 활성으로 초고분자량의 을레핀계 중합체의 중합이 가능하다. 따라서， 다른 특성을 갖는 촉매와 흔성으로 사용하는 경우에도 활성의 저하없이 고분자량의 특성을 만족시키는 을레핀계 증합체를' 제조할 수 있어， 고분자의 을레핀계 중합체를 포함하면서 넓은 분자량 분포를 갖는 올레핀계 중합체를 용이하게 제조할 수 있다. In addition, even when the polymerization 'reaction including hydrogen is carried out to prepare an olefin polymer having a high molecular weight and a wide molecular weight distribution, the first metallocene compound of the formula according to the present invention exhibits low hydrogen reaction properties. It is still possible to polymerize ultra high molecular weight olepin-based polymers with high activity. Therefore, even when used in combination with a catalyst having different properties, it is possible to prepare an ' ulrepin-based polymer that satisfies the high molecular weight characteristics without degrading the activity, and thus contains an olefinic polymer of the polymer and has a wide molecular weight distribution. System polymers can be easily produced.
상기 화학식 1의 제 1 메탈로센 화합물은 인데노인돌 유도체 및 /또는 플루오렌 유도체를 브릿지 화합물로 연결하여 리간드 화합물로 제조한 다음, 금속 전구체 화합물을 투입하여 메탈레이션 (metallation)을 수행함으로써 수득될 수 있다. 상기 제 1 메탈로센 화합물의 제조방법은 후술하는 실시예에 구체화하영 설명한다.  The first metallocene compound of Chemical Formula 1 may be prepared by connecting an indenoindole derivative and / or fluorene derivative with a bridge compound to prepare a ligand compound, and then performing metallation by introducing a metal precursor compound. Can be. The manufacturing method of the said 1st metallocene compound is demonstrated to an Example mentioned later.
본 발명의 흔성 담지 메탈로센 촉매의 제조방법에 있어서, 상기 제 2 메탈로센 화합물은 하기 화학식 3 내지 5로 표시되는 화합물 중 선택되는 1종 이상일 수 있다.  In the method for preparing a common supported metallocene catalyst of the present invention, the second metallocene compound may be at least one selected from compounds represented by the following Chemical Formulas 3 to 5.
[화학식 3] [Formula 3]
Figure imgf000015_0002
Figure imgf000015_0002
상기 화학식 3에서，  In Chemical Formula 3,
M1은 4족 전이금속이고; Cpl 및 Cp2는 서로 동일하거나 상이하고, 각각 독립적으로 시클로펜타디엔닐, 인데닐, 4,5,6,7-테트라하이드로 -1 -인데닐， 및 풀루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고, 이들은 탄소수 1 내지 20의 탄화수소로 치환돨 수 있으며; M 1 is a Group 4 transition metal; Cp l and Cp 2 are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and pulluorenyl radicals One, they may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
Ra 및 Rb는 서로 동일하거나 상이하고， 각각 독립적으로 수소, C1 내지R a and R b are the same as or different from each other, and each independently hydrogen, C1 to
C20의 알킬, C1 내지 C10의 알콕시, C2 내지 C20의 알콕시알킬, C6 내지 C20의 아릴, C6 내지 C10의 아릴옥시, C2 내지 C20의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C8 내지 C40의 아릴알케닐, 또는 C2 내지 C10의 알키닐이고; C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl Arylalkenyl of C8 to C40, or alkynyl of C2 to C10;
Z1은 할로겐 원자, C1 내지 C20의 알킬, C2 내지 C10의 알케닐, C7 내지Z 1 is a halogen atom, C 1 to C 20 alkyl, C 2 to C 10 alkenyl, C 7 to
C40의 알킬아릴, C7 내지 C40의 아릴알킬, C6 내지 C20의 아릴, 치환되거나 치환되지 않은 C1 내지 C20의 알킬리덴, 치환되거나 치환되지 않은 아미노기, C2 내지 C20의 알킬알콕시, 또는 C7 내지 C40의 아릴알콕시이고; C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene, substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 aryl Alkoxy;
n은 1 또는 0 이고;  n is 1 or 0;
[화학식 4] [Formula 4]
Figure imgf000016_0001
Figure imgf000016_0001
상기 화학식 4에서,  In Chemical Formula 4,
M2는 4족 전이 금속이고; M 2 is a Group 4 transition metal;
Cp3 및 Cp4는 서로 동일하거나 상이하고, 각각 독립적으로 시클로펜타디에닐, 인데닐, 4,5,6,7-테트라하이드로 -1-인데닐 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고, 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며;Cp 3 and Cp 4 are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals They may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
c 및 Rd는 서로 동일하거나 상이하고， 각각 독립적으로 수소, C1 내지 C20의 알킬， C1 내지 C10의 알콕시, C2 내지 C20의 알콕시알킬, C6 내지 C20의 아릴, C6 내지 C10의 아릴옥시, C2 내지 C20의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C8 내지 C40의 아릴알케닐， 또는 C2 내지 C10의 알키닐이고; c and R d are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z2는 할로겐 원자， C1 내지 C20의 알킬, C2 내지 C10의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬， C6 내지 C20의 아릴, 치환되거나 치환되지 않은 C1 내지 C20의 알킬리덴， 치환되거나 치환되지 않은 아미노기, C2 내지 C20의 알킬알콕시，또는 C7 내지 C40의 아릴알콕시이고; Z 2 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , Substituted or unsubstituted amino group, C2 Alkylalkoxy to C20 or arylalkoxy of C7 to C40;
B1은 Cp3Rc 고리와 Cp4Rd 고리를 가교 결합시키거나, 하나의 Cp4Rd 고리를 M2에 가교 결합시키는， 탄소, 게르마늄, 규소, 인 또는 질소 원자 함유 라디칼 중 하나 이상 또는 이들의 조합이고; B 1 is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp 3 R c ring and the Cp 4 R d ring or crosslinks one Cp 4 R d ring with M 2 Or a combination thereof;
m은 1 또는 0 이고;  m is 1 or 0;
[화학삭 5]  [Chemical Machining 5]
(Cp5Re)B2(J)M3Z3 2 (Cp 5 R e ) B 2 (J) M 3 Z 3 2
상기 화학식 5에서，  In Chemical Formula 5,
M3은 4족 전이 금속이고; M 3 is a Group 4 transition metal;
Cp5는 시클로펜타디에닐， 인데닐, 4,5,6,그테트라하이드로 -1-인데닐 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고, 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며; Cp 5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6, gtetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms And;
Re는 수소, C1 내지 C20의 알킬, C1 내지 C10의 알콕시, C2 내지 C20의 알콕시알킬, C6 내지 C20의 아릴， C6 내지 C10의 아릴옥시， C2 내지 C20의 알케닐， C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C8. 내지 C40의 아릴알케닐， 또는 C2 내지 C 10의 알키닐이고; R e is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl , C7-C40 arylalkyl, C8. Arylalkenyl from C40 to alkynyl from C2 to C10;
Z3은 할로겐 원자, C1 내지 C20의 알킬, C2 내지 C10의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C6 내지 C20의 아릴, 치환되거나 치환되지 않은 C1 내지 C20의 알킬리덴, 치환되거나 치환되지 않은 아미노기， C2 내지 C20의 알킬알콕시 , 또는 C7 내지 C40의 아릴알콕시이고; Z 3 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , Substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
B2는 Cp5Re 고리와 J를 가교 결합시키는 탄소, 게르마늄, 규소, 인 또는 질소 원자 함유 라디칼중 하나 이상 또는 이들의 조합이고; B 2 is one or more or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp 5 R e ring and J;
J는 NRf, 0， PRf 및 S로 이루어진 군에서 선택된 어느 하나이고, 상기 Rf는 C1 내지 C20의 알킬， 아릴， 치환된 알킬 또는 치환된 아릴이다. J is any one selected from the group consisting of NR f , 0, PR f and S, wherein R f is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl.
상기 화학식 4에서， m이 1인 경우는 Cp3Rc 고리와 Cp4Rd 고리 또는 Cp4Rd 고리와 M2가 B1에 의해 가교 결합된 브릿지 화합물 구조인 것을 의미하며, m이 0인 경우는 비가교 화합물 구조를 의미한다. In Formula 4, when m is 1, it means that a Cp 3 R c ring and a Cp 4 R d ring or a Cp 4 R d ring and M 2 is a bridge compound structure crosslinked by B 1 , and m is 0. In the case of, it means a non-crosslinked compound structure.
상기 화학식 3으로 표시되는 화합물로는 예를 들어 하기 구조식들 중 하나로 표시되는 화합물일 수 있으나, 이에만 한정되는 것은 아니다. The compound represented by Chemical Formula 3 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.
Figure imgf000018_0001
Figure imgf000018_0001
Figure imgf000018_0002
Figure imgf000018_0002
상기 화학식 4로 표시되는 화합물로는 예를 들어 하기 구조식 하나로 표시되는 화합물일 수 있으나, 이에만 한정되는 것은 아니다. The compound represented by Chemical Formula 4 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.
Figure imgf000019_0001
Figure imgf000019_0001
표시되는 화합물일 수 있으나, 이에만 한정되는 것은 아니다 The compound may be represented, but is not limited thereto.
Figure imgf000020_0001
상기 흔성 담지 메탈로센 촉매는 상기 화학식 1로 표시돠는 제 1 메탈로센 화합물의 1종 이상과, 상기 화학식 3 내지 화학식 5로 표시되는 화합물 중 선택되는 제 2 메탈로센 화합물의 1종 이상올 조촉매 화합물과 함께 담체에 흔성 담지한 것이다.
Figure imgf000020_0001
The common supported metallocene catalyst may include at least one of the first metallocene compound represented by Formula 1 and at least one of the second metallocene compound selected from the compounds represented by Formulas 3 to 5. It is commonly supported on the carrier together with all cocatalyst compounds.
상기 흔성 담지 메탈로센 촉매의 화학식 1로 표시되는 제 1 메탈로센 화합물은 주로 높은 SCB(short chain branch) 함량을 가지는 고분자량의 공증합체를 만드는데 기여하고, 화학식 3으로 표시되는 제 2 메탈로센 화합물은 주로 낮은 The first metallocene compound represented by Formula 1 of the common supported metallocene catalyst contributes to making a high molecular weight co-polymer having a high SCB (short chain branch) content, and the second metal represented by Formula 3 Sen compound is mainly low
SCB 함량을 가지는 저분자량의 공중합체를 만드는데 기여할 수 있다. 또한， 화학식 4 또는 5로 표시되는 제 2 메탈로센 화합물은 중간 정도의 SCB 함량을 가지는 저분자량의 공중합체를 만드는데 기여할 수 있다. It can contribute to making low molecular weight copolymers with SCB content. In addition, the second metallocene compound represented by Formula 4 or 5 may contribute to making a low molecular weight copolymer having a moderate SCB content.
본 발명의 일 실시예에 따르면, 상기 -흔성 담지 메탈로센 촉매는 화학식 1의 제 1 메탈로센 화합물 1종 이상과, 화학식 3의 제 2 메탈로센 화합물 1종 이상을 포함할 수 있다.  According to an embodiment of the present invention, the -commonly supported metallocene catalyst may include at least one first metallocene compound of Formula 1 and at least one second metallocene compound of Formula 3.
본 발명의 다른 일 실시예에 따르면, 상기 흔성 담지 메탈로센 촉매는 화학식 i의 제 1 메탈로센 화합물 1종 이상과, 및 화학식 3의 제 2 메탈로센 화합물 1종 이상에 더하여, 화학식 4 또는 화학식 5의 제 2 메탈로센 화합물을 1종 이상 포함할 수 있다. According to another embodiment of the present invention, the common supported metallocene catalyst is In addition to at least one first metallocene compound of formula i and at least one second metallocene compound of formula 3, at least one second metallocene compound of formula 4 or formula 5 may be included. .
본 발명에 따른 흔성 담지 메탈로센 촉매의 제조방법에 있어서, 상기 제 1 메탈로센 화합물은 인데노 인돌 유도체와 플루오렌 유도체가 브릿지 화합물에 의해 가교된 리간드 구조를 형성하며， 리간드 구조에 루이스 염기로 작용할 수 있는 비공유 전자쌍을 가짐으로써 담체의 루이스 산 특성을 지니는 표면에 담지되어 담지 시에도 높은 증합 활성을 나타낸다. 또한 전자적으로 풍부한 인데노 인돌기 및 /또는 플루오렌기를 포함함에 따라 활성이 높고, 적절한 입체 장애와 리간드의 전자적인 효과로 인해 수소 반응성이 낮을 뿐 아니라 수소가 존재하는 상황에서도 높은 활성어 유지된다. 따라서, 이러한 전이금속 화합물을 이용하여 흔성 담지 메탈로센 촉매를 만드는 경우， 인데노인돌 유도체의 질소 원자가 자라나는 고분자 사슬의 베타-수소를 수소결합에 의해 안정화시켜 초고분자량의 올레핀계 중합체를 중합할 수 있다.  In the method for preparing a common supported metallocene catalyst according to the present invention, the first metallocene compound forms a ligand structure in which an indeno indole derivative and a fluorene derivative are crosslinked by a bridge compound, and a Lewis base in the ligand structure. By having a non-covalent electron pair that can act as a support on the surface having the Lewis acid characteristics of the carrier it shows a high polymerization activity even when supported. In addition, it is highly active as it contains an electronically rich indeno indole group and / or fluorene group, and due to proper steric hindrance and the electronic effect of the ligand, the hydrogen reactivity is low and the activity is maintained even in the presence of hydrogen. Therefore, when making a common supported metallocene catalyst using such a transition metal compound, it is possible to polymerize ultra-high molecular weight olefin polymer by stabilizing beta-hydrogen of a polymer chain in which nitrogen atoms of indenoindole derivatives grow by hydrogen bonding. have.
또한, 발명의 제조방법에 따라 수득된 흔성 담지 메탈로센 촉매에서는 상기 화학식 1로 표시되는 제 1 메탈로센 화합물 및 상기 화학식 3 내지 5로 표시되는 제 2 메탈로센 화합물을 포함하여, 서로 다른 종류의 메탈로센 화합물을 적어도 2종 이상 포함함으로써 높은 SCB 함량을 가지는 고분자량의 올레핀계 공중합체이면서, 동시에 분자량 분포가 넓어 물성이 우수할 뿐만 아니라 가공성도 우수한 올레핀 중합체를 제조할 수 있다.  In addition, the common supported metallocene catalyst obtained according to the preparation method of the present invention includes a first metallocene compound represented by Chemical Formula 1 and a second metallocene compound represented by Chemical Formulas 3 to 5, and different from each other. By including at least two or more kinds of metallocene compounds, an olefin polymer having a high molecular weight olefin copolymer having a high SCB content and having a wide molecular weight distribution at the same time, having excellent physical properties and excellent processability, can be prepared.
본 발명에 따른 흔성 담지 메탈로센 촉매의 제조방법에 있어서， 상기 메탈로센 화합물을 활성화하기 위하여 담체에 함께 담지되는 조촉매로는 13족 금속을 포함하는 유기 금속 화합물로서， 일반적인 메탈로센 촉매 하에 을레핀을 중합할 때 사용될 수 있는 것이라면 특별히 한정되는 것은 아니다.  In the method for preparing a common supported metallocene catalyst according to the present invention, the cocatalyst supported on a carrier for activating the metallocene compound is an organometallic compound containing a Group 13 metal, and a general metallocene catalyst. It will not be specifically limited if it can be used when superposing | polymerizing eluene under.
구체적으로, 상기 조촉매 화합물은 하기 화학식 6의 알루미늄 함유 제 1 조촉매, 및 하기 화학식 7의 보레이트계 제 2 조촉매 중 하나 이상을 포함할 수 있다.  Specifically, the cocatalyst compound may include at least one of an aluminum-containing first cocatalyst of Formula 6 and a borate-based second cocatalyst of Formula 7 below.
[화학식 6]  [Formula 6]
-[Al(R18)-0-]k- 화학식 6에서, R1S은 각각 독립적으로 할로겐, 할로겐 치환 또는 비치환된 탄소수 1 내지 20의 하이드로카빌기이고, k는 2 이상의 정수이고， -[Al (R 18 ) -0-] k -In formula (6), each R 1S is independently halogen, halogen substituted or unsubstituted. A hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,
[화학식 7]  [Formula 7]
T+[BG4]" T + [BG 4 ] "
화학식 7에서， T+은 +1가의 다원자 이온이고 , B는 +3 산화 상태의 붕소이고 G는 각각 독립적으로 하이드라이드기, 디알킬아미도기, 할라이드기， 알콕사이드기， 아릴옥사이드기, 하이드로카빌기， 할로카빌기 및 할로-치환된 하이드로카빌기로 이루어진 군에서 선택되고, 상기 G는 20개 이하의 탄소를 가지나, 단 하나 이하의 위치에사 G는 할라이드기이다. In Formula 7, T + is a + monovalent polyatomic ion, B is boron in the +3 oxidation state, and G is independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryl oxide group, a hydrocar It is selected from the group consisting of bil group, halocarbyl group and halo-substituted hydrocarbyl group, wherein G has 20 carbons or less, but at one or less positions, G is a halide group.
이러한 게 1 및 제 2 조촉매의 사용에 의해， 최종 제조된 폴리올레핀의 분자량 분포가 보다 균일하게 되면서， 중합 활성이 향상될 수 있다.  By using the first and second cocatalysts, the molecular weight distribution of the finally produced polyolefin can be made more uniform, and the polymerization activity can be improved.
상기 화학식 6의 제 1 조촉매는 선형， 원형 또는 망상형으로 반복단위가 결합된 알킬알루미녹산계 화합물로 될 수 있고, 이러한 제 1 조촉매의 구체적인 예로는, 메틸알루미녹산 (MAO), 에틸알루미녹산, 이소부틸알루미녹산 또는 부틸알루미녹산 등을 들 수 있다.  The first cocatalyst of Chemical Formula 6 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular, or reticular form. Specific examples of the first cocatalyst include methylaluminoxane (MAO) and ethylalumina. Noxic acid, isobutyl aluminoxane, or butyl aluminoxane etc. are mentioned.
또한， 상기 화학식 7의 제 2 조촉매는 삼치환된 암모늄염， 또는 디알킬 암모늄염, 삼치환된 포스포늄염 형태의 보레이트계 화합물로 될 수 있다. 이러한 제 2 조촉매의 구체적인 예로는, 트리메탈암모늄 테트라페닐보레이트, 메틸디옥타데실암모늄 테트라페닐보레이트， 트리에틸암모늄 테트라페닐보레이트, 트리프로필암모늄 테트라페닐보레이트， 트리 (n-부틸)암모늄 테트라페닐보레이트， 메틸테트라데사이클로옥타데실암모늄 테트라페닐보레이트， Ν,Ν-디메틸아닐늄 테트라페닐보레이트, Ν,Ν-디에틸아닐늄 테트라페닐보레이트， Ν,Ν-디메틸 (2,4,6- 트리메틸아닐늄)테트라페닐보레이트, 트리메틸암모늄 테트라키스 (펜타플로오로페닐)보레이트, 메틸디테트라데실암모늄 테트라키스 (펜타페닐)보레이트, 메틸디옥타데실암모늄 테트라키스 (펜타플루오로페닐)보레이트, 트리에틸암모늄， 테트라키스 (펜타플루오로페닐)보레이트,  In addition, the second cocatalyst of Formula 7 may be a borate-based compound in the form of a trisubstituted ammonium salt, or a dialkyl ammonium salt, a trisubstituted phosphonium salt. Specific examples of such a second cocatalyst include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate ， Methyltetracyclooctadecylammonium tetraphenylborate ， Ν, Ν-dimethylanile tetraphenylborate, Ν, Ν-diethylaninynium tetraphenylborate ， Ν, Ν-dimethyl (2,4,6-trimethylaninium Tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, triethylammonium, tetra Kiss (pentafluorophenyl) borate,
트리프로필암모늄테트라키스 (펜타프루오로페닐)보레이트 트리 (η-부틸)암모늄 테트라키스 (펜타플루오로페닐)보레이트, 트리 (2급- 부틸)암모늄테트라키스 (펜타플루오로페닐)보레이트， Ν,Ν-디메틸아닐늄 테트라키스 (펜타플루오로페닐)보레이트, Ν,Ν- 디에틸아닐늄테트라키스 (펜타플루오로페닐)보레이트， N, N-디메틸 (2,4,6- 트리메틸아닐늄)테트라키스 (펜타플루오로페닐)보레이트, Tripropylammonium tetrakis (pentafluorophenyl) borate tri ( η -butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate ， Ν, Ν-dimethylaninium tetrakis (pentafluorophenyl) borate, Ν, Ν- Diethylaninium tetrakis (pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylaninynium) tetrakis (pentafluorophenyl) borate,
트리메틸암모늄테트라키스 (2,3,4,6-테트라플루오로페닐)보레이트, 트리에틸암모늄 테트라키스 (2,3 ,4,6-테트라플루오로페닐)보레이트, 트리프로필암모늄 테트라키스 (2,3,4,6-테트라플루오로페닐)보레이트, 트리 (n-부틸)암모늄 테트라키스 (2,3,4,6-,테트라플루오로페닐)보레이트, 디메틸 (t-부틸)암모늄 테트라키스 (2,3,4,6-테트라플루오로페닐)보레이트, Ν,Ν-디메틸아닐늄 테트라키스 (2,3,4,6-테트라풀루오로페닐)보레이트, Ν,Ν-디에틸아닐늄 테트라키스 (2,3,4,6-테트라플루오로페닐)보레이트 또는 Ν,Ν-디메틸 -(2,4,6- 트리메틸아닐늄)테트라키스 -(2,3,4,6-테트라플루오로페닐)보레이트 등의 삼치환된 암모늄염 형태의 보레이트계 화합물; 디옥타데실암모늄 테트라키스 (펜타플루오로페닐)보레이트, 디테트라데실암모늄 테트라키스 (펜타홀루오로페닐)보레이트 또는 디사이클로핵실암모늄 테트라키스 (펜타홀루오로페닐)보레이트 등의 디알킬암모늄염 형태의 보레이트계 화합물; 또는 트리페닐포스포늄 테트라키스 (펜타플루오로페닐)보레이트, 메틸디옥타데실포스포늄 테트라키스 (펜타플루오로페닐)보레이트 또는 트리 (2,6-, 디메틸페닐)포스포늄 테트라키스 (펜타폴루오로페닐)보레이트 등의 삼치환된 포스포늄염 형태의 보레이트계 화합물 둥을 들 수 있다. Trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3 , 4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-, tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2, 3,4,6-tetrafluorophenyl) borate, Ν, Ν-dimethylaninium tetrakis (2,3,4,6-tetrafluorofluorophenyl) borate, Ν, Ν-diethylaninynium tetrakis ( 2,3,4,6-tetrafluorophenyl) borate or Ν, Ν-dimethyl- (2,4,6-trimethylaninynium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate Borate compounds in the form of trisubstituted ammonium salts such as; In the form of dialkylammonium salts such as dioctadecylammonium tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentaholurophenyl) borate or dicyclonucleoammonium tetrakis (pentaholurophenyl) borate Borate compounds; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentapolouro) And borate-based compounds in the form of trisubstituted phosphonium salts such as phenyl) borate.
상술한 바와 같은 흔성 담지 메탈로센 촉매는, 담체에 제 1 조촉매 화합물을 담지시키는 단계， 상기 제 1 조촉매 화합물이 담지된 담체에 하기 화학식 1로 표시되는 제 1 메탈로센 화합물 1종 이상, 및 하기 화학식 3 내지 5로 표시되는 화합물 중에서 선택되는 제 2 메탈로센 화합물 1종 이상을 담지시키는 단계; 및 상기 제 1 조촉매 화합물, 제 1 메탈로센 화합물, 및 체 2 메탈로센 회"합물이 담지된 담체에 제 2 조촉매 화합물을 담지시키는 단계로 제조된다.  The common supported metallocene catalyst as described above may include the steps of: supporting a first cocatalyst compound on a carrier; at least one first metallocene compound represented by the following Formula 1 on a carrier on which the first cocatalyst compound is supported: And supporting at least one second metallocene compound selected from compounds represented by Formulas 3 to 5; And supporting the second cocatalyst compound on a carrier on which the first cocatalyst compound, the first metallocene compound, and the sieve 2 metallocene association " are supported.
즉, 준비된 담체에 먼저 화학식 6으로 표시되는 제 1 조촉매 화합물을 담지한다. 다음에, 상기 제 1 조촉매 화합물이 담지된 담체쎄 제 1 메탈로센 화합물 및 제 2 메탈로센 화합물을 담지한다. 이때 상기 제 1 및 제 2 메탈로센 화합물간의 담지 순서는 제한되지 않으며, 제 1 메탈로센 화합물을 먼저 담지시키거나, 제 2 메탈로센 화합물을 먼저 담지시킬 수 있다. 다음에, 상기 제 1 조촉매 화합물， 제 1 메탈로센 화합물, 및 제 2 메탈로센 .화합물이 모두 담지된 담체에 마지막으로 화학식 7로 표시되는 제 2 조촉매 화합물을 담지한다. That is, the first cocatalyst compound represented by Chemical Formula 6 is first supported on the prepared carrier. Next, the first metallocene compound and the second metallocene compound are supported on the carrier on which the first cocatalyst compound is supported. In this case, the supporting order between the first and second metallocene compounds is not limited, and the first metallocene compound may be first supported or the second metallocene compound may be first supported. Next, all of the first cocatalyst compound, the first metallocene compound, and the second metallocene compound are supported. Finally, the carrier carries the second cocatalyst compound represented by the formula (7).
상기와 같이 제 1 조촉매 화합물 -> 제 1 및 제 2 메탈로센 화합물 -> 제 2 조촉매 화합물로 순차적으로 담지함으로써, 먼저 담지한 제 1 조촉매 화합물이 담체 표면의 하이드록시 그룹과 미리 반웅하며, 수분 및 촉매 이물질과 같은 불순물에 대한 스캐빈저 (scavenger) 역할을 함으로써 균일한 촉매 제조에 도움을 줄 수 있다. 이에, 상기 제 1 조촉매 화합물의 담지 이후에 담지하는 제 1 및 제 2 메탈로센 촉매들이 비활성화될 가능성이 줄어들어 고활성의 담지 촉매를 제조할 수 있다ᅳ  By sequentially supporting the first cocatalyst compound-> the first and the second metallocene compound-> the second cocatalyst compound as described above, the first supported promoter compound is reacted with the hydroxy group on the surface of the carrier in advance. In addition, it can help to prepare a uniform catalyst by acting as a scavenger for impurities such as moisture and catalyst foreign matter. Accordingly, the possibility of deactivating the first and second metallocene catalysts supported after the supporting of the first cocatalyst compound can be reduced, thereby preparing a supported catalyst having high activity.
본 발명에 따른 흔성 담지 메탈로센 촉매의 제조방법에 있어서, 화학식 1로 표시되는 제 1 메탈로센 화합물 및 화학식 3 내지 5로 표시되는 제 2 메탈로센 화합물에 포함되는 전체 전이금속 대 담체의 질량비는 1 ： 10 내지 1 ： 1 ,000 일 수 있다. 상기 질량비로 담체 및 메탈로센 화합물을 포함할 때， 최적의 형상을 나타낼 수 있다. ' In the method for preparing a common supported metallocene catalyst according to the present invention, the total transition metal to the carrier contained in the first metallocene compound represented by Formula 1 and the second metallocene compound represented by Formulas 3 to 5 The mass ratio may be 1:10 to 1: 1.000. When the carrier and the metallocene compound are included in the mass ratio, the optimum shape can be exhibited. '
또한， 조촉매 화합물 대 담체의 질량비는 1 ： 1 내지 1 ： 100 일 수 있다. 또한, 화학식 1로 표시되는 제 1 메탈로센 화합물 대 화학식 3 내지 5로 표시되는 제 2 메탈로센 화합물의 질량비는 10： 1 내지 1 ： 10, 바람직하게는 5 : 1 내지 1 : 5 일 수 있다. 상기 질량비로 조촉매 및 메탈로센 화합물을 포함할 때, 활성 및 고분자 미세구조를 최적화할 수 있다.  In addition, the mass ratio of the promoter compound to the carrier may be from 1: 1 to 1: 100. In addition, the mass ratio of the first metallocene compound represented by Formula 1 to the second metallocene compound represented by Formulas 3 to 5 is 10: 1 to 1:10, preferably 5: 1 to 1: 5 days. have. When the cocatalyst and the metallocene compound are included in the mass ratio, the active and polymer microstructures can be optimized.
본 발명에 따른 흔성 담지 메탈로센 촉매의 제조방법에 있어서, 상기 담체로는 표면에 하이드록시기를 함유하는 담체를 사용할 수 있으며, 바람직하게는 건조되어 표면에 수분이 제거된, 반웅성이 큰 하이드록시기와 실록산기를 가지고 있는 담체를 사용할 수 있다.  In the method for preparing a common supported metallocene catalyst according to the present invention, a carrier containing a hydroxyl group on the surface may be used, and preferably, a semi-astringent hydride is dried to remove moisture from the surface. The carrier which has a hydroxy group and a siloxane group can be used.
예컨대, 고온에서 건조된 실리카, 실리카 -알루미나, 및 실리카 -마그네시아 등이 사용될 수 있고, 이들은 통상적으로 Na20, K2C03, BaS04, 및 Mg(N03)2 등의 산화물， 탄산염, 황산염, 및 질산염 성분을 함유할 수 있다. For example, silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, which are typically oxides, carbonates, such as Na 2 O, K 2 C0 3 , BaS0 4 , and Mg (N0 3 ) 2 , Sulfate, and nitrate components.
상기 담체의 건조 온도는 200 내지 800°C가 바람직하고, 300 내지 600°C가 더욱 바람직하며, 300 내지 400 °C가 가장 바람직하다. 상기 담체의 건조 온도가 200 °C 미만인 경우 수분이 너무 많아서 표면의 수분과 조촉매가 반웅하게 되고， 80CTC를 초과하는 경우에는 담체 표면의 기공들이 합쳐지면서 표면적이 줄어들며, 또한 표면에 하이드록시기가 많이 없어지고 실록산기만 남게 되어 조촉매와의 반웅자리가 감소하기 때문에 바람직하지 않다. The drying temperature of the carrier is preferably 200 to 800 ° C., more preferably 300 to 600 ° C., most preferably 300 to 400 ° C. When the drying temperature of the carrier is less than 200 ° C, there is too much moisture to react with the surface moisture and the promoter, and when it exceeds 80 CTC, the surface area decreases as the pores on the surface of the carrier are combined, and more hydroxyl groups are present on the surface. Disappear and only siloxane remains, and with the promoter It is not desirable because the reaction sign is reduced.
상기 담체 표면의 하이드록시기 양은 0.1 내지 10 mmol/g이 바람직하며, 0.5 내지 5 mmol/g일 때 더욱 바람직하다. 상기 담체 표면에 있는 하이드록시기의 양은 담체의 제조방법 및 조건 또는 건조 조건, 예컨대 은도， 시간， 진공 또는 스프레이 건조 등에 의해 조절할 수 있다.  The amount of hydroxy groups on the surface of the carrier is preferably 0.1 to 10 mmol / g, more preferably 0.5 to 5 mmol / g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions such as silver, time, vacuum or spray drying.
상기 하이드록시기의 양이 0.1 ' mmol/g 미만이면 조촉매와의 반웅자리가 적고, 10 mmol/g을 초과하면 담체 입자 표면에 존재하는 하이드록시기 이외에 수분에서 기인한 것일 가능성이 있기 때문에 바람직하지 않다.  If the amount of the hydroxy group is less than 0.1 'mmol / g, the reaction space with the promoter is small, and if the amount of the hydroxy group is more than 10 mmol / g, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. Not.
본 발명의 제조방법에 따라 수득된 흔성 담지 메탈로센 촉매는 그 자체로서 .을레핀계 단량체의 중합에 사용될 수 있다. 또한, 본 발명에 따른 흔성 담지 메탈로센 촉매는 을레핀계 단량체와 접촉 반웅되어 예비 중합된 촉매로 제조하여 사용할 수도 있으며, 예컨대 촉매를 별도로 에틸렌, 프로필렌， 1-부텐, 1- 헥센, 1-옥텐 등과 같은 을레핀계 단량체와 접촉시켜 예비 중합된 촉매로 제조하여 사용할 수도 있다.  The common supported metallocene catalyst obtained according to the preparation method of the present invention can be used by itself for the polymerization of .lefin-based monomers. In addition, the common supported metallocene catalyst according to the present invention may be prepared by using a pre-polymerized catalyst in contact with an olefinic monomer. For example, the catalyst may be used separately from ethylene, propylene, 1-butene, 1-hexene, and 1-octene. It may be prepared and used as a prepolymerized catalyst by contacting with an olefinic monomer such as the like.
본 발명에 따른 흔성 담지 메탈로센 촉매의 제조방법에 있어서, 상기 제 1 메탈로센 화합물을 담지시키는 단계 및 상기 제 2 메탈로센 화합물을 담지시키는 단계의 순서는 필요에 따라 바뀔 수 있다. 즉, 상기 제 1 메탈로센 화합물을 담체에 먼저 담지시킨 후, 상기 제 2 메탈로센 화합물을 추가로 담지하여 흔성 담지 메탈로센 촉매를 제조하거나, 또는 상기 제 2 메탈로센 화합물을 담체에 먼저 담지시킨 후, 상기 제 1 메탈로센 화합물을 추가로 담지하여 흔성 담지 메탈로센 촉매를 제조할 수도 있다.  In the method for preparing a common supported metallocene catalyst according to the present invention, the order of the step of supporting the first metallocene compound and the step of supporting the second metallocene compound may be changed as necessary. That is, the first metallocene compound is first supported on a carrier, and then the second metallocene compound is further supported to prepare a common supported metallocene catalyst, or the second metallocene compound is supported on the carrier. After supporting first, the common metallocene catalyst may be prepared by further supporting the first metallocene compound.
상기와 같은 흔성 담지 메탈로센 촉매의 제조시, 온도는 약 0 내지 약 100°C , 압력은 상압인 조건에서 수행할 수 있으나, 이에 한정되는 것은 아니다. 상기와 같은 본 발명의 제조방법에 따라 수득된 흔성 담지 메탈로센 촉매의 존재하에 을레핀계 단량체를 중합함으로써, 을레핀계 중합체를 제조할 수 있다. 상기 올레핀계 단량체는 에틸렌, 알파-을레핀, 사이클릭 을레핀, 이중 결합을 2개 이상 가지고 있는 디엔 올레핀 또는 트리엔 올레핀일 수 있다. In preparing the common supported metallocene catalyst as described above, the temperature may be performed at a condition of about 0 to about 100 ° C. and a pressure of normal pressure, but is not limited thereto. In the presence of the common supported metallocene catalyst obtained according to the preparation method of the present invention as described above, the olefinic polymer can be prepared by polymerizing the olefinic monomers. The olefinic monomer may be ethylene, alpha-olefin, cyclic olefin, diene olefin or triene olefin having two or more double bonds.
상기 올레핀계 단량체의 구체적인 예로서, 에틸렌, 프로필렌, 1-부텐, 1-펜텐, 4-메틸 -1 -펜텐, 1-핵센， 1-헵텐, 1-옥텐, 1-데센， 1-운데센， 1-도데센, 1-테트라데센, 1 - 핵사데센, 1-아이토센, 노보넨, 노보나디엔， 에틸리덴노보넨， 페닐노보넨, 비닐노보넨, 디사이클로펜타디엔， 1,4-부타디엔, 1,5-펜타디엔， 1 ,6-핵사디엔, 스티렌, 알파-메틸스티렌, 디비닐벤젠, 3-클로로메틸스티렌 등을 들 수 있으며, 이들 단량체를 2종 이상 흔합하여 공중합할 수도 있다. Specific examples of the olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-nucleadecene, 1-aitosen, norbornene, norbonadiene, ethylidene norbornene, phenylnorbornene, Vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-nuxadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like. You may mix and copolymerize 2 or more types of these monomers.
상기 중합 반응은 하나의 연속식 슬러리 중합 반웅기, 루프 슬러리 반웅기， 기상 반웅기 또는 용액 반웅기를 이용하여 하나의 올레핀계 단량체로 호모중합하거나 또는 2종 이상의 단량체로 공중합하여 진행할 수 있다.  The polymerization reaction may be carried out by homopolymerization with one olefinic monomer or copolymerization with two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.
상기 흔성 담지 메탈로센 촉매는 탄소수 5 내지 12의 지방족 탄화수소 용매, 예를 들면 펜탄, 핵산, 헵탄, 노난, 데칸, 및 이들의 이성질체와 를루엔, 벤젠과 같은 방향족 탄화수소 용매， 디클로로메탄, 클로로벤젠과 같은 염소원자로 치환된 탄화수소 용매 등에 용해하거나 희석하여 주입할 수 있다. 여기에 사용되는 용매는 소량의 알킬 알투마늄 리함으로써 촉매 독으로 작용하는 소량의 물 또는 공기 등을 제거하여 사용하는 것이 바람직하며， 조촉매를 더 사용하여 실시하는 것도 가능하다.  The common supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, nucleic acid, heptane, nonane, decane, and isomers thereof, and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane and chlorobenzene. It may be dissolved or diluted and injected into a hydrocarbon solvent substituted with a chlorine atom such as. The solvent used herein is preferably used by removing a small amount of water or air, which acts as a catalyst poison, by using a small amount of alkyl aluminum, and may be carried out by further using a promoter.
본 발명의 제조방법에 따라 수득된 흔성 담지 메탈로센 촉매를 이용하여 올레핀계 중합체를 제조할 경우, 저분자량 부분의 SCB 함량이 낮고, 고분자량 부분의 SCB 함량이 높은 BOCD 구조의 넓은 분자량 분포를 가지는 올레핀계 증합체를 제조할 수 있다. 상기 올레핀계 중합체는 물성이 우수할 뿐만 아니라， 가공성 또한 우수한 효과가 있다.  When the olefin polymer is prepared using the common supported metallocene catalyst obtained according to the production method of the present invention, a low molecular weight portion has a wide molecular weight distribution of the BOCD structure having a low SCB content and a high SCB content of the high molecular weight portion. Eggplant can produce an olefin-based polymer. The olefin polymer not only has excellent physical properties but also has excellent workability.
예를 들어, 본 발명의 제조방법에 따라 수득된 흔성 담지 메탈로센 촉매를 이용하여 제조된 올레핀계 중합체는 약 30만 이상 또는 약 35만 이상의 높은. 증량 평균 분자량을 나타낼 수 있다.  For example, olefinic polymers prepared using common supported metallocene catalysts obtained in accordance with the process of the present invention have a high content of at least about 300,000 or at least about 350,000. Increased average molecular weight can be indicated.
약 3.0 내지 약 8.0, 바람직하게는 약 4.0 내지 약 8.0, 보다 바람직하게는 5.0 내지 약 8.0의 넓은 분자량 분포 (PDI)를 보여 우수한 가공성을 나타낼 수 있다. 이하, 본 발명의 실시예를 통해 본 발명에 대해 상세히 설명한다. 그러나, 본 발명의 실시예들은 여러 가지 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들로 인하여 한정되는 식으로 해석되어서는 안.된다.  A broad molecular weight distribution (PDI) of about 3.0 to about 8.0, preferably about 4.0 to about 8.0, more preferably 5.0 to about 8.0 can be seen to show excellent processability. Hereinafter, the present invention will be described in detail through embodiments of the present invention. However, embodiments of the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited by the embodiments described below.
<실시예 > <Example>
제 1 메탈로센 화합물의 제조 실시예  Preparation Example of First Metallocene Compound
제조예 1 Preparation Example 1
Figure imgf000027_0001
Figure imgf000027_0001
1-1 리간드화합물의 제조 1-1 Preparation of Ligand Compound
fluorene 2 g을 5 mL MTBE, hexane 100 mL에 녹여 2.5 M n-BuLi hexane solution 5.5 mL를 dry ice/acetone bath에서 적가하여 상온에서 밤새 교반하였다. (6-(tert- butoxy)hexyl)dichloro(methyl)silane 3.6 g-i: 핵산 (hexane) 50 mL에 녹여 dry ice/acetone bath하에서 fluorene-Li 슬러리를 30분 동안 transfer하여 상온에서 밤새 교반하였다. 이와 동시에 5,8-dimethyl-5,10-dihydroindeno[l,2-b]indole (12 mmol, 2.8 g) 또한 THF 60 mL에 녹여 2.5M n-BuLi hexane solution 5.5 mL를 dry ice/acetone bath에서 적가하여 상은에서 밤새 교반하였다. fluorene과 (6-(tert-butoxy)hexyl)dichloro(methyl)silane 과의 반응 용액을 NMR 샘플링하여 반응 완료를 확인한 후 5,8-dimethyl-5,10- dihydroindeno[ 1 ,2-b] indole- Li solution을 dry ice/acetone bath하에서 transfer하였다 . 상온에서 밤새 교반하였다. 반응 후 ether/water로 추출 (extraction)하여 유기층의 잔류수분을 MgS04로 제거 후 리간드 화합물 (Mw 597.90, 12 mmol)을 얻었으며 이성질체 (isomer) 두 개가 생성되었음을 1H-NMR에서 확인할 수 있었다. 2 g of fluorene was dissolved in 5 mL MTBE and 100 mL of hexane, and 5.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath, followed by stirring at room temperature overnight. 3.6 gi of (6- (tert-butoxy) hexyl) dichloro (methyl) silane: dissolved in 50 mL of nucleic acid (hexane), the fluorene-Li slurry was transferred for 30 minutes under a dry ice / acetone bath and stirred at room temperature overnight. At the same time, 5,8-dimethyl-5,10-dihydroindeno [l, 2-b] indole (12 mmol, 2.8 g) was also dissolved in 60 mL of THF and 5.5 mL of 2.5M n-BuLi hexane solution in a dry ice / acetone bath. It was added dropwise and the mixture was stirred overnight at silver. NMR sampling the reaction solution between fluorene and (6- (tert-butoxy) hexyl) dichloro (methyl) silane to confirm the completion of the reaction, followed by 5,8-dimethyl-5,10-dihydroindeno [1, 2-b] indole- Li solution was transferred under dry ice / acetone bath. Stir overnight at room temperature. After the reaction was extracted with ether / water (extraction) to remove the residual moisture of the organic layer with MgS0 4 and to obtain a ligand compound (Mw 597.90, 12 mmol), it was confirmed in 1H-NMR that two isomers were formed.
Ή NMR (500 MHz, d6-benzene): -0.30 - -0.18 (3H, d), 0.40 (2H, m), 0.65 ~ 1.45 NMR (500 MHz, d6-benzene): -0.30--0.18 (3H, d), 0.40 (2H, m), 0.65-1.45
(8H, m), 1.12 (9H, d), 2.36 ~ 2.40 (3H, d), 3.17 (2H, m), 3.41 ~ 3.43 (3H, d), 4.17 〜 4.21 (1H, d), 4.34 - 4.38 (1H, d), 6.90 ~ 7.80 (15H, m) (8H, m), 1.12 (9H, d), 2.36-2.40 (3H, d), 3.17 (2H, m), 3.41-3.43 (3H, d), 4.17-4.21 (1H, d), 4.34-4.38 (1H, d), 6.90-7.80 (15H, m)
1-2 메탈로센 화합물의 제조  Preparation of 1-2 metallocene compound
상기 1-1에서 합성한 리간드 화합물 7.2 g (12 mmol)을 diethylether 50 mL에 녹여 2.5 M n-BuLi hexane solution 11.5 mL를 dry ice/acetone bath에서 적가하여 상온에서 밤새 교반하였다. 진공 건조하여 갈색 (brown color)의 sticky oil을 얻었다. 를루엔에 녹여 슬러리를 얻었다. ZrCl4(THF)2를 준비하고 를루엔 50 mL를 넣어 슬러리로 준비하였다. ZrCl4(THF)2의 50 mL를루엔 슬러리를 dry ice/acetone bath에서 transfer하였다. 상온에서 밤새 교반함에 따라 보라색 (violet color)으로 변화하였다. 반웅 용액을 필터하여 LiCl을 제거하였다. 여과액 (filtrate)의 를루엔을 진공 건조하여 제거한 후 핵산을 넣고 1시간 동안 sonication하였다. 슬러리를 필터하여 여과된 고체 (filtered solid)인 질은 보라색 (dark violet)의 메탈로센 화합물 6 g (Mw 758.02, 7.92 mmol, yield 66mol%)을 얻었다. 1H-NMR상에서 두 개의 isomer가 관찰되었다. 7.2 g (12 mmol) of the ligand compound synthesized in 1-1 was dissolved in 50 mL of diethylether, and 11.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath, followed by stirring at room temperature overnight. Drying in vacuo gave a brown colored sticky oil. It was dissolved in toluene to obtain a slurry. ZrCl 4 (THF) 2 was prepared, and 50 mL of toluene was added to prepare a slurry. 50 mL of ZrCl 4 (THF) 2 was transferred to a luene slurry in a dry ice / acetone bath. The solution was changed to violet color at room temperature overnight. The reaction solution was filtered to remove LiCl. The toluene of the filtrate was removed by vacuum drying, and the nucleic acid was added and sonicated for 1 hour. The slurry was filtered to obtain 6 g of a dark violet metallocene compound (Mw 758.02, 7.92 mmol, yield 66 mol%). Two isomers were observed on 1 H-NMR.
Ή NMR (500 MHz, CDC13): 1.19 (9H, d), 1.71 (3H, d), 1.50 ~ 1.70(4H, m), 1.79(2H, m), 1.98 ~ 2.19(4H, m), 2.58(3H, s), 3.38 (2H, m), 3.91 (3H, d), 6.66 ~ 7.88 (15H, m) NMR (500 MHz, CDC1 3 ): 1.19 (9H, d), 1.71 (3H, d), 1.50-1.70 (4H, m), 1.79 (2H, m), 1.98-2.19 (4H, m), 2.58 (3H, s), 3.38 (2H, m), 3.91 (3H, d), 6.66-7.88 (15H, m)
Figure imgf000028_0001
Figure imgf000028_0001
2-1 리간드 화합물의 제조  Preparation of 2-1 Ligand Compound
250 mL flask에 5-methyl-5,10-dihydiOm(ieno[l,2-b]indole 2.63 g (12 mmol)을 넣고 THF 50 mL에 녹인 후 2.5M n-BuLi hexane solution 6 mL를 dr yice/acetone bath에서 적가하여 상온에서 밤새 교반하였다. 또 다른 250 mL flask에 (6-(tert- butoxy)hexyl)dichloro(methyl)silane 1.62 g(6 mmol)¾r hexane 100 mL에 녹여 준비한 후 dry ice/acetone bath 하에서 5-methyl-5,10-dihydroindeno[l,2-b]indole의 lithiated solution에 천천히 적가하여 상온에서 밤새 교반하였다. 반웅 후 ether/water로 추출하여 유기층의 잔류수분을 MgS04로 제거 후 진공 건조하여 리간드 화합물 3.82 g (6 mmol)을 얻었으며 이를 1H-NMR에서 확인하였다. A 250 mL flask 5-methyl- 5, 10-dihydiOm (ieno [l, 2-b] indole 2.63 g ( after putting 12 mmol) was dissolved in THF 50 mL 2.5M n-BuLi hexane solution 6 mL of dr yice / The solution was added dropwise in an acetone bath and stirred overnight at room temperature, and dissolved in 100 mL of (6- (tert-butoxy) hexyl) dichloro (methyl) silane in 100 mL of (6- (tert-butoxy) hexyl) dichloro (methyl) silane) in another 250 mL flask, followed by dry ice / acetone After slowly adding dropwise to a lithiated solution of 5-methyl-5,10-dihydroindeno [l, 2-b] indole in a bath and stirring at room temperature overnight, the reaction mixture was extracted with ether / water and the residual moisture of the organic layer was removed with MgS0 4 . Drying in vacuo gave 3.82 g (6 mmol) of ligand compound which was confirmed by 1 H-NMR.
Ή NMR (500 MHz, CDC13): -0.33 (3H, m), 0.86 ~ 1.53 (10H, m), 1.16 (9H, d), 3.18 (2H, m), 4.07 (3H, d), 4.12 (3H, d), 4.17 (1H, d), 4.25 (1H, d), 6.95 ~ 7.92 (16H, m)  NMR (500 MHz, CDC13): -0.33 (3H, m), 0.86 to 1.53 (10H, m), 1.16 (9H, d), 3.18 (2H, m), 4.07 (3H, d), 4.12 (3H , d), 4.17 (1H, d), 4.25 (1H, d), 6.95-7.92 (16H, m)
2-2 메탈로센 화합물의 제조  2-2 Preparation of Metallocene Compound
상기 2-1에서 합성한 리간드 화합물 3.82 g (6 mmol)을 toluene 100 mL와 MTBE 5 mL에 녹인 후 2.5M n-BuLi hexane solution 5.6 mL(14 mmol)를 dryice/acetone bath에서 적가하여 상온에서 밤새 교반하였다. 또 다른 flask에 ZrCL»(THF)2 2.26 g (6 mmol)을 준비하고 toluene 100ml를 넣어 슬러리로 준비하였다. ZrCl4(THF)2의 toluene slurry를 litiation된 리간드에 dry ice/acetone bath에서 transfer하였다. 상온에서 밤새 교반하였고 violet color로 변화하였다. 반웅 용액을 필터하여 LiCl을 제거한 후 얻어진 여액을 진공 건조하여 hexane을 넣고 sonication하였다. 슬러리를 필터하여 filtered solid인 dark violet 의 메탈로센 화합물 3.40 g (yield 71.1mol%)을 얻었다. 3.82 g (6 mmol) of the ligand compound synthesized in 2-1 above was dissolved in 100 mL of toluene and 5 mL of MTBE, and then 5.6 mL (14 mmol) of 2.5M n-BuLi hexane solution was driedice / acetone. It was added dropwise in the bath and stirred overnight at room temperature. In another flask, 2.26 g (6 mmol) of ZrCL »(THF) 2 was prepared, and 100 ml of toluene was added to prepare a slurry. Toluene slurry of ZrCl 4 (THF) 2 was transferred to litiated ligand in a dry ice / acetone bath. It stirred at room temperature overnight and it changed into violet color. The reaction solution was filtered to remove LiCl, and the filtrate was dried in vacuo, and hexane was added to sonication. The slurry was filtered to obtain 3.40 g (yield 71.1 mol%) of a metal violet compound of dark violet as a filtered solid.
Ή NMR (500 MHz, CDC13): 1.74 (3H, d), 0.85 ~ 2.33(1 OH, m), 1.29(9H, d), 3.87 (3H, s), 3.92 (3H, s), 3.36(2H, m), 6.48 ~ 8.10 (16H, m) 제 2 메탈로센 화합물의 제조실시예  NMR (500 MHz, CDC13): 1.74 (3H, d), 0.85-2.33 (1 OH, m), 1.29 (9H, d), 3.87 (3H, s), 3.92 (3H, s), 3.36 (2H m), 6.48-8.10 (16H, m) Preparation Example of Second Metallocene Compound
제조예 3  Preparation Example 3
.6-클로로핵사놀 (6-chlorohexanol)을 사용하여 문헌 (Tetrahedron Lett. 2951 (1988))에 제시된 방법으로 t-Butyl-0-(CH2)6-Cl을. 쎄조하고, 여기에 NaCp를 반웅시켜 8 -0- ¾)6-^¾를 얻었다 (수율 60%, b.p. 80°C / 0.1 mmHg). Use 6-chlorohexanol to prepare t-Butyl-0- (CH 2 ) 6 -Cl using the method presented in Tetrahedron Lett. 2951 (1988) . Wash, and NaCp was reacted here to give 8 -0- ¾) 6- ^ ¾ (yield 60%, bp 80 ° C / 0.1 mm Hg).
또한, -78 °C에서 t-Butyl-0-(CH2)6-C5H5를 THF에 녹이고, 노르말 부틸리튬 (n- BuLi)을 천천히 가한 후， 실온으로 승온시킨 후, 8시간 반웅시켰다. 그 용액을 다시 -78 °C에서 ZrCl4(THF)2(1.70g, 4.50mmol)/THF(30m )의 서스펜젼 (suspension) 용액에 기 합성된 리튬염 (lithium salt) 용액을 천천히 가하고 실온에서 6시간 동안 더 반웅시켰다. Further, t-Butyl-0- (CH 2 ) 6 -C 5 H 5 was dissolved in THF at -78 ° C, and normal butyllithium (n-BuLi) was slowly added, followed by heating to room temperature, followed by an 8 hour reaction. I was. The solution was slowly added to a pre-synthesized lithium salt solution at -78 ° C to a suspension solution of ZrCl 4 (THF) 2 (1.70 g, 4.50 mmol) / THF (30 m) at room temperature. Recoiled for 6 hours more.
모든 휘발성 물질을 진공 건조하고, 얻어진 오일성 액체 물질에 헥산 (hexane) 용매를 가하여 걸러내었다. 걸러낸 용액을 진공 건조한 후, 핵산을 가해 저온 (-20°C)에서 침전물을 유도하였다. 얻어진 침전물을 저온에서 걸러내어 흰색 고체 형태의 [tBu-0-(C¾)6-C5H4]2ZrCl2화합물을 얻었다 (수율 92%). All volatiles were dried in vacuo and the resulting oily liquid material was filtered off by addition of hexane solvent. After the filtered solution was dried in vacuo, nucleic acid was added to induce precipitate at low temperature (-20 ° C). The obtained precipitate was filtered at low temperature to give a [tBu-0- (C¾) 6 -C 5 H 4 ] 2 ZrCl 2 compound as a white solid (yield 92%).
Ή NMR (300 MHz, CDC13): 6.28 (t, J = 2.6 Hz, 2 H), 6.19 (t, J = 2.6 Hz, 2 H), 3.31NMR (300 MHz, CDC1 3 ): 6.28 (t, J = 2.6 Hz, 2H), 6.19 (t, J = 2.6 Hz, 2H), 3.31
(t, 6.6 Hz, 2 H), 2.62 (t, J = 8 Hz), 1.7 - 1.3 (m, 8 H), 1.17 (s, 9 H). (t, 6.6 Hz, 2H), 2.62 (t, J = 8 Hz), 1.7-1.3 (m, 8H), 1.17 (s, 9H).
13C NMR (CDCI3): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00. 제조예 4 (tBu-O-(CH?½)(CH Si(C (CH^4)(tBu-NUiCl? 의 제조 13 C NMR (CDCI 3 ): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00. Preparation Example 4 (tBu-O- (CH ? ½) (CH Si (C (CH ^ 4) (tBu-NUiCl ? Preparation of ? )
상온에서 50 g의 Mg(s)를 10 L 반웅기에 가한 후, THF 300 mL을 가하였다 . 12 0.5 g 정도를 가한 후, 반웅기 온도를 50 °C로 유지하였다. 반웅기 온도가 안정화된 후 250 g의 6-t-부록시핵실 클로라이드 (6-t-buthoxyhexyl chloride)를 피딩펌프 (feeding pump)를 이용하여 5 mL/min의 속도로 반웅기에 가하였다. 6-t- 부록시핵실 클로라이드를 가함에 따라 반응기 온도가 4 내지 5 °C정도 상승하는 것을 관찰하였다. 계속적으로 6-t-부톡시핵실 클로라이드을 가하면서 12 시간 교반하였다. 반응 12시간 후 검은색의 반응용액을 얻었다. 생성된 검은색의 용액 2 mL 취한 뒤 물을 가하여 유기층을 얻어 1H-NMR을 통해 6-t-부톡시핵산 (6-t- buthoxyhexane)을 확인하였다. 상기 6ᅳ t-부특시핵산으로부터 그리냐드 (Gringanrd) 반웅이 잘 진행되었음을 알 수 있었다. 그리하여 6-t-부특시핵실 마그네슘 클로라어—(6-t-buthoxyhexyl magnesium chloride)를 합성하였다. 50 g of Mg (s) was added to a 10 L reaction vessel at room temperature, followed by 300 mL of THF. After adding 0.5 g of 1 2 , the reaction temperature was maintained at 50 ° C. After the reaction temperature was stabilized, 250 g of 6-t-buthoxyhexyl chloride was added to the reaction vessel at a rate of 5 mL / min using a feeding pump. It was observed that the reactor temperature rose by 4-5 ° C. with the addition of 6-t-appendix nucleus chloride. The mixture was stirred for 12 hours while adding 6-t-butoxynuxyl chloride. After 12 hours, a black reaction solution was obtained. 2 mL of the resulting black solution was taken and water was added thereto to obtain an organic layer. 6-t-butoxynucleic acid (6-t-buthoxyhexane) was confirmed by 1 H-NMR. It can be seen that the Gringanrd reaction progressed well from the 6 ′ t-subspecific nucleic acid. Thus 6-t-buthoxyhexyl magnesium chloride was synthesized.
MeSiCl3 500 g과 1 L의 THF를 반웅기에 가한 후 반웅기 온도를 -20°C까지 넁각하였다. 합성한 6-t-부특시핵실 마그네슘 클로라이드 중 560 g을 피딩펌프를 이용하여 5 mL/min의 속도로 반웅기에 가하였다. 그리냐드 시약 (Grignard reagent)의 피딩 (feeding)이 끝난 후 반웅기 온도를 천천히 상온으로 올리면서 12시간 교반하였다. 반응 12시간 후 흰색의 MgCl2염이 생성되는 것을 확인하였다. 핵산 4 L을 가하여 랩도리 (labdori)을 통해 염을 제거하여 필터용액을 얻었다. 얻은 필터용액을 반응기에 가한 후 70°C에서 핵산을 제거하여 엷은 노란색의 액체를 얻었다. 얻은 액체를 1H-NMR을 통해 원하는 메틸 (6-t-부록시 핵실)디클로로실란 {Methyl(6-t-buthoxy hexyl)dichlorosilane} 화합물임을 확인하였다. After adding 500 g of MeSiCl 3 and 1 L of THF to the reaction vessel, the reaction temperature was adjusted to -20 ° C. 560 g of the synthesized 6-t-subsilicate magnesium chloride was added to the reaction vessel at a rate of 5 mL / min using a feeding pump. After feeding the Grignard reagent, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours, it was confirmed that a white MgCl 2 salt was produced. 4 L of nucleic acid was added to remove the salt through a labdori to obtain a filter solution. After adding the obtained filter solution to the reactor, the nucleic acid was removed at 70 ° C to obtain a pale yellow liquid. It was identified as methyl (6-t- Appendix haeksil upon) the desired liquid obtained by the 1H-NMR dichlorosilane {Methyl (6 -t-buthoxy hexyl ) dichlorosilane} compound.
1H-NMR (CDC13): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 1 H-NMR (CDC13): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7
(s, 3H) (s, 3H)
테트라메틸시클로펜타디엔 (tetramethylcyclopentadiene) 1.2 mol (150 g)와 2.4 L의 THF를 반응기에 가한 후 반응기 온도를 -20°C로 넁각하였다. n-BuLi 480 mL 피딩펌프를 이용하여 5 mL/min의 속도로 반웅기에 가하였다. n-BuLi을 가한 후 반웅기 온도를 천천히 상온으로 을리면서 12시간 교반하였다. 반응 12시간 후, 당량의 메틸 (6-t-부톡시 핵실)디클로로실란 (Methyl(6-t-buthoxy hexyl)dichlorosilane) (326 g, 350 mL)을 빠르게 반웅기에 가하였다. 반응기 온도를 천천히 상온으로 올리면서 12시간 교반한 후 다시 반웅기 온도를 0°C로 냉각시킨 후 2당량의 t- BuNH2을 가하였다. 반웅기 은도를 천천히 상온으로 을리면서 12시간 교반하였다. 반웅 12시간 후 THF을 제거하고 4 L의 핵산을 가하여 랩도리를 통해 염을 제거한 필터용액을 얻었다. 필터용액을 다시 반웅기에 가한 후, 핵산을 70 °C에서 제거하여 노란색의 용액을 얻었다. 얻을 노란색의 용액을 1H-NMR을 통해 메틸 (6- t-부록시핵실) (테트라메틸 CpH)t-부틸아미노실란 (Methyl(6-t- buthoxyhexyl)(tetramethylCpH)t-Butylaminosilane) 화합물임을 확인하였다. 1.2 mol (150 g) of tetramethylcyclopentadiene and 2. 4 L of THF were added to the reactor, and the reactor temperature was changed to -20 ° C. The reaction was added at a rate of 5 mL / min using an n-BuLi 480 mL feeding pump. After n-BuLi was added, the reaction mixture was stirred for 12 hours while slowly warming to room temperature. After the reaction was 12 hours and the equivalent amount of methyl quickly (6 -t- butoxy haeksil) dichlorosilane (Methyl (6 -t-buthoxy hexyl ) dichlorosilane) (326 g, 350 mL) was added to the semi-unggi. After stirring for 12 hours while slowly raising the temperature of the reactor to room temperature, the reaction mixture was cooled to 0 ° C. again and then 2 equivalents of t- BuNH 2 was added. Banunggi silverware was stirred for 12 hours slowly at room temperature. After 12 hours of reaction, THF was removed and 4 L of nucleic acid was added to obtain a filter solution from which salts were removed through labdori. After the filter solution was added to the reaction vessel again, the nucleic acid was removed at 70 ° C. to obtain a yellow solution. The yellow solution obtained was identified as methyl (6-t-butoxynucleosil) (tetramethyl CpH) t-butylaminosilane (Methyl (6-t-buthoxyhexyl) (tetramethylCpH) t-Butylaminosilane) compound by 1 H-NMR. .
n-BuLi과 리간드 디메틸 (테트라메틸 CpH)t-부틸아민실란 n-BuLi and ligand dimethyl (tetramethyl CpH) t-butylaminesilane
(Dirnethyl(tetramethylCpH)t-Butylaminosilane)로부터 THF용액에서 합성한 8 °C의 리간드의 디리튬염에 TiCl3(THF)3(10 mmol)을 빠르게 가하였다. 반웅용액을 천천히 -78 °C에서 상온으로 올리면서 12시간 교반하였다. 12시간 교반 후， 상은에서 당량의 PbCl2(10mmol)를 반웅용액에 가한 후 12시간 교반하였다. 12시간 교반 후, 푸른색을 피는 질은 검은색의 용액을 얻었다. 생성된 반응용액에서 THF를 제거ᅳ한 후 핵산을 가하여 생성물을 필터하였다. 얻을 필터용액에서 핵산을 제거한 후, 1H-NMR로부터 원하는 ([methyl(6-t-buthoxyhexyl)silyl( 5-tetmmethylCp)(t- Butylamido)]TiCl2)인 (tBu-0-(CH2)6)(CH3)Si(C5(CH3)4)(tBu-N)TiCl2 임을 확인하였다. TiCl 3 (THF) 3 (10 mmol) was rapidly added to the dilithium salt of 8 ° C ligand synthesized from (Dirnethyl (tetramethylCpH) t-Butylaminosilane) in THF solution. The reaction solution was stirred for 12 hours while slowly raising the temperature to -78 ° C. After stirring for 12 hours, an equivalent amount of PbCl 2 (10 mmol) was added to the semi-aqueous solution in silver, followed by stirring for 12 hours. After stirring for 12 hours, the blue vagina obtained a black solution. After removing THF from the reaction solution, nucleic acid was added to filter the product. After removing the nucleic acid from the resulting filter solution, the desired ([methyl (6-t-buthoxyhexyl) silyl (5-tetmmethylCp) (t- Butylamido)] TiCl 2 ) was removed from 1H-NMR (tBu-0- (CH 2 ) 6 It was confirmed that (CH 3 ) Si (C 5 (CH 3 ) 4 ) (tBu-N) TiCl 2 .
1H-NMR (CDC13): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 ~ 0.8 (m), 1.4 (s, 9H), 1.2(s, 9H), 0.7 (s, 3H) 1 H-NMR (CDC1 3 ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 to 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H), 0.7 (s, 3 H)
<흔성 담지 촉매의 제조 실시예 > <Example of preparing a supported catalyst>
실시예 1  Example 1
1-1 담지체 건조  1-1 Carrier drying
실리카 (Grace Davison사 제조 SYLOPOL 948)를 400°C의 온도에서 15 시간 동안 진공을 가한 상태에서 탈수하였다. Silica (SYLOPOL 948, manufactured by Grace Davison) was dehydrated under vacuum at a temperature of 400 ° C. for 15 hours.
1-2 담지 촉매 제조  1-2 Supported Catalyst Preparation
건조된 실리카 10 g를 유리 반웅기에 넣고, 를루엔 100 mL을 추가로 넣고 교반을 한다. 10 wt% 메틸알루미녹산 (MAO)/를루엔 용액을 50 mL를 가하여 40 °C에서 교반하며 천천히 반웅시켰다. 이 후 충분한 양의 를루엔으로 세척하여 반응하지 않은 알루미늄 화합물을 제거하고, 감압하여 남아 있는 를루엔을 제거하였다. 다시 를루엔 100 mL를 투입한 후， 상기 제조예 1에서 제조된 메탈로센 촉매 0.25 mmol-ir 를루엔에 녹여 같이 투입하여 1시간 동안 반웅을 시켰다. 반응이 끝난 후, 상기 제조예 3에서 제조된 메탈로센 촉매 0.25 mm이을 를루엔에 녹여 투입한 후， 1시간 동안 반웅을 추가로 시켰다. 반웅이 끝난 후, 교반을 멈추고 를루엔층을 분리제거 후, 아닐리늄 보레이트 (N, N-dimethylanilinium tetrakis(pentafluorophenyl)borate, AB) 1.0 mm 을 투입하고 1시간 동안 교반을 시킨 후, 50°C에서 감압하여 를루엔을 제거하여, 담지 촉매를 제조하였다. 시예 2 10 g of dried silica is placed in a glass reactor, and 100 ml of toluene is added and stirred. 50 mL of 10 wt% methylaluminoxane (MAO) / luene solution was added and the reaction was slowly reacted at 40 ° C. with stirring. Thereafter, the mixture was washed with a sufficient amount of toluene to remove unreacted aluminum compound, and reduced pressure to remove remaining toluene. 100 mL of toluene was added again, and then 0.25 mmol-ir of the metallocene catalyst prepared in Preparation Example 1 was dissolved in toluene and added together to react for 1 hour. I was. After the reaction was completed, 0.25 mm of the metallocene catalyst prepared in Preparation Example 3 was dissolved in toluene, and then reaction was added for 1 hour. After banung is over, after separating and removing the toluene layer to stop the stirring, anilinium borate in (N, N-dimethylanilinium tetrakis ( pentafluorophenyl) borate, AB) it introduced a 1.0 mm and then the mixture was stirred for one hour, 50 ° C Toluene was removed under reduced pressure to prepare a supported catalyst. Example 2
실시예 1에서 제조예 1의 메탈로센 촉매 0.25 mmol 대신 제조예 2의 메탈로센 촉매 0.25 mmd을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 담지 촉매를 제조하였다. 시예 3  The supported catalyst was prepared in the same manner as in Example 1, except that 0.25 mmd of the metallocene catalyst of Preparation Example 2 was used instead of 0.25 mmol of the metallocene catalyst of Preparation Example 1 in Example 1. Example 3
상기 실시예 1에서 제조예 1의 메탈로센 촉매 0.25 mmol 반웅 1시간이 끝난 후, 제조예 4의 메탈로센 촉매 0.25 mmol 반응 1시간을 추가로 진행한다. 이 후, 제조예 3의 메탈로센 촉매 0.25. mmol 반응을 진행하는 것을 제외하고는 동일한 방법으로 담지 촉매를 제조하였다. 시예 4  After 1 hour of 0.25 mmol reaction of the metallocene catalyst of Preparation Example 1 in Example 1 was completed, the reaction of 0.25 mmol of the metallocene catalyst of Preparation Example 4 was further performed. Thereafter, the metallocene catalyst 0.25 of Preparation Example 3. The supported catalyst was prepared in the same manner except that the mmol reaction was carried out. Example 4
상기 실시예 3에서 처음에 반응시킨 제조예 1의 메탈로센 촉매 0.25 mmol 대신 제조예 2의 메탈로센 촉매 0.25 mmol 반웅을 사용한 것을 제외하고는 동일한 방법으로 담지 촉매를 제조하였다. 실시예 5  The supported catalyst was prepared in the same manner as in Example 3, except that 0.25 mmol reaction of the metallocene catalyst of Preparation Example 2 was used instead of 0.25 mmol of the metallocene catalyst of Preparation Example 1 initially reacted. Example 5
상기 실시예 3에서 처음에 반웅시킨 제조예 1의 메탈로센 촉매 0.25 mmol 대신 제조예 2의 메탈로센 촉매 0.25 mmol 반웅을 먼저 진행한다. 이후 두 번째 촉매로 제조예 1의 메탈로센 촉매 0.25 mmol 을 사용하고, 마지막으로 제조예 3의 메탈로센 촉매를 사용하는 것을 제외하고는 동일한 방법으로 담지 촉매를 제조하였다. 비교예 1 건조된 실리카 10 g를 유리 반웅기에 넣고, 틀루엔 100 mL을 추가로 넣고 교반을 한다. 10 wt% 메틸알루미녹산 (MAO)/를루엔 용액을 50 mL를 가하여 40°C에서 교반하며 천천히 반응시켰다. 이 후 충분한 양의 를루엔으로 세척하여 반웅하지 않은 알루미늄 화합물을 제거하고, 감압하여 남아 있는 를루엔을 제거하였다. 다시 를루엔 100 mL를 투입한 후， 상기 제조예 3에서 제조된 메탈로센 촉매 0.25 mmol을 를루엔에 녹여 같이 투입하여 1시간 동안 반응을 시켰다. 반웅이 끝난 후， 50 °C에서 감압하여 를루엔을 제거하여, 담지 촉매를 제조하였다. 비교예 2 Instead of 0.25 mmol of the metallocene catalyst of Preparation Example 1, which was initially reacted in Example 3, 0.25 mmol of the metallocene catalyst of Preparation Example 2 was first performed. Thereafter, 0.25 mmol of the metallocene catalyst of Preparation Example 1 was used as the second catalyst, and finally, the supported catalyst was prepared in the same manner except that the metallocene catalyst of Preparation Example 3 was used. Comparative Example 1 10 g of dried silica is placed in a glass reactor, and 100 ml of toluene is added and stirred. 50 mL of 10 wt% methylaluminoxane (MAO) / luene solution was added thereto, followed by slow reaction at 40 ° C. with stirring. This was followed by washing with a sufficient amount of toluene to remove the unreacted aluminum compound, and to remove the remaining toluene under reduced pressure. 100 mL of toluene was added again, and 0.25 mmol of the metallocene catalyst prepared in Preparation Example 3 was dissolved in toluene, and then reacted for 1 hour. After the reaction was completed, toluene was removed under reduced pressure at 50 ° C., to carry a supported catalyst. Comparative Example 2
상기 비교예 1에서 처음에 반응시킨 제조예 3의 메탈로센 촉매 0.25 mmol 대신 제조예 4의 메탈로센 촉매 0.25 mmol 반웅을 사용한 것을 제외하고는 동일한 방법으로 담지 촉매를 제조하였다. 비교예 3  The supported catalyst was prepared in the same manner except that 0.25 mmol reaction of the metallocene catalyst of Preparation Example 4 was used instead of 0.25 mmol of the metallocene catalyst of Preparation Example 3, which was initially reacted in Comparative Example 1. Comparative Example 3
상기 비교예 2에서 처음에 반응시킨 제조예 4의 메탈로센 촉매 0.25 mmol 반응 이후， 제조예 3의 메탈로센 촉매 0.25 mmol 반응을 추가로 진행한 것을 제외하고는 동일한 방법으로 담지 촉매를 제조하였다. 비교예 4  After the 0.25 mmol reaction of the metallocene catalyst of Preparation Example 4, which was first reacted in Comparative Example 2, the supported catalyst was prepared in the same manner except that the 0.25 mmol reaction of the metallocene catalyst of Preparation Example 3 was further performed. . Comparative Example 4
상기 비교예 3에서 마지막에 아닐리늄 보레이트 (Ν,Ν-dimethylanilinium tetrakis(pentafluorophenyl)borate, AB) 1.0 mmol을 투입한 것을 제외하고는 동일한 방법으로 담지 촉매를 제조하였다.  The supported catalyst was prepared in the same manner as in Comparative Example 3, except that 1.0 mmol of anilinium borate (Ν, Ν-dimethylanilinium tetrakis (pentafluorophenyl) borate, AB) was finally added.
<실험예 > Experimental Example
에틸렌 -1-핵센 공중합  Ethylene-1-Nexene Copolymerization
상기 실시예 1 내지 5 및 비교예 1 내지 4 에서 제조한 각각의 담지 촉매 50 mg을 드라이박스에서 정량하여 50 mL의 유리병에 각각 담은 후 고무 격막으로 밀봉하여 드라이박스에서 꺼내어 주입할 촉매를 준비하였다. 중합은 기계식 교반기가 장착된 온도 조절이 가능하고 고압에서 이용되는 2L 금속 합금 반웅기에서 수행하였다. 50 mg of each of the supported catalysts prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were quantified in a dry box, respectively, placed in a 50 mL glass bottle, sealed with a rubber diaphragm, and taken out of the dry box to prepare a catalyst for injection. It was. Polymerization is a 2L metal alloy used at high pressure with temperature control equipped with a mechanical stirrer It was carried out in the counterunggi.
이 반웅기에 l .O mmol 트리에틸알루미늄 (triethylaluminum)이 들어 있는 헥산 1 L와 1-핵센 (5mL)을 주입하고, 상기 준비한 각각의 담지 촉매를 반웅기에 공기 접촉 없이 투입한 후, 80 °C에서 기체 에틸렌 단량체를 9 Kgf/cm2의 압력으로 계속적으로 가하면서 1시간 동안 중합하였다. 증합의 종결은 먼저 교반을 멈춘 후 에틸렌을 배기시켜 제거함으로써 완료시켰다. Into this reaction, 1 L of hexane and 1-nuxene (5 mL) containing lO mmol triethylaluminum were charged, and each of the supported catalysts was introduced into the reactor without air contact, followed by 80 ° C. The gas ethylene monomer at C was polymerized for 1 hour with continuous addition of pressure at 9 Kgf / cm 2 . Termination of the polymerization was completed by first stopping the stirring and then evacuating and removing ethylene.
이로부터 얻어진 중합체는 중합 용매를 여과시켜 대부분을 제거한 후 80 "C 진공 오븐에서 4 시간 동안 건조시켰다.  The polymer obtained therefrom was filtered off to remove most of the polymerization solvent and then dried in an 80 " C vacuum oven for 4 hours.
상기에서 제조한 각각의 촉매에 대한 중합 조건, 에틸렌 /1-핵센 중합 활성， 얻어진 중합체의 분자량 및 분자량 분포를 하기 표 1에 나타내었다.  The polymerization conditions, ethylene / 1-nuxene polymerization activity, molecular weight and molecular weight distribution of the obtained polymer for each catalyst prepared above are shown in Table 1 below.
【표 1】 Table 1
Figure imgf000034_0001
상기 표 2를 참고하면, 본 발명의 흔성 담지 촉매에 대한 실시예 1 내지 5는 2종 이상의 메탈로센 화합물을 포함하면서도, 단일 촉매 또는 제 2 메탈로센 화합물만을 포함하는 비교예보다 훨씬 높은 활성, 높은 분자량 및 넓은 분자량 분포를 가지는 중합체를 제조할 수 있음을 알 수 있다.
Figure imgf000034_0001
Referring to Table 2, Examples 1 to 5 for the common supported catalyst of the present invention include two or more metallocene compounds, but have a much higher activity than the comparative example including only a single catalyst or a second metallocene compound. It can be seen that a polymer having a high molecular weight and a broad molecular weight distribution can be prepared.

Claims

【특허청구범위】  [Patent Claims]
【청구항 1】  [Claim 1]
담체에 제 1 조촉매 화합물을 담지시키는 단계;  Supporting the first cocatalyst compound on a carrier;
상기 제 1 조촉매 화합물이 담지된 담체에 하기 화학식 1로 표시되는 제 1 메탈로센 화합물 1종 이상, 및 하기 화학식 3 내지 5로 표시되는 화합물 중에서 선택되는 제 2 메.탈로센 화합물 1종 이상을 담지시키는 단계; 및  At least one first metallocene compound represented by the following Formula 1 on the carrier on which the first cocatalyst compound is loaded, and at least one second methalocene compound selected from the compounds represented by the following Formulas 3 to 5 Supporting the step; And
상기 제 1 조촉매 화합물, 제 1 메탈로센 화합물, 및 제 2 메탈로센 화합물이 담지된 담체에 제 2 조촉매 화합물을 담지시키는 단계를 포함하는 흔성 담지 메탈로센 촉매의 제조방법:  A method for preparing a common supported metallocene catalyst comprising the step of supporting a second promoter catalyst on a carrier on which the first cocatalyst compound, the first metallocene compound, and the second metallocene compound are supported:
[  [
Figure imgf000035_0001
Figure imgf000035_0001
상기 화학식 1에서,  In Chemical Formula 1,
A는 수소, 할로겐， C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C6 내지 C20의 아릴기, C7 내지 C20의 알킬아릴기, C7 내지 C20의 아릴알킬기, C1 내지 C20의 알콕시기, C2 내지 C20의 알콕시알킬기, C3 내지 C20의 헤테로시클로알킬기, 또는 C5 내지 C20의 헤테로아릴기이고;  A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 A C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
D는 ᅳ으， -S-, -N(R)- 또는 -Si(R)(R')- 이고, 여기서 R 및 R'.은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 할로겐, C1，내지 C20의 알킬기, C2 내지 C20의 알케닐기, 또는 C6 내지 C20의 아릴기이고;  D is-, -S-, -N (R)-or -Si (R) (R ')-, wherein R and R'. Are the same as or different from each other, and are each independently hydrogen, halogen, C1, to An alkyl group of C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20;
L은 C1 내지 C10의 직쇄 또는 분지쇄 알킬렌기이고;  L is a C1 to C10 straight or branched chain alkylene group;
B는 탄소, 실리콘 또는 게르마늄이고;  B is carbon, silicon or germanium;
Q는 수소, 할로겐, C1 내지 C20의 알킬기， C2 내지 C20의 알케닐기, C6 내지 C20의 아릴기, C7 내지 C20의 알킬아릴기, 또는 C7 내지 C20의 아릴알킬기이고;  Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group;
M은 4족 전이금속이며;  M is a Group 4 transition metal;
X1 및 X2는 서로 동일하거나 상이하고, 각각 독립적으로 할로겐， C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C6 내지 C20의 아릴기, 니트로기, O 2015/056974 X 1 and X 2 are the same as or different from each other, and each independently halogen, C 1 to C 20 alkyl group, C 2 to C 20 alkenyl group, C 6 to C 20 aryl group, nitro group, O 2015/056974
아미도기, CI 내지 C20의 알킬실릴기， C1 내지 C20의 알콕시기, 또는 C1 내지 C20의 술폰네이트기이고; Amido groups, CI to C20 alkylsilyl groups, C1 to C20 alkoxy groups, or C1 to C20 sulfonate groups;
. C1 및 C2는 서로 동일하거나 상이하고, 각각 독립적으로 하기 화학식 2a, 화학식 2b 또는 하기 화학식 2c 중 하나로 표시되고， 단, C1 및 C2가 모두 화학식 2c인 경우는 제외하며; . C 1 and C 2 are the same as or different from each other, and are each independently represented by one of the following Chemical Formula 2a, Chemical Formula 2b, or Chemical Formula 2c, except that both C 1 and C 2 are Chemical Formula 2c;
[  [
Figure imgf000036_0001
Figure imgf000036_0001
[  [
Figure imgf000036_0002
Figure imgf000036_0002
[  [
Figure imgf000036_0003
Figure imgf000036_0003
상기 화학식 2a, 2b 및 2c에서, R1 내지 R17 및 R1' 내지 R9'는 서로 동일하거나 상이하고, 각각 독립적으로 수소， 할로겐, C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기， C1 내지 C20의 알킬실릴기， C1 내지 C20의 실릴알킬기, C1 내지 C20의 알콕시실릴기， C1 내지 C20의 알콕시기， C6 내지 C20의 아릴기, C7 내지 C20의 알킬아릴기, 또는 C7 내지 C20의 아릴알킬기이며， 상기 R10 내지 R17 중 서로 인접하는 2개 이상이 서로 연결되어 치환 또는 비치환된 지방족 또는 방향족 고리를 형성할 수 있고; In Formulas 2a, 2b and 2c, R1 to R17 and R1 'to R9' are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 alkyl Silyl group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, Two or more adjacent to each other of R10 to R17 are linked to each other to be substituted or unsubstituted aliphatic Or can form an aromatic ring;
[화학식 3]  [Formula 3]
(Cp^^niCp^^M^1,^ (Cp ^^ n iCp ^^ M ^ 1 , ^
상기 화학식 3에서,  In Chemical Formula 3,
M1은 4족 전이금속이고; M 1 is a Group 4 transition metal;
Cpl 및 Cp2는 서로 동일하거나 상이하고, 각각 독립적으로 시클로펜타디엔닐, 인데닐， 4,5,6,7-테트라하이드로 -1-인데닐, 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고, 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며; C p l and Cp 2 are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;
Ra 및 Rb는 서로 동일하거나 상이하고, 각각 독립적으로 수소, C1 내지R a and R b are the same as or different from each other, and each independently hydrogen, C1 to
C20의 알킬, C1 내지 C10의 알콕시, C2 내지 C20의 알콕시알킬， C6 내지 C20의 아릴, C6 내지 C10의 아릴옥시, C2 내지 C20의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬， C8 내지 C40의 아릴알케닐, 또는 C2 내지 C10의 알키닐이고; C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl Arylalkenyl of C8 to C40, or alkynyl of C2 to C10;
Z'은 할로겐 원자, C1 내지 C20의 알킬, C2 내지 C10의 알케닐, C7 내지 Z 'is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to
C40의 알킬아릴, C7 내지 C40의 아릴알킬, C6 내지 C20의 아릴, 치환되거나 치환되지 않은 C1 내지 C20의 알킬리덴， 치환되거나 치환되지 않은 아미노기, C2 내지 C20의 알킬알콕시，또는 C7 내지 C40의 아릴알콕시이고; C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene, substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 aryl Alkoxy;
n은 1 또는 0 이고;  n is 1 or 0;
[화학식 4]  [Formula 4]
(Cp3Rc) mB'(Cp4Rd)M2Z2 3-m , (Cp 3 R c ) m B '(Cp 4 R d ) M 2 Z 2 3-m ,
상기 화학식 4에서，  In Chemical Formula 4,
M2는 4족 전이 금속이고; M 2 is a Group 4 transition metal;
Cp3 및 Cp4는 서로 동일하거나 상이하고, 각각 독립적으로 시클로펜타디에닐, 인데닐， 4,5,6,7-테트라하이드로 -1-인데닐 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고, 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며; Cp 3 and Cp 4 are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals They may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
RC 및 Rd는 서로 동일하거나 상이하고， 각각 독립적으로 수소， C1 내지R C and R d are the same as or different from each other, and each independently hydrogen, C1 to
C20의 알킬， C1 내지 C10의 알콕시 , C2 내지 C20의 알콕시알킬， C6 내지 C20의 아릴， C6 내지 C10의 아릴옥시, C2 내지 C20의 알케닐， C7 내지 C40의 알킬아릴， C7 내지 C40의 아릴알킬, C8 내지 C40의 아릴알케닐, 또는 C2 내지 C10의 알키닐이고; C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7-C40 arylalkyl, C8-C40 arylalkenyl, or C2-C10 alkynyl;
Z2는 할로겐 원자， C1 내지 C20의 알킬， C2 내지 C10의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C6 내지 C20의 아릴， 치환되거나 치환되지 않은 C1 내지 C20의 알킬리덴， 치환되거나 치환되지 않은 아미노기, C2 내지 C20의 알킬알콕시 , 또는 C7 내지 C40의 아릴알콕시이고; Z 2 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene Or a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
B1은 Cp3Rc 고리와 Cp4Rd 고리를 가교 결합시키거나, 하나의 Cp4Rd 고리를 M2에 가교 결합시키는, 탄소, 게르마늄, 규소, 인 또는 질소 원자 함유 라디칼 중 하나 이상 또는 이들의 조합이고; B 1 is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp 3 R c ring with the Cp 4 R d ring or crosslinks one Cp 4 R d ring with M 2 Or a combination thereof;
m은 1 또는 0 이고;  m is 1 or 0;
[화학식 5]  [Formula 5]
(Cp5Re)B2(J)M3Z3 2 (Cp 5 R e ) B 2 (J) M 3 Z 3 2
상기 화학식 5에서,  In Chemical Formula 5,
M3은 4족 전이 금속이고; M 3 is a Group 4 transition metal;
Cp5는 시클로펜타디에닐, 인데닐, 4,5,6,7-테트라하이드로 -1-인데닐 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고， 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며; Cp 5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms Can be;
Re는 수소, C1 내지 C20의 알킬， C1 내지 C10의 알콕시， C2 내지 C20의 알콕시알킬， C6 내지 C20의 아릴, C6 내지 C10의 아릴옥시, C2 내지 C20의 알케닐, C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C8 내지 C40의 아릴알케닐, 또는 C2 내지 C10의 알키닐이고; R e is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl C7-C40 arylalkyl, C8-C40 arylalkenyl, or C2-C10 alkynyl;
Z3은 할로겐 원자, C1 내지 C20의 알킬， C2 내지 C10의 알케닐， C7 내지 C40의 알킬아릴, C7 내지 C40의 아릴알킬, C6 내지 C20의 아릴, 치환되거나 치환되지 않은 C1 내지 C20의 알킬리덴， 치환되거나 치환되지 않은 아미노기, C2 내지 C20의 알킬알콕시，또는 C7 내지 C40의 아릴알콕시이고； Z 3 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene Or a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
B2는 Cp5Re 고리와 J를 가교 결합시키는 탄소， 게르마늄, 규소, 인 또는 질소 원자 함유 라디칼중 하나 이상 또는 이들의 조합이고; B 2 is one or more or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp 5 R e ring and J;
J는 NRf, 0, PRf 및 S로 이루어진 군에서 선택된 어느 하나이고, 상기 Rf는 C1 내지 C20의 알킬， 아릴, 치환된 알킬 또는 치환된 아릴이다ᅳ 【청구항 2】 J is any one selected from the group consisting of NR f , 0, PR f and S, wherein R f is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl [Claim 2]
제 1항에 있어서, 상기 화학식 2a, 2b 및 2c의 R1 내지 R17 및 R1' 내지 R9'는 각각 독립적으로 수소, 메틸기, 에틸기, 프로필기, 이소프로필기, n-부틸기， tert-부틸기, 펜틸기, 핵실기; 헵틸기, 옥틸기, 페닐기, 할로겐기, 트리메틸실릴기， 트리에틸실릴기， 트리프로필실릴기, 트리부틸실릴기, 트리이소프로필실릴기, 트리메틸실릴메틸기, 메톡시기, 또는 에록시기인 흔성 담지 메탈로센 촉매의 제조방법. 【청구항 3】  According to claim 1, wherein in Formulas 2a, 2b and 2c R1 to R17 and R1 'to R9' are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, Pentyl group, nuclear group; Common supported metals that are heptyl, octyl, phenyl, halogen, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, methoxy or hydroxy Method for preparing a rosene catalyst. [Claim 3]
제 1항에 있어서， 상기 화학식 1의 L은 C4 내지 C8의 직쇄 또는 분지쇄 알킬렌기인 흔성 담지 메탈로센 촉매의 제조방법.  The method for preparing a common supported metallocene catalyst according to claim 1, wherein L in Formula 1 is a C4 to C8 linear or branched alkylene group.
【청구항 4】 [Claim 4]
거) 1항에 있어서, 상기 화학식 1의 A는 수소, 메틸기, 에틸기， 프로필기, 이소프로필기 , η-부틸기, tert-부틸기， 메록시메틸기, tert-부록시메틸기， 1-에톡시에틸기， 1_메틸 -1-메특시에틸기, 테트라하이드로피라닐기， 또는 테트라하이드로퓨라닐기인 흔성 담지 메탈로센 촉매의 제조방법.  (4) The compound of Formula 1, wherein A is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, η-butyl group, tert-butyl group, methoxymethyl group, tert-butoxymethyl group, 1-ethoxy A method for producing a common supported metallocene catalyst, which is an ethyl group, 1_methyl-1-methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group.
【청구항 5】 [Claim 5]
제 1항에 있어서, 상기 화학식 1로 표시되는 제 1 메탈로센 화합물은 하기 구조식 중 하나인 흔성 담지 메탈로센 촉매의 제조방법:  The method of claim 1, wherein the first metallocene compound represented by Chemical Formula 1 is one of the following structural formulas:
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000041_0001
089600/Μ0ΖΗΜ/Χ3<Ι 17.69S0/S10Z OAV
Figure imgf000042_0001
089600 / Μ0ΖΗΜ / Χ3 <Ι 17.69S0 / S10Z OAV
Figure imgf000042_0001
【청구항 6】 [Claim 6]
게 1항에 있어서, 상기 화학식 3으로 표시되는 제 2 메탈로센 화합물은 하기 구조식들 중 하나인 흔성 담지 메 제조방법:  The method of claim 1, wherein the second metallocene compound represented by Chemical Formula 3 is one of the following structural formulas:
Figure imgf000042_0002
Figure imgf000042_0002
Figure imgf000043_0001
Figure imgf000043_0001
Figure imgf000043_0002
Figure imgf000043_0002
Figure imgf000043_0003
Figure imgf000043_0003
42 42
Figure imgf000044_0001
Figure imgf000044_0001
【청구항 8】 [Claim 8]
제 1항에 있어서, 상기 화학식 5^ 표시되는 제 2 메탈로센 화합물은 하기 구조식들 중 하나인 흔성 담지 메탈로센 촉매의 제조방법: .  The method of claim 1, wherein the second metallocene compound represented by Chemical Formula 5 ^ is one of the following structural formulas:
Figure imgf000044_0002
Figure imgf000045_0001
Figure imgf000044_0002
Figure imgf000045_0001
【청구항 9】 [Claim 9]
제 1항에 있어서, 상기 제 1 조촉매 화합물은 하기 화학식 6으로 표시되고, 상기 제 2 조촉매 화합물은 하기 화학식 7로 표시되는, 흔성 담지 메탈로센 - 촉매의 제조방법:  The method of claim 1, wherein the first cocatalyst compound is represented by the following Chemical Formula 6, and the second cocatalyst compound is represented by the following Chemical Formula 7.
[화학샥 6]  [Chemistry 샥 6]
-[Al(Rls)-0-]k- 화학식 6에서， R18은 각각 독립적으로 할로겐, 할로겐 치환 또는 비치환된 탄소수 1 내지 20의 하이드로카빌기이고, k는 2 이상의 정수이고, -[Al (R ls ) -0-] k -In formula 6 , R 18 is each independently a halogen, halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,
[화학식 7]  [Formula 7]
T+[BG4]- 화학식 7에서 , T+은 +1가의 다원자 이온이고， Β는 +3 산화 상태의 붕소이고: G는 각각 독립적으로 하이드라이드기， 디알킬아미도기, 할라이드기, 알콕사이드기, 아릴옥사이드기, 하아드로카빌기， 할로카빌기 및 할로-치환된 하이드로카빌기로 이루어진 군에서 선택되고, 상기 G는 20개 이하의 탄소를 가지나, 단 하나 이하의 위치에서 G는 할라이드기이다. T + [BG 4 ]-In formula 7, T + is a + monovalent polyatomic ion, Β is a boron in +3 oxidation state : G is independently a hydride group, a dialkylamido group, a halide group, an alkoxide Group, an aryloxide group, a hadrocarbyl group, a halocarbyl group and a halo-substituted hydrocarbyl group, wherein G has up to 20 carbons, but at only one position G is a halide group to be.
【청구항 10】 [Claim 10]
제 1항에 있어서, 상기 제 1 메탈로센 화합물 및 제 2 메탈로센 화합물의 전이금속 대 담체의 질량비는 1 ： 10 내지 1 ： 1,000 인 흔성 담지 메탈로센 촉매의 제조방법.  The method of claim 1, wherein the mass ratio of the transition metal to the carrier of the first metallocene compound and the second metallocene compound is from 1: 10 to 1: 1,000.
【청구항 11】  [Claim 11]
게 1항에 있어서, 상기 조촉매 화합물 대 담체의 질량비는 1： 1 내지 1： 100 인 흔성 담지 메탈로센 촉매의 제조방법.  The method for preparing a common supported metallocene catalyst according to claim 1, wherein the mass ratio of the cocatalyst compound to the carrier is from 1: 1 to 1: 100.
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