WO2017138783A1 - Novel ligand compound and transition metal compound - Google Patents

Novel ligand compound and transition metal compound Download PDF

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WO2017138783A1
WO2017138783A1 PCT/KR2017/001503 KR2017001503W WO2017138783A1 WO 2017138783 A1 WO2017138783 A1 WO 2017138783A1 KR 2017001503 W KR2017001503 W KR 2017001503W WO 2017138783 A1 WO2017138783 A1 WO 2017138783A1
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formula
carbon atoms
compound
added
mmol
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PCT/KR2017/001503
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French (fr)
Korean (ko)
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한효정
이은정
이충훈
박인성
김슬기
나영훈
최익제
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주식회사 엘지화학
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Priority claimed from KR1020170018307A external-priority patent/KR101931234B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/749,309 priority Critical patent/US10538603B2/en
Priority to CN201780002867.2A priority patent/CN107922382B/en
Priority to EP17750475.0A priority patent/EP3318560B1/en
Publication of WO2017138783A1 publication Critical patent/WO2017138783A1/en
Priority to US16/698,047 priority patent/US10723818B2/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • the present invention relates to novel ligand compounds and transition metal compounds.
  • Metallocene catalysts for olefin polymerization have been developed for a long time.
  • Metallocene compounds are generally used by activation with aluminoxanes, boranes, borates or other activators.
  • a metallocene compound having a ligand including a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator.
  • the chloride group of such a metallocene compound is substituted with another ligand (eg, benzyl or trimethylsilylmethyl group (—CH 2 SiMe 3 )), an example showing an effect such as increased catalytic activity has been reported.
  • another ligand eg, benzyl or trimethylsilylmethyl group (—CH 2 SiMe 3 )
  • metallocenes composed of (cyclopentadienyl) (indenyl) and (cyclopentadienyl) (fluorenyl) metallocene, (substituted indenyl) (cyclopentadienyl), and the like are known. have.
  • the catalyst compositions of the non-crosslinkable metallocenes do not sufficiently exhibit the polymerization activity of olefins and have difficulty in polymerizing high molecular weight polyolefins.
  • the problem to be solved of the present invention is to provide a novel ligand compound.
  • Another problem to be solved of the present invention is to provide a novel transition metal compound.
  • R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and having 7 carbon atoms.
  • Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms;
  • the aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2.
  • R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms.
  • R 1 to R 8 Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms;
  • the aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2;
  • Q 1 and Q 2 are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. , Alkyl amido having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;
  • M is Ti, Zr or Hf.
  • novel ligand compound and the transition metal compound according to the present invention have a high comonomer incorporation effect in the preparation of olefin polymer having low density and high molecular weight, and thus may be usefully used as a catalyst for polymerization reaction.
  • the ligand compound of the present invention is represented by the following formula (1).
  • R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms.
  • a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms;
  • the aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2.
  • R 1 to R 9 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms. There is; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
  • the ligand compound of Formula 1 may be any one of the following compounds:
  • transition metal compound according to the present invention may be represented by the formula (2).
  • R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms.
  • R 1 to R 8 Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms;
  • the aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms;
  • n is 1 or 2;
  • Q 1 and Q 2 are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms.
  • M is Ti, Zr or Hf.
  • Q 1 and Q 2 are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms. Can be.
  • R 1 to R 9 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms. There is; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
  • the compound of Formula 2 may be any one of the following compounds:
  • halogen means fluorine, chlorine, bromine or iodine, unless stated otherwise.
  • alkyl refers to a straight or branched chain hydrocarbon residue unless otherwise indicated.
  • alkenyl refers to a straight or branched alkenyl group unless otherwise indicated.
  • the branched chain is alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms.
  • the silyl group is trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris ( Trimethylsilyl) silyl and the like, but are not limited to these examples.
  • the aryl group preferably has 6 to 20 carbon atoms, and specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.
  • the alkylaryl group means an aryl group substituted by the alkyl group.
  • the arylalkyl group means an alkyl group substituted by the aryl group.
  • the ring means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 carbon atoms and containing one or more hetero atoms, and may be a single ring or a condensed ring of two or more rings.
  • the heterocyclic group may or may not be substituted with an alkyl group. Examples thereof include indolin, tetrahydroquinoline, and the like, but the present invention is not limited thereto.
  • the alkyl amino group means an amino group substituted by the alkyl group, and there are a dimethylamino group, a diethylamino group, and the like, but is not limited thereto.
  • the aryl group preferably has 6 to 20 carbon atoms, specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto. no.
  • the ligand compound of the present invention can be prepared through the preparation method as follows, specifically, the ligand compound represented by the formula (1) of the present invention (1) by reacting the compound of the formula (3) and the compound of the formula (4) Preparing the compound of 5; And (2) reacting the compound of Formula 5 with the compound of Formula 6 to produce a compound of Formula 1.
  • R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, and having 7 to 20 carbon atoms.
  • Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms;
  • the aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2.
  • R 1 to R 9 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or 7 to 20 carbon atoms. May be arylalkyl; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
  • step (1) the compound of Formula 3 is prepared by reacting the compound of Formula 3 with the compound of Formula 4.
  • step (1) may be carried out in the presence of a palladium catalyst in the basic conditions, wherein the reaction may be carried out in an organic solvent such as toluene.
  • the palladium catalyst is tetrakis (triphenylphosphine) palladium [Pd (PPh 3 ) 4 ], palladium chloride (PdCl 2 ), palladium acetate (Pd (OAc) 2 ), bis (dibenzylideneacetone) palladium (Pd ( dba) 2 ) and Pd (tBu 3 P 2 ).
  • the type of the base for achieving the base conditions is not particularly limited, but specific examples include tBuOLi, potassium triphosphate (K 3 PO 4 ), potassium carbonate (K 2 CO 3 ), cesium carbonate (Cs 2 CO 3 ), and fluorinated Potassium (KF), sodium fluoride (NaF), cesium fluoride (CsF), tetrabutylammonium fluoride (TBAF), or mixtures thereof.
  • K 3 PO 4 potassium triphosphate
  • K 2 CO 3 potassium carbonate
  • Cs 2 CO 3 cesium carbonate
  • KF fluorinated Potassium
  • NaF sodium fluoride
  • CsF cesium fluoride
  • TBAF tetrabutylammonium fluoride
  • the reaction of step (1) may be carried out by a method of reacting for 1 hour to 48 hours, specifically 2 hours to 12 hours in the temperature range of 0 °C to 140 °C, specifically 40 °C to 100 °C have.
  • the compound of Formula 3 and the compound of Formula 4 may first be added to a separate solvent, and then mixed again, and a palladium catalyst may be added after mixing.
  • a palladium catalyst may be added after mixing.
  • the compound of Formula 3 may be added to a mixed solvent of alcohol such as water and ethanol, and the compound of Formula 4 may be added to a solvent such as toluene.
  • the compound of Formula 3 may be prepared by a reaction represented by the following Scheme 2.
  • R 6 to R 9 and n in the scheme are as defined in Formula 3.
  • the compound of Formula 3-1 is added to an organic solvent such as hexane, and n-BuLi is added in a temperature range of -80 ° C to 0 ° C.
  • the n-BuLi may be reacted with a molar ratio of 1: 1 to 1: 2 with respect to the compound of Formula 3-1, and specifically, may be reacted with a molar ratio of 1: 1.1 to 1: 1.2.
  • the mixture was reacted at room temperature for 1 to 48 hours, and then filtered. Then, a solvent was added to the obtained compound, and CO 2 was added by bubbling at a temperature of -160 ° C to -20 ° C.
  • the compound of -2 can be obtained.
  • t-BuLi is added to the obtained compound of Formula 3-2 and reacted at a temperature range of -80 ° C to 0 ° C
  • the compound of Formula 3-3 can be obtained.
  • 2-isopropyloxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added to the compound of Formula 3-3 at a temperature of -150 ° C to -20 ° C, The reaction is carried out by gradually raising the temperature to room temperature, whereby the compound of Chemical Formula 3 can be obtained.
  • HCl and ethyl acetate (EA) were added, and the organic layer was washed with NaOH and NaHCO 3 , followed by a process of drying moisture with MgSO 4 .
  • step (2) the compound of Formula 5 is prepared by reacting the compound of Formula 5 with the compound of Formula 6.
  • step (2) R 2 is introduced into the compound of Formula 5 by reacting the compound of Formula 5 with the organolithium compound of Formula 6.
  • step (2) the compound of Formula 5 and the compound of Formula 6 may be reacted with a molar ratio of 1: 1 to 1: 3, and specifically, may be reacted at a molar ratio of 1: 1 to 1: 2. .
  • the reaction of step (2) may be carried out by adding a compound of Chemical Formula 6 to the compound of Chemical Formula 5 in a temperature range of -160 ° C to -20 ° C, and then reacting. It can be made by the method of reacting by adding the compound of Formula 6 to the compound of Formula 5 in the temperature range of 40 °C.
  • the reaction may be made in an organic solvent such as diethyl ether, and may be quenched with NH 4 Cl or the like after the reaction is completed.
  • the compound of Chemical Formula 1 prepared through the steps (1) and (2) may additionally undergo a recrystallization step (3), thus, the method for preparing a transition metal compound according to an example of the present invention may be performed after the step (2).
  • the method may further include recrystallizing the compound of Chemical Formula 1.
  • the recrystallization may be performed using an organic solvent such as toluene, such as a reaction solvent, and purified through recrystallization to obtain a pure compound of Formula 1.
  • organic solvent such as toluene, such as a reaction solvent
  • the transition metal compound represented by Formula 2 of the present invention comprises the steps of (a) preparing a compound of Formula 7 by reacting the ligand compound of Formula 1 with an organolithium compound; And (b) reacting a compound of Formula 7 with a compound of Formula 8 to produce a compound of Formula 2.
  • R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms.
  • a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms;
  • the aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2;
  • Q 1 and Q 2 are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. , Alkyl amido having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;
  • X is halogen
  • M is Ti, Zr or Hf.
  • each of R 1 to R 9 may independently be hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms;
  • Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms;
  • the aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
  • the method for preparing a transition metal compound of the present invention may include the step of further reacting the compound of Formula 2 with a Grignard reagent of the formula (9).
  • Q is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, and having 1 to 20 carbon atoms.
  • the compound of Formula 2 reacts with the Grignard reagent of Formula 9 may be Q 1 , Q 2 or both are halogen. That is, in one example of the present invention, when Q 1 , Q 2 of Formula 8, or both of them are halogen, a compound in which Q 1 , Q 2 , or both of which are bonded to M in Formula 2 is halogen is prepared. In this case, Q 1 , Q 2 , or both in Formula 2 may be substituted with Q in halogen through an additional reaction with the Grignard reagent of Formula 9.
  • step (a) the compound of Formula 1 is prepared by reacting the compound of Formula 1 with an organolithium compound.
  • the compound of Formula 1 and the organolithium compound may be reacted with a molar ratio of 1: 1 to 1: 3, and specifically, may be reacted at a molar ratio of 1: 1 to 1: 2.
  • step (1) may be performed under an organic solvent such as diethoxyethane and ether, and may be performed by adding the organic lithium compound to the compound of Formula 1 under an organic solvent.
  • organic solvent such as diethoxyethane and ether
  • the organolithium compound may be at least one selected from the group consisting of n-butyllithium, sec-butyllithium, methyllithium, ethyllithium, isopropyllithium, cyclohexylithium, allyllithium, vinyllithium, phenyllithium and benzyllithium. .
  • step (a) is carried out by the method of reacting for 1 to 6 hours, specifically 1 to 4 hours after adding the organolithium compound to the compound of Formula 1 in the temperature range of -78 °C to 0 °C Can be. At this time, the reaction temperature may be less than 20 °C, specifically -78 °C to 0 °C.
  • step (b) the compound of formula 7 is prepared by reacting the compound of formula 7 obtained in step (a) with the compound of formula 8.
  • step (b) the compound of Formula 7 and the compound of Formula 8 may be reacted with a molar ratio of 1: 0.8 to 1: 1.8, and specifically, may be reacted at a molar ratio of 1: 1 to 1: 1.2. .
  • step (b) The reaction of step (b) is heated to a temperature range of 40 ° C to 140 ° C, specifically 70 ° C to 120 ° C, and then reacted for 1 to 48 hours, specifically for 1 to 4 hours. It may be carried out, the reaction in step (a) and step (b) may be made in one step.
  • step (a) and step (b) after adding the organolithium compound to the compound of Chemical Formula 1 at a temperature range of -20 ° C to 30 ° C, a compound of Chemical Formula 8 is further added, and then 40 After the temperature is raised to a temperature range of °C to 140 °C, specifically 70 °C to 120 °C, it may be carried out by a method for reacting for 1 to 48 hours, specifically 1 to 4 hours.
  • transition metal compound of Formula 2 may be prepared.
  • the transition metal compound prepared by the additional reaction may be represented by any one of the following Chemical Formulas 9a to 9c.
  • transition metal compound according to the present invention alone or in addition to the transition metal compound in the form of a composition further comprising one or more of the cocatalyst compounds represented by the following formulas (10), (11) and (12), the polymerization reaction It can be used as a catalyst.
  • R 7 may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
  • n is an integer of 2 or more
  • R 7 is as defined in Formula 10 above;
  • J is aluminum or boron
  • E is a neutral or cationic Lewis base
  • H is a hydrogen atom
  • Z is a Group 13 element
  • A may be the same or different from each other, and each independently is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with one or more hydrogen atoms, halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy. .
  • Examples of the compound represented by the formula (10) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like, and more preferred compound is methyl aluminoxane.
  • Examples of the compound represented by Formula 11 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.
  • Examples of the compound represented by Formula 12 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N -Diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium
  • aluminoxane may be used, and more specifically, it may be methylaluminoxane (MAO), which is an alkylaluminoxane.
  • MAO methylaluminoxane
  • the catalyst composition may comprise the steps of: 1) contacting a transition metal compound represented by Formula 2 with a compound represented by Formula 10 or Formula 11 to obtain a mixture; And 2) it can be prepared by a method comprising the step of adding a compound represented by the formula (12) to the mixture.
  • the catalyst composition may be prepared by a method of contacting the transition metal compound represented by Formula 2 with the compound represented by Formula 10 as a second method.
  • the molar ratio of the transition metal compound represented by the formula (2) / compound represented by the formula (10) or formula (11) is preferably 1 / 5,000 to 1/2, more Preferably it is 1 / 1,000-1/10, Most preferably, it is 1/500-1/20.
  • the amount of the alkylating agent is so small that there is a problem that the alkylation of the metal compound does not proceed completely.
  • the molar ratio of the transition metal compound represented by Formula 2 to the compound represented by Formula 12 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1/5. To 1; When the molar ratio of the transition metal compound represented by Chemical Formula 2 to the compound represented by Chemical Formula 12 is greater than 1, the amount of the activator is relatively small, and thus the activity of the catalyst composition generated due to the incomplete activation of the metal compound. If the molar ratio is less than 1/25, the activation of the metal compound is completely made, but the excess of the activator, the cost of the catalyst composition is not economical or the purity of the resulting polymer is poor.
  • the molar ratio of the transition metal compound represented by the formula (2) / compound represented by the formula (10) is preferably 1 / 10,000 to 1/10, more preferably 1 / 5,000 to 1/100, most preferably 1 / 3,000 to 1/500. If the molar ratio is greater than 1/10, the amount of the activator is relatively small, so that the activation of the metal compound is not fully performed, resulting in a decrease in the activity of the resulting catalyst composition. Although the activation is complete, there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior with the excess activator remaining.
  • the transition metal compound according to the present invention when used as a catalyst for the polymerization reaction, it may be used as a catalyst for the polymerization reaction in the form of a composition further comprising a chain shuttle agent.
  • the chain shuttleling agent means a compound which can be characterized by being able to exchange polymeric chains (ie, polymer chains or fragments) between two or more active catalyst sites of two olefin polymerization catalysts under olefin polymerization conditions.
  • the two olefin polymerization catalyst may be a transition metal compound of the present invention. That is, delivery of the polymer fragment occurs at one or more of the active sites of the transition metal compound.
  • chain shuttle agents include trialkyl aluminum and dialkyl zinc compounds, in particular triethylaluminum, tri (i-propyl) aluminum, tri (i-butyl) aluminum, tri (n-hexyl) aluminum, tri (n-octyl) Aluminum, triethylgallium or diethylzinc, and also organometallic compounds, specifically tri ((C 1 -C 8 ) alkyl) aluminum or di ((C 1 -C 8 ) alkyl) zinc compounds, in particular Stoichiometric amounts of triethylaluminum, tri (i-propyl) aluminum, tri (i-butyl) aluminum, tri (n-hexyl) aluminum, tri (n-octyl) aluminum or diethylzinc (number of hydrocarbyl groups Primary or secondary amines, primary or secondary phosphines, thiols, or hydroxyl compounds, in particular bis (trimethylsilyl) amine, t-butyl zinc
  • amine, phosphine, thiol or hydroxyl reagent is used so that one or more hydrocarbyl groups remain per metal atom.
  • the main reaction products of the above combinations which are most preferred for use in the present invention as shuttles are n-octylaluminum di (bis (trimethylsilyl) amide), i-propylaluminum bis (dimethyl (t-butyl) siloxane), And n-octyl aluminum di (pyridinyl-2-methoxide), i-butyl aluminum bis (dimethyl (t-butyl) siloxane), i-butyl aluminum di (bis (trimethylsilyl) amide), n-octyl aluminum Di (pyridine-2-methoxide), i-butylaluminum bis (di (n-pentyl) amide), n-octyl aluminum bis (2,6-di-t-butylphenoxide), n
  • a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene, toluene, or the like may be used.
  • the catalyst composition may include the transition metal compound and the cocatalyst compound in a form supported on a carrier.
  • the polymerization reaction for polymerizing the olefinic monomer in the presence of the catalyst composition comprising the transition metal compound is a solution polymerization process, using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor or a solution reactor, It may be carried out by a slurry process or a gas phase process. It can also proceed by homopolymerization with one olefin monomer or copolymerization with two or more monomers.
  • Polymerization of the polyolefin may be carried out by reacting at a temperature of about 25 °C to about 500 °C and about 1 to about 100 kgf / cm 2 .
  • the polymerization of the polyolefin may be carried out at a temperature of about 25 °C to about 500 °C, preferably about 25 °C to 200 °C, more preferably about 50 °C to 100 °C.
  • the reaction pressure is about 1 kgf / cm 2 to about 100 kgf / cm 2 , preferably about 1 kgf / cm 2 To about 50 kgf / cm 2 , more preferably about 5 kgf / cm 2 To about 40 kgf / cm 2 .
  • examples of the polymerizable olefin monomer using the transition metal compound and the promoter according to an embodiment of the present invention include ethylene, alpha-olefin, cyclic olefin, and the like, and a diene olefin having two or more double bonds.
  • the monomer or the triene olefin monomer can also be polymerized.
  • olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- itocene and the like, may be a copolymer copolymerized by mixing two or more thereof.
  • the polyolefin may be a propylene polymer, but is not limited thereto.
  • the polymer may be either a homo polymer or a copolymer.
  • the olefin polymer is a copolymer of ethylene and other comonomers
  • the monomers constituting the copolymer consist of ethylene and propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene It is preferred that it is at least one comonomer selected from the group.
  • Br-imine toluene solution was transferred to a solution of Na 2 CO 3 and THQ-borolane, and Pd (PPh 3 ) 4 (0.018 g, 0.0156 mmol, 0.3 mol% Pd) was added thereto. After stirring for 4 hours at 70 °C cooled to room temperature. The organic layer was extracted with toluene / brine and dried with Na 2 SO 4 (0.98 g product, 47% yield).
  • N- (2,6-diisopropylphenyl) -1- (6- (1,2,3,4-tetrahydroquinolin-8-yl) pyridin-2-yl) methanimine prepared above (0.95 g , 2.39 mmol, 1 eq) was dissolved in diethyl ether (23.9 mL) and the temperature was lowered to ⁇ 78 ° C., followed by addition of phenyl lithium (3.583 mL, 6.45 mmol, 2.7 eq, 1.8 M in DBE). At the end of the reaction, the reaction was quenched with 1N NH 4 Cl and worked up with diethyl ether and water. 1.2 g (quantitative yield) of an orange solid was obtained.
  • the synthesized ligand precursor (750 mg, 1.886 mmol, 1 eq) was dissolved in diethyl ether (18.86 mL) and the temperature was lowered to -78 ° C, followed by phenyl lithium (2.83 mL, 5.093 mmol, 2.7 eq, 1.8 M in DBE) was added. At the end of the reaction, the reaction was quenched with 1N NH 4 Cl and worked up with diethyl ether and water. This resulted in 880 mg (quantitative yield) of ligand.
  • Br-imine toluene solution was transferred to a solution of THQ-borolane followed by Pd (PPh 3 ) 4 (0.0301 g, 0.026 mmol, 0.3 mol% Pd). After stirring for 4 hours at 70 °C cooled to room temperature. The organic layer was extracted with toluene / brine and dried with Na 2 SO 4 . The product could be obtained in 3.08 g, 86% yield.
  • N- (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinoline-8-, which is a ligand precursor prepared in b) of Example 5
  • pyridin-2-yl) methaneimine (1.31 g, 3.178 mmol, 1 eq) was dissolved in diethyl ether (31.78 mL) and the temperature was lowered to -78 ° C.
  • N-([1,1'-biphenyl] -2-yl (6-((S) -2-methyl-1,2,3,4-tetrahydroquinolin-8-yl prepared in Example 7 above) ) Pyridin-2-yl) methyl) -2,6-diisopropyl aniline (2.38 g, 4.2064 mmol, 1 eq) and toluene (14.02 mL, 0.3 M) were added and stirred, followed by n-BuLi (3.533 mL, 8.834). mmol, 2.1 eq) was added dropwise. HfCl 4 (1.415 g, 4.417 mmol, 1.05 eq) was added and heated at 90-100 ° C.
  • MeTHQ-borolane methyltetrahydroquinoline-borolane
  • N- (t-butyl) -1- (6-bromopyridin-2-yl) methanimine toluene solution was transferred to a solution of Na 2 CO 3 and THQ-borolane, followed by Pd (PPh 3 ) 4 ( 0.043 g, 0.0373 mmol, 0.3 mol% Pd) was added. After stirring overnight at 70 ° C., it was cooled to room temperature. The organic layer was extracted with tolu / brine and dried over Na 2 SO 4 . EtOH and MeOH were tried to make a solid, but the solid was not well formed and the next reaction was to be carried out with the starting material (70% purity). The product was obtained in 4 g,> 100% yield as an orange oil.
  • N- (t-butyl) -1- (6- (1,2,3,4-tetrahydro-2-methylquinolin-8-yl) pyridin-2-yl) methanimine prepared above (1.17 g, 3.806 mmol, 1 eq) was dissolved in diethyl ether (0.1 M), and the temperature was lowered to -78 ° C. Then, phenyl lithium (5.71 mL, 10.275 mmol, 2.7 eq) was added thereto, and the temperature was raised to room temperature. After reacting overnight, TLC was checked and the reaction was quenched with 1 N NH 4 Cl, and then worked up with diethyl ether and water. After drying the moisture with Na 2 SO 4 , the solvent was vacuum dried with a Rotavapor. Orange oil was obtained in 1.52 g> 100% yield.
  • N- (t-butyl) -1- (6- (1,2,3,4-tetrahydro-2-methylquinolin-8-yl) pyridin-2-yl) which is a ligand precursor prepared in Example 17
  • Methaneimine was dissolved in diethyl ether (30.25 mL, 0.1 M), and 1-lithium-2-isopropylbenzene prepared above was transferred thereto. After reacting at room temperature overnight, the reaction was checked by TLC, and when the reaction was completed, the reaction was quenched with 1 N NH 4 Cl, and the organic layer was worked up with ether / H 2 O, and then dried with Na 2 SO 4 . The solvent was vacuum dried with a Rotavapor. An orange oil was obtained at 1.14 g,> 100%.
  • N-((6- (1,2,3,4-tetrahydro-2-methylquinolin-8yl) pyridin-2-yl) (2-isopropylphenyl) methyl which is a ligand synthesized in Example 9 above -t-butan-1-amine (1.23 g, 2.876 mmol, 1 eq) was dissolved in toluene (9.587 mL, 0.3 M) and stirred, followed by n-BuLi (2.416 mL, 6.0401 mmol, 2.1 eq) at -40 ° C. Added dropwise. HfCl 4 (0.967 g, 3.0198 mmol, 1.05 eq) was added thereto and heated at 90 to 100 ° C. for 2 hours.
  • N- (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinoline-8-, which is a ligand precursor prepared in b) of Example 5 I) pyridin-2-yl) methaneimine (1.5 g, 3.644 mmol, 1 eq) was dissolved in diethyl ether (36.44 mL) and the temperature was lowered to -78 ° C.
  • N- (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinoline-8-, which is a ligand precursor prepared in b) of Example 5 I) pyridin-2-yl) methaneimine (2.146 g, 5.215 mmol, 1 eq) was dissolved in diethyl ether (52.15 mL) and the temperature was lowered to -78 ° C.
  • Hexane solvent (1.0 L), octene (280 mL), and ethylene (35 bar) were added to the 2 L autoclave reactor, the pressure was adjusted to 500 psi at high pressure argon pressure, and the temperature of the reactor was preheated to 120 ° C.
  • 10 equivalents of 5 ⁇ 10 ⁇ 6 M dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst was added to a reactor under high pressure argon pressure, and the transition metal of Example 1-1 treated with triisobutylaluminum compound Compound (1 ⁇ 10 ⁇ 6 M, 2.0 mL) was placed in a catalyst storage tank and then placed in a reactor under high pressure argon pressure.
  • the polymerization reaction proceeded for 10 minutes.
  • the heat of reaction was removed through a cooling coil inside the reactor to keep the polymerization temperature as constant as possible.
  • the remaining gas was drained, the polymer solution was discharged to the bottom of the reactor, and excess ethanol was added to cool, thereby inducing precipitation.
  • the obtained polymer was washed two to three times with ethanol and acetone, and then dried in a 90 ° C. vacuum oven for at least 12 hours to prepare an ethylene-octene copolymer.
  • each transition metal compound as shown in Table 6 was treated with a triisobutylaluminum compound, respectively. Except what was used, the ethylene-octene copolymer was manufactured by the method similar to Example 1-A.
  • Catalytic Activity Determined from the molar ratio of the transition metal compound to the total yield of the copolymer produced. Specifically, the mass of a portion of the reaction solution taken after completion of the polymerization reaction and the portion of the copolymer were heated at 120 ° C. for 10 minutes to remove all the hexane solvent and residual monomers, and to measure the mass of the remaining copolymer. The ratio of the values was calculated, and the catalytic activity was calculated using the mass of the resulting copolymer, the number of moles of the transition metal compound used in the polymerization reaction, and the polymerization time.
  • Example 1-1 Example 1-1 2.7
  • Example 1-B Example 1-2 0.8
  • Example 2-A Example 2-1 5.6
  • Example 2-B Example 2-2 0.74
  • Example 3-A Example 3-1 1.0
  • Example 4-A Example 4-1 2.2
  • Example 5-A Example 5-1 2.3
  • Example 6-A Example 6-1 5.3
  • Example 7-A Example 7-1 2.7
  • Example 10-A Example 10-1 2.3
  • Example 11-A Example 11-1 1.5
  • MI Melt index
  • density density
  • melting point of the copolymers prepared in Examples 6-A, 7-A, and 10-A were measured in the following manners, and the results are shown in Table 7 below. .
  • MI Melt index
  • Tm Melting point
  • Example 6-1 5.3 0.02 0.865 50.3
  • Example 7-A Example 7-1 2.7 0.02 0.883 72.9
  • Example 10-A Example 10-1 2.3 0.01 0.873 60.9
  • Examples 6-1, 7-1, and Example 6-A prepared by using the transition metal compounds of Examples 6-1, 7-1, and 10-1, which are examples of the transition metal compounds of the present invention
  • the polymers of A, and 10-A exhibited a low melt index (MI) of 0.02 or less, showing a high molecular weight, and a density of 0.883 g / cc or less.
  • the polymers of Examples 6-A and 10-A prepared using the transition metal compounds of Examples 6-1 and 10-1 have a low melt index (MI) of less than 0.02 with a low density of 0.873 g / cc or less. ) And low density and high molecular weight.

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Abstract

The present invention relates to a novel ligand compound represented by chemical formula 1, and a novel transition metal compound represented by chemical formula 2. According to the present invention, the novel ligand compound and transition metal compound have a high comonomer incorporation effect on the preparation of an olefin-based polymer having a high molecular weight while having a low density, thereby being usable as a catalyst for a polymerization reaction.

Description

신규한 리간드 화합물 및 전이금속 화합물Novel Ligand Compounds and Transition Metal Compounds
[관련출원과의 상호 인용][Cross-cited with Related Applications]
본 출원은 2016년 02월 12일자 한국 특허 출원 제10-2016-0016517호 및 2017년 02월 09일자 한국 특허 출원 제10-2017-0018307호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된　모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0016517 dated February 12, 2016 and Korean Patent Application No. 10-2017-0018307 dated February 09, 2017. All content disclosed in the literature is included as part of this specification.
[기술분야][Technical Field]
본 발명은 신규한 리간드 화합물 및 전이금속 화합물에 관한 것이다.The present invention relates to novel ligand compounds and transition metal compounds.
올레핀 중합용 메탈로센 촉매는 오랜 기간 발전해왔다. 메탈로센 화합물은 일반적으로 알루미녹산, 보레인, 보레이트 또는 다른 활성화제를 이용하여 활성화시켜 사용한다. 예를 들어, 사이클로펜타다이에닐기를 포함한 리간드와 두 개의 시그마 클로라이드 리간드를 갖는 메탈로센 화합물은 알루미녹산을 활성화제로 사용한다. 이러한 메탈로센 화합물의 클로라이드기를 다른 리간드로(예를 들어, 벤질 또는 트리메틸실릴메틸기(-CH2SiMe3)) 치환하는 경우 촉매 활성도 증가 등의 효과를 나타내는 예가 보고되었다.Metallocene catalysts for olefin polymerization have been developed for a long time. Metallocene compounds are generally used by activation with aluminoxanes, boranes, borates or other activators. For example, a metallocene compound having a ligand including a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. When the chloride group of such a metallocene compound is substituted with another ligand (eg, benzyl or trimethylsilylmethyl group (—CH 2 SiMe 3 )), an example showing an effect such as increased catalytic activity has been reported.
Dow 사가 1990년대 초반 [Me2Si(Me4C5)NtBu]TiCl2 (Constrained-Geometry Catalyst, CGC)를 미국특허 제5,064,802호 등에서 개시하였는데, 에틸렌과 알파-올레핀의 공중합 반응에서 CGC가 기존까지 알려진 메탈로센 촉매들에 비해 우수한 측면을 크게 다음과 같이 두 가지로 요약할 수 있다: Dow disclosed [Me 2 Si (Me 4 C 5 ) NtBu] TiCl 2 (Constrained-Geometry Catalyst, CGC) in U.S. Patent No. 5,064,802 in the early 1990s. The advantages over the known metallocene catalysts can be summarized in two main ways:
(1) 높은 중합 온도에서도 높은 활성도를 나타내면서 고분자량의 중합체를 생성하며, (1) to produce high molecular weight polymers with high activity even at high polymerization temperatures;
(2) 1-헥센 및 1-옥텐과 같은 입체적 장애가 큰 알파-올레핀의 공중합성도 매우 뛰어나다는 점이다. (2) The copolymerization of alpha-olefins with high steric hindrances such as 1-hexene and 1-octene is also excellent.
그 외에도 중합 반응 시, CGC의 여러 가지 특성들이 점차 알려지면서 이의 유도체를 합성하여 중합 촉매로 사용하고자 하는 노력이 학계 및 산업계에서 활발히 이루어졌다.In addition, during the polymerization reaction, various characteristics of CGC are gradually known, and efforts to synthesize derivatives thereof and use them as polymerization catalysts have been actively conducted in academia and industry.
그 중 하나의 접근 방법으로 실리콘 브릿지 대신에 다른 다양한 브릿지 및 질소 치환체가 도입된 금속 화합물의 합성과 이를 이용한 중합이 시도되었다. 최근까지 알려진 대표적인 금속 화합물들은 CGC 구조의 실리콘 브릿지 대신에 포스포러스, 에틸렌 또는 프로필렌, 메틸리덴 및 메틸렌 브릿지가 각각 도입되어 있으나, 에틸렌 중합 또는 에틸렌과 알파올레핀의 공중합에의 적용시에 CGC 대비하여 중합 활성도나 공중합 성능 등의 측면에서 뛰어난 결과들을 나타내지 못하였다.One approach has been to synthesize metal compounds in which various bridges and nitrogen substituents are introduced instead of silicon bridges and to polymerize them. Representative metal compounds known until recently are phosphorus, ethylene or propylene, methylidene and methylene bridges instead of CGC-structured silicon bridges, but polymerized against CGC when applied to ethylene polymerization or copolymerization of ethylene and alphaolefin. It did not show excellent results in terms of activity or copolymerization performance.
다른 접근 방법으로는 상기 CGC의 아미도 리간드 대신에 옥시도 리간드로 구성된 화합물들이 많이 합성되었으며, 이를 이용한 중합도 일부 시도되었다.In another approach, many compounds composed of an oxido ligand instead of the amido ligand of CGC have been synthesized, and some polymerization has been attempted using the compound.
또한, 다양한 비대칭성 비가교형 메탈로센이 개발되었다. 예를 들어, (싸이클로펜타디에닐)(인데닐) 및 (싸이클로펜타디에닐)(플루오레닐)메탈로센, (치환된 인데닐)(싸이클로펜타디에닐)로 이루어진 메탈로센 등이 알려져 있다. In addition, various asymmetric uncrosslinked metallocenes have been developed. For example, metallocenes composed of (cyclopentadienyl) (indenyl) and (cyclopentadienyl) (fluorenyl) metallocene, (substituted indenyl) (cyclopentadienyl), and the like are known. have.
그러나, 상업적 활용면에서, 상기 비가교성 메탈로센의 촉매 조성물들은 올레핀의 중합 활성을 충분히 발휘하지 못하고, 높은 분자량의 폴리올레핀을 중합하기 어려운 단점이 있다.However, in terms of commercial applications, the catalyst compositions of the non-crosslinkable metallocenes do not sufficiently exhibit the polymerization activity of olefins and have difficulty in polymerizing high molecular weight polyolefins.
본 발명의 해결하고자 하는 과제는 신규한 리간드 화합물을 제공하는 것이다. The problem to be solved of the present invention is to provide a novel ligand compound.
본 발명의 다른 해결하고자 하는 과제는 신규한 전이금속 화합물을 제공하는 것이다.Another problem to be solved of the present invention is to provide a novel transition metal compound.
상기 과제를 해결하기 위하여, 본 발명은 In order to solve the above problems, the present invention
하기 화학식 1로 표시되는 리간드 화합물을 제공한다:It provides a ligand compound represented by the following formula (1):
[화학식 1][Formula 1]
Figure PCTKR2017001503-appb-I000001
Figure PCTKR2017001503-appb-I000001
상기 화학식 1에서, R1 내지 R9는 각각 독립적으로 수소, 실릴, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 탄소수 7 내지 20의 아릴알킬, 또는 탄소수 1 내지 20의 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이고; 상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며; 상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있고; n은 1 또는 2이다. In Formula 1, R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and having 7 carbon atoms. A metalloid radical of group 14 metal substituted with arylalkyl of 20 to 20, or hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2.
또한, 상기 다른 과제를 해결하기 위하여, 본 발명은 Moreover, in order to solve the said another subject, this invention is
하기 화학식 2로 표시되는 전이금속 화합물을 제공한다:It provides a transition metal compound represented by the formula (2):
[화학식 2][Formula 2]
Figure PCTKR2017001503-appb-I000002
Figure PCTKR2017001503-appb-I000002
상기 화학식 2에서, In Chemical Formula 2,
R1 내지 R9는 각각 독립적으로 수소, 실릴, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 탄소수 7 내지 20의 아릴알킬, 또는 탄소수 1 내지 20의 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이고; R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms;
상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며; 상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있고; n은 1 또는 2이고;Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2;
Q1 및 Q2는 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 6 내지 20의 아릴, 탄소수 6 내지 20의 알킬아릴, 탄소수 7 내지 20의 아릴알킬, 탄소수 1 내지 20의 알킬 아미도, 탄소수 6 내지 20의 아릴 아미도, 또는 탄소수 1 내지 20의 알킬리덴이며;Q 1 and Q 2 are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. , Alkyl amido having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;
M은 Ti, Zr 또는 Hf이다.M is Ti, Zr or Hf.
본 발명에 따른 신규한 리간드 화합물 및 전이금속 화합물은 저밀도이면서 고분자량을 가지는 올레핀계 중합체의 제조에 있어 높은 코모노머 혼성(comonomer incorporation) 효과를 가지므로 중합 반응의 촉매로 유용하게 사용될 수 있다.The novel ligand compound and the transition metal compound according to the present invention have a high comonomer incorporation effect in the preparation of olefin polymer having low density and high molecular weight, and thus may be usefully used as a catalyst for polymerization reaction.
이하, 본 발명에 대한 이해를 돕기 위해 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.
본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
본 발명의 리간드 화합물은 하기 화학식 1로 표시된다. The ligand compound of the present invention is represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2017001503-appb-I000003
Figure PCTKR2017001503-appb-I000003
상기 화학식 1에서, In Chemical Formula 1,
R1 내지 R9는 각각 독립적으로 수소, 실릴, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 탄소수 7 내지 20의 아릴알킬, 또는 탄소수 1 내지 20의 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이고; 상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며; 상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있고; n은 1 또는 2이다.R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2.
또한, 상기 화학식 1에서, R1 내지 R9는 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 또는 탄소수 7 내지 20의 아릴알킬일 수 있고; 상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며; 상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있다. In addition, in Formula 1, R 1 to R 9 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms. There is; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
본 발명의 일례에 있어서, 상기 화학식 1의 리간드 화합물은 하기 화합물 중 어느 하나일 수 있다:In one embodiment of the present invention, the ligand compound of Formula 1 may be any one of the following compounds:
[화학식 1a][Formula 1a]
Figure PCTKR2017001503-appb-I000004
Figure PCTKR2017001503-appb-I000004
[화학식 1b][Formula 1b]
Figure PCTKR2017001503-appb-I000005
Figure PCTKR2017001503-appb-I000005
[화학식 1c][Formula 1c]
Figure PCTKR2017001503-appb-I000006
Figure PCTKR2017001503-appb-I000006
[화학식 1d][Formula 1d]
Figure PCTKR2017001503-appb-I000007
Figure PCTKR2017001503-appb-I000007
[화학식 1e][Formula 1e]
Figure PCTKR2017001503-appb-I000008
Figure PCTKR2017001503-appb-I000008
[화학식 1f][Formula 1f]
Figure PCTKR2017001503-appb-I000009
Figure PCTKR2017001503-appb-I000009
[화학식 1g][Formula 1g]
Figure PCTKR2017001503-appb-I000010
Figure PCTKR2017001503-appb-I000010
[화학식 1h][Formula 1h]
Figure PCTKR2017001503-appb-I000011
Figure PCTKR2017001503-appb-I000011
[화학식 1i]Formula 1i]
Figure PCTKR2017001503-appb-I000012
Figure PCTKR2017001503-appb-I000012
[화학식 1j][Formula 1j]
Figure PCTKR2017001503-appb-I000013
Figure PCTKR2017001503-appb-I000013
[화학식 1k][Formula 1k]
Figure PCTKR2017001503-appb-I000014
Figure PCTKR2017001503-appb-I000014
한편, 본 발명에 따른 전이금속 화합물은 하기 화학식 2로 표시될 수 있다. On the other hand, the transition metal compound according to the present invention may be represented by the formula (2).
[화학식 2][Formula 2]
Figure PCTKR2017001503-appb-I000015
Figure PCTKR2017001503-appb-I000015
상기 화학식 2에서, In Chemical Formula 2,
R1 내지 R9는 각각 독립적으로 수소, 실릴, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 탄소수 7 내지 20의 아릴알킬, 또는 탄소수 1 내지 20의 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이고; R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms;
상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며; 상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있고; n은 1 또는 2이고; Q1 및 Q2는 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 6 내지 20의 아릴, 탄소수 6 내지 20의 알킬아릴, 탄소수 7 내지 20의 아릴알킬, 탄소수 1 내지 20의 알킬 아미도, 탄소수 6 내지 20의 아릴 아미도, 또는 탄소수 1 내지 20의 알킬리덴이고; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2; Q 1 and Q 2 are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. , Alkyl amido having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;
M은 Ti, Zr 또는 Hf이다.M is Ti, Zr or Hf.
또한, 상기 화학식 2에서, Q1 및 Q2는 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 6 내지 20의 아릴, 탄소수 6 내지 20의 알킬아릴, 또는 탄소수 7 내지 20의 아릴알킬일 수 있다. In addition, in Formula 2, Q 1 and Q 2 are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms. Can be.
또한, 상기 화학식 2에서, R1 내지 R9는 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 또는 탄소수 7 내지 20의 아릴알킬일 수 있고; 상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며; 상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있다. In addition, in Formula 2, R 1 to R 9 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms. There is; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
본 발명의 일례에 있어서, 상기 화학식 2의 화합물은 하기 화합물 중 어느 하나일 수 있다:In one embodiment of the present invention, the compound of Formula 2 may be any one of the following compounds:
[화학식 2a][Formula 2a]
Figure PCTKR2017001503-appb-I000016
Figure PCTKR2017001503-appb-I000016
[화학식 2b][Formula 2b]
Figure PCTKR2017001503-appb-I000017
Figure PCTKR2017001503-appb-I000017
[화학식 2c][Formula 2c]
Figure PCTKR2017001503-appb-I000018
Figure PCTKR2017001503-appb-I000018
[화학식 2d][Formula 2d]
Figure PCTKR2017001503-appb-I000019
Figure PCTKR2017001503-appb-I000019
[화학식 2e][Formula 2e]
Figure PCTKR2017001503-appb-I000020
Figure PCTKR2017001503-appb-I000020
[화학식 2f][Formula 2f]
Figure PCTKR2017001503-appb-I000021
Figure PCTKR2017001503-appb-I000021
[화학식 2g][Formula 2g]
Figure PCTKR2017001503-appb-I000022
Figure PCTKR2017001503-appb-I000022
[화학식 2h][Formula 2h]
Figure PCTKR2017001503-appb-I000023
Figure PCTKR2017001503-appb-I000023
[화학식 2i][Formula 2i]
Figure PCTKR2017001503-appb-I000024
Figure PCTKR2017001503-appb-I000024
[화학식 2j][Formula 2j]
Figure PCTKR2017001503-appb-I000025
Figure PCTKR2017001503-appb-I000025
[화학식 2k][Formula 2k]
Figure PCTKR2017001503-appb-I000026
Figure PCTKR2017001503-appb-I000026
[화학식 2l][Formula 2l]
Figure PCTKR2017001503-appb-I000027
Figure PCTKR2017001503-appb-I000027
[화학식 2m][Formula 2m]
Figure PCTKR2017001503-appb-I000028
Figure PCTKR2017001503-appb-I000028
[화학식 2n][Formula 2n]
Figure PCTKR2017001503-appb-I000029
Figure PCTKR2017001503-appb-I000029
[화학식 2o][Formula 2o]
Figure PCTKR2017001503-appb-I000030
Figure PCTKR2017001503-appb-I000030
[화학식 2p][Formula 2p]
Figure PCTKR2017001503-appb-I000031
Figure PCTKR2017001503-appb-I000031
[화학식 2q][Formula 2q]
Figure PCTKR2017001503-appb-I000032
Figure PCTKR2017001503-appb-I000032
[화학식 2r][Formula 2r]
Figure PCTKR2017001503-appb-I000033
Figure PCTKR2017001503-appb-I000033
[화학식 2s][Formula 2s]
Figure PCTKR2017001503-appb-I000034
Figure PCTKR2017001503-appb-I000034
[화학식 2t][Formula 2t]
Figure PCTKR2017001503-appb-I000035
Figure PCTKR2017001503-appb-I000035
[화학식 2u][Formula 2u]
Figure PCTKR2017001503-appb-I000036
Figure PCTKR2017001503-appb-I000036
[화학식 2v][Formula 2v]
.
Figure PCTKR2017001503-appb-I000037
.
Figure PCTKR2017001503-appb-I000037
또한, 상기 화학식 2a 내지 화학식 2v 이외에 화학식 2의 화합물의 구체적인 각 치환기 및 이들의 조합을 하기 표 1 내지 5에 나타내었다.In addition, the specific substituents of the compounds of Formula 2 and combinations thereof in addition to the Formulas 2a to 2v are shown in Tables 1 to 5 below.
Figure PCTKR2017001503-appb-T000001
Figure PCTKR2017001503-appb-T000001
Figure PCTKR2017001503-appb-T000002
Figure PCTKR2017001503-appb-T000002
Figure PCTKR2017001503-appb-T000003
Figure PCTKR2017001503-appb-T000003
Figure PCTKR2017001503-appb-T000004
Figure PCTKR2017001503-appb-T000004
Figure PCTKR2017001503-appb-T000005
Figure PCTKR2017001503-appb-T000005
본 명세서에서 정의된 각 치환기에 대하여 상세히 설명하면 다음과 같다.Each substituent defined in the present specification will be described in detail as follows.
본 명세서에 사용되는 용어 '할로겐'은 다른 언급이 없으면, 불소, 염소, 브롬 또는 요오드를 의미한다. As used herein, the term "halogen" means fluorine, chlorine, bromine or iodine, unless stated otherwise.
본 명세서에 사용되는 용어 '알킬'은 다른 언급이 없으면, 직쇄 또는 분지쇄의 탄화수소 잔기를 의미한다. As used herein, the term 'alkyl' refers to a straight or branched chain hydrocarbon residue unless otherwise indicated.
본 명세서에 사용되는 용어 '알케닐'은 다른 언급이 없으면, 직쇄 또는 분지쇄의 알케닐기을 의미한다. As used herein, the term 'alkenyl' refers to a straight or branched alkenyl group unless otherwise indicated.
상기 분지쇄는 탄소수 1 내지 20의 알킬; 탄소수 2 내지 20의 알케닐; 탄소수 6 내지 20의 아릴; 탄소수 7 내지 20의 알킬아릴; 또는 탄소수 7 내지 20의 아릴알킬일 수 있다.The branched chain is alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms.
본 발명의 일례에 따르면, 상기 실릴기는 트리메틸실릴, 트리에틸실릴, 트리프로필실릴, 트리부틸실릴, 트리헥실실릴, 트리이소프로필실릴, 트리이소부틸실릴, 트리에톡시실릴, 트리페닐실릴, 트리스(트리메틸실릴)실릴 등이 있으나, 이들 예로만 한정되는 것은 아니다.According to one embodiment of the present invention, the silyl group is trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris ( Trimethylsilyl) silyl and the like, but are not limited to these examples.
본 발명의 일례에 따르면, 상기 아릴기는 탄소수 6 내지 20인 것이 바람직하며, 구체적으로 페닐, 나프틸, 안트라세닐, 피리딜, 디메틸아닐리닐, 아니솔릴 등이 있으나, 이들 예로만 한정되는 것은 아니다.According to an example of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.
상기 알킬아릴기는 상기 알킬기에 의하여 치환된 아릴기를 의미한다.The alkylaryl group means an aryl group substituted by the alkyl group.
상기 아릴알킬기는 상기 아릴기에 의하여 치환된 알킬기를 의미한다.The arylalkyl group means an alkyl group substituted by the aryl group.
상기 고리(또는 헤테로 고리기)는 탄소수 5 내지 20개의 고리 원자를 가지며 1개 이상의 헤테로 원자를 포함하는 1가의 지방족 또는 방향족의 탄화수소기를 의미하며, 단일 고리 또는 2 이상의 고리의 축합 고리일 수 있다. 또한, 상기 헤테로 고리기는 알킬기로 치환되거나 치환되지 않을 수 있다. 이들의 예로는 인돌린, 테트라하이드로퀴놀린 등을 들 수 있지만, 본 발명이 이들로만 한정되는 것은 아니다.The ring (or heterocyclic group) means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 carbon atoms and containing one or more hetero atoms, and may be a single ring or a condensed ring of two or more rings. In addition, the heterocyclic group may or may not be substituted with an alkyl group. Examples thereof include indolin, tetrahydroquinoline, and the like, but the present invention is not limited thereto.
상기 알킬 아미노기는 상기 알킬기에 의하여 치환된 아미노기를 의미하며, 디메틸아미노기, 디에틸아미노기 등이 있으나, 이들 예로만 한정된 것은 아니다.The alkyl amino group means an amino group substituted by the alkyl group, and there are a dimethylamino group, a diethylamino group, and the like, but is not limited thereto.
본 발명의 일 실시예에 따르면, 상기 아릴기는 탄소수 6 내지 20인 것이 바람직하며, 구체적으로 페닐, 나프틸, 안트라세닐, 피리딜, 디메틸아닐리닐, 아니솔릴 등이 있으나, 이들 예로만 한정되는 것은 아니다.According to one embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto. no.
본 발명의 리간드 화합물은 하기와 같은 제조방법을 통하여 제조될 수 있으며, 구체적으로 본 발명의 화학식 1로 표시되는 리간드 화합물은 (1) 하기 화학식 3의 화합물과 하기 화학식 4의 화합물을 반응시켜 하기 화학식 5의 화합물을 제조하는 단계; 및 (2) 하기 화학식 5의 화합물과 하기 화학식 6의 화합물을 반응시켜 하기 화학식 1의 화합물을 제조하는 단계를 포함하는 방법에 의해 제조될 수 있다. The ligand compound of the present invention can be prepared through the preparation method as follows, specifically, the ligand compound represented by the formula (1) of the present invention (1) by reacting the compound of the formula (3) and the compound of the formula (4) Preparing the compound of 5; And (2) reacting the compound of Formula 5 with the compound of Formula 6 to produce a compound of Formula 1.
[화학식 1][Formula 1]
Figure PCTKR2017001503-appb-I000038
Figure PCTKR2017001503-appb-I000038
[화학식 3][Formula 3]
Figure PCTKR2017001503-appb-I000039
Figure PCTKR2017001503-appb-I000039
[화학식 4][Formula 4]
Figure PCTKR2017001503-appb-I000040
Figure PCTKR2017001503-appb-I000040
[화학식 5][Formula 5]
Figure PCTKR2017001503-appb-I000041
Figure PCTKR2017001503-appb-I000041
[화학식 6][Formula 6]
Figure PCTKR2017001503-appb-I000042
Figure PCTKR2017001503-appb-I000042
상기 화학식 1, 및 화학식 3 내지 6에서, R1 내지 R9는 각각 독립적으로 수소, 실릴, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 탄소수 7 내지 20의 아릴알킬, 또는 탄소수 1 내지 20의 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이고; 상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며; 상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있고; n은 1 또는 2이다.In Formula 1 and Formulas 3 to 6, R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, and having 7 to 20 carbon atoms. A metalloid radical of a Group 14 metal substituted with an alkylaryl, an arylalkyl having 7 to 20 carbon atoms, or a hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2.
또한, 상기 화학식 1, 및 3 내지 6에서, R1 내지 R9는 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 또는 탄소수 7 내지 20의 아릴알킬일 수 있고; 상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며; 상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있다. In addition, in Chemical Formulas 1 and 3 to 6, R 1 to R 9 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or 7 to 20 carbon atoms. May be arylalkyl; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
(1) 화학식 3의 화합물과 화학식 4의 화합물을 반응시켜 화학식 5의 화합물을 제조하는 단계(1) preparing a compound of formula 5 by reacting a compound of formula 3 with a compound of formula 4
[반응식 1] Scheme 1
Figure PCTKR2017001503-appb-I000043
Figure PCTKR2017001503-appb-I000043
단계 (1)에서는 화학식 3의 화합물과 화학식 4의 화합물을 반응시켜 화학식 5의 화합물을 제조한다.In step (1), the compound of Formula 3 is prepared by reacting the compound of Formula 3 with the compound of Formula 4.
상기 단계 (1)의 반응은 염기 조건에서 팔라듐 촉매의 존재 하에 이루어질 수 있으며, 이때 상기 반응은 톨루엔 등의 유기 용매 중에서 이루어질 수 있다.The reaction of step (1) may be carried out in the presence of a palladium catalyst in the basic conditions, wherein the reaction may be carried out in an organic solvent such as toluene.
상기 팔라듐 촉매는 테트라키스(트리페닐포스핀)팔라듐[Pd(PPh3)4], 팔라듐클로라이드(PdCl2), 팔라듐아세테이트(Pd(OAc)2), 비스(디벤질리덴아세톤)팔라듐(Pd(dba)2) 및 Pd(tBu3P2)로 이루어진 군으로부터 선택된 1종 이상일 수 있다. The palladium catalyst is tetrakis (triphenylphosphine) palladium [Pd (PPh 3 ) 4 ], palladium chloride (PdCl 2 ), palladium acetate (Pd (OAc) 2 ), bis (dibenzylideneacetone) palladium (Pd ( dba) 2 ) and Pd (tBu 3 P 2 ).
상기 염기 조건을 이루기 위한 염기의 종류는 특별히 한정되지 않으나, 구체적인 예로는 tBuOLi, 제삼인산칼륨(K3PO4), 탄산칼륨(K2CO3), 탄산세슘(Cs2CO3), 플루오르화 칼륨(KF), 플루오르화 나트륨(NaF), 플루오르화 세슘(CsF), 테트라부틸암모니움플루오라이드(TBAF), 또는 이들의 혼합물을 들 수 있다.The type of the base for achieving the base conditions is not particularly limited, but specific examples include tBuOLi, potassium triphosphate (K 3 PO 4 ), potassium carbonate (K 2 CO 3 ), cesium carbonate (Cs 2 CO 3 ), and fluorinated Potassium (KF), sodium fluoride (NaF), cesium fluoride (CsF), tetrabutylammonium fluoride (TBAF), or mixtures thereof.
상기 단계 (1)의 반응은 0℃ 내지 140℃의 온도 범위, 구체적으로 40℃ 내지 100℃의 온도 범위에서 1시간 내지 48시간, 구체적으로 2시간 내지 12시간 동안 반응시키는 방법에 의해 수행될 수 있다.The reaction of step (1) may be carried out by a method of reacting for 1 hour to 48 hours, specifically 2 hours to 12 hours in the temperature range of 0 ℃ to 140 ℃, specifically 40 ℃ to 100 ℃ have.
상기 화학식 3의 화합물과 상기 화학식 4의 화합물은 우선적으로 각각 별도의 용매에 첨가된 후, 다시 혼합될 수 있으며, 혼합 이후에 팔라듐 촉매가 첨가될 수 있다. 예컨대, 상기 화학식 3의 화합물은 물과 에탄올 등의 알코올의 혼합 용매에 첨가될 수 있고, 상기 화학식 4의 화합물은 톨루엔 등의 용매에 첨가될 수 있다. The compound of Formula 3 and the compound of Formula 4 may first be added to a separate solvent, and then mixed again, and a palladium catalyst may be added after mixing. For example, the compound of Formula 3 may be added to a mixed solvent of alcohol such as water and ethanol, and the compound of Formula 4 may be added to a solvent such as toluene.
이때, 상기 화학식 3의 화합물은 하기 반응식 2로 나타내는 반응에 의해 제조될 수 있다.In this case, the compound of Formula 3 may be prepared by a reaction represented by the following Scheme 2.
[반응식 2]Scheme 2
Figure PCTKR2017001503-appb-I000044
Figure PCTKR2017001503-appb-I000044
상기 반응식에서 R6 내지 R9 및 n은 상기 화학식 3에서 정의한 바와 같다.R 6 to R 9 and n in the scheme are as defined in Formula 3.
화학식 3-1의 화합물을 헥산 등의 유기 용매에 넣고, -80℃ 내지 0℃의 온도 범위에서 n-BuLi을 첨가한다. 이때, 상기 n-BuLi은 상기 화학식 3-1의 화합물에 대하여 1:1 내지 1:2의 몰비로 반응될 수 있고, 구체적으로 1:1.1 내지 1:1.2의 몰비로 반응될 수 있다. n-BuLi의 첨가 후 실온에서 1 내지 48 시간 동안 반응시킨 후, 이를 여과한 다음, 얻어진 화합물에 용매를 넣고, -160℃ 내지 -20℃의 온도에서 CO2를 버블링하여 가함으로써 상기 화학식 3-2의 화합물을 얻을 수 있다. 얻어진 화학식 3-2의 화합물에 t-BuLi을 넣고, -80℃ 내지 0℃의 온도 범위에서 반응시키면 상기 화학식 3-3의 화합물을 얻을 수 있다. 상기 화학식 3-3의 화합물에 2-아이소프로필옥시-4,4,5,5-테트라메틸-1,3,2-디옥사보롤란을 -150℃ 내지 -20℃의 온도에서 첨가한 후, 상온까지 서서히 승온시켜 반응을 진행하여, 상기 화학식 3의 화합물을 얻을 수 있다. 이때 HCl과 에틸아세테이트(EA)를 넣고, 유기층을 NaOH와 NaHCO3로 세척한 후, MgSO4로 수분을 건조시키는 과정이 이루어질 수 있다.The compound of Formula 3-1 is added to an organic solvent such as hexane, and n-BuLi is added in a temperature range of -80 ° C to 0 ° C. In this case, the n-BuLi may be reacted with a molar ratio of 1: 1 to 1: 2 with respect to the compound of Formula 3-1, and specifically, may be reacted with a molar ratio of 1: 1.1 to 1: 1.2. After addition of n-BuLi, the mixture was reacted at room temperature for 1 to 48 hours, and then filtered. Then, a solvent was added to the obtained compound, and CO 2 was added by bubbling at a temperature of -160 ° C to -20 ° C. The compound of -2 can be obtained. When t-BuLi is added to the obtained compound of Formula 3-2 and reacted at a temperature range of -80 ° C to 0 ° C, the compound of Formula 3-3 can be obtained. 2-isopropyloxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added to the compound of Formula 3-3 at a temperature of -150 ° C to -20 ° C, The reaction is carried out by gradually raising the temperature to room temperature, whereby the compound of Chemical Formula 3 can be obtained. At this time, HCl and ethyl acetate (EA) were added, and the organic layer was washed with NaOH and NaHCO 3 , followed by a process of drying moisture with MgSO 4 .
(2) 화학식 5의 화합물과 화학식 6의 화합물을 반응시켜 화학식 1의 화합물을 제조하는 단계(2) preparing a compound of formula 1 by reacting a compound of formula 5 with a compound of formula 6
[반응식 3]Scheme 3
Figure PCTKR2017001503-appb-I000045
Figure PCTKR2017001503-appb-I000045
단계 (2)에서는 화학식 5의 화합물과 화학식 6의 화합물을 반응시켜 화학식 1의 화합물을 제조한다.In step (2), the compound of Formula 5 is prepared by reacting the compound of Formula 5 with the compound of Formula 6.
상기 단계 (2)에서는 상기 화학식 5의 화합물에 화학식 6의 유기 리튬 화합물을 반응시켜 상기 화학식 5의 화합물에 R2를 도입한다. In step (2), R 2 is introduced into the compound of Formula 5 by reacting the compound of Formula 5 with the organolithium compound of Formula 6.
상기 단계 (2)에서 상기 화학식 5의 화합물과 상기 화학식 6의 화합물은 1:1 내지 1:3의 몰비를 가지고 반응될 수 있고, 구체적으로 1:1 내지 1:2의 몰비로 반응될 수 있다.In step (2), the compound of Formula 5 and the compound of Formula 6 may be reacted with a molar ratio of 1: 1 to 1: 3, and specifically, may be reacted at a molar ratio of 1: 1 to 1: 2. .
상기 단계 (2)의 반응은 -160℃ 내지 -20℃의 온도 범위에서 상기 화학식 5의 화합물에 상기 화학식 6의 화합물을 가한 후 반응시키는 방법에 의해 수행될 수 있으며, 구체적으로 -120℃ 내지 -40℃의 온도 범위에서 상기 화학식 5의 화합물에 상기 화학식 6의 화합물을 가하여 반응시키는 방법에 의해 이루어질 수 있다. 상기 반응은 디에틸 에터 등의 유기 용매 중에서 이루어질 수 있고, 반응이 끝나면 NH4Cl 등으로 퀀치(quench)이 이루어질 수 있다.The reaction of step (2) may be carried out by adding a compound of Chemical Formula 6 to the compound of Chemical Formula 5 in a temperature range of -160 ° C to -20 ° C, and then reacting. It can be made by the method of reacting by adding the compound of Formula 6 to the compound of Formula 5 in the temperature range of 40 ℃. The reaction may be made in an organic solvent such as diethyl ether, and may be quenched with NH 4 Cl or the like after the reaction is completed.
상기 단계 (1) 및 (2)를 거쳐 제조된 화학식 1의 화합물은 추가적으로 (3) 재결정화 단계를 거칠 수 있으며, 따라서 본 발명의 일례에 따른 전이금속 화합물의 제조방법은 상기 단계 (2) 이후, (3) 상기 화학식 1의 화합물을 재결정화 하는 단계를 추가로 포함할 수 있다. The compound of Chemical Formula 1 prepared through the steps (1) and (2) may additionally undergo a recrystallization step (3), thus, the method for preparing a transition metal compound according to an example of the present invention may be performed after the step (2). (3) The method may further include recrystallizing the compound of Chemical Formula 1.
상기 재결정화는 반응 용매와 같은 톨루엔 등의 유기 용매를 이용하여 이루어질 수 있으며, 재결정화를 통해 정제하여 순수한 화학식 1의 화합물을 얻을 수 있다.The recrystallization may be performed using an organic solvent such as toluene, such as a reaction solvent, and purified through recrystallization to obtain a pure compound of Formula 1.
또한, 본 발명의 화학식 2로 표시되는 전이금속 화합물은 (a) 상기 화학식 1의 리간드 화합물과 유기 리튬 화합물을 반응시켜 화학식 7의 화합물을 제조하는 단계; 및 (b) 하기 화학식 7의 화합물을 하기 화학식 8의 화합물과 반응시켜 하기 화학식 2의 화합물을 제조하는 단계를 포함하는 방법에 의해 제조될 수 있다. In addition, the transition metal compound represented by Formula 2 of the present invention comprises the steps of (a) preparing a compound of Formula 7 by reacting the ligand compound of Formula 1 with an organolithium compound; And (b) reacting a compound of Formula 7 with a compound of Formula 8 to produce a compound of Formula 2.
[화학식 1][Formula 1]
Figure PCTKR2017001503-appb-I000046
Figure PCTKR2017001503-appb-I000046
[화학식 2][Formula 2]
Figure PCTKR2017001503-appb-I000047
Figure PCTKR2017001503-appb-I000047
[화학식 7][Formula 7]
Figure PCTKR2017001503-appb-I000048
Figure PCTKR2017001503-appb-I000048
[화학식 8][Formula 8]
Figure PCTKR2017001503-appb-I000049
Figure PCTKR2017001503-appb-I000049
상기 화학식에서, In the above formula,
R1 내지 R9는 각각 독립적으로 수소, 실릴, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 탄소수 7 내지 20의 아릴알킬, 또는 탄소수 1 내지 20의 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이고; 상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며; 상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있고; n은 1 또는 2이고;R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2;
Q1 및 Q2는 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 6 내지 20의 아릴, 탄소수 6 내지 20의 알킬아릴, 탄소수 7 내지 20의 아릴알킬, 탄소수 1 내지 20의 알킬 아미도, 탄소수 6 내지 20의 아릴 아미도, 또는 탄소수 1 내지 20의 알킬리덴이고;Q 1 and Q 2 are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. , Alkyl amido having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;
X는 할로겐이며;X is halogen;
M은 Ti, Zr 또는 Hf이다.M is Ti, Zr or Hf.
또한, 상기 R1 내지 R9는 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 또는 탄소수 7 내지 20의 아릴알킬일 수 있고; 상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며; 상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있다.In addition, each of R 1 to R 9 may independently be hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
또한, 본 발명의 전이금속 화합물의 제조방법은 상기 화학식 2의 화합물을 하기 화학식 9의 그리나드(grignard) 시약과 추가로 반응시키는 단계를 포함할 수 있다. In addition, the method for preparing a transition metal compound of the present invention may include the step of further reacting the compound of Formula 2 with a Grignard reagent of the formula (9).
[화학식 9][Formula 9]
Figure PCTKR2017001503-appb-I000050
Figure PCTKR2017001503-appb-I000050
상기 화학식 9에서, Q는 수소, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 6 내지 20의 아릴, 탄소수 6 내지 20의 알킬아릴, 탄소수 7 내지 20의 아릴알킬, 탄소수 1 내지 20의 알킬 아미도, 탄소수 6 내지 20의 아릴 아미도, 또는 탄소수 1 내지 20의 알킬리덴이다. In Formula 9, Q is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, and having 1 to 20 carbon atoms. 20 alkyl amido, C6-C20 aryl amido, or C1-C20 alkylidene.
이때, 상기 화학식 9의 그리나드 시약과 반응이 이루어지는 상기 화학식 2의 화합물은 Q1, Q2 또는 이들 모두가 할로겐인 것일 수 있다. 즉, 본 발명의 일례에 있어서, 상기 화학식 8의 Q1, Q2, 또는 이들 모두가 할로겐일 경우, 상기 화학식 2에서 M에 결합된 Q1, Q2, 또는 이들 모두가 할로겐인 화합물이 제조되고, 이 경우 상기 화학식 9의 그리나드 시약과의 추가적인 반응을 통하여, 상기 화학식 2에서 Q1, Q2, 또는 이들 모두를 할로겐에서 상기 Q로 치환시킬 수 있다.In this case, the compound of Formula 2 reacts with the Grignard reagent of Formula 9 may be Q 1 , Q 2 or both are halogen. That is, in one example of the present invention, when Q 1 , Q 2 of Formula 8, or both of them are halogen, a compound in which Q 1 , Q 2 , or both of which are bonded to M in Formula 2 is halogen is prepared. In this case, Q 1 , Q 2 , or both in Formula 2 may be substituted with Q in halogen through an additional reaction with the Grignard reagent of Formula 9.
(a) 화학식 1의 화합물과 유기 리튬 화합물을 반응시켜 화학식 7의 화합물을 제조하는 단계(a) preparing a compound of formula 7 by reacting a compound of formula 1 with an organolithium compound
Figure PCTKR2017001503-appb-I000051
Figure PCTKR2017001503-appb-I000051
단계 (a)에서는 화학식 1의 화합물과 유기 리튬 화합물을 반응시켜 화학식 7의 화합물을 제조한다.In step (a), the compound of Formula 1 is prepared by reacting the compound of Formula 1 with an organolithium compound.
상기 단계 (1)에서 상기 화학식 1의 화합물과 상기 유기 리튬 화합물은 1:1 내지 1:3의 몰비를 가지고 반응될 수 있고, 구체적으로 1:1 내지 1:2의 몰비로 반응될 수 있다.In the step (1), the compound of Formula 1 and the organolithium compound may be reacted with a molar ratio of 1: 1 to 1: 3, and specifically, may be reacted at a molar ratio of 1: 1 to 1: 2.
상기 단계 (1)의 반응은 디에톡시에탄, 에테르와 같은 유기 용매 하에서 이루어질 수 있으며, 유기 용매 하의 상기 화학식 1의 화합물에 상기 유기 리튬 화합물을 가함으로써 이루어질 수 있다.The reaction of step (1) may be performed under an organic solvent such as diethoxyethane and ether, and may be performed by adding the organic lithium compound to the compound of Formula 1 under an organic solvent.
상기 유기 리튬 화합물은 n-부틸리튬, sec-부틸리튬, 메틸리튬, 에틸리튬, 이소프로필리튬, 사이클로헥실리튬, 알릴리튬, 비닐리튬, 페닐리튬 및 벤질리튬으로 이루어진 군으로부터 선택된 1종 이상일 수 있다. The organolithium compound may be at least one selected from the group consisting of n-butyllithium, sec-butyllithium, methyllithium, ethyllithium, isopropyllithium, cyclohexylithium, allyllithium, vinyllithium, phenyllithium and benzyllithium. .
상기 단계 (a)의 반응은 -78℃ 내지 0℃의 온도 범위에서 상기 화학식 1의 화합물에 상기 유기 리튬 화합물을 가한 후 1 내지 6시간 동안, 구체적으로 1 내지 4시간 동안 반응시키는 방법에 의해 수행될 수 있다. 이때, 반응온도는 20℃ 미만, 구체적으로 -78℃ 내지 0℃일 수 있다.The reaction of step (a) is carried out by the method of reacting for 1 to 6 hours, specifically 1 to 4 hours after adding the organolithium compound to the compound of Formula 1 in the temperature range of -78 ℃ to 0 ℃ Can be. At this time, the reaction temperature may be less than 20 ℃, specifically -78 ℃ to 0 ℃.
(b) 화학식 7의 화합물을 하기 화학식 8의 화합물과 반응시켜 하기 화학식 2의 화합물을 제조하는 단계; 및(b) reacting a compound of Formula 7 with a compound of Formula 8 to prepare a compound of Formula 2; And
Figure PCTKR2017001503-appb-I000052
Figure PCTKR2017001503-appb-I000052
단계 (b)에서는 단계 (a)에서 얻어진 화학식 7의 화합물을 화학식 8의 화합물과 반응시켜 화학식 2의 화합물을 제조한다.In step (b), the compound of formula 7 is prepared by reacting the compound of formula 7 obtained in step (a) with the compound of formula 8.
상기 단계 (b)에서 상기 화학식 7의 화합물과 상기 화학식 8의 화합물은 1:0.8 내지 1:1.8의 몰비를 가지고 반응될 수 있고, 구체적으로 1:1 내지 1:1.2의 몰비로 반응될 수 있다.In step (b), the compound of Formula 7 and the compound of Formula 8 may be reacted with a molar ratio of 1: 0.8 to 1: 1.8, and specifically, may be reacted at a molar ratio of 1: 1 to 1: 1.2. .
상기 단계 (b)의 반응은 40℃ 내지 140℃의 온도 범위, 구체적으로 70℃ 내지 120℃의 온도 범위로 승온 시킨 후, 1 내지 48 시간 동안, 구체적으로 1 내지 4시간 동안 반응시키는 방법에 의해 수행될 수 있으며, 상기 단계 (a)와 상기 단계 (b)에서의 반응은 한 스텝으로 이루어질 수도 있다. The reaction of step (b) is heated to a temperature range of 40 ° C to 140 ° C, specifically 70 ° C to 120 ° C, and then reacted for 1 to 48 hours, specifically for 1 to 4 hours. It may be carried out, the reaction in step (a) and step (b) may be made in one step.
즉, 상기 단계 (a) 및 단계 (b)의 반응은 -20℃ 내지 30℃의 온도 범위에서 상기 화학식 1의 화합물에 상기 유기 리튬 화합물을 가한 후, 추가로 화학식 8의 화합물을 가한 다음, 40℃ 내지 140℃의 온도 범위, 구체적으로 70℃ 내지 120℃의 온도 범위로 승온 시킨 후, 1 내지 48 시간 동안, 구체적으로 1 내지 4시간 동안 반응시키는 방법에 의해 수행될 수 있다. That is, in the reaction of step (a) and step (b), after adding the organolithium compound to the compound of Chemical Formula 1 at a temperature range of -20 ° C to 30 ° C, a compound of Chemical Formula 8 is further added, and then 40 After the temperature is raised to a temperature range of ℃ to 140 ℃, specifically 70 ℃ to 120 ℃, it may be carried out by a method for reacting for 1 to 48 hours, specifically 1 to 4 hours.
이로써, 상기 화학식 2의 전이금속 화합물을 제조할 수 있다. Thus, the transition metal compound of Formula 2 may be prepared.
또한, 상기 화학식 2의 전이금속 화합물에서 상기 Q1, Q2 또는 이들 모두가 할로겐일 때에는 상기 화학식 9의 그리나드 시약과 추가적인 반응이 이루어질 수 있다. 이때, 상기 화학식 2의 전이금속 화합물과 상기 화학식 9의 그리나드 시약과의 반응은 알려져 있는 그리나드 반응에 따라 이루어질 수 있다. In addition, when Q 1 , Q 2 or both of them are halogen in the transition metal compound of Formula 2, an additional reaction may be performed with the Grignard reagent of Formula 9. In this case, the reaction between the transition metal compound of Formula 2 and the Grignard reagent of Formula 9 may be performed according to a known Grignard reaction.
상기 추가적인 반응에 따라 제조되는 전이금속 화합물은 하기 화학식 9a 내지 9c 중 어느 하나로 나타낼 수 있다.The transition metal compound prepared by the additional reaction may be represented by any one of the following Chemical Formulas 9a to 9c.
[화학식 9a][Formula 9a]
Figure PCTKR2017001503-appb-I000053
Figure PCTKR2017001503-appb-I000053
[화학식 9b][Formula 9b]
Figure PCTKR2017001503-appb-I000054
Figure PCTKR2017001503-appb-I000054
[화학식 9c][Formula 9c]
Figure PCTKR2017001503-appb-I000055
Figure PCTKR2017001503-appb-I000055
보다 구체적으로, 본 발명에 따른 전이금속 화합물은 단독으로 또는 상기 전이금속 화합물 이외에 하기 화학식 10, 화학식 11 및 화학식 12로 표시되는 조촉매 화합물 중 1종 이상을 추가로 포함하는 조성물 형태로, 중합 반응의 촉매로 사용될 수 있다.More specifically, the transition metal compound according to the present invention alone or in addition to the transition metal compound in the form of a composition further comprising one or more of the cocatalyst compounds represented by the following formulas (10), (11) and (12), the polymerization reaction It can be used as a catalyst.
<화학식 10><Formula 10>
-[Al(R7)-O]m--[Al (R 7 ) -O] m-
상기 화학식 10에서,In Chemical Formula 10,
R7은 서로 동일하거나 다를 수 있으며, 각각 독립적으로 할로겐; 탄소수 1 내지 20의 탄화수소; 또는 할로겐으로 치환된 탄소수 1 내지 20의 탄화수소이고;R 7 may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
m은 2 이상의 정수이며;m is an integer of 2 or more;
<화학식 11><Formula 11>
J(R7)3 J (R 7 ) 3
상기 화학식 11에서,In Chemical Formula 11,
R7은 상기 화학식 10에서 정의된 바와 같고;R 7 is as defined in Formula 10 above;
J는 알루미늄 또는 보론이며;J is aluminum or boron;
<화학식 12><Formula 12>
[E-H]+[ZA4]- 또는 [E]+[ZA4]- [EH] + [ZA 4] - or [E] + [ZA 4] -
상기 화학식 12에서,In Chemical Formula 12,
E는 중성 또는 양이온성 루이스 염기이고;E is a neutral or cationic Lewis base;
H는 수소 원자이며;H is a hydrogen atom;
Z는 13족 원소이고;Z is a Group 13 element;
A는 서로 동일하거나 다를 수 있으며, 각각 독립적으로 1 이상의 수소 원자가 할로겐, 탄소수 1 내지 20의 탄화수소, 알콕시 또는 페녹시로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기 또는 탄소수 1 내지 20의 알킬기이다.A may be the same or different from each other, and each independently is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with one or more hydrogen atoms, halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy. .
상기 화학식 10으로 표시되는 화합물의 예로는 메틸알루미녹산, 에틸알루미녹산, 이소부틸알루미녹산, 부틸알루미녹산 등이 있으며, 더욱 바람직한 화합물은 메틸알루미녹산이다.Examples of the compound represented by the formula (10) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like, and more preferred compound is methyl aluminoxane.
상기 화학식 11로 표시되는 화합물의 예로는 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 디메틸클로로알루미늄, 트리이소프로필알루미늄, 트리-s-부틸알루미늄, 트리사이클로펜틸알루미늄, 트리펜틸알루미늄, 트리이소펜틸알루미늄, 트리헥실알루미늄, 트리옥틸알루미늄, 에틸디메틸알루미늄, 메틸디에틸알루미늄, 트리페닐알루미늄, 트리-p-톨릴알루미늄, 디메틸알루미늄메톡시드, 디메틸알루미늄에톡시드, 트리메틸보론, 트리에틸보론, 트리이소부틸보론, 트리프로필보론, 트리부틸보론 등이 포함되며, 더욱 바람직한 화합물은 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄 중에서 선택된다.Examples of the compound represented by Formula 11 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.
상기 화학식 12로 표시되는 화합물의 예로는 트리에틸암모늄테트라페닐보론, 트리부틸암모늄테트라페닐보론, 트리메틸암모늄테트라페닐보론, 트리프로필암모늄테트라페닐보론, 트리메틸암모늄테트라(p-톨릴)보론, 트리메틸암모늄테트라(o,p-디메틸페닐)보론, 트리부틸암모늄테트라(p-트리플루오로메틸페닐)보론, 트리메틸암모늄테트라(p-트리플루오로메틸페닐)보론, 트리부틸암모늄테트라펜타플루오로페닐보론, N,N-디에틸아닐리늄테트라페닐보론, N,N-디에틸아닐리늄테트라펜타플루오로페닐보론, 디에틸암모늄테트라펜타플루오로페닐보론, 트리페닐포스포늄테트라페닐보론, 트리메틸포스포늄테트라페닐보론, 디메틸아닐리늄 테트라키스(펜타플루오로페닐) 보레이트, 트리에틸암모늄테트라페닐알루미늄, 트리부틸암모늄테트라페닐알루미늄, 트리메틸암모늄테트라페닐알루미늄, 트리프로필암모늄테트라페닐알루미늄, 트리메틸암모늄테트라(p-톨릴)알루미늄, 트리프로필암모늄테트라(p-톨릴)알루미늄, 트리에틸암모늄테트라(o,p-디메틸페닐)알루미늄, 트리부틸암모늄테트라(p-트리플루오로메틸페닐)알루미늄, 트리메틸암모늄테트라(p-트리플루오로메틸페닐)알루미늄, 트리부틸암모늄테트라펜타플루오로페닐알루미늄, N,N-디에틸아닐리늄테트라페닐알루미늄, N,N-디에틸아닐리늄테트라펜타플루오로페닐알루미늄, 디에틸암모늄테트라펜타텐트라페닐알루미늄, 트리페닐포스포늄테트라페닐알루미늄, 트리메틸포스포늄테트라페닐알루미늄, 트리프로필암모늄테트라(p-톨릴)보론, 트리에틸암모늄테트라(o,p-디메틸페닐)보론, 트리페닐카보늄테트라(p-트리플루오로메틸페닐)보론 또는 트리페닐카보늄테트라펜타플루오로페닐보론 등을 들 수 있다.Examples of the compound represented by Formula 12 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N -Diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, dimethyl Aninium tetrakis (pentafluorophenyl) borate, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, tetra Methylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributyl Ammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N -Diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra (p-tolyl) boron, triethyl Ammonium tetra (o, p-dimethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron or triphenylcarbo Tetra-pentafluoropropane, and the like phenylboronic.
구체적으로 알루미녹산을 사용할 수 있으며, 더욱 구체적으로는 알킬알루미녹산인 메틸알루미녹산(MAO)일 수 있다.Specifically, aluminoxane may be used, and more specifically, it may be methylaluminoxane (MAO), which is an alkylaluminoxane.
상기 촉매 조성물은, 첫 번째 방법으로서 1) 상기 화학식 2로 표시되는 전이금속 화합물과 상기 화학식 10 또는 화학식 11로 표시되는 화합물을 접촉시켜 혼합물을 얻는 단계; 및 2) 상기 혼합물에 상기 화학식 12로 표시되는 화합물을 첨가하는 단계를 포함하는 방법으로 제조될 수 있다.The catalyst composition may comprise the steps of: 1) contacting a transition metal compound represented by Formula 2 with a compound represented by Formula 10 or Formula 11 to obtain a mixture; And 2) it can be prepared by a method comprising the step of adding a compound represented by the formula (12) to the mixture.
또한, 상기 촉매 조성물은, 두 번째 방법으로서 상기 화학식 2로 표시되는 전이금속 화합물과 상기 화학식 10으로 표시되는 화합물을 접촉시키는 방법으로 제조될 수 있다.In addition, the catalyst composition may be prepared by a method of contacting the transition metal compound represented by Formula 2 with the compound represented by Formula 10 as a second method.
상기 촉매 조성물의 제조방법 중에서 첫 번째 방법의 경우에, 상기 화학식 2로 표시되는 전이금속 화합물/상기 화학식 10 또는 화학식 11로 표시되는 화합물의 몰 비율은 1/5,000 내지 1/2이 바람직하고, 더욱 바람직하게는 1/1,000 내지 1/10 이고, 가장 바람직하게는 1/500 내지 1/20이다. 상기 화학식 2로 표시되는 전이금속 화합물/상기 화학식 10 또는 화학식 11로 표시되는 화합물의 몰 비율이 1/2을 초과하는 경우에는 알킬화제의 양이 매우 작아 금속 화합물의 알킬화가 완전히 진행되지 못하는 문제가 있고, 몰 비율이 1/5,000 미만인 경우에는 금속 화합물의 알킬화는 이루어지지만, 남아있는 과량의 알킬화제와 상기 화학식 12의 화합물인 활성화제 간의 부반응으로 인하여 알킬화된 금속 화합물의 활성화가 완전히 이루어지지 못하는 문제가 있다. 또한, 상기 화학식 2로 표시되는 전이금속 화합물/상기 화학식 12로 표시되는 화합물의 몰 비율은 1/25 내지 1이 바람직하고, 더욱 바람직하게는 1/10 내지 1이고, 가장 바람직하게는 1/5 내지 1이다. 상기 화학식 2로 표시되는 전이금속 화합물/상기 화학식 12로 표시되는 화합물의 몰 비율이 1을 초과하는 경우에는 활성화제의 양이 상대적으로 적어 금속 화합물의 활성화가 완전히 이루어지지 못해 생성되는 촉매 조성물의 활성도가 떨어지는 문제가 있고, 몰 비율이 1/25 미만인 경우에는 금속 화합물의 활성화가 완전히 이루어지지만, 남아 있는 과량의 활성화제로 촉매 조성물의 단가가 경제적이지 못하거나 생성되는 고분자의 순도가 떨어지는 문제가 있다.In the case of the first method of the preparation method of the catalyst composition, the molar ratio of the transition metal compound represented by the formula (2) / compound represented by the formula (10) or formula (11) is preferably 1 / 5,000 to 1/2, more Preferably it is 1 / 1,000-1/10, Most preferably, it is 1/500-1/20. When the molar ratio of the transition metal compound represented by the formula (2) / compound represented by the formula (10) or formula (11) is more than 1/2, the amount of the alkylating agent is so small that there is a problem that the alkylation of the metal compound does not proceed completely. In the case where the molar ratio is less than 1 / 5,000, alkylation of the metal compound is performed, but there is a problem that the activation of the alkylated metal compound is not completely performed due to a side reaction between the remaining excess alkylating agent and the activator of the compound of Formula 12. . In addition, the molar ratio of the transition metal compound represented by Formula 2 to the compound represented by Formula 12 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1/5. To 1; When the molar ratio of the transition metal compound represented by Chemical Formula 2 to the compound represented by Chemical Formula 12 is greater than 1, the amount of the activator is relatively small, and thus the activity of the catalyst composition generated due to the incomplete activation of the metal compound. If the molar ratio is less than 1/25, the activation of the metal compound is completely made, but the excess of the activator, the cost of the catalyst composition is not economical or the purity of the resulting polymer is poor.
상기 촉매 조성물의 제조방법 중에서 두 번째 방법의 경우에, 상기 화학식 2로 표시되는 전이금속 화합물/화학식 10으로 표시되는 화합물의 몰 비율은 1/10,000 내지 1/10 이 바람직하며, 더욱 바람직하게는 1/5,000 내지 1/100이고, 가장 바람직하게는 1/3,000 내지 1/500이다. 상기 몰 비율이 1/10을 초과하는 경우에는 활성화제의 양이 상대적으로 적어 금속 화합물의 활성화가 완전히 이루어지지 못해 생성되는 촉매 조성물의 활성도가 떨어지는 문제가 있고, 1/10,000 미만인 경우에는 금속 화합물의 활성화가 완전히 이루어지지만, 남아 있는 과량의 활성화제로 촉매 조성물의 단가가 경제적이지 못하거나 생성되는 고분자의 순도가 떨어지는 문제가 있다.In the case of the second method of the preparation method of the catalyst composition, the molar ratio of the transition metal compound represented by the formula (2) / compound represented by the formula (10) is preferably 1 / 10,000 to 1/10, more preferably 1 / 5,000 to 1/100, most preferably 1 / 3,000 to 1/500. If the molar ratio is greater than 1/10, the amount of the activator is relatively small, so that the activation of the metal compound is not fully performed, resulting in a decrease in the activity of the resulting catalyst composition. Although the activation is complete, there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior with the excess activator remaining.
또한, 본 발명의 일례에 있어서, 본 발명에 따른 전이금속 화합물이 중합 반응의 촉매로 사용되는 경우에, 사슬 셔틀링제를 추가로 포함하는 조성물 형태로, 중합 반응의 촉매로 사용될 수 있다.In addition, in one example of the present invention, when the transition metal compound according to the present invention is used as a catalyst for the polymerization reaction, it may be used as a catalyst for the polymerization reaction in the form of a composition further comprising a chain shuttle agent.
상기 사슬 셔틀링제는 올레핀 중합 조건 하에, 2개의 올레핀 중합 촉매의 2개 이상의 활성 촉매 부위 사이에서 중합체성 사슬(즉, 중합체 사슬 또는 단편)을 교환하게 할 수 있는 것을 특징으로 할 수 있는 화합물을 의미하며, 이때 상기 2개의 올레핀 중합 촉매는 본 발명의 전이금속 화합물일 수 있다. 즉, 중합체 단편의 전달은 전이금속 화합물의 활성 부위들 중 하나 이상에서 일어난다.The chain shuttleling agent means a compound which can be characterized by being able to exchange polymeric chains (ie, polymer chains or fragments) between two or more active catalyst sites of two olefin polymerization catalysts under olefin polymerization conditions. In this case, the two olefin polymerization catalyst may be a transition metal compound of the present invention. That is, delivery of the polymer fragment occurs at one or more of the active sites of the transition metal compound.
상기 사슬 셔틀링제의 예로는 트리알킬 알루미늄 및 다이알킬 아연 화합물, 특히 트리에틸알루미늄, 트리(i-프로필)알루미늄, 트리(i-부틸)알루미늄, 트리(n-헥실)알루미늄, 트리(n-옥틸)알루미늄, 트리에틸갈륨 또는 다이에틸아연을 들 수 있고, 또한 유기금속 화합물, 구체적으로 트리((C1-C8)알킬) 알루미늄 또는 다이((C1-C8)알킬) 아연 화합물, 특히 트리에틸알루미늄, 트리(i-프로필) 알루미늄, 트리(i-부틸)알루미늄, 트리(n-헥실)알루미늄, 트리(n-옥틸)알루미늄 또는 다이에틸아연을 화학양론적 양(하이드로카빌 기의 수 대비) 미만의 1급 또는 2급 아민, 1급 또는 2급 포스핀, 티올, 또는 하이드록실 화합물, 특히 비스(트리메틸실릴)아민, t-부틸(다이메틸)실란올, 2-하이드록시메틸피리딘, 다이(n-펜틸)아민, 2,6-다이(t-부틸)페놀, 에틸(1-나프틸)아민, 비스(2,3,6,7-다이벤조-1-아자사이클로헵탄아민), 다이페닐포스핀, 2,6-다이(t-부틸)티오페놀 또는 2,6-다이페닐페놀과 조합하여 형성된 반응 생성물 또는 혼합물을 들 수 있다. 바람직하게는, 충분한 아민, 포스핀, 티올 또는 하이드록실 시약은, 금속 원자 당 하나 이상의 하이드로카빌 기가 잔류하도록 사용된다. 셔틀링제로서 본 발명에서의 사용에 가장 바람직한 상기의 조합의 주요 반응 생성물은 n-옥틸알루미늄 다이(비스(트리메틸실릴)아미드), i-프로필알루미늄 비스(다이메틸(t-부틸)실록사이드), 및 n-옥틸알루미늄 다이(피리딘일-2-메톡사이드), i-부틸알루미늄 비스(다이메틸(t-부틸)실록산), i-부틸알루미늄 다이(비스(트리메틸실릴)아미드), n-옥틸알루미늄 다이(피리딘-2-메톡사이드), i-부틸알루미늄 비스(다이(n-펜틸)아미드), n-옥틸알루미늄 비스(2,6-다이-t-부틸페녹사이드), n-옥틸알루미늄 다이(에틸(1-나프틸)아미드), 에틸알루미늄 비스(t-부틸다이메틸실록사이드), 에틸알루미늄 다이(비스(트리메틸실릴)아미드), 에틸알루미늄 비스(2,3,6,7-다이벤조-1-아자사이클로헵탄아미드), n-옥틸알루미늄 비스(2,3,6,7-다이벤조-1-아자사이클로헵탄아미드), n-옥틸알루미늄 비스(다이메틸(t-부틸)실록사이드), 에틸아연(2,6-다이페닐페녹사이드), 및 에틸아연 (t-부톡사이드)이다.Examples of such chain shuttle agents include trialkyl aluminum and dialkyl zinc compounds, in particular triethylaluminum, tri (i-propyl) aluminum, tri (i-butyl) aluminum, tri (n-hexyl) aluminum, tri (n-octyl) Aluminum, triethylgallium or diethylzinc, and also organometallic compounds, specifically tri ((C 1 -C 8 ) alkyl) aluminum or di ((C 1 -C 8 ) alkyl) zinc compounds, in particular Stoichiometric amounts of triethylaluminum, tri (i-propyl) aluminum, tri (i-butyl) aluminum, tri (n-hexyl) aluminum, tri (n-octyl) aluminum or diethylzinc (number of hydrocarbyl groups Primary or secondary amines, primary or secondary phosphines, thiols, or hydroxyl compounds, in particular bis (trimethylsilyl) amine, t-butyl (dimethyl) silanol, 2-hydroxymethylpyridine , Di (n-pentyl) amine, 2,6-di (t-butyl) phenol, ethyl (1-naphthyl) amine, bis ( Reaction product formed in combination with 2,3,6,7-dibenzo-1-azacycloheptanamine), diphenylphosphine, 2,6-di (t-butyl) thiophenol or 2,6-diphenylphenol Or mixtures. Preferably, sufficient amine, phosphine, thiol or hydroxyl reagent is used so that one or more hydrocarbyl groups remain per metal atom. The main reaction products of the above combinations which are most preferred for use in the present invention as shuttles are n-octylaluminum di (bis (trimethylsilyl) amide), i-propylaluminum bis (dimethyl (t-butyl) siloxane), And n-octyl aluminum di (pyridinyl-2-methoxide), i-butyl aluminum bis (dimethyl (t-butyl) siloxane), i-butyl aluminum di (bis (trimethylsilyl) amide), n-octyl aluminum Di (pyridine-2-methoxide), i-butylaluminum bis (di (n-pentyl) amide), n-octyl aluminum bis (2,6-di-t-butylphenoxide), n-octyl aluminum di ( Ethyl (1-naphthyl) amide), ethylaluminum bis (t-butyldimethylsiloxane), ethylaluminum di (bis (trimethylsilyl) amide), ethylaluminum bis (2,3,6,7-dibenzo- 1-azacycloheptanamide), n-octylaluminum bis (2,3,6,7-dibenzo-1-azacycloheptanamide), n-octylalu A titanium bis (dimethyl (t- butyl) siloxane side), ethyl zinc (2,6-diphenyl-phenoxide), and zinc acetate (t- butoxide).
상기 촉매 조성물의 제조시에 반응 용매로서 펜탄, 헥산, 헵탄 등과 같은 탄화수소계 용매, 또는 벤젠, 톨루엔 등과 같은 방향족계 용매가 사용될 수 있다.In preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene, toluene, or the like may be used.
또한, 상기 촉매 조성물은 상기 전이금속 화합물과 조촉매 화합물을 담체에 담지된 형태로 포함할 수 있다.In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a form supported on a carrier.
구체적으로, 상기 전이금속 화합물을 포함하는 촉매 조성물의 존재 하에 올레핀계 단량체를 중합하는 중합 반응은 하나의 연속식 슬러리 중합 반응기, 루프 슬러리 반응기, 기상 반응기 또는 용액 반응기 등을 이용하여, 용액 중합 공정, 슬러리 공정 또는 기상 공정에 의해 수행될 수 있다. 또한 하나의 올레핀 단량체로 호모중합하거나 또는 2종 이상의 단량체로 공중합하여 진행할 수 있다.Specifically, the polymerization reaction for polymerizing the olefinic monomer in the presence of the catalyst composition comprising the transition metal compound is a solution polymerization process, using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor or a solution reactor, It may be carried out by a slurry process or a gas phase process. It can also proceed by homopolymerization with one olefin monomer or copolymerization with two or more monomers.
상기 폴리올레핀의 중합은 약 25℃ 내지 약 500℃의 온도 및 약 1 내지 약 100 kgf/cm2에서 반응시켜 수행할 수 있다. Polymerization of the polyolefin may be carried out by reacting at a temperature of about 25 ℃ to about 500 ℃ and about 1 to about 100 kgf / cm 2 .
구체적으로, 상기 폴리올레핀의 중합은 약 25℃ 내지 약 500℃, 바람직하게는 약 25℃ 내지 200℃, 보다 바람직하게는 약 50℃ 내지 100℃의 온도에서 수행할 수 있다. 또한 반응 압력은 약 1 kgf/cm2 내지 약 100 kgf/cm2, 바람직하게는 약 1 kgf/cm2 내지 약 50 kgf/cm2, 보다 바람직하게는 약 5 kgf/cm2 내지 약 40 kgf/cm2에서 수행할 수 있다.Specifically, the polymerization of the polyolefin may be carried out at a temperature of about 25 ℃ to about 500 ℃, preferably about 25 ℃ to 200 ℃, more preferably about 50 ℃ to 100 ℃. In addition, the reaction pressure is about 1 kgf / cm 2 to about 100 kgf / cm 2 , preferably about 1 kgf / cm 2 To about 50 kgf / cm 2 , more preferably about 5 kgf / cm 2 To about 40 kgf / cm 2 .
또한, 본 발명의 일 실시예에 따른 상기 전이금속 화합물 및 조촉매를 사용한 중합 가능한 올레핀계 단량체의 예로는 에틸렌, 알파-올레핀, 사이클릭 올레핀 등이 있으며, 이중 결합을 2개 이상 가지고 있는 디엔 올레핀계 단량체 또는 트리엔 올레핀계 단량체 등도 중합 가능하다. In addition, examples of the polymerizable olefin monomer using the transition metal compound and the promoter according to an embodiment of the present invention include ethylene, alpha-olefin, cyclic olefin, and the like, and a diene olefin having two or more double bonds. The monomer or the triene olefin monomer can also be polymerized.
본 발명에 따라 제조되는 폴리올레핀에 있어서, 상기 올레핀계 단량체의 구체적인 예로는 에틸렌, 프로필렌, 1-부텐, 1-펜텐, 4-메틸-1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-데센, 1-운데센, 1-도데센, 1-테트라데센, 1-헥사데센, 1-아이토센 등이 있으며, 이들을 2종 이상 혼합하여 공중합한 공중합체일 수 있다.In the polyolefin prepared according to the present invention, specific examples of the olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- itocene and the like, may be a copolymer copolymerized by mixing two or more thereof.
상기 폴리올레핀은 프로필렌 중합체일 수 있으나, 이에만 한정되는 것은 아니다.The polyolefin may be a propylene polymer, but is not limited thereto.
상기 중합체는 호모 중합체 또는 공중합체가 모두 가능하다. 상기 올레핀 중합체가 에틸렌과 다른 공단량체의 공중합체인 경우에, 상기 공중합체를 구성하는 단량체는 에틸렌 및 프로필렌, 1-부텐, 1-헥센, 및 4-메틸-1-펜텐, 및 1-옥텐으로 이루어진 군에서 선택된 하나 이상의 공단량체인 것이 바람직하다.The polymer may be either a homo polymer or a copolymer. When the olefin polymer is a copolymer of ethylene and other comonomers, the monomers constituting the copolymer consist of ethylene and propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene It is preferred that it is at least one comonomer selected from the group.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 기재한다. 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위를 한정하고자 하는 것은 아니다.Hereinafter, preferred examples will be described to aid in understanding the present invention. The following examples are merely to illustrate the invention, but are not intended to limit the scope of the invention.
리간드 및 전이금속 화합물의 합성Synthesis of Ligands and Transition Metal Compounds
유기 시약 및 용매는 알드리치(Aldrich)사와 머크(Merck)사에서 구입하여 표준 방법으로 정제하여 사용하였다. 합성의 모든 단계에서 공기와 수분의 접촉을 차단하여 실험의 재현성을 높였다. 화합물의 구조를 입증하기 위해 500 MHz 핵자기 공명기(NMR)를 이용하여 각각 스펙트럼과 도식을 얻었다.Organic reagents and solvents were purchased from Aldrich and Merck and purified using standard methods. At all stages of the synthesis, the contact between air and moisture was blocked to increase the reproducibility of the experiment. To verify the structure of the compounds, spectra and plots were obtained using 500 MHz nuclear magnetic resonance (NMR), respectively.
<실시예>< Example >
실시예 1: 리간드 화합물의 합성Example 1 Synthesis of Ligand Compound
a) 8-(4,4,5,5-a) 8- (4,4,5,5- 테트라메틸Tetramethyl -1,3,2--1,3,2- 디옥사보롤란Dioxaborolan -2-일)-1,2,3,4--2-yl) -1,2,3,4- 테트라하이드로퀴놀린의Tetrahydroquinoline 제조 Produce
Figure PCTKR2017001503-appb-I000056
Figure PCTKR2017001503-appb-I000056
쉬렝크 플라스크에 THQ(6 g, 45.05 mmol, 1eq)를 넣은 뒤 진공 건조(vacuum dry)하고, 여기에 헥산(150 mL, 0.3 M)을 첨가한 후 -20℃에서 n-BuLi(19.82 mL, 49.56 mmol, 1.1 eq, 2.5 M in hexane)을 첨가하였다. 이것을 밤새 상온에서 반응시킨 뒤 리튬 화합물을 여과하여 얻었다. 이렇게 얻어진 리튬 화합물(3 g, 21.56 mmol, 1 eq)에 디에틸 에터(53.9 mL, 0.4 M)를 넣고 -78℃에서 CO2 버블링을 하였다. 이를 상온에 밤새 방치한 뒤 -20℃에서 THF(1.1 eq, 1.71 g, 23.72 mmol)를 첨가하였다. 여기에 t-BuLi(13.95 mL, 23.72 mmol, 1.1 eq, 1.7 M)를 넣어 -20℃에서 2시간 동안 반응시킨 뒤 2-아이소프로필-4,4,5,5-테트라메틸-1,3,2-디옥사보롤란(10.03 g, 53.9 mmol, 2.5 eq)을 -78℃에서 첨가하였다. 상온으로 서서히 승온시킨 뒤 반응이 끝난 후 0℃에서 1M HCl 수용액과 EA를 넣었다. 유기층을 1M NaOH와 1M NaHCO3로 세척한 후 MgSO4로 수분을 건조시켰다. 노란색 오일인 생성물을 1.4 g, 25% 수율로 얻었다. THQ (6 g, 45.05 mmol, 1eq) was added to the Schlenk flask, followed by vacuum dry, hexane (150 mL, 0.3 M) was added thereto, and n-BuLi (19.82 mL, 49.56 mmol, 1.1 eq, 2.5 M in hexane) was added. After reacting this at room temperature overnight, the lithium compound was filtered out. Diethyl ether (53.9 mL, 0.4 M) was added to a lithium compound (3 g, 21.56 mmol, 1 eq) thus obtained, followed by CO 2 bubbling at -78 ° C. After standing at room temperature overnight, THF (1.1 eq, 1.71 g, 23.72 mmol) was added at -20 ° C. To this was added t-BuLi (13.95 mL, 23.72 mmol, 1.1 eq, 1.7 M) and reacted at -20 ° C for 2 hours, followed by 2-isopropyl-4,4,5,5-tetramethyl-1,3, 2-dioxaborolane (10.03 g, 53.9 mmol, 2.5 eq) was added at -78 ° C. After slowly raising the temperature to room temperature, after the reaction was completed, 1M HCl aqueous solution and EA were added at 0 ° C. The organic layer was washed with 1M NaOH and 1M NaHCO 3 and dried with MgSO 4 . The product, a yellow oil, was obtained in 1.4 g, 25% yield.
1H-NMR (CDCl3): 7.42 (d, 1H), 6.97 (d, 1H), 6.48 (t, 1H), 5.70 (s, 1H), 3.34 (m, 2H), 2.73 (t, 2H), 1.90 (m, 2H), 1.31 (s, 12H)1 H-NMR (CDCl 3 ): 7.42 (d, 1H), 6.97 (d, 1H), 6.48 (t, 1H), 5.70 (s, 1H), 3.34 (m, 2H), 2.73 (t, 2H), 1.90 (m, 2H), 1.31 (s, 12H)
b) N-(2,6-디이소프로필페닐)-1-(6-브로모피리딘-2-일)메탄이민의 제조b) Preparation of N- (2,6-diisopropylphenyl) -1- (6-bromopyridin-2-yl) methanimine
2-포르밀-6-브로모피리딘(9.22 g, 49.57 mmol, 1 eq)에 p-톨루엔설폰산(3 방울), 몰레큘라 시브(molecular sieve, 1 g)를 넣은 후, 톨루엔(100 mL)을 첨가하였다. 여기에 2,6-디이소프로필 아닐린(9.66 g, 54.52 mmol, 1.1 eq)을 첨가하고 70℃에서 12시간 교반한 후, 실온으로 냉각하였다. 몰레큘라 시브를 여과한 뒤 용매를 제거하고, 고체가 생성되도록 진공 건조시켰다. 50℃ 가열 상태에서 MeOH를 첨가한 다음 실온으로 냉각하여 고체를 얻었다. 이것을 1차 여과하여 고체를 얻어내고, 2차로 이를 냉장고에서 재결정하여 2차 고체를 얻었다. 이를 통하여 고체 15.5 g을 90.5% 수율로 얻을 수 있었다. To 2-formyl-6-bromopyridine (9.22 g, 49.57 mmol, 1 eq) was added p -toluenesulfonic acid (3 drops) and molecular sieve (1 g), followed by toluene (100 mL). Was added. To this was added 2,6-diisopropyl aniline (9.66 g, 54.52 mmol, 1.1 eq) and stirred at 70 ° C. for 12 hours, followed by cooling to room temperature. The molecular sieve was filtered off and the solvent was removed and vacuum dried to produce a solid. MeOH was added at 50 ° C. and then cooled to room temperature to obtain a solid. This was first filtered to give a solid, which was secondly recrystallized in a refrigerator to obtain a secondary solid. This gave 15.5 g of solid in 90.5% yield.
c) N-(2,6- 디이소프로필페닐 )-1-(6-(1,2,3,4- 테트라하이드로퀴놀린 -8-일)피리딘-2-일)메탄이민의 제조 c) Preparation of N- (2,6 -diisopropylphenyl ) -1- (6- (1,2,3,4- tetrahydroquinolin- 8-yl) pyridin - 2 -yl) methanimine
Figure PCTKR2017001503-appb-I000057
Figure PCTKR2017001503-appb-I000057
상기에서 제조된 N-(2,6-디이소프로필페닐)-1-(6-브로모피리딘-2-일)메탄이민(1.799 g, 5.209 mmol, 1 eq)에 톨루엔(8 mL)을 넣고 교반하는 한편, 이와 별도로 Na2CO3(1.380 g, 13.0225 mmol, 2.5 eq)와 테트라하이드로퀴놀린-보롤란(THQ-보롤란)(1.350 g, 5.209 mmol, 1 eq)을 H2O(1.6 mL)와 EtOH(1.6 mL) 1:1인 용매에 넣고 교반하였다. Toluene (8 mL) was added to N- (2,6-diisopropylphenyl) -1- (6-bromopyridin-2-yl) methaneimine (1.799 g, 5.209 mmol, 1 eq) prepared above. While stirring, Na 2 CO 3 (1.380 g, 13.0225 mmol, 2.5 eq) and tetrahydroquinoline-borolane (THQ-borolane) (1.350 g, 5.209 mmol, 1 eq) were added with H 2 O (1.6 mL). ) And EtOH (1.6 mL) 1: 1 and added to the solvent and stirred.
Br-이민 톨루엔 용액을 Na2CO3와 THQ-보롤란의 용액으로 옮긴 뒤, 여기에 Pd(PPh3)4(0.018 g, 0.0156 mmol, 0.3 mol% Pd)를 넣었다. 70℃에서 4 시간 동안 교반한 뒤 실온으로 냉각시켰다. 유기층을 톨루엔/염수(brine)로 추출하고 Na2SO4로 수분을 건조시켰다(생성물 0.98 g, 수율 47%).Br-imine toluene solution was transferred to a solution of Na 2 CO 3 and THQ-borolane, and Pd (PPh 3 ) 4 (0.018 g, 0.0156 mmol, 0.3 mol% Pd) was added thereto. After stirring for 4 hours at 70 ℃ cooled to room temperature. The organic layer was extracted with toluene / brine and dried with Na 2 SO 4 (0.98 g product, 47% yield).
1H-NMR (toluene_d8): 8.88 (s, 1H), 8.38 (s, 1H), 7.92 (d, 1H), 7.33 1 H-NMR (toluene_d8): 8.88 (s, 1H), 8.38 (s, 1H), 7.92 (d, 1H), 7.33
(d, 2H), 7.20 (t, 1H), 7.18 (t, 2H), 6.91 (d, 1H), 6.63 (t, 1H), 3.20 (m, 4H), 2.62 (m, 2H), 1.63 (m, 2H), 1.20 (d, 12H)(d, 2H), 7.20 (t, 1H), 7.18 (t, 2H), 6.91 (d, 1H), 6.63 (t, 1H), 3.20 (m, 4H), 2.62 (m, 2H), 1.63 ( m, 2H), 1.20 (d, 12H)
d) 2,6-d) 2,6- 디이소프로필Diisopropyl -N-(-N- ( 페닐Phenyl (6-(1,2,3,4-(6- (1,2,3,4- 테트라하이드로퀴놀린Tetrahydroquinoline -8-일)피리딘-2-일)메틸)아닐린의 제조Preparation of -8-yl) pyridin-2-yl) methyl) aniline
Figure PCTKR2017001503-appb-I000058
Figure PCTKR2017001503-appb-I000058
상기에서 제조된 N-(2,6-디이소프로필페닐)-1-(6-(1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메탄이민(0.95 g, 2.39 mmol, 1 eq)을 디에틸 에터(23.9 mL)에 녹이고 -78℃로 온도를 낮춘 뒤, 페닐 리튬(3.583 mL, 6.45 mmol, 2.7 eq, 1.8 M in DBE)을 넣었다. 반응이 끝나면 1 N NH4Cl로 퀀치(quench)하고 디에틸 에터와 물로 워크-업(work-up)하였다. 오렌지색 고체를 1.2 g(정량수율) 수득하였다. N- (2,6-diisopropylphenyl) -1- (6- (1,2,3,4-tetrahydroquinolin-8-yl) pyridin-2-yl) methanimine prepared above (0.95 g , 2.39 mmol, 1 eq) was dissolved in diethyl ether (23.9 mL) and the temperature was lowered to −78 ° C., followed by addition of phenyl lithium (3.583 mL, 6.45 mmol, 2.7 eq, 1.8 M in DBE). At the end of the reaction, the reaction was quenched with 1N NH 4 Cl and worked up with diethyl ether and water. 1.2 g (quantitative yield) of an orange solid was obtained.
1H-NMR(toluene_d8): 8.01 (s, 1H), 7.41 (d, 2H), 7.31 (d, 1H), 7.15 (m, 4H), 7.06 (m, 3H), 6.86 (d, 2H), 6.73 (t, 1H), 6.61 (t, 1H), 5.24 (d, 1H), 4.32 (d, 1H), 3.05 (m, 2H), 3.0 (m, 2H), 2.52 (m, 2H), 1.52 (m, 2H), 1.01 (m, 12H)1 H-NMR (toluene_d8): 8.01 (s, 1H), 7.41 (d, 2H), 7.31 (d, 1H), 7.15 (m, 4H), 7.06 (m, 3H), 6.86 (d, 2H), 6.73 (t, 1H), 6.61 (t, 1H), 5.24 (d, 1H), 4.32 (d, 1H), 3.05 (m, 2H), 3.0 (m, 2H), 2.52 (m, 2H), 1.52 ( m, 2H), 1.01 (m, 12H)
실시예 1-1: 전이 금속 화합물의 합성(화학식 2a) Example 1-1: Synthesis of Transition Metal Compound (Formula 2a)
Figure PCTKR2017001503-appb-I000059
Figure PCTKR2017001503-appb-I000059
상기 실시예 1의 d)에서 제조된 2,6-디이소프로필-N-(페닐(6-(1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메틸)아닐린(0.8 g, 1.682 mmol, 1 eq)과 톨루엔(5.607 mL, 0.3 M)을 넣고 교반한 후, n-BuLi(1.413 mL, 3.532 mmol, 2.1 eq)을 적가하였다. HfCl4(0.566 g, 1.766 mmol, 1.0 eq)를 넣고 2 시간 동안 90℃ 내지 100℃에서 가열시켰다. 반응이 끝난 후 온도를 식히고 MeMgBr(1.962 mL, 5.887 mmol, 3.5 eq, 3.0 M in DEE)을 넣어 상온에서 밤새 반응시켰다. 용매를 진공 건조(vacuum dry)한 후 여과하였다. 노란색 고체 588 mg을 51.2% 수율로 얻을 수 있었다.2,6-diisopropyl-N- (phenyl (6- (1,2,3,4-tetrahydroquinolin-8-yl) pyridin-2-yl) methyl) prepared in Example 1 d) After stirring with aniline (0.8 g, 1.682 mmol, 1 eq) and toluene (5.607 mL, 0.3 M), n-BuLi (1.413 mL, 3.532 mmol, 2.1 eq) was added dropwise. HfCl 4 (0.566 g, 1.766 mmol, 1.0 eq) was added and heated at 90 ° C. to 100 ° C. for 2 hours. After the reaction, the temperature was cooled and MeMgBr (1.962 mL, 5.887 mmol, 3.5 eq, 3.0 M in DEE) was added and allowed to react at room temperature overnight. The solvent was vacuum dried and then filtered. 588 mg of a yellow solid could be obtained in 51.2% yield.
1H-NMR (toluene_d8): 7.29 (d, 1H), 7.20 (d, 1H), 7.12 (m, 1H), 7.11 (m, 2H), 7.05 (m, 6H), 6.89 (t, 1H), 6.67 (t, 1H), 6.51 (d, 1H), 5.93 (s, 1H), 4.38 (d, 1H), 3.89 (t, 1H), 3.49 (t, 1H), 3.11 (m, 1H), 2.86 (m, 1H), 2.63 (m, 1H), 1.95 (m, 2H), 1.43 (d, 3H), 1.23 (d, 3H), 1.01 (d, 3H), 0.56 (s, 3H), 0.46 (d, 3H), 0.00 (s, 3H)1 H-NMR (toluene_d8): 7.29 (d, 1H), 7.20 (d, 1H), 7.12 (m, 1H), 7.11 (m, 2H), 7.05 (m, 6H), 6.89 (t, 1H), 6.67 (t, 1H), 6.51 (d, 1H), 5.93 (s, 1H), 4.38 (d, 1H), 3.89 (t, 1H), 3.49 (t, 1H), 3.11 (m, 1H), 2.86 ( m, 1H), 2.63 (m, 1H), 1.95 (m, 2H), 1.43 (d, 3H), 1.23 (d, 3H), 1.01 (d, 3H), 0.56 (s, 3H), 0.46 (d , 3H), 0.00 (s, 3H)
실시예 1-2: 전이 금속 화합물의 합성(화학식 2b)Example 1-2: Synthesis of Transition Metal Compound (Formula 2b)
Figure PCTKR2017001503-appb-I000060
Figure PCTKR2017001503-appb-I000060
상기 실시예 1의 d)에서 제조된 2,6-디이소프로필-N-(페닐(6-(1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메틸)아닐린(0.82 g, 1.724 mmol, 1 eq)을 톨루엔(5.747 mL, 0.3 M)에 넣고 교반한 후, n-BuLi(1.45 mL, 3.6204 mmol, 2.1 eq)을 적가하였다. ZrCl4(0.422 g, 1.810 mmol, 1.05 eq)를 넣고 2 시간 동안 90 내지 100℃에서 가열하였다. 2,6-diisopropyl-N- (phenyl (6- (1,2,3,4-tetrahydroquinolin-8-yl) pyridin-2-yl) methyl) prepared in Example 1 d) Aniline (0.82 g, 1.724 mmol, 1 eq) was added to toluene (5.747 mL, 0.3 M), stirred, and n-BuLi (1.45 mL, 3.6204 mmol, 2.1 eq) was added dropwise. ZrCl 4 (0.422 g, 1.810 mmol, 1.05 eq) was added thereto and heated at 90 to 100 ° C. for 2 hours.
반응이 끝난 후 온도를 식히고 MeMgBr(2.011 mL, 6.034 mmol, 3.5 eq, 3.0M in DEE)을 넣어 상온에서 밤새 반응시켰다. 용매를 진공 건조(vacuum dry)한 후 여과하였다. 셀라이트 여과된 여액을 건조시키고 여기에 헥산을 넣고 교반한 뒤 진공 건조(vacuum dry)하고 다시 펜탄을 넣고 교반한 다음, 진공 건조(vacuum dry)시켰다. 고체가 얻어지면 여기에 펜탄을 넣고 침전시켜 촉매를 얻어낸다. 오렌지색 고체를 672 mg, 65.5% 수율로 얻을 수 있었다.After the reaction, the temperature was cooled and MeMgBr (2.011 mL, 6.034 mmol, 3.5 eq, 3.0 M in DEE) was added and allowed to react at room temperature overnight. The solvent was vacuum dried and then filtered. The celite filtered filtrate was dried and added to hexane and stirred, followed by vacuum dry, and again with pentane and stirred, followed by vacuum dry. Once a solid is obtained, pentane is added and precipitated to obtain a catalyst. An orange solid was obtained in 672 mg, 65.5% yield.
1H-NMR (toluene_d8): 7.30 (d, 1H), 7.20 (d, 1H), 7.12 (m, 2H), 7.06 (m, 7H), 6.89 (t, 1H), 6.67 (t, 1H), 6.54 (d, 1H), 5.73 (s, 1H), 4.80 (d, 1H), 3.99 (m, 1H), 3.57 (t, 1H), 3.07 (m, 1H), 2.86 (m, 1H), 2.67 (m, 1H), 1.95 (m, 2H), 1.45 (d, 3H), 1.21 (d, 3H), 0.96 (d, 3H), 0.68 (s, 3H), 0.50 (d, 3H), 0.09 (s, 3H)1 H-NMR (toluene_d8): 7.30 (d, 1H), 7.20 (d, 1H), 7.12 (m, 2H), 7.06 (m, 7H), 6.89 (t, 1H), 6.67 (t, 1H), 6.54 (d, 1H), 5.73 (s, 1H), 4.80 (d, 1H), 3.99 (m, 1H), 3.57 (t, 1H), 3.07 (m, 1H), 2.86 (m, 1H), 2.67 ( m, 1H), 1.95 (m, 2H), 1.45 (d, 3H), 1.21 (d, 3H), 0.96 (d, 3H), 0.68 (s, 3H), 0.50 (d, 3H), 0.09 (s , 3H)
실시예 2: 리간드 화합물의 합성Example 2: Synthesis of Ligand Compound
2,6-2,6- 디이소프로필Diisopropyl -N-((2--N-((2- 이소프로필페닐Isopropylphenyl )(6-(1,2,3,4-) (6- (1,2,3,4- 테트라하이드로퀴놀린Tetrahydroquinoline -8-일)피리딘-2-일)메틸)아닐린의 합성Synthesis of -8-yl) pyridin-2-yl) methyl) aniline
Figure PCTKR2017001503-appb-I000061
Figure PCTKR2017001503-appb-I000061
1-Br-2-이소프로필벤젠(2.13 g, 10.67 mmol, 2.7 eq)을 THF(21.38 mL)에 넣고 -78℃에서 t-BuLi(13.62 mL)을 넣었다. 이것을 2시간 동안 반응시킨 뒤 상온으로 승온시켰다. 1-Br-2-isopropylbenzene (2.13 g, 10.67 mmol, 2.7 eq) was added to THF (21.38 mL) and t-BuLi (13.62 mL) at -78 ° C. After reacting for 2 hours, the temperature was raised to room temperature.
N-(2,6-디이소프로필페닐)-1-(6-(1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메탄이민에 디에틸 에터를 넣고 큐멘 리튬을 -78℃에서 적가하였다. 상온으로 승온시켜 밤새 반응시킨 뒤 1 N NH4Cl로 퀀치(quench)하고 에터/H2O 워크-업을 실시하였다. Na2SO4로 수분을 건조시킨 뒤 회전 증발 농축기(Rotavapor)로 용매를 진공 건조(vacuum dry)시켰다. 깨끗한 노란색 오일을 2.22 g, 정량수율로 얻을 수 있었다. Diethyl ether was added to N- (2,6-diisopropylphenyl) -1- (6- (1,2,3,4-tetrahydroquinolin-8-yl) pyridin-2-yl) methanimine and cumene Lithium was added dropwise at -78 ° C. The reaction mixture was warmed to room temperature overnight, quenched with 1 N NH 4 Cl, and ether / H 2 O work-up was performed. The moisture was dried over Na 2 SO 4 and then the solvent was vacuum dried with a Rotavapor. A clear yellow oil was obtained in 2.22 g, quantitative yield.
1H-NMR (toluene_d8): 7.97 (s, 1H), 7.66 (d, 1H), 7.30 (d, 1H), 7.14 (m, 8H), 6.83 (d, 1H), 6.56 (t, 1H), 5.61 (d, 1H), 4.04 (d, 1H), 2.9 (m, 5H), 2.5 (m, 2H), 1.51 (m, 2H), 1.01 (d, 12H), 1.00 (d, 3H), 0.97 (d, 3H)1 H-NMR (toluene_d8): 7.97 (s, 1H), 7.66 (d, 1H), 7.30 (d, 1H), 7.14 (m, 8H), 6.83 (d, 1H), 6.56 (t, 1H), 5.61 (d, 1H), 4.04 (d, 1H), 2.9 (m, 5H), 2.5 (m, 2H), 1.51 (m, 2H), 1.01 (d, 12H), 1.00 (d, 3H), 0.97 ( d, 3H)
실시예 2-1: 전이금속 화합물의 합성(화학식 2c)Example 2-1: Synthesis of Transition Metal Compound (Formula 2c)
Figure PCTKR2017001503-appb-I000062
Figure PCTKR2017001503-appb-I000062
상기 실시예 2에서 얻은 2,6-디이소프로필-N-((2-이소프로필페닐)(6-(1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메틸)아닐린(1 g, 1.9314 mmol, 1 eq)과 톨루엔(6.433 mL, 0.3 M)을 넣고 교반한 다음, n-BuLi(1.622 mL, 4.056 mmol, 2.1 eq)을 적가하였다. HfCl4(0.619 g, 1.9314 mmol, 1.0 eq)를 넣고 2시간 동안 90 내지 100℃에서 가열시켰다. 반응이 끝난 후 온도를 식히고 MeMgBr(2.2533 mL, 6.76 mmol, 3.5 eq, 3.0 M in DEE)을 넣어 상온에서 밤새 반응시켰다. 용매를 진공 건조(vacuum dry)한 후 여과하였다. 노란색 고체를 680 mg, 33% 수율로 얻을 수 있었다.2,6-diisopropyl-N-((2-isopropylphenyl) (6- (1,2,3,4-tetrahydroquinolin-8-yl) pyridin-2-yl) obtained in Example 2 above Methyl) aniline (1 g, 1.9314 mmol, 1 eq) and toluene (6.433 mL, 0.3 M) were added and stirred, and n-BuLi (1.622 mL, 4.056 mmol, 2.1 eq) was added dropwise. HfCl 4 (0.619 g, 1.9314 mmol, 1.0 eq) was added and heated at 90-100 ° C. for 2 hours. After the reaction, the temperature was cooled and MeMgBr (2.2533 mL, 6.76 mmol, 3.5 eq, 3.0 M in DEE) was added and reacted at room temperature overnight. The solvent was vacuum dried and then filtered. A yellow solid could be obtained in 680 mg, 33% yield.
1H-NMR (toluene_d8): 7.29 (m, 2H), 7.21 (d, 1H), 7.10 (m, 6H), 6.88 (t, 1H), 6.89 (t, 1H), 6.68 (t, 1H), 6.60 (d, 1H), 6.55 (s, 1H), 4.42 (d, 1H), 3.93 (m, 1H), 3.49 (t, 1H), 3.19 (m, 1H), 2.82 (m, 2H), 2.67 (m, 1H), 1.97 (m, 2H), 1.41 (d, 3H), 1.18 (m, 6H), 1.01 (d, 3H), 0.70 (d, 3H), 0.60 (s, 3H), 0.45 (d, 3H), 0.03 (s, 3H)1 H-NMR (toluene_d8): 7.29 (m, 2H), 7.21 (d, 1H), 7.10 (m, 6H), 6.88 (t, 1H), 6.89 (t, 1H), 6.68 (t, 1H), 6.60 (d, 1H), 6.55 (s, 1H), 4.42 (d, 1H), 3.93 (m, 1H), 3.49 (t, 1H), 3.19 (m, 1H), 2.82 (m, 2H), 2.67 ( m, 1H), 1.97 (m, 2H), 1.41 (d, 3H), 1.18 (m, 6H), 1.01 (d, 3H), 0.70 (d, 3H), 0.60 (s, 3H), 0.45 (d , 3H), 0.03 (s, 3H)
실시예 2-2: 전이금속 화합물의 합성(화학식 2d)Example 2-2: Synthesis of Transition Metal Compound (Formula 2d)
Figure PCTKR2017001503-appb-I000063
Figure PCTKR2017001503-appb-I000063
상기 실시예 2에서 얻은 2,6-디이소프로필-N-((2-이소프로필페닐)(6-(1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메틸)아닐린(1.32 g, 2.5494 mmol, 1 eq)과 톨루엔(8.5 mL, 0.3 M)을 넣고 교반시킨 후 n-BuLi(2.1415 mL, 5.354 mmol, 2.1 eq)을 적가하였다. ZrCl4(0.594 g, 2.5494 mmol, 1.05 eq)를 넣고 2시간 동안 90 내지 100℃에서 가열시켰다.2,6-diisopropyl-N-((2-isopropylphenyl) (6- (1,2,3,4-tetrahydroquinolin-8-yl) pyridin-2-yl) obtained in Example 2 above Methyl) aniline (1.32 g, 2.5494 mmol, 1 eq) and toluene (8.5 mL, 0.3 M) were added thereto, followed by stirring. Then n-BuLi (2.1415 mL, 5.354 mmol, 2.1 eq) was added dropwise. ZrCl 4 (0.594 g, 2.5494 mmol, 1.05 eq) was added and heated at 90-100 ° C. for 2 hours.
반응이 끝난 후 온도를 식히고 MeMgBr(2.974 mL, 8.923 mmol, 3.5 eq, 3.0 M in DEE)을 넣고 상온에서 밤새 반응시켰다. 용매를 진공 건조(vacuum dry)한 후 여과시켰다. 셀라이트 여과된 여액을 건조시키고 여기에 헥산을 넣고 교반한 뒤 진공 건조(vacuum dry)하고 다시 펜탄을 넣고 교반한 뒤 진공 건조(vacuum dry)하였다. 고체가 얻어지면 여기에 펜탄을 넣고 침전시켜 촉매를 얻어낸다. 오렌지색 고체를 310 mg, 20% 수율로 얻을 수 있었다.After the reaction was completed, the temperature was cooled and MeMgBr (2.974 mL, 8.923 mmol, 3.5 eq, 3.0 M in DEE) was added and reacted at room temperature overnight. The solvent was vacuum dried and then filtered. The celite filtered filtrate was dried and hexane was added thereto, followed by stirring, followed by vacuum drying. Again, pentane was added thereto, followed by stirring, followed by vacuum drying. Once a solid is obtained, pentane is added and precipitated to obtain a catalyst. An orange solid could be obtained in 310 mg, 20% yield.
1H-NMR (toluene_d8): 7.26 (m, 2H), 7.23 (d, 1H), 7.10 (m, 6H), 7.02 (m, 1H), 6.87 (t, 1H), 6.69 (t, 1H), 6.64 (d, 1H), 6.36 (s, 1H), 4.85 (d, 1H), 4.03 (m, 1H), 3.56 (t, 1H), 3.15 (m, 1H), 2.85 (m, 2H), 2.67 (m, 1H), 1.97 (m, 2H), 1.42 (d, 3H), 1.17 (m, 6H), 0.94 (d, 3H), 0.71 (m, 6H), 0.49 (d, 3H), 0.12 (d, 3H)1 H-NMR (toluene_d8): 7.26 (m, 2H), 7.23 (d, 1H), 7.10 (m, 6H), 7.02 (m, 1H), 6.87 (t, 1H), 6.69 (t, 1H), 6.64 (d, 1H), 6.36 (s, 1H), 4.85 (d, 1H), 4.03 (m, 1H), 3.56 (t, 1H), 3.15 (m, 1H), 2.85 (m, 2H), 2.67 ( m, 1H), 1.97 (m, 2H), 1.42 (d, 3H), 1.17 (m, 6H), 0.94 (d, 3H), 0.71 (m, 6H), 0.49 (d, 3H), 0.12 (d , 3H)
실시예Example 3: 리간드 화합물의 합성 3: Synthesis of Ligand Compound
a) 메틸-7-(4,4,5,5-테트라메틸-1,3,2-디옥사보롤란-2-일)인돌린의 합성a) Synthesis of methyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) indolin
Figure PCTKR2017001503-appb-I000064
Figure PCTKR2017001503-appb-I000064
2-메틸인돌린(10 g, 75.08 mmol, 1 eq)을 헥산(250 mL, 0.3 M)에 녹인 뒤 n-BuLi(33.03 mL, 82.59 mol, 1.1 eq)을 넣어 리튬치환반응(lithiation)하고 밤새 반응을 진행한 뒤 여과하여 고체를 얻었다.Dissolve 2-methylindoline (10 g, 75.08 mmol, 1 eq) in hexane (250 mL, 0.3 M), add n-BuLi (33.03 mL, 82.59 mol, 1.1 eq) to perform lithium lithiation overnight. After the reaction was carried out to obtain a solid by filtration.
수득한 리튬 화합물(5.52 g, 39.675 mmol, 1 eq)에 디에틸 에터(99.2 mL, 0.4 M)를 넣고 -78℃에서 CO2 버블링을 하였다. 이를 상온에서 하루 교반한 뒤 -20℃에서 THF(1.1 eq, 3.54 mL, 43.643 mmol, 1.1 eq)를 첨가하였다. Diethyl ether (99.2 mL, 0.4 M) was added to the obtained lithium compound (5.52 g, 39.675 mmol, 1 eq), and CO 2 bubbling was performed at -78 ° C. After stirring at room temperature for one day, THF (1.1 eq, 3.54 mL, 43.643 mmol, 1.1 eq) was added at -20 ° C.
여기에 t-BuLi(27.8 mL, 43.643 mmol, 1.1 eq, 1.57 M)을 넣어 -20℃에서 2시간 동안 반응시킨 뒤 2-아이소프로필-4,4,5,5-테트라메틸-1,3,2-디옥사보롤란(20.24 g, 99.19 mmol, 2.5 eq)을 -78℃에서 첨가하였다. 상온으로 서서히 승온시킨 뒤 반응이 끝난 후 0℃에서 1M HCl 수용액과 EA를 넣었다. 유기층을 1 M NaOH와 1 M NaHCO3로 세척한 후 MgSO4로 H2O를 건조시켰다. 이를 통해 베이지색 고체 3.1 g을 30% 수율로 얻을 수 있었다.To this, t-BuLi (27.8 mL, 43.643 mmol, 1.1 eq, 1.57 M) was added and reacted at -20 ° C for 2 hours, followed by 2-isopropyl-4,4,5,5-tetramethyl-1,3, 2-dioxaborolane (20.24 g, 99.19 mmol, 2.5 eq) was added at -78 ° C. After slowly raising the temperature to room temperature, after the reaction was completed, 1M HCl aqueous solution and EA were added at 0 ° C. The organic layer was washed with 1 M NaOH and 1 M NaHCO 3 and then H 2 O was dried over MgSO 4 . This gave 3.1 g of a beige solid in 30% yield.
1H-NMR (CDCl3): 7.36 (d, 1H), 7.08 (d, 1H), 6.58 (t, 1H), 4.93 (s, 1H), 4.01 (m, 1H), 3.07 (m, 1H), 2.60 (m, 1H), 1.31 (s, 12H), 1.25 (s, 3H)1 H-NMR (CDCl 3): 7.36 (d, 1H), 7.08 (d, 1H), 6.58 (t, 1H), 4.93 (s, 1H), 4.01 (m, 1H), 3.07 (m, 1H), 2.60 (m, 1 H), 1.31 (s, 12 H), 1.25 (s, 3 H)
b) N-(2,6-b) N- (2,6- 디이소프로필페닐Diisopropylphenyl )-1-(6-(2-) -1- (6- (2- 메틸인돌린Methylindoline -7-일)피리딘-2-일)-7-yl) pyridin-2-yl) 메탄이민의Methaneimine 제조 Produce
Figure PCTKR2017001503-appb-I000065
Figure PCTKR2017001503-appb-I000065
상기에서 제조된 N-(2,6-디이소프로필페닐)-1-(6-브로모피리딘-2-일)메탄이민(3 g, 8.69 mmol, 1 eq)에 톨루엔(13.33 mL)을 넣고 교반하는 한편, 이와 별도로 Na2CO3(2.303 g, 21.725 mmol, 2.5 eq)와 2 M 2-메틸-7-(4,4,5,5-테트라메틸-1,3,2-디옥사보롤란-2-일)인돌린(I-보롤란)(2.25 g, 8.69 mmol, 1 eq)을 H2O(2.66 mL)와 EtOH(2.66 mL) 1:1인 용매에 넣고 교반하였다. Toluene (13.33 mL) was added to N- (2,6-diisopropylphenyl) -1- (6-bromopyridin-2-yl) methanimine (3 g, 8.69 mmol, 1 eq) prepared above. While stirring, Na 2 CO 3 (2.303 g, 21.725 mmol, 2.5 eq) and 2 M 2-methyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxabo Rolan-2-yl) indoline (I-borolane) (2.25 g, 8.69 mmol, 1 eq) was added to a solvent of H 2 O (2.66 mL) and EtOH (2.66 mL) 1: 1 and stirred.
Br-이민 톨루엔 용액을 I-보롤란의 용액으로 옮긴 뒤, 여기에 Pd(PPh3)4(0.0301 g, 0.026 mmol, 0.3 mol% Pd)를 넣었다. 70℃에서 4시간 동안 교반한 뒤 실온으로 냉각시켰다. 유기층을 톨루엔/염수(brine)로 추출하고 Na2SO4로 수분을 건조시켰다. 생성물을 1.78 g, 52% 수율로 얻을 수 있었다.Br-imine toluene solution was transferred to a solution of I-borolane, followed by Pd (PPh 3 ) 4 (0.0301 g, 0.026 mmol, 0.3 mol% Pd). After stirring for 4 hours at 70 ℃ cooled to room temperature. The organic layer was extracted with toluene / brine and dried with Na 2 SO 4 . The product could be obtained in 1.78 g, 52% yield.
1H-NMR (toluene_d8): 8.38 (s, 1H), 7.86 (d, 1H), 7.66 (s, 1H), 7.38 (d, 2H), 7.19 (t, 1H), 7.13 (m, 3H), 6.68 (t, 1H), 3.89 (m, 1H), 3.15 (m, 2H), 2.89 (m, 1H), 2.40 (m, 1H), 1.18 (m, 12H), 1.1 (m, 3H)1 H-NMR (toluene_d8): 8.38 (s, 1H), 7.86 (d, 1H), 7.66 (s, 1H), 7.38 (d, 2H), 7.19 (t, 1H), 7.13 (m, 3H), 6.68 (t, 1H), 3.89 (m, 1H), 3.15 (m, 2H), 2.89 (m, 1H), 2.40 (m, 1H), 1.18 (m, 12H), 1.1 (m, 3H)
c) 2,6-c) 2,6- 디이소프로필Diisopropyl -N-((6-(2--N-((6- (2- 메틸인돌린Methylindoline -7-일)피리딘-2-일)(페닐)-7-yl) pyridin-2-yl) (phenyl) 메틸methyl )아닐린의 제조Preparation of Aniline
Figure PCTKR2017001503-appb-I000066
Figure PCTKR2017001503-appb-I000066
리간드 전구체에 페닐을 붙이기 위해서, 합성된 리간드 전구체(750 mg, 1.886 mmol, 1 eq)를 디에틸 에터(18.86 mL)에 녹이고 -78℃로 온도를 낮춘 뒤, 페닐 리튬(2.83 mL, 5.093 mmol, 2.7 eq, 1.8 M in DBE)을 넣었다. 반응이 끝나면 1 N NH4Cl로 퀀치(quench)하고 디에틸 에터와 물로 워크-업(work-up)하였다. 이로써, 리간드를 880 mg(정량수율) 수득하였다. To attach phenyl to the ligand precursor, the synthesized ligand precursor (750 mg, 1.886 mmol, 1 eq) was dissolved in diethyl ether (18.86 mL) and the temperature was lowered to -78 ° C, followed by phenyl lithium (2.83 mL, 5.093 mmol, 2.7 eq, 1.8 M in DBE) was added. At the end of the reaction, the reaction was quenched with 1N NH 4 Cl and worked up with diethyl ether and water. This resulted in 880 mg (quantitative yield) of ligand.
1H-NMR (toluene_d8): 7.40 (m, 3H), 7.24 (d, 1H), 7.14 (m, 3H), 7.06 (m, 4H), 6.92 (m, 2H), 6.74 (d, 1H), 6.65 (m, 1H), 5.26 (m, 1H), 4.34 (m, 1H), 3.74 (m, 1H), 3.05 (m, 2H), 2.83 (m, 1H), 2.35 (m, 1H), 1.02 (m, 12H), 0.93 (m, 3H)1 H-NMR (toluene_d8): 7.40 (m, 3H), 7.24 (d, 1H), 7.14 (m, 3H), 7.06 (m, 4H), 6.92 (m, 2H), 6.74 (d, 1H), 6.65 (m, 1H), 5.26 (m, 1H), 4.34 (m, 1H), 3.74 (m, 1H), 3.05 (m, 2H), 2.83 (m, 1H), 2.35 (m, 1H), 1.02 ( m, 12H), 0.93 (m, 3H)
실시예 3-1: 전이금속 화합물의 합성(화학식 2e)Example 3-1: Synthesis of Transition Metal Compound (Formula 2e)
Figure PCTKR2017001503-appb-I000067
Figure PCTKR2017001503-appb-I000067
상기 실시예 3의 d)에서 합성된 리간드인 2,6-디이소프로필-N-((6-(2-메틸인돌린-7-일)피리딘-2-일)(페닐)메틸)아닐린(0.7 g, 1.4716 mmol, 1 eq)과 톨루엔(4.905 mL, 0.3 M)을 넣고 교반한 n-BuLi(1.236 mL, 3.09 mmol, 2.1 eq)을 적가하였다. HfCl4(0.495 g, 1.5452 mmol, 1.05 eq)를 넣고 2시간 동안 90 내지 100℃에서 가열하였다. 반응이 끝난 후 온도를 식히고 MeMgBr(1.72 mL, 5.1506 mmol, 3.5 eq, 3.0 M in DEE)을 넣어 실온에서 밤새 반응시켰다. 용매를 진공 건조(vacuum dry)한 후 여과하였다. 셀라이트 여과된 여액을 건조시키고 여기에 헥산을 넣고 교반한 뒤 진공 건조(vacuum dry)하고 다시 펜탄을 넣고 교반한 뒤 진공 건조(vacuum dry)시켰다. 고체가 얻어지면 여기에 펜탄을 넣고 침전시켜 표제 화합물인 촉매를 노란색의 고체 492 mg, 49% 수율로 얻을 수 있었다. 2,6-diisopropyl-N-((6- (2-methylindolin-7-yl) pyridin-2-yl) (phenyl) methyl) aniline which is a ligand synthesized in d) of Example 3 0.7 g, 1.4716 mmol, 1 eq) and toluene (4.905 mL, 0.3 M) were added and stirred n-BuLi (1.236 mL, 3.09 mmol, 2.1 eq) was added dropwise. HfCl 4 (0.495 g, 1.5452 mmol, 1.05 eq) was added thereto and heated at 90 to 100 ° C. for 2 hours. After the reaction, the temperature was cooled and MeMgBr (1.72 mL, 5.1506 mmol, 3.5 eq, 3.0 M in DEE) was added and allowed to react at room temperature overnight. The solvent was vacuum dried and then filtered. The celite filtered filtrate was dried, and hexane was added thereto, followed by stirring, followed by vacuum drying. Then, pentane was added thereto, followed by stirring, followed by vacuum drying. When a solid was obtained, pentane was added and precipitated to obtain the title compound of the catalyst as a yellow solid (492 mg, 49% yield).
1H-NMR (toluene_d8): 7.40 (d, 1H), 7.30 (d, 1H), 7.17 (d, 2H), 7.04 (m, 6H), 6.91 (t, 2H), 6.67 (t, 1H), 6.45 (d, 1H), 5.72 (s, 1H), 4.99 (m, 1H), 3.83 (m, 1H), 3.26 (m, 1H), 3.03 (m, 1H), 2.50 (d, 1H), 1.44 (d, 3H), 1.32 (d, 3H), 1.17 (d, 3H), 0.95 (d, 3H), 0.70 (s, 3H), 0.49 (d, 3H), 0.16 (s, 3H)1 H-NMR (toluene_d8): 7.40 (d, 1H), 7.30 (d, 1H), 7.17 (d, 2H), 7.04 (m, 6H), 6.91 (t, 2H), 6.67 (t, 1H), 6.45 (d, 1H), 5.72 (s, 1H), 4.99 (m, 1H), 3.83 (m, 1H), 3.26 (m, 1H), 3.03 (m, 1H), 2.50 (d, 1H), 1.44 ( d, 3H), 1.32 (d, 3H), 1.17 (d, 3H), 0.95 (d, 3H), 0.70 (s, 3H), 0.49 (d, 3H), 0.16 (s, 3H)
실시예 4: 리간드 화합물의 합성Example 4: Synthesis of Ligand Compound
2,6-2,6- 디이소프로필Diisopropyl -N-((2--N-((2- 이소프로필페닐Isopropylphenyl )(6-(2-) (6- (2- 메틸인돌린Methylindoline -7-일)피리딘-2-일)메틸)아닐린의 제조Preparation of -7-yl) pyridin-2-yl) methyl) aniline
Figure PCTKR2017001503-appb-I000068
Figure PCTKR2017001503-appb-I000068
1-Br-2-이소프로필벤젠(1.352 g, 6.79 mmol, 2.7 eq)에 THF (13.58mL)를 넣고 -78℃에서 t-BuLi(8.65mL)을 넣었다. 이를 2시간 동안 반응시킨 뒤 상온으로 승온시켰다. 리간드 전구체(1 g, 2.515 mmol, 1 eq)에 디에틸 에터 25.15 mL)를 넣고 큐멘 리튬을 -78℃에서 적가하였다. 상온으로 승온하여 밤새 반응시킨 뒤 1 N NH4Cl로 퀀치(quench)하고, Ether/H2O 워크-업(work-up)을 하였다. Na2SO4로 수분을 건조시킨 뒤 회전 증발 농축기(Rotavapor)로 용매를 진공 건조시켰다. 노란색 오일을 1.49 g, 정량수율로 얻을 수 있었다.To 1-Br-2-isopropylbenzene (1.352 g, 6.79 mmol, 2.7 eq) was added THF (13.58 mL) and t-BuLi (8.65 mL) at -78 ° C. After reacting for 2 hours, the temperature was raised to room temperature. To the ligand precursor (1 g, 2.515 mmol, 1 eq) was added 25.15 mL of diethyl ether) and cumene lithium was added dropwise at -78 ° C. The reaction mixture was warmed to room temperature overnight, quenched with 1 N NH 4 Cl, and ether / H 2 O work-up was performed. The moisture was dried over Na 2 SO 4 and then the solvent was dried in vacuo using a Rotavapor. Yellow oil was obtained in 1.49 g, quantitative yield.
1H-NMR (toluene_d8): 7.75 - 5.60 (m, 15H), 4.08 - 2.30 (m, 7H), 1.13 - 1.02 (m, 21H)1 H-NMR (toluene_d8): 7.75-5.60 (m, 15H), 4.08-2.30 (m, 7H), 1.13-1.02 (m, 21H)
실시예 4-1: 전이금속 화합물의 합성(화학식 2g)Example 4-1: Synthesis of Transition Metal Compound (Formula 2g)
Figure PCTKR2017001503-appb-I000069
Figure PCTKR2017001503-appb-I000069
상기 실시예 4에서 합성된 리간드인 2,6-디이소프로필-N-((2-이소프로필페닐)(6-(2-메틸인돌린-7-일)피리딘-2-일)메틸)아닐린(1.17 g, 2.26 mmol, 1 eq)과 톨루엔(7.533 mL, 0.3 M)을 넣고 교반한 후 n-BuLi(1.898 mL, 4.745 mmol, 2.1 eq)을 적가하였다. HfCl4(0.724 g, 2.26 mmol, 1.05 eq)를 넣고 2시간 동안 90 내지 100℃에서 가열하였다. 반응이 끝난 후 온도를 식히고 MeMgBr(2.637 mL, 7.91 mmol, 3.5 eq, 3.0 M in DEE)을 넣어 실온에서 밤새 반응시켰다. 용매를 진공 건조(vacuum dry) 한 후 여과시켰다. 셀라이트 여과된 여액을 건조시키고 여기에 헥산을 넣고 교반한 뒤 진공 건조하고, 다시 펜탄을 넣고 교반한 뒤 진공 건조시켰다. 고체가 얻어지면 여기에 펜탄을 넣고 침전시켜 노란색 고체 400 mg을 25% 수율로 얻을 수 있었다.2,6-diisopropyl-N-((2-isopropylphenyl) (6- (2-methylindolin-7-yl) pyridin-2-yl) methyl) aniline, the ligand synthesized in Example 4 above (1.17 g, 2.26 mmol, 1 eq) and toluene (7.533 mL, 0.3 M) were added thereto, followed by stirring. Then n-BuLi (1.898 mL, 4.745 mmol, 2.1 eq) was added dropwise. HfCl 4 (0.724 g, 2.26 mmol, 1.05 eq) was added thereto and heated at 90 to 100 ° C. for 2 hours. After the reaction, the temperature was cooled and MeMgBr (2.637 mL, 7.91 mmol, 3.5 eq, 3.0 M in DEE) was added and allowed to react at room temperature overnight. The solvent was filtered off after vacuum dry. The celite filtered filtrate was dried and hexane was added thereto, stirred and dried in vacuo, and then pentane was added and stirred, followed by vacuum drying. When a solid was obtained, pentane was added and precipitated to obtain 400 mg of a yellow solid in 25% yield.
1H-NMR (toluene_d8): 7.37 (d, 1H), 7.28 (d, 2H), 7.18 (d, 1H), 7.10 (m, 5H), 6.89 (t, 1H), 6.67 (t, 1H), 6.59 (d, 1H), 6.42 (s, 1H), 5.01 (m, 1H), 3.92 (m, 1H), 3.26 (m, 1H), 3.10 (m, 1H), 2.84 (m, 1H), 2.52 (d, 1H), 1.40 (d, 3H), 1.34 (d, 3H), 1.16 (dd, 6H), 0.95 (d, 3H), 0.74 (s, 3H), 0.68 (d, 3H), 0.45 (d, 3H), 0.20 (s, 3H)1 H-NMR (toluene_d8): 7.37 (d, 1H), 7.28 (d, 2H), 7.18 (d, 1H), 7.10 (m, 5H), 6.89 (t, 1H), 6.67 (t, 1H), 6.59 (d, 1H), 6.42 (s, 1H), 5.01 (m, 1H), 3.92 (m, 1H), 3.26 (m, 1H), 3.10 (m, 1H), 2.84 (m, 1H), 2.52 ( d, 1H), 1.40 (d, 3H), 1.34 (d, 3H), 1.16 (dd, 6H), 0.95 (d, 3H), 0.74 (s, 3H), 0.68 (d, 3H), 0.45 (d , 3H), 0.20 (s, 3H)
실시예 5: 리간드 화합물의 합성Example 5: Synthesis of Ligand Compound
a) 2-a) 2- 메틸methyl -8-(4,4,5,5--8- (4,4,5,5- 테트라메틸Tetramethyl -1,3,2--1,3,2- 디옥사보롤란Dioxaborolan -2-일)-1,2,3,4--2-yl) -1,2,3,4- 테트라하이드로퀴놀린의Tetrahydroquinoline 제조 Produce
Figure PCTKR2017001503-appb-I000070
Figure PCTKR2017001503-appb-I000070
쉬렝크 플라스크에 2-메틸-THQ(10 g, 67.925 mmol, 1 eq)를 넣은 뒤 진공 건조(vacuum dry)하고 여기에 헥산(226 mL, 0.3 M)을 첨가한 후 -20℃에서 n-BuLi(29.89 mL, 74.718 mmol, 1.1 eq, 2.5 M in hexane)을 첨가하였다. 이것을 밤새 상온에서 반응시킨 뒤 리튬 화합물을 여과하여 얻었다. 이렇게 얻어진 리튬 화합물(10.40 g, 67.925 mmol, 1 eq)에 디에틸 에터(113.21 mL, 0.4 M)를 넣고 -78℃에서 CO2 버블링을 하였다. 이를 상온에 밤새 방치한 뒤 -20℃에서 THF(1.1 eq, 5.388 g, 74.72 mmol)를 첨가하였다. 여기에 t-BuLi(47.6 mL, 74.72 mmol, 1.1 eq, 1.7 M)을 넣어 -20℃에서 2시간 동안 반응시킨 뒤, 2-아이소프로필-4,4,5,5-테트라메틸-1,3,2-디옥사보롤란(31.6g, 169.8 mmol, 2.5 eq)을 -78℃에서 첨가하였다. 상온으로 서서히 승온시킨 뒤 반응이 끝난 후 0℃에서 1M HCl 수용액과 EA를 넣었다. 유기층을 1 M NaOH와 1 M NaHCO3로 세척한 후 MgSO4로 수분을 건조시켰다. 노란색 고체인 생성물을 9.9 g, 53.4% 수율로 얻을 수 있었다.In a Schlenk flask, 2-methyl-THQ (10 g, 67.925 mmol, 1 eq) was added, followed by vacuum dry, to which hexane (226 mL, 0.3 M) was added, followed by n-BuLi at -20 ° C. (29.89 mL, 74.718 mmol, 1.1 eq, 2.5 M in hexane) was added. After reacting this at room temperature overnight, the lithium compound was filtered out. Diethyl ether (113.21 mL, 0.4 M) was added to a lithium compound (10.40 g, 67.925 mmol, 1 eq) thus obtained, followed by CO 2 bubbling at -78 ° C. After standing at room temperature overnight, THF (1.1 eq, 5.388 g, 74.72 mmol) was added at -20 ° C. Then t-BuLi (47.6 mL, 74.72 mmol, 1.1 eq, 1.7 M) was added and reacted at -20 ° C for 2 hours, followed by 2-isopropyl-4,4,5,5-tetramethyl-1,3 , 2-dioxaborolane (31.6 g, 169.8 mmol, 2.5 eq) was added at -78 ° C. After slowly raising the temperature to room temperature, after the reaction was completed, 1M HCl aqueous solution and EA were added at 0 ° C. The organic layer was washed with 1 M NaOH and 1 M NaHCO 3 and dried with MgSO 4 . The product was obtained as a yellow solid in 9.9 g, 53.4% yield.
1H-NMR (CDCl3): 7.45 (d, 1H), 7.01 (d, 1H), 6.52 (t, 1H), 5.83 (s, 1H), 3.48 (m, 1H), 2.80 (m, 2H), 1.91 (m, 1H), 1.58 (m, 1H), 1.35 (s, 12H), 1.26 (s, 3H)1 H-NMR (CDCl 3 ): 7.45 (d, 1H), 7.01 (d, 1H), 6.52 (t, 1H), 5.83 (s, 1H), 3.48 (m, 1H), 2.80 (m, 2H), 1.91 (m, 1H), 1.58 (m, 1H), 1.35 (s, 12H), 1.26 (s, 3H)
b) N-(2,6-b) N- (2,6- 디이소프로필페닐Diisopropylphenyl )-1-(6-(2-) -1- (6- (2- 메틸methyl -1,2,3,4--1,2,3,4- 테트라하이드로퀴놀린Tetrahydroquinoline -8-일)피리딘-2-일)메탄이민의 제조Preparation of -8-yl) pyridin-2-yl) methaneimine
Figure PCTKR2017001503-appb-I000071
Figure PCTKR2017001503-appb-I000071
상기에서 제조된 N-(2,6-디이소프로필페닐)-1-(6-브로모피리딘-2-일)메탄이민(3 g, 8.69 mmol, 1 eq)에 톨루엔(13.33mL)을 넣고 교반하는 한편, 이와 별도로 Na2CO3(2.303 g, 21.725 mmol, 2.5 eq)와 THQ-보롤란(2.373 g, 8.69 mmol, 1 eq)을 H2O(2.66 mL)와 EtOH(2.66 mL) 1:1인 용매에 넣고 교반하였다. Toluene (13.33 mL) was added to N- (2,6-diisopropylphenyl) -1- (6-bromopyridin-2-yl) methaneimine (3 g, 8.69 mmol, 1 eq) prepared above. While stirring, separate Na 2 CO 3 (2.303 g, 21.725 mmol, 2.5 eq) and THQ-borolane (2.373 g, 8.69 mmol, 1 eq) with H 2 O (2.66 mL) and EtOH (2.66 mL) 1 It was put into a solvent of 1: 1 and stirred.
Br-이민 톨루엔 용액을 THQ-보롤란의 용액으로 옮긴 뒤 여기에 Pd(PPh3)4(0.0301 g, 0.026 mmol, 0.3 mol% Pd)를 넣었다. 70℃에서 4시간 동안 교반한 뒤 실온으로 냉각시켰다. 유기층을 톨루엔/염수(brine)로 추출하고 Na2SO4로 수분을 건조시켰다. 생성물을 3.08 g, 86% 수율로 얻을 수 있었다.Br-imine toluene solution was transferred to a solution of THQ-borolane followed by Pd (PPh 3 ) 4 (0.0301 g, 0.026 mmol, 0.3 mol% Pd). After stirring for 4 hours at 70 ℃ cooled to room temperature. The organic layer was extracted with toluene / brine and dried with Na 2 SO 4 . The product could be obtained in 3.08 g, 86% yield.
1H-NMR (toluene_d8): 8.96 (s, 1H), 8.41 (s, 1H), 7.92 (d, 1H), 7.33 (d, 2H), 7.19 (t, 1H), 7.13 (m, 3H), 6.94 (d, 1H), 6.64 (m, 1H), 3.30 (m, 1H), 3.16 (m, 2H), 2.72 (m, 1H), 2.61 (m, 1H), 1.56 (m, 1H), 1.36 (m, 1H), 1.19 (m, 12H), 1.05 (d, 3H)1 H-NMR (toluene_d8): 8.96 (s, 1H), 8.41 (s, 1H), 7.92 (d, 1H), 7.33 (d, 2H), 7.19 (t, 1H), 7.13 (m, 3H), 6.94 (d, 1H), 6.64 (m, 1H), 3.30 (m, 1H), 3.16 (m, 2H), 2.72 (m, 1H), 2.61 (m, 1H), 1.56 (m, 1H), 1.36 ( m, 1H), 1.19 (m, 12H), 1.05 (d, 3H)
c) 2,6-c) 2,6- 디이소프로필Diisopropyl -N-((6-(2--N-((6- (2- 메틸methyl -1,2,3,4--1,2,3,4- 테트라하이드로퀴놀린Tetrahydroquinoline -8-일)피리딘-2-일)(페닐)메틸)아닐린의 제조Preparation of -8-yl) pyridin-2-yl) (phenyl) methyl) aniline
Figure PCTKR2017001503-appb-I000072
Figure PCTKR2017001503-appb-I000072
합성된 리간드 전구체인 N-(2,6-디이소프로필페닐)-1-(6-(2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메탄이민(1 g, 2.43 mmol, 1 eq)을 디에틸 에터(24.3 mL)에 녹이고 -78℃로 온도를 낮춘 뒤, 페닐 리튬(3.645 mL, 6.561 mmol, 2.7 eq, 1.8 M in DBE)을 넣었다. 반응이 끝나면 1 N NH4Cl로 퀀치(quench)하고 디에틸 에터와 물로 워크-업(work-up)하였다. 생성물을 1.2 g(정량수율) 수득하였다. N- (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) pyridin-2-yl) as a synthesized ligand precursor Methaneimine (1 g, 2.43 mmol, 1 eq) was dissolved in diethyl ether (24.3 mL) and the temperature was lowered to −78 ° C., followed by addition of phenyl lithium (3.645 mL, 6.561 mmol, 2.7 eq, 1.8 M in DBE). . At the end of the reaction, the reaction was quenched with 1N NH 4 Cl and worked up with diethyl ether and water. 1.2 g (quantitative yield) of the product was obtained.
1H-NMR (toluene_d8): 8.20 (s, 1H), 7.33-6.64 (m, 14H), 5.25 (m, 1H), 4.51 (m, 1H), 3.20 (m, 1H), 3.13 (m, 2H), 2.63 (m, 1H), 2.58 (m, 1H), 1.53 (m, 1H), 1.34 (m, 1H), 1.04 (m, 12H), 0.84 (m, 3H)1 H-NMR (toluene_d8): 8.20 (s, 1H), 7.33-6.64 (m, 14H), 5.25 (m, 1H), 4.51 (m, 1H), 3.20 (m, 1H), 3.13 (m, 2H) , 2.63 (m, 1H), 2.58 (m, 1H), 1.53 (m, 1H), 1.34 (m, 1H), 1.04 (m, 12H), 0.84 (m, 3H)
실시예 5-1: 전이금속 화합물의 합성(화학식 2i)Example 5-1: Synthesis of Transition Metal Compound (Formula 2i)
Figure PCTKR2017001503-appb-I000073
Figure PCTKR2017001503-appb-I000073
상기 실시예 5의 c)에서 제조된 리간드인 2,6-디이소프로필-N-((6-(2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)(페닐)메틸)아닐린(0.8 g, 1.634 mmol, 1 eq)과 톨루엔(5.44 mL, 0.3 M)을 넣고 교반시킨 후 n-BuLi(1.3722 mL, 3.431 mmol, 2.1 eq)을 적가하였다. HfCl4(0.549 g, 1.716 mmol, 1.05 eq)를 넣고 2시간 동안 90 내지 100℃에서 가열하였다.2,6-diisopropyl-N-((6- (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) pyridine-2, which is a ligand prepared in Example 5c) -Yl) (phenyl) methyl) aniline (0.8 g, 1.634 mmol, 1 eq) and toluene (5.44 mL, 0.3 M) were added and stirred, and n-BuLi (1.3722 mL, 3.431 mmol, 2.1 eq) was added dropwise. HfCl 4 (0.549 g, 1.716 mmol, 1.05 eq) was added thereto and heated at 90 to 100 ° C. for 2 hours.
반응이 끝난 후 온도를 식히고 MeMgBr(1.906 mL, 5.719 mmol, 3.5 eq, 3.0 M in DEE)를 넣어 상온에서 밤새 반응시켰다. 용매를 진공 건조(vacuum dry)시킨 후 여과하였다. 셀라이트 여과된 여액을 건조시키고 여기에 헥산을 넣고 교반한 뒤 진공 건조하고, 다시 펜탄을 넣고 교반한 뒤 진공 건조하였다. 고체가 얻어지면 여기에 펜탄을 넣고 침전시켜 노란색 고체인 촉매를 430 mg, 41% 수율로 얻을 수 있었다.After the reaction, the temperature was cooled and MeMgBr (1.906 mL, 5.719 mmol, 3.5 eq, 3.0 M in DEE) was added and allowed to react at room temperature overnight. The solvent was vacuum dried and then filtered. The celite filtered filtrate was dried and hexane was added thereto, stirred, and dried in vacuo, and then pentane was added and stirred, followed by vacuum drying. When a solid was obtained, pentane was added and precipitated to obtain a catalyst as a yellow solid in 430 mg, 41% yield.
1H-NMR (toluene_d8): 7.31 (d, 1H), 7.20 (d, 1H), 7.10 (m, 9H), 6.89 (t, 1H), 6.68 (t, 1H), 6.52 (d, 1H), 5.90 (s, 1H), 4.80 (s, 1H), 3.90 (m, 1H), 3.04 (m, 2H), 2.61 (m, 1H), 2.19 (m, 1H), 1.80 (m, 1H), 1.45 (d, 3H), 1.30 (d, 3H), 1.18 (d, 3H), 0.95 (d, 3H), 0.62 (s, 3H), 0.50 (d, 3H), -0.02 (s, 3H)1 H-NMR (toluene_d8): 7.31 (d, 1H), 7.20 (d, 1H), 7.10 (m, 9H), 6.89 (t, 1H), 6.68 (t, 1H), 6.52 (d, 1H), 5.90 (s, 1H), 4.80 (s, 1H), 3.90 (m, 1H), 3.04 (m, 2H), 2.61 (m, 1H), 2.19 (m, 1H), 1.80 (m, 1H), 1.45 ( d, 3H), 1.30 (d, 3H), 1.18 (d, 3H), 0.95 (d, 3H), 0.62 (s, 3H), 0.50 (d, 3H), -0.02 (s, 3H)
실시예 6: 리간드 화합물의 합성Example 6: Synthesis of Ligand Compound
2,6-2,6- 디이소프로필Diisopropyl -N-((2--N-((2- 이소프로필페닐Isopropylphenyl )(6-(2-) (6- (2- 메틸methyl -1,2,3,4--1,2,3,4- 테트라하이드로퀴놀린Tetrahydroquinoline -8-일)피리딘-2-일)메틸)아닐린의 제조Preparation of -8-yl) pyridin-2-yl) methyl) aniline
Figure PCTKR2017001503-appb-I000074
Figure PCTKR2017001503-appb-I000074
1-Br-2-이소프로필벤젠(1.306 g, 6.561 mmol, 2.7 eq)에 THF(13.122 mL)를 넣고 -78℃에서 t-BuLi(8.36 mL)을 넣었다. 이것을 2시간 동안 반응시킨 뒤 상온으로 승온시켜 리튬 큐멘을 제조하였다. 상기 실시예 5의 b)에서 제조된 리간드 전구체인 N-(2,6-디이소프로필페닐)-1-(6-(2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메탄이민(1 g, 2.43mmol, 1eq)에 디에틸 에터(24.3mL)를 넣고 상기 리튬 큐멘을 -78℃에서 적가하였다. 상온으로 승온시켜 밤새 반응시킨 뒤 1 N NH4Cl로 퀀치(quench)하고 Ether/H2O로 워크-업(work-up) 하였다. Na2SO4로 수분을 건조시킨 뒤 회전 증발 농축기(rotavapor)로 용매를 진공 건조시켰다. 노란색 오일을 1.48 g, 정량수율로 얻을 수 있었다.To 1-Br-2-isopropylbenzene (1.306 g, 6.561 mmol, 2.7 eq) was added THF (13.122 mL) and t-BuLi (8.36 mL) at -78 ° C. After reacting for 2 hours, the temperature was raised to room temperature, thereby preparing lithium cumene. N- (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinoline-8-, which is a ligand precursor prepared in b) of Example 5 Diethyl ether (24.3 mL) was added to 1) pyridin-2-yl) methanimine (1 g, 2.43 mmol, 1 eq) and the lithium cumene was added dropwise at -78 ° C. The reaction mixture was warmed to room temperature overnight, quenched with 1 N NH 4 Cl, and worked up with Ether / H 2 O. The moisture was dried over Na 2 SO 4 and then the solvent was dried in vacuo using a rotavapor. The yellow oil was obtained in 1.48 g, quantitative yield.
1H-NMR (toluene_d8): 8.30 - 5.60 (m, 15H), 4.73 - 2.59 (m, 10H), 1.14 - 0.84 (m, 21H)1 H-NMR (toluene_d8): 8.30-5.60 (m, 15H), 4.73-2.59 (m, 10H), 1.14-0.84 (m, 21H)
실시예 6-1: 전이금속 화합물의 합성(화학식 2k)Example 6-1: Synthesis of Transition Metal Compound (Formula 2k)
Figure PCTKR2017001503-appb-I000075
Figure PCTKR2017001503-appb-I000075
상기 실시예 6에서 제조된 리간드인 2,6-디이소프로필-N-((2-이소프로필페닐)(6-(2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메틸)아닐린(1.21 g, 2.27 mmol, 1 eq)과 톨루엔(7.567 mL, 0.3 M)을 넣고 교반시킨 후 n-BuLi(1.907 mL, 4.767 mmol, 2.1 eq)을 적가하였다. HfCl4(0.7634 g, 2.3835 mmol, 1.05 eq)를 넣고 2시간 동안 90 내지 100℃에서 가열하였다. 반응이 끝난 후 온도를 식히고 MeMgBr(2.65 mL, 7.945 mmol, 3.5 eq, 3.0 M in DEE)을 넣어 상온에서 밤새 반응시켰다. 용매를 진공 건조(vacuum dry)시킨 후 여과하였다. 셀라이트 여과된 여액을 건조시키고 여기에 헥산을 넣고 교반한 뒤 진공 건조시킨 다음, 다시 펜탄을 넣고 교반한 뒤 진공 건조시켰다. 고체가 얻어지면 여기에 펜탄을 넣고 침전시켜 노란색 고체인 촉매를 320 mg, 19% 수율로 얻을 수 있었다.2,6-diisopropyl-N-((2-isopropylphenyl) (6- (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) which is a ligand prepared in Example 6 ) Pyridin-2-yl) methyl) aniline (1.21 g, 2.27 mmol, 1 eq) and toluene (7.567 mL, 0.3 M) were added and stirred, followed by the dropwise addition of n-BuLi (1.907 mL, 4.767 mmol, 2.1 eq). . HfCl 4 (0.7634 g, 2.3835 mmol, 1.05 eq) was added thereto and heated at 90 to 100 ° C. for 2 hours. After the reaction, the temperature was cooled and MeMgBr (2.65 mL, 7.945 mmol, 3.5 eq, 3.0 M in DEE) was added and allowed to react at room temperature overnight. The solvent was vacuum dried and then filtered. The celite filtered filtrate was dried and hexane was added thereto, stirred, and dried in vacuo. Then, pentane was added and stirred, followed by vacuum drying. When a solid was obtained, pentane was added and precipitated to obtain a catalyst as a yellow solid in 320 mg, 19% yield.
1H-NMR (toluene_d8): 7.34 (d, 1H), 7.32 (d, 1H), 7.20 (d, 1H), 7.12 (m, 3H), 7.10 (m, 1H), 7.07 (m, 3H), 6.86 (t, 1H), 6.69 (t, 1H), 6.60 (d, 1H), 6.523 (s, 1H), 4.82 (m, 1H), 3.95 (m, 1H), 3.10 (m, 1H), 3.01 (m, 1H), 2.79 (m, 1H), 2.63 (m, 1H), 2.20 (m, 1H), 1.83 (m, 1H), 1.42 (d, 3H), 1.31 (d, 3H), 1.13 (m, 6H), 0.93 (d, 3H), 0.71 (d, 3H), 0.65 (s, 3H), 0.48 (d, 3H), 0.01 (s, 3H)1 H-NMR (toluene_d8): 7.34 (d, 1H), 7.32 (d, 1H), 7.20 (d, 1H), 7.12 (m, 3H), 7.10 (m, 1H), 7.07 (m, 3H), 6.86 (t, 1H), 6.69 (t, 1H), 6.60 (d, 1H), 6.523 (s, 1H), 4.82 (m, 1H), 3.95 (m, 1H), 3.10 (m, 1H), 3.01 ( m, 1H), 2.79 (m, 1H), 2.63 (m, 1H), 2.20 (m, 1H), 1.83 (m, 1H), 1.42 (d, 3H), 1.31 (d, 3H), 1.13 (m , 6H), 0.93 (d, 3H), 0.71 (d, 3H), 0.65 (s, 3H), 0.48 (d, 3H), 0.01 (s, 3H)
실시예 7: 리간드 화합물의 합성Example 7: Synthesis of Ligand Compound
N-([1,1'-비페닐]-2-일(6-((S)-2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메틸)-2,6-디이소프로필 아닐린의 제조N-([1,1'-biphenyl] -2-yl (6-((S) -2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) pyridin-2-yl) Preparation of Methyl) -2,6-Diisopropyl Aniline
Figure PCTKR2017001503-appb-I000076
Figure PCTKR2017001503-appb-I000076
상기 실시예 5의 b)에서 제조된 리간드 전구체인 N-(2,6-디이소프로필페닐)-1-(6-(2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메탄이민(1.31 g, 3.178 mmol, 1 eq)을 디에틸 에터(31.78 mL)에 녹이고 -78℃로 온도를 낮췄다. 2-Br-비페닐(2 g, 8.580 mmol, 2.7 eq)을 THF(17.16 mL)에 녹인 후, t-BuLi(10.86 mL, 17.16 mmol, 5.4 eq)을 넣어 리튬 치환 반응을 시켰다. 리튬 치환 반응이 완료되면 이를 N-(2,6-디이소프로필페닐)-1-(6-(2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메탄이민의 용액에 옮기고, 반응이 끝나면 1 N NH4Cl로 퀀치(quench)하고 디에틸 에터와 물로 워크-업(work-up)하였다. 이를 통해 생성물을 2.38 g, 100% 수율로 수득하였다. N- (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinoline-8-, which is a ligand precursor prepared in b) of Example 5 Il) pyridin-2-yl) methaneimine (1.31 g, 3.178 mmol, 1 eq) was dissolved in diethyl ether (31.78 mL) and the temperature was lowered to -78 ° C. 2-Br-biphenyl (2 g, 8.580 mmol, 2.7 eq) was dissolved in THF (17.16 mL), and then t-BuLi (10.86 mL, 17.16 mmol, 5.4 eq) was added for lithium substitution. When the lithium substitution reaction is completed, it is N- (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) pyridine-2- Transfer to a solution of 1) methaneimine, and after completion of the reaction, quench with 1 N NH 4 Cl and work-up with diethyl ether and water. This gave the product 2.38 g, 100% yield.
1H-NMR (toluene_d8): 8.50 - 6.64 (m, 18H), 5.50 - 1.48 (m, 9H), 0.9 (m, 15H)1 H-NMR (toluene_d8): 8.50-6.64 (m, 18H), 5.50-1.48 (m, 9H), 0.9 (m, 15H)
실시예 7-1: 전이금속 화합물의 합성(화학식 2m)Example 7-1: Synthesis of Transition Metal Compound (Formula 2m)
Figure PCTKR2017001503-appb-I000077
Figure PCTKR2017001503-appb-I000077
상기 실시예 7에서 제조된 N-([1,1'-비페닐]-2-일(6-((S)-2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메틸)-2,6-디이소프로필 아닐린(2.38 g, 4.2064 mmol, 1 eq)과 톨루엔(14.02 mL, 0.3 M)을 넣고 교반시킨 후 n-BuLi (3.533 mL, 8.834 mmol, 2.1 eq)을 적가하였다. HfCl4(1.415 g, 4.417 mmol, 1.05 eq)를 넣고 2시간 동안 90 내지 100℃에서 가열하였다. 반응이 끝난 후 온도를 식히고 MeMgBr(4.907 mL, 14.72 mmol, 3.5 eq, 3.0 M in DEE)을 넣어 상온에서 밤새 반응시켰다. 용매를 진공 건조(vacuum dry)한 후 여과하였다. 생성물을 290 mg, 10% 수율로 얻을 수 있었다.N-([1,1'-biphenyl] -2-yl (6-((S) -2-methyl-1,2,3,4-tetrahydroquinolin-8-yl prepared in Example 7 above) ) Pyridin-2-yl) methyl) -2,6-diisopropyl aniline (2.38 g, 4.2064 mmol, 1 eq) and toluene (14.02 mL, 0.3 M) were added and stirred, followed by n-BuLi (3.533 mL, 8.834). mmol, 2.1 eq) was added dropwise. HfCl 4 (1.415 g, 4.417 mmol, 1.05 eq) was added and heated at 90-100 ° C. for 2 hours. After the reaction, the temperature was cooled and MeMgBr (4.907 mL, 14.72 mmol, 3.5 eq, 3.0 M in DEE) was added and allowed to react at room temperature overnight. The solvent was vacuum dried and then filtered. The product could be obtained in 290 mg, 10% yield.
1H-NMR (toluene_d8): 7.63 (d, 1H), 7.26 (d, 2H), 7.15 (m, 4H), 7.10 (m, 2H), 7.07 (m, 4H), 7.03 (m, 3H), 6.67 (t, 2H), 6.02 (s, 1H), 4.84 (m, 1H), 4.13 (m, 1H), 2.990 (m, 1H), 2.60 (m, 2H), 2.18 (m, 1H), 1.82 (m, 1H), (m, 1H), 1.47 (d, 3H), 1.30 (d, 3H), 0.80 (d, 3H), 0.72 (s, 3H), 0.61 (d, 3H), 0.29 (d, 3H), 0.01 (s, 3H)1 H-NMR (toluene_d8): 7.63 (d, 1H), 7.26 (d, 2H), 7.15 (m, 4H), 7.10 (m, 2H), 7.07 (m, 4H), 7.03 (m, 3H), 6.67 (t, 2H), 6.02 (s, 1H), 4.84 (m, 1H), 4.13 (m, 1H), 2.990 (m, 1H), 2.60 (m, 2H), 2.18 (m, 1H), 1.82 ( m, 1H), (m, 1H), 1.47 (d, 3H), 1.30 (d, 3H), 0.80 (d, 3H), 0.72 (s, 3H), 0.61 (d, 3H), 0.29 (d, 3H), 0.01 (s, 3H)
실시예 8: 리간드 화합물의 합성Example 8: Synthesis of Ligand Compound
a) N-(t-부틸)-1-(6-브로모피리딘-2-일)메탄이민의 제조a) Preparation of N- (t-butyl) -1- (6-bromopyridin-2-yl) methanimine
Figure PCTKR2017001503-appb-I000078
Figure PCTKR2017001503-appb-I000078
2-포르밀-6-브로모피리딘(3 g, 16.13 mmol, 1 eq), p-톨루엔설폰산(3 방울), 및 몰레큘라 시브(molecular sieve, 1 g)를 쉬렝크 플라스크에 넣은 후, 톨루엔(32.26 mL, 0.5 M)을 첨가하였다. 여기에 t-BuNH2(1.30 g, 17.74 mmol, 1.1 eq)를 넣고, 70℃에서 밤새 교반한 후, 실온으로 냉각하였다. 몰레큘라 시브를 여과한 뒤 용매를 진공 건조하여 제거하고, 차가운 MeOH를 이용해서 침전시켜 고체가 생성되도록 하여 생성물을 수득하였다. 이를 통하여 흰색 고체 3.2 g을 82.3% 수율로 얻을 수 있었다. 2-formyl-6-bromopyridine (3 g, 16.13 mmol, 1 eq), p -toluenesulfonic acid (3 drops), and molecular sieve (1 g) were placed in a Schlenk flask, Toluene (32.26 mL, 0.5 M) was added. T-BuNH 2 (1.30 g, 17.74 mmol, 1.1 eq) was added thereto, stirred at 70 ° C. overnight, and then cooled to room temperature. The molecular sieve was filtered off and the solvent was removed by vacuum drying and precipitated using cold MeOH to give a solid to yield the product. This gave 3.2 g of a white solid in 82.3% yield.
b) N-(t-부틸)-1-(6-(1,2,3,4-b) N- (t-butyl) -1- (6- (1,2,3,4- 테트라하이드로Tetrahydro -2--2- 메틸퀴놀린Methylquinoline -8-일)피리딘-2-일)메탄이민의 제조Preparation of -8-yl) pyridin-2-yl) methaneimine
Figure PCTKR2017001503-appb-I000079
Figure PCTKR2017001503-appb-I000079
상기에서 제조된 N-(t-부틸)-1-(6-브로모피리딘-2-일)메탄이민(3 g, 12.44 mmol, 1 eq)을 톨루엔(20 mL)에 넣고 교반하는 한편, 이와 별도로 Na2CO3(3.30 g, 31.1 mmol, 2.5 eq)와 메틸테트라하이드로퀴놀린-보롤란(MeTHQ-보롤란)(3.4 g, 12.44 mmol, 1 eq)을 H2O(4 mL)와 EtOH(4 mL) 1:1인 용매에 넣고 교반하였다. N- (t-butyl) -1- (6-bromopyridin-2-yl) methanimine (3 g, 12.44 mmol, 1 eq) prepared above was added to toluene (20 mL) and stirred, Separately Na 2 CO 3 (3.30 g, 31.1 mmol, 2.5 eq) and methyltetrahydroquinoline-borolane (MeTHQ-borolane) (3.4 g, 12.44 mmol, 1 eq) were added with H 2 O (4 mL) and EtOH ( 4 mL) was added to a 1: 1 solvent and stirred.
N-(t-부틸)-1-(6-브로모피리딘-2-일)메탄이민 톨루엔 용액을 Na2CO3와 THQ-보롤란의 용액으로 옮긴 뒤, 여기에 Pd(PPh3)4(0.043 g, 0.0373 mmol, 0.3 mol% Pd)를 넣었다. 70℃에서 밤새 교반한 뒤 실온으로 냉각시켰다. 유기층을 톨루/염수(brine)로 추출하고 Na2SO4로 수분을 건조시켰다. EtOH 와 MeOH 를 이용하여 고체를 만들어 보려고 했으나, 고체가 잘 생기지 않아서 출발물질이 포함된 상태로 다음 반응을 진행하여야 하였다(70% 순도). 생성물은 오렌지색 오일로 4 g, >100% 수율로 얻을 수 있었다.N- (t-butyl) -1- (6-bromopyridin-2-yl) methanimine toluene solution was transferred to a solution of Na 2 CO 3 and THQ-borolane, followed by Pd (PPh 3 ) 4 ( 0.043 g, 0.0373 mmol, 0.3 mol% Pd) was added. After stirring overnight at 70 ° C., it was cooled to room temperature. The organic layer was extracted with tolu / brine and dried over Na 2 SO 4 . EtOH and MeOH were tried to make a solid, but the solid was not well formed and the next reaction was to be carried out with the starting material (70% purity). The product was obtained in 4 g,> 100% yield as an orange oil.
c) 2-c) 2- 메틸methyl -N-((6-(2--N-((6- (2- 메틸methyl -1,2,3,4--1,2,3,4- 테트라하이드로메틸퀴놀린Tetrahydromethylquinoline -8-일)피리딘-2-일)(페닐)메틸)프로판-2-아민의 제조Preparation of -8-yl) pyridin-2-yl) (phenyl) methyl) propan-2-amine
Figure PCTKR2017001503-appb-I000080
Figure PCTKR2017001503-appb-I000080
상기에서 제조된 N-(t-부틸)-1-(6-(1,2,3,4-테트라하이드로-2-메틸퀴놀린-8-일)피리딘-2-일)메탄이민(1.17 g, 3.806 mmol, 1 eq)을 디에틸 에터(0.1 M)에 녹이고 -78℃로 온도를 낮춘 뒤, 페닐 리튬(5.71 mL, 10.275 mmol, 2.7 eq)을 넣고 상온으로 승온시켰다. 밤새 반응시킨뒤 TLC로 체크한 뒤 반응이 끝나면 1 N NH4Cl로 퀀치(quench)하고 디에틸 에터와 물로 워크-업(work-up)하였다. Na2SO4로 수분을 건조시킨 뒤, 회전 증발 농축기(Rotavapor)로 용매를 진공 건조(vacuum dry)시켰다. 오렌지색 오일을 1.52 g >100% 수율로 수득하였다. N- (t-butyl) -1- (6- (1,2,3,4-tetrahydro-2-methylquinolin-8-yl) pyridin-2-yl) methanimine prepared above (1.17 g, 3.806 mmol, 1 eq) was dissolved in diethyl ether (0.1 M), and the temperature was lowered to -78 ° C. Then, phenyl lithium (5.71 mL, 10.275 mmol, 2.7 eq) was added thereto, and the temperature was raised to room temperature. After reacting overnight, TLC was checked and the reaction was quenched with 1 N NH 4 Cl, and then worked up with diethyl ether and water. After drying the moisture with Na 2 SO 4 , the solvent was vacuum dried with a Rotavapor. Orange oil was obtained in 1.52 g> 100% yield.
1H-NMR (toluene_d8): 8.52 (m, 12H), 5.14 (m, 1H), 3.34 - 1.38 (m, 6H), 1.05 (s, 3H), 1.01 (s, 9H)1 H-NMR (toluene_d8): 8.52 (m, 12H), 5.14 (m, 1H), 3.34-1.38 (m, 6H), 1.05 (s, 3H), 1.01 (s, 9H)
실시예 8-1: 전이금속 화합물의 합성(화학식 2o)Example 8-1: Synthesis of Transition Metal Compound (Formula 2o)
Figure PCTKR2017001503-appb-I000081
Figure PCTKR2017001503-appb-I000081
상기 실시예 8의 c)에서 합성된 리간드인 N-((6-(1,2,3,4-테트라하이드로-2-메틸퀴놀린-8일)피리딘-2-일)(페닐)메틸)-t-부탄-1-아민(0.86g, 2.2305mmol, 1eq)을 톨루엔(7.435 mL, 0.3 M)에 녹이고 교반한 후 -40℃에서 n-BuLi(1.874 mL, 4.684 mmol, 2.1 eq)을 적가하였다. HfCl4(0.75015 g, 2.342 mmol, 1.05 eq)를 넣고 2 시간 동안 90 내지 100℃에서 가열하였다. N-((6- (1,2,3,4-tetrahydro-2-methylquinolin-8yl) pyridin-2-yl) (phenyl) methyl)-which is a ligand synthesized in c) of Example 8 t-butan-1-amine (0.86 g, 2.2305 mmol, 1 eq) was dissolved in toluene (7.435 mL, 0.3 M), stirred and n-BuLi (1.874 mL, 4.684 mmol, 2.1 eq) was added dropwise at -40 ° C. . HfCl 4 (0.75015 g, 2.342 mmol, 1.05 eq) was added thereto and heated at 90 to 100 ° C. for 2 hours.
반응이 끝난 후 온도를 식히고 MeMgBr(2.602 mL, 7.807 mmol, 3.5 eq, 3.0 M in DEE)를 넣어 상온에서 밤새 반응시켰다. 용매를 진공 건조한 후 여과하였다. 갈색(brown) 고체인 생성물을 210 mg, 16% 수율로 얻을 수 있었다. NMR 상으로 이성질체가 존재함을 알 수 있었다.After the reaction, the temperature was cooled and MeMgBr (2.602 mL, 7.807 mmol, 3.5 eq, 3.0 M in DEE) was added and reacted at room temperature overnight. The solvent was dried in vacuo and filtered. A brown solid product was obtained in 210 mg, 16% yield. It was found that isomers existed on NMR.
1H-NMR (toluene_d8): 7.40 - 6.60 (m, 11H), 5.84 (m, 1H), 5.00 - 1.8 (m, 5H), 1.53 - 0.18 (m, 18H)1 H-NMR (toluene_d8): 7.40-6.60 (m, 11H), 5.84 (m, 1H), 5.00-1.8 (m, 5H), 1.53-0.18 (m, 18H)
실시예 9: 리간드 화합물의 합성Example 9: Synthesis of Ligand Compound
N-((2-N-((2- 이소프로필페닐Isopropylphenyl )(6-(2-) (6- (2- 메틸methyl -1,2,3,4--1,2,3,4- 테트라하이드로퀴놀린Tetrahydroquinoline -8-일)피리딘-2-일)-2-메틸프로판-2-아민의 제조Preparation of -8-yl) pyridin-2-yl) -2-methylpropan-2-amine
Figure PCTKR2017001503-appb-I000082
Figure PCTKR2017001503-appb-I000082
1-Br-2-이소프로필벤젠(1.626g, 8.167mmol, 2.7 eq)을 THF(21.38 mL)에 넣고 -78℃에서 t-BuLi(10.404 mL, 16.335 mmol, 5.4 eq)을 넣었다. 이것을 2시간 동안 반응시킨 뒤 상온으로 승온시켜 1-리튬-2-이소프로필벤젠을 얻었다. 1-Br-2-isopropylbenzene (1.626 g, 8.167 mmol, 2.7 eq) was added to THF (21.38 mL) and t-BuLi (10.404 mL, 16.335 mmol, 5.4 eq) was added at -78 ° C. After reacting for 2 hours, the temperature was raised to room temperature to obtain 1-lithium-2-isopropylbenzene.
상기 실시예 17에서 제조된 리간드 전구체인 N-(t-부틸)-1-(6-(1,2,3,4-테트라하이드로-2-메틸퀴놀린-8-일)피리딘-2-일)메탄이민을 디에틸 에터(30.25 mL, 0.1 M)에 녹인 뒤, 상기에서 제조된 1-리튬-2-이소프로필벤젠을 이에 옮겼다. 상온에서 밤새 반응시킨 뒤, TLC로 반응을 체크하여 반응이 완료되면 1 N NH4Cl로 퀀치(quench)하고 유기층을 에터/H2O 워크-업한 다음, Na2SO4로 수분을 건조시켰다. 뒤 회전 증발 농축기(Rotavapor)로 용매를 진공 건조(vacuum dry)시켰다. 오렌지색 오일을 1.14 g, >100%로 얻을 수 있었다.N- (t-butyl) -1- (6- (1,2,3,4-tetrahydro-2-methylquinolin-8-yl) pyridin-2-yl) which is a ligand precursor prepared in Example 17 Methaneimine was dissolved in diethyl ether (30.25 mL, 0.1 M), and 1-lithium-2-isopropylbenzene prepared above was transferred thereto. After reacting at room temperature overnight, the reaction was checked by TLC, and when the reaction was completed, the reaction was quenched with 1 N NH 4 Cl, and the organic layer was worked up with ether / H 2 O, and then dried with Na 2 SO 4 . The solvent was vacuum dried with a Rotavapor. An orange oil was obtained at 1.14 g,> 100%.
1H-NMR (toluene_d8): 8.28 - 6.62 (m, 11H), 5.52 (s, 1H), 3.66 - 1.40 (m, 7H), 1.14 (s, 3H), 1.06 (s, 15H)1 H-NMR (toluene_d8): 8.28-6.62 (m, 11H), 5.52 (s, 1H), 3.66-1.40 (m, 7H), 1.14 (s, 3H), 1.06 (s, 15H)
실시예 9-1: 전이금속 화합물의 합성(화학식 2q)Example 9-1: Synthesis of Transition Metal Compound (Formula 2q)
<전이 금속 화합물의 합성>Synthesis of Transition Metal Compound
Figure PCTKR2017001503-appb-I000083
Figure PCTKR2017001503-appb-I000083
상기 실시예 9에서 합성된 리간드인 N-((6-(1,2,3,4-테트라하이드로-2-메틸퀴놀린-8일)피리딘-2-일)(2-이소프로필페닐)메틸)-t-부탄-1-아민(1.23 g, 2.876 mmol, 1 eq)을 톨루엔(9.587 mL, 0.3 M)에 녹이고 교반한 후 -40℃에서 n-BuLi(2.416 mL, 6.0401 mmol, 2.1 eq)을 적가하였다. HfCl4(0.967 g, 3.0198 mmol, 1.05 eq)를 넣고 2 시간 동안 90 내지 100℃에서 가열하였다. N-((6- (1,2,3,4-tetrahydro-2-methylquinolin-8yl) pyridin-2-yl) (2-isopropylphenyl) methyl, which is a ligand synthesized in Example 9 above -t-butan-1-amine (1.23 g, 2.876 mmol, 1 eq) was dissolved in toluene (9.587 mL, 0.3 M) and stirred, followed by n-BuLi (2.416 mL, 6.0401 mmol, 2.1 eq) at -40 ° C. Added dropwise. HfCl 4 (0.967 g, 3.0198 mmol, 1.05 eq) was added thereto and heated at 90 to 100 ° C. for 2 hours.
반응이 끝난 후 온도를 식히고 MeMgBr(3.355 mL, 10.066 mmol, 3.5 eq, 3.0 M in DEE)를 넣어 상온에서 밤새 반응시켰다. 용매를 진공 건조한 후 여과하였다. 얻어진 생성물은 여러 이성질체가 존재하는 것으로 보였고, 갈색(brown) 고체인 생성물을 588 mg, 32% 수율로 얻을 수 있었다. After the reaction, the temperature was cooled and MeMgBr (3.355 mL, 10.066 mmol, 3.5 eq, 3.0 M in DEE) was added and reacted at room temperature overnight. The solvent was dried in vacuo and filtered. The product obtained appeared to be in the presence of several isomers, which gave 588 mg, 32% yield of a brown solid product.
1H-NMR (toluene_d8): 7.38 - 6.52 (m, 10H), 5.04 - 2.47 (m, 7H), 1.489 - 0.88 (m, 24H) 1 H-NMR (toluene_d8): 7.38-6.52 (m, 10H), 5.04-2.47 (m, 7H), 1.489-0.88 (m, 24H)
실시예 10: 리간드 화합물의 합성Example 10 Synthesis of Ligand Compound
2,6-2,6- 디이소프로필Diisopropyl -N-((6-(2--N-((6- (2- 메틸methyl -1,2,3,4--1,2,3,4- 테트라하이드로퀴놀린Tetrahydroquinoline -8-일)피리딘-2-일)(나프틸)메틸)아닐린의 제조Preparation of -8-yl) pyridin-2-yl) (naphthyl) methyl) aniline
Figure PCTKR2017001503-appb-I000084
Figure PCTKR2017001503-appb-I000084
상기 실시예 5의 b)에서 제조된 리간드 전구체인 N-(2,6-디이소프로필페닐)-1-(6-(2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메탄이민(1.5 g, 3.644 mmol, 1 eq)을 디에틸 에터(36.44 mL)에 녹이고 -78℃로 온도를 낮췄다. 1-브로모나프탈렌(2.04 g, 9.84 mmol, 2.7 eq)을 THF(19.68 mL)에 녹인 후, t-BuLi(12.53 mL, 19.68 mmol, 5.4 eq)을 넣어 리튬 치환 반응을 시켰다. 리튬 치환 반응이 완료되면 이를 N-(2,6-디이소프로필페닐)-1-(6-(2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메탄이민의 용액에 옮기고, 반응이 끝나면 1 N NH4Cl로 퀀치(quench)하고 디에틸 에터와 물로 워크-업(work-up)하였다. 이를 통해 생성물인 노란색 오일을 1.93 g, 98% 수율로 수득하였다. N- (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinoline-8-, which is a ligand precursor prepared in b) of Example 5 I) pyridin-2-yl) methaneimine (1.5 g, 3.644 mmol, 1 eq) was dissolved in diethyl ether (36.44 mL) and the temperature was lowered to -78 ° C. 1-bromonaphthalene (2.04 g, 9.84 mmol, 2.7 eq) was dissolved in THF (19.68 mL), and then t-BuLi (12.53 mL, 19.68 mmol, 5.4 eq) was added for lithium substitution. When the lithium substitution reaction is completed, it is N- (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) pyridine-2- Transfer to a solution of 1) methaneimine, and after completion of the reaction, quench with 1 N NH 4 Cl and work-up with diethyl ether and water. This gave 1.93 g, 98% yield of the product as a yellow oil.
1H-NMR (toluene_d8): 8.401 - 5.909 (m, 17H), 4.45 - 1.20 (10H, m), 1.09 - 0.38 (m, 15H)1 H-NMR (toluene_d8): 8.401-5.909 (m, 17H), 4.45-1.20 (10H, m), 1.09-0.38 (m, 15H)
실시예 10-1Example 10-1 : 전이금속 화합물의 합성(화학식 2s): Synthesis of Transition Metal Compound (Formula 2s)
Figure PCTKR2017001503-appb-I000085
Figure PCTKR2017001503-appb-I000085
상기 실시예 10에서 제조된 리간드인 2,6-디이소프로필-N-((6-(2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)(나프틸)메틸)아닐린(1.13 g, 2.0935 mmol, 1 eq)과 톨루엔(6.98 mL, 0.3 M)을 넣고 교반시킨 후 n-BuLi(1.76 mL, 4.396 mmol, 2.1 eq)을 적가하였다. HfCl4(0.704 g, 2.198 mmol, 1.05 eq)를 넣고 2시간 동안 90 내지 100℃에서 가열하였다.2,6-diisopropyl-N-((6- (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) pyridin-2-yl) which is a ligand prepared in Example 10 (Naphthyl) methyl) aniline (1.13 g, 2.0935 mmol, 1 eq) and toluene (6.98 mL, 0.3 M) were added thereto, followed by stirring. Then n-BuLi (1.76 mL, 4.396 mmol, 2.1 eq) was added dropwise. HfCl 4 (0.704 g, 2.198 mmol, 1.05 eq) was added thereto and heated at 90 to 100 ° C. for 2 hours.
반응이 끝난 후 온도를 식히고 MeMgBr(2.44 mL, 7.33 mmol, 3.5 eq, 3.0 M in DEE)을 넣어 상온에서 밤새 반응시켰다. 용매를 진공 건조(vacuum dry)시킨 후 여과하였다. 생성물은 노란색 고체로 210 mg, 13% 수율로 얻을 수 있었다.After the reaction, the temperature was cooled and MeMgBr (2.44 mL, 7.33 mmol, 3.5 eq, 3.0 M in DEE) was added and allowed to react at room temperature overnight. The solvent was vacuum dried and then filtered. The product was obtained in 210 mg, 13% yield as a yellow solid.
1H-NMR (toluene_d8): 7.60 - 6.38 (m, 16H), 4.87 (m, 1H), 3.27 - 1.81 (m, 7H), 1.30 - 0.0 (m, 2H)1 H-NMR (toluene_d8): 7.60-6.38 (m, 16H), 4.87 (m, 1H), 3.27-1.81 (m, 7H), 1.30-0.0 (m, 2H)
실시예 11: 리간드 화합물의 합성Example 11: Synthesis of Ligand Compound
2,6-2,6- 디이소프로필Diisopropyl -N-((6-(2--N-((6- (2- 메틸methyl -1,2,3,4--1,2,3,4- 테트라하이드로퀴놀린Tetrahydroquinoline -8-일)피리딘-2-일)(4-tert-부틸페닐)메틸)아닐린의 제조Preparation of 8-yl) pyridin-2-yl) (4-tert-butylphenyl) methyl) aniline
Figure PCTKR2017001503-appb-I000086
Figure PCTKR2017001503-appb-I000086
상기 실시예 5의 b)에서 제조된 리간드 전구체인 N-(2,6-디이소프로필페닐)-1-(6-(2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메탄이민(2.146 g, 5.215 mmol, 1 eq)을 디에틸 에터(52.15 mL)에 녹이고 -78℃로 온도를 낮췄다. 1-tert-부틸-4-브로모페닐(3 g, 14.08 mmol, 2.7 eq)을 THF(28.16 mL)에 녹인 후, t-BuLi(17.82 mL, 28.161 mmol, 5.4 eq)을 넣어 리튬 치환 반응을 시켰다. 리튬 치환 반응이 완료되면 이를 N-(2,6-디이소프로필페닐)-1-(6-(2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)메탄이민의 용액에 옮기고, 반응이 끝나면 1 N NH4Cl로 퀀치(quench)하고 디에틸 에터와 물로 워크-업(work-up)하였다. 이를 통해 생성물인 오렌지색 고체를 2.0 g, 70% 수율로 수득하였다.N- (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinoline-8-, which is a ligand precursor prepared in b) of Example 5 I) pyridin-2-yl) methaneimine (2.146 g, 5.215 mmol, 1 eq) was dissolved in diethyl ether (52.15 mL) and the temperature was lowered to -78 ° C. Dissolve 1-tert-butyl-4-bromophenyl (3 g, 14.08 mmol, 2.7 eq) in THF (28.16 mL), add t-BuLi (17.82 mL, 28.161 mmol, 5.4 eq) to perform lithium substitution. I was. When the lithium substitution reaction is completed, it is N- (2,6-diisopropylphenyl) -1- (6- (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) pyridine-2- Transfer to a solution of 1) methaneimine, and after completion of the reaction, quench with 1 N NH 4 Cl and work-up with diethyl ether and water. This resulted in 2.0 g, 70% yield of the product as an orange solid.
1H-NMR (toluene_d8): 8.23 - 6.64 (m, 14H), 5.33 - 1.50 (m, 9H), 1.21 - 0.99 (m, 24H)1 H-NMR (toluene_d8): 8.23-6.64 (m, 14H), 5.33-1.50 (m, 9H), 1.21-0.99 (m, 24H)
실시예 11-1: 전이금속 화합물의 합성(화학식 2u)Example 11-1: Synthesis of Transition Metal Compound (Formula 2u)
Figure PCTKR2017001503-appb-I000087
Figure PCTKR2017001503-appb-I000087
상기 실시예 11에서 제조된 리간드인 2,6-디이소프로필-N-((6-(2-메틸-1,2,3,4-테트라하이드로퀴놀린-8-일)피리딘-2-일)(4-tert-부틸페닐)메틸)아닐린(1 g, 1.832 mmol, 1 eq)과 톨루엔(6.107 mL, 0.3 M)을 넣고 교반시킨 후 n-BuLi(1.539 mL, 3.847 mmol, 2.1 eq)을 적가하였다. HfCl4(0.616 g, 1.9236 mmol, 1.05 eq)를 넣고 2시간 동안 90 내지 100℃에서 가열하였다.2,6-diisopropyl-N-((6- (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) pyridin-2-yl) which is a ligand prepared in Example 11 (4-tert-butylphenyl) methyl) aniline (1 g, 1.832 mmol, 1 eq) and toluene (6.107 mL, 0.3 M) were added thereto, stirred, and n-BuLi (1.539 mL, 3.847 mmol, 2.1 eq) was added dropwise. It was. HfCl 4 (0.616 g, 1.9236 mmol, 1.05 eq) was added thereto and heated at 90 to 100 ° C. for 2 hours.
반응이 끝난 후 온도를 식히고 MeMgBr(2.137 mL, 6.412 mmol, 3.5 eq, 3.0 M in DEE)을 넣어 상온에서 밤새 반응시켰다. 용매를 진공 건조(vacuum dry)시킨 후 여과하였다. 빨간색 고체인 생성물을 1.04 g, 75% 수율로 수득하였다. After the reaction, the temperature was cooled and MeMgBr (2.137 mL, 6.412 mmol, 3.5 eq, 3.0 M in DEE) was added and reacted at room temperature overnight. The solvent was vacuum dried and then filtered. The product was obtained as a red solid in 1.04 g, 75% yield.
1H-NMR (toluene_d8): 7.32 - 5.93 (m, 13H), 4.81 - 1.80 (m, 8H), 1.15 -0.00 (m, 30H)1 H-NMR (toluene_d8): 7.32-5.93 (m, 13H), 4.81-1.80 (m, 8H), 1.15 -0.00 (m, 30H)
실시예 1-A : 에틸렌-옥텐 공중합체의 제조Example 1-A: Preparation of Ethylene-Octene Copolymer
2L 오토클레이브 반응기에 헥산 용매(1.0 L)와 옥텐(280 mL), 에틸렌(35 bar)을 가한 후, 고압 아르곤 압력으로 500 psi가 되도록 압력을 맞추고 반응기의 온도를 120℃로 예열하였다. 5×10-6 M의 디메틸아닐리늄 테트라키스(펜타플로로페닐)보레이트 조촉매 10 당량을 고압 아르곤 압력을 가하여 반응기에 넣고, 트리이소부틸알루미늄 화합물로 처리된 상기 실시예 1-1의 전이금속 화합물(1×10-6 M, 2.0 mL)을 촉매 저장탱크에 넣은 후 고압의 아르곤 압력을 가하여 반응기에 넣었다. 중합 반응은 10분간 진행하였다. 반응열은 반응기 내부의 냉각 코일을 통해 제거하여 중합 온도를 최대한 일정하게 유지하였다. 중합 반응을 10분간 진행한 후, 남은 가스를 빼내고 고분자 용액을 반응기의 하부로 배출시키고 과량의 에탄올을 가하여 냉각시켜 침전을 유도하였다. 얻어진 고분자를 에탄올 및 아세톤으로 각각 2 내지 3회 세척한 후, 90℃ 진공 오븐에서 12시간 이상 건조하여 에틸렌-옥텐 공중합체를 제조하였다.Hexane solvent (1.0 L), octene (280 mL), and ethylene (35 bar) were added to the 2 L autoclave reactor, the pressure was adjusted to 500 psi at high pressure argon pressure, and the temperature of the reactor was preheated to 120 ° C. 10 equivalents of 5 × 10 −6 M dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst was added to a reactor under high pressure argon pressure, and the transition metal of Example 1-1 treated with triisobutylaluminum compound Compound (1 × 10 −6 M, 2.0 mL) was placed in a catalyst storage tank and then placed in a reactor under high pressure argon pressure. The polymerization reaction proceeded for 10 minutes. The heat of reaction was removed through a cooling coil inside the reactor to keep the polymerization temperature as constant as possible. After the polymerization reaction was performed for 10 minutes, the remaining gas was drained, the polymer solution was discharged to the bottom of the reactor, and excess ethanol was added to cool, thereby inducing precipitation. The obtained polymer was washed two to three times with ethanol and acetone, and then dried in a 90 ° C. vacuum oven for at least 12 hours to prepare an ethylene-octene copolymer.
실시예 1-B, 2-A 내지 11-A : 에틸렌-옥텐 공중합체의 제조Example 1-B, 2-A to 11-A: Preparation of Ethylene-Octene Copolymer
상기 실시예 1-A에서 트리이소부틸알루미늄 화합물로 처리된 상기 실시예 1-1의 전이금속 화합물을 대신하여 하기 표 6에 나타낸 바와 같은 각각의 전이금속 화합물을 트리이소부틸알루미늄 화합물로 처리하여 각각 사용한 것을 제외하고는, 실시예 1-A와 마찬가지의 방법으로 에틸렌-옥텐 공중합체를 제조하였다.In place of the transition metal compound of Example 1-1 treated with the triisobutylaluminum compound in Example 1-A, each transition metal compound as shown in Table 6 was treated with a triisobutylaluminum compound, respectively. Except what was used, the ethylene-octene copolymer was manufactured by the method similar to Example 1-A.
실험예 1 : 촉매 활성도의 측정Experimental Example 1 Measurement of Catalyst Activity
상기 실시예 1-A 내지 7-A, 10-A 및 11-A에서의 공중합체 제조시의 촉매활성도를 하기와 같은 방법으로 각각 측정하고, 그 결과를 하기 표 6에 나타내었다.The catalytic activity in preparing the copolymers in Examples 1-A to 7-A, 10-A, and 11-A was measured in the following manner, and the results are shown in Table 6 below.
촉매 활성도: 제조한 공중합체 총 수득량에 대한 전이금속 화합물의 투입 몰비로부터 구하였다. 상세하게는, 중합 반응 완료 후 취한 반응 용액 일부분의 질량을 측정한 값과, 그 공중합체 일부분을 120℃에서 10분 동안 가열하여 헥산 용매와 잔류 단량체를 모두 제거하고 남은 공중합체의 질량을 측정한 값의 비율을 계산하고, 이에 기반하여 생성된 공중합체의 질량과 중합 반응에 사용한 전이금속 화합물의 몰수 및 중합 시간을 이용하여 촉매활성도를 계산하였다.Catalytic Activity: Determined from the molar ratio of the transition metal compound to the total yield of the copolymer produced. Specifically, the mass of a portion of the reaction solution taken after completion of the polymerization reaction and the portion of the copolymer were heated at 120 ° C. for 10 minutes to remove all the hexane solvent and residual monomers, and to measure the mass of the remaining copolymer. The ratio of the values was calculated, and the catalytic activity was calculated using the mass of the resulting copolymer, the number of moles of the transition metal compound used in the polymerization reaction, and the polymerization time.
전이금속화합물Transition metal compound 촉매 활성도(KgPE/mmol)Catalytic activity (KgPE / mmol)
실시예 1-AExample 1-A 실시예 1-1Example 1-1 2.72.7
실시예 1-BExample 1-B 실시예 1-2Example 1-2 0.80.8
실시예 2-AExample 2-A 실시예 2-1Example 2-1 5.65.6
실시예 2-BExample 2-B 실시예 2-2Example 2-2 0.740.74
실시예 3-AExample 3-A 실시예 3-1Example 3-1 1.01.0
실시예 4-AExample 4-A 실시예 4-1Example 4-1 2.22.2
실시예 5-AExample 5-A 실시예 5-1Example 5-1 2.32.3
실시예 6-AExample 6-A 실시예 6-1Example 6-1 5.35.3
실시예 7-AExample 7-A 실시예 7-1Example 7-1 2.72.7
실시예 10-AExample 10-A 실시예 10-1Example 10-1 2.32.3
실시예 11-AExample 11-A 실시예 11-1Example 11-1 1.51.5
상기 표 6에서 확인할 수 있는 바와 같이, 실시예 1-1 내지 7-1, 10-1, 및 11-1의 전이금속 화합물은 에틸렌-옥텐 공중합체의 제조에 있어서 촉매 활성을 나타내었다. As can be seen in Table 6, the transition metal compounds of Examples 1-1 to 7-1, 10-1, and 11-1 exhibited catalytic activity in the preparation of the ethylene-octene copolymer.
실험예 2 : 물성의 측정Experimental Example 2 Measurement of Physical Properties
상기 실시예 6-A, 7-A 및 10-A에서 제조된 공중합체의 용융지수(MI), 밀도, 및 녹는점을 하기와 같은 방법으로 각각 측정하고, 그 결과를 하기 표 7에 나타내었다.Melt index (MI), density, and melting point of the copolymers prepared in Examples 6-A, 7-A, and 10-A were measured in the following manners, and the results are shown in Table 7 below. .
(1) 중합체의 용융지수(melt index, MI): ASTM D-1238(조건 E, 190℃, 2.16kg 하중)로 측정하였다. (1) Melt index (MI) of the polymer: measured by ASTM D-1238 (Condition E, 190 ° C, 2.16 kg load).
(2) 중합체의 밀도(Density): ASTM D-792로 측정하였다.(2) Density of the polymer: measured by ASTM D-792.
(3) 녹는점(Tm): TA사의 Q100을 사용하여 측정하였다.(3) Melting point (Tm): Measured using Q100 of TA Corporation.
전이금속화합물Transition metal compound 촉매 활성도(KgPE/mmol)Catalytic activity (KgPE / mmol) MI(g/10min)MI (g / 10min) 밀도(g/cc)Density (g / cc) 녹는점(℃)Melting Point (℃)
실시예 6-AExample 6-A 실시예 6-1Example 6-1 5.35.3 0.020.02 0.8650.865 50.350.3
실시예 7-AExample 7-A 실시예 7-1Example 7-1 2.72.7 0.020.02 0.8830.883 72.972.9
실시예 10-AExample 10-A 실시예 10-1Example 10-1 2.32.3 0.010.01 0.8730.873 60.960.9
상기 표 7에서 확인할 수 있는 바와 같이, 본 발명의 전이금속 화합물의 일례인 실시예 6-1, 7-1, 및 10-1의 전이금속 화합물을 사용하여 제조된 실시예 6-A, 7-A, 및 10-A의 중합체는 0.02 이하의 낮은 용융지수(MI)를 나타내어 고분자량을 나타내었으며, 0.883 g/cc 이하의 밀도를 나타내었다. 특히, 실시예 6-1 및 10-1의 전이금속 화합물을 사용하여 제조된 실시예 6-A 및 10-A의 중합체는 0.873 g/cc 이하의 낮은 밀도와 함께 0.02 이하의 낮은 용융지수(MI)를 나타내어 저밀도이면서 고분자량을 나타내었다. As can be seen in Table 7, Examples 6-1, 7-1, and Example 6-A prepared by using the transition metal compounds of Examples 6-1, 7-1, and 10-1, which are examples of the transition metal compounds of the present invention, The polymers of A, and 10-A exhibited a low melt index (MI) of 0.02 or less, showing a high molecular weight, and a density of 0.883 g / cc or less. In particular, the polymers of Examples 6-A and 10-A prepared using the transition metal compounds of Examples 6-1 and 10-1 have a low melt index (MI) of less than 0.02 with a low density of 0.873 g / cc or less. ) And low density and high molecular weight.

Claims (11)

  1. 하기 화학식 1로 표시되는 리간드 화합물:Ligand compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2017001503-appb-I000088
    Figure PCTKR2017001503-appb-I000088
    상기 화학식 1에서, R1 내지 R9는 각각 독립적으로 수소, 실릴, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 탄소수 7 내지 20의 아릴알킬, 또는 탄소수 1 내지 20의 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이고; 상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며; 상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있고; n은 1 또는 2이다. In Formula 1, R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and having 7 carbon atoms. A metalloid radical of group 14 metal substituted with arylalkyl of 20 to 20, or hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2.
  2. 제 1 항에 있어서, The method of claim 1,
    상기 화학식 1에서, R1 내지 R9는 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 또는 탄소수 7 내지 20의 아릴알킬이고; 상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며; 상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있는, 리간드 화합물.In Formula 1, R 1 to R 9 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
  3. 제 1 항에 있어서, The method of claim 1,
    상기 화학식 1의 화합물은 하기 화합물 중 어느 하나인 리간드 화합물:The compound of Formula 1 is any one of the following compounds:
    [화학식 1a][Formula 1a]
    Figure PCTKR2017001503-appb-I000089
    Figure PCTKR2017001503-appb-I000089
    [화학식 1b][Formula 1b]
    Figure PCTKR2017001503-appb-I000090
    Figure PCTKR2017001503-appb-I000090
    [화학식 1c][Formula 1c]
    Figure PCTKR2017001503-appb-I000091
    Figure PCTKR2017001503-appb-I000091
    [화학식 1d][Formula 1d]
    Figure PCTKR2017001503-appb-I000092
    Figure PCTKR2017001503-appb-I000092
    [화학식 1e][Formula 1e]
    Figure PCTKR2017001503-appb-I000093
    Figure PCTKR2017001503-appb-I000093
    [화학식 1f][Formula 1f]
    Figure PCTKR2017001503-appb-I000094
    Figure PCTKR2017001503-appb-I000094
    [화학식 1g][Formula 1g]
    Figure PCTKR2017001503-appb-I000095
    Figure PCTKR2017001503-appb-I000095
    [화학식 1h][Formula 1h]
    Figure PCTKR2017001503-appb-I000096
    Figure PCTKR2017001503-appb-I000096
    [화학식 1i]Formula 1i]
    Figure PCTKR2017001503-appb-I000097
    Figure PCTKR2017001503-appb-I000097
    [화학식 1j][Formula 1j]
    Figure PCTKR2017001503-appb-I000098
    Figure PCTKR2017001503-appb-I000098
    [화학식 1k][Formula 1k]
    Figure PCTKR2017001503-appb-I000099
    .
    Figure PCTKR2017001503-appb-I000099
    .
  4. 하기 화학식 2로 표시되는 전이금속 화합물:A transition metal compound represented by the following formula (2):
    [화학식 2][Formula 2]
    Figure PCTKR2017001503-appb-I000100
    Figure PCTKR2017001503-appb-I000100
    상기 화학식 2에서, In Chemical Formula 2,
    R1 내지 R9는 각각 독립적으로 수소, 실릴, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 탄소수 7 내지 20의 아릴알킬, 또는 탄소수 1 내지 20의 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이고; R 1 to R 9 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms;
    상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며; 상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있고; n은 1 또는 2이고; Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2;
    Q1 및 Q2는 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 6 내지 20의 아릴, 탄소수 6 내지 20의 알킬아릴, 탄소수 7 내지 20의 아릴알킬, 탄소수 1 내지 20의 알킬 아미도, 탄소수 6 내지 20의 아릴 아미도, 또는 탄소수 1 내지 20의 알킬리덴이며; Q 1 and Q 2 are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, and carbon atoms. Alkyl amido of 1 to 20, aryl amido of 6 to 20 carbon atoms, or alkylidene of 1 to 20 carbon atoms;
    M은 Ti, Zr 또는 Hf이다.M is Ti, Zr or Hf.
  5. 제 4 항에 있어서, The method of claim 4, wherein
    상기 화학식 2에서, Q1 및 Q2는 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 6 내지 20의 아릴, 탄소수 6 내지 20의 알킬아릴, 또는 탄소수 7 내지 20의 아릴알킬인, 전이금속 화합물.In Formula 2, Q1 and Q2 are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms. compound.
  6. 제 4 항에 있어서, The method of claim 4, wherein
    상기 R1 내지 R9는 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 또는 탄소수 7 내지 20의 아릴알킬이고; R 1 to R 9 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms;
    상기 R1 내지 R8 중 서로 인접하는 2 이상은 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며;Two or more adjacent to each other of R 1 to R 8 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms;
    상기 지방족 고리 또는 방향족 고리는 할로겐, 탄소수 1 내지 20의 알킬, 또는 탄소수 6 내지 20의 아릴로 치환될 수 있는, 전이금속 화합물.The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
  7. 제 4 항에 있어서, The method of claim 4, wherein
    상기 화학식 2의 화합물은 하기 화합물 중 어느 하나인 전이금속 화합물:Compound of Formula 2 is a transition metal compound of any one of the following compounds:
    [화학식 2a][Formula 2a]
    Figure PCTKR2017001503-appb-I000101
    Figure PCTKR2017001503-appb-I000101
    [화학식 2b][Formula 2b]
    Figure PCTKR2017001503-appb-I000102
    Figure PCTKR2017001503-appb-I000102
    [화학식 2c][Formula 2c]
    Figure PCTKR2017001503-appb-I000103
    Figure PCTKR2017001503-appb-I000103
    [화학식 2d][Formula 2d]
    Figure PCTKR2017001503-appb-I000104
    Figure PCTKR2017001503-appb-I000104
    [화학식 2e][Formula 2e]
    Figure PCTKR2017001503-appb-I000105
    Figure PCTKR2017001503-appb-I000105
    [화학식 2f][Formula 2f]
    Figure PCTKR2017001503-appb-I000106
    Figure PCTKR2017001503-appb-I000106
    [화학식 2g][Formula 2g]
    Figure PCTKR2017001503-appb-I000107
    Figure PCTKR2017001503-appb-I000107
    [화학식 2h][Formula 2h]
    Figure PCTKR2017001503-appb-I000108
    Figure PCTKR2017001503-appb-I000108
    [화학식 2i][Formula 2i]
    Figure PCTKR2017001503-appb-I000109
    Figure PCTKR2017001503-appb-I000109
    [화학식 2j][Formula 2j]
    Figure PCTKR2017001503-appb-I000110
    Figure PCTKR2017001503-appb-I000110
    [화학식 2k][Formula 2k]
    Figure PCTKR2017001503-appb-I000111
    Figure PCTKR2017001503-appb-I000111
    [화학식 2l][Formula 2l]
    *
    Figure PCTKR2017001503-appb-I000112
    *
    Figure PCTKR2017001503-appb-I000112
    [화학식 2m][Formula 2m]
    Figure PCTKR2017001503-appb-I000113
    Figure PCTKR2017001503-appb-I000113
    [화학식 2n][Formula 2n]
    Figure PCTKR2017001503-appb-I000114
    Figure PCTKR2017001503-appb-I000114
    [화학식 2o][Formula 2o]
    Figure PCTKR2017001503-appb-I000115
    Figure PCTKR2017001503-appb-I000115
    [화학식 2p][Formula 2p]
    Figure PCTKR2017001503-appb-I000116
    Figure PCTKR2017001503-appb-I000116
    [화학식 2q][Formula 2q]
    Figure PCTKR2017001503-appb-I000117
    Figure PCTKR2017001503-appb-I000117
    [화학식 2r][Formula 2r]
    Figure PCTKR2017001503-appb-I000118
    Figure PCTKR2017001503-appb-I000118
    [화학식 2s][Formula 2s]
    Figure PCTKR2017001503-appb-I000119
    Figure PCTKR2017001503-appb-I000119
    [화학식 2t][Formula 2t]
    Figure PCTKR2017001503-appb-I000120
    Figure PCTKR2017001503-appb-I000120
    [화학식 2u][Formula 2u]
    Figure PCTKR2017001503-appb-I000121
    Figure PCTKR2017001503-appb-I000121
    [화학식 2v][Formula 2v]
    Figure PCTKR2017001503-appb-I000122
    .
    Figure PCTKR2017001503-appb-I000122
    .
    상기 화학식에서 Me는 메틸을 나타낸다.Me in the above formula represents methyl.
  8. 제 4 항에 따른 전이금속 화합물을 포함하는 촉매 조성물. Catalyst composition comprising the transition metal compound according to claim 4.
  9. 제 8 항에 따른 촉매 조성물이 담체에 담지된 담지 촉매. A supported catalyst on which the catalyst composition according to claim 8 is supported on a carrier.
  10. 제 8 항에 따른 촉매 조성물을 이용하여 제조된 중합체.A polymer prepared using the catalyst composition according to claim 8.
  11. 제 10 항에 있어서,The method of claim 10,
    상기 중합체는 폴리올레핀계 중합체인 것을 특징으로 하는 중합체.Wherein said polymer is a polyolefin-based polymer.
PCT/KR2017/001503 2016-02-12 2017-02-10 Novel ligand compound and transition metal compound WO2017138783A1 (en)

Priority Applications (4)

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US15/749,309 US10538603B2 (en) 2016-02-12 2017-02-10 Ligand compound and transition metal compound
CN201780002867.2A CN107922382B (en) 2016-02-12 2017-02-10 Novel ligand compound and transition metal compound
EP17750475.0A EP3318560B1 (en) 2016-02-12 2017-02-10 Novel ligand compound and transition metal compound
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KR20060058679A (en) * 2003-07-14 2006-05-30 에퀴스타 케미칼즈, 엘피 Olefin polymerization with pyridine moiety-containing singe-site catalysts
KR20080101542A (en) * 2007-05-18 2008-11-21 주식회사 엘지화학 Method for preparing olefin polymer using transition metal catalyst having better copolymerization
KR20100024963A (en) * 2007-06-26 2010-03-08 사노피-아벤티스 A transition metal catalyzed synthesis of 2h-indazoles
KR20130089490A (en) * 2012-02-02 2013-08-12 에스케이이노베이션 주식회사 NEW TRANSITION METAL COMPLEX HAVING QUINOLIN-1(2H)-YL GROUP AND CATALYST COMPOSITION CONTAINING THE SAME FOR OLEFIN POLYMERIZATION, AND METHODS FOR PREPARING ETHYLENE HOMOPOLYMERS OR COPOLYMERS OF ETHYLENE AND α-OLEFINS USING THE SAME

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US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
KR19990007920A (en) * 1995-04-17 1999-01-25 폰테놋 제이 릭 Transition metal catalysts based on bidentate ligands containing pyridine or quinoline residues
KR20060058679A (en) * 2003-07-14 2006-05-30 에퀴스타 케미칼즈, 엘피 Olefin polymerization with pyridine moiety-containing singe-site catalysts
KR20080101542A (en) * 2007-05-18 2008-11-21 주식회사 엘지화학 Method for preparing olefin polymer using transition metal catalyst having better copolymerization
KR20100024963A (en) * 2007-06-26 2010-03-08 사노피-아벤티스 A transition metal catalyzed synthesis of 2h-indazoles
KR20130089490A (en) * 2012-02-02 2013-08-12 에스케이이노베이션 주식회사 NEW TRANSITION METAL COMPLEX HAVING QUINOLIN-1(2H)-YL GROUP AND CATALYST COMPOSITION CONTAINING THE SAME FOR OLEFIN POLYMERIZATION, AND METHODS FOR PREPARING ETHYLENE HOMOPOLYMERS OR COPOLYMERS OF ETHYLENE AND α-OLEFINS USING THE SAME

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