WO2017138783A1 - Nouveau composé ligand et composé de métal de transition - Google Patents

Nouveau composé ligand et composé de métal de transition 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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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/ko
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/zh
Priority to EP17750475.0A priority patent/EP3318560B1/fr
Publication of WO2017138783A1 publication Critical patent/WO2017138783A1/fr
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

La présente invention décrit un nouveau composé ligand représenté par la formule chimique 1, et un nouveau composé métal de transition représenté par la formule chimique 2. Selon la présente invention, le nouveau composé ligand et le nouveau composé métal de transition possèdent un effet d'incorporation élevé de comonomère sur la préparation d'un polymère à base d'oléfine possédant un poids moléculaire élevé tout en possédant une faible densité, étant ainsi utilisables comme catalyseur servant à une réaction de polymérisation.
PCT/KR2017/001503 2016-02-12 2017-02-10 Nouveau composé ligand et composé de métal de transition WO2017138783A1 (fr)

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CN201780002867.2A CN107922382B (zh) 2016-02-12 2017-02-10 新型配体化合物和过渡金属化合物
EP17750475.0A EP3318560B1 (fr) 2016-02-12 2017-02-10 Nouveau composé ligand et composé de métal de transition
US16/698,047 US10723818B2 (en) 2016-02-12 2019-11-27 Compound and transition metal compound

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
KR19990007920A (ko) * 1995-04-17 1999-01-25 폰테놋 제이 릭 피리딘 또는 퀴놀린 잔기를 함유하는 비덴테이트 리간드 기본의 전이금속 촉매
KR20060058679A (ko) * 2003-07-14 2006-05-30 에퀴스타 케미칼즈, 엘피 피리딘 부분-함유 단일-부위 촉매를 이용한 올레핀 중합
KR20080101542A (ko) * 2007-05-18 2008-11-21 주식회사 엘지화학 공중합성이 뛰어난 전이금속 촉매를 이용한 올레핀중합체의 제조 방법
KR20100024963A (ko) * 2007-06-26 2010-03-08 사노피-아벤티스 2ｈ-인다졸의 전이금속 촉매화 합성
KR20130089490A (ko) * 2012-02-02 2013-08-12 에스케이이노베이션 주식회사 퀴놀린-1(2Ｈ)-일기를 갖는 새로운 전이금속 화합물, 이를 포함한 올레핀 중합용 전이금속 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
KR19990007920A (ko) * 1995-04-17 1999-01-25 폰테놋 제이 릭 피리딘 또는 퀴놀린 잔기를 함유하는 비덴테이트 리간드 기본의 전이금속 촉매
KR20060058679A (ko) * 2003-07-14 2006-05-30 에퀴스타 케미칼즈, 엘피 피리딘 부분-함유 단일-부위 촉매를 이용한 올레핀 중합
KR20080101542A (ko) * 2007-05-18 2008-11-21 주식회사 엘지화학 공중합성이 뛰어난 전이금속 촉매를 이용한 올레핀중합체의 제조 방법
KR20100024963A (ko) * 2007-06-26 2010-03-08 사노피-아벤티스 2ｈ-인다졸의 전이금속 촉매화 합성
KR20130089490A (ko) * 2012-02-02 2013-08-12 에스케이이노베이션 주식회사 퀴놀린-1(2Ｈ)-일기를 갖는 새로운 전이금속 화합물, 이를 포함한 올레핀 중합용 전이금속 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법

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