KR20170110400A - Novel transition metal compound and preparing method for polymer using the same - Google Patents

Abstract

The present invention relates to a novel transition metal compound into which a heteroaromatic ligand represented by the general formula (1) is introduced, and a process for preparing a polymer using the novel transition metal compound. The novel transition metal compound according to the present invention can be prepared by controlling the steric effect of a heteroatomic ligand Since polymers having excellent physical properties can be produced, they can be usefully used as catalysts for polymerization.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel transition metal compound having a heteroaromatic ligand and a method for producing a polymer using the same. BACKGROUND ART [0002]

The present invention relates to a novel transition metal compound into which a heteroaromatic ligand is introduced and a process for producing a polymer using the same. More particularly, the present invention relates to a heteroaromatic ligand capable of producing a polymer having excellent physical properties by controlling the steric effect of a heteroatomic ligand A transition metal compound catalyst into which an aromatic ligand is introduced, and a process for producing a polymer using the same.

Dow, in the early 1990s, [Me ₂ Si (Me ₄ C ₅ ) N t Bu] TiCl ₂ (U.S. Patent No. 5,064,802) discloses that the CGC is superior to conventional metallocene catalysts in the copolymerization reaction of ethylene and alpha-olefins (hereinafter referred to as " Constrained-Geometry Catalyst " (1) high molecular weight polymers exhibiting high activity even at high polymerization temperatures; (2) alpha-olefins with high steric hindrance such as 1-hexene and 1-octene; The copolymerization is also excellent. In addition, various characteristics of CGC were gradually known during the polymerization reaction, and efforts to synthesize the derivative and use it as a polymerization catalyst have actively been made in academia and industry.

One approach has been attempted to synthesize and polymerize metal compounds in which various other bridges and nitrogen substituents have been introduced instead of silicon bridges. Representative metal compounds known until recently are as follows (Chem. Rev. 2003, 103, 283).

(1), ethylene or propylene (2), methylidene (3), and methylene (4) bridges were introduced in place of the silicon bridge of the CGC structure, Or in the case of copolymerization with an alpha-olefin, no improvement in terms of activity or copolymerization performance versus CGC was obtained.

In addition, as another approach, a large amount of compounds composed of oxydolides were synthesized instead of the amido ligands of CGC, and some polymerization using the compounds was attempted. The examples are summarized as follows.

Compound (5) is reported by T. J. Marks et al. In which Cp (cyclopentadiene) derivatives and oxydolides are crosslinked by ortho-phenylene groups (Organometallics 1997, 16, 5958). Compounds having the same cross-linking and polymerization using them have also been reported by Mu et al. (Organometallics 2004, 23, 540). Also, Rothwell et al. (Chem. Commun. 2003, 1034) have reported that an indenyl ligand and an oxydol ligand are bridged by the same ortho-phenylene group. Compound (6) is reported by Whitby et al. (Organometallics 1999, 18, 348) in which a cyclopentenylidene ligand and an oxydoligand are bridged by three carbon atoms (Syndiotactic ) Was reported to exhibit activity in polystyrene polymerization. Similar compounds have also been reported by Hessen et al. (Organometallics 1998, 17, 1652). Compound (7) is reported by Rau et al. And is characterized in that it exhibits activity in ethylene polymerization and ethylene / 1-hexene copolymerization at high temperature and high pressure (210 ° C., 150 MPa) (J. Organomet. . Then, the catalyst synthesis (8) having similar structure and the high temperature and high pressure polymerization using the same were patented by Sumitomo Co. (US Patent No. 6,548,686). However, among the above attempts, only a few catalysts have actually been applied to commercial plants. Therefore, a catalyst showing improved polymerization performance is required, and a method of simply producing such catalysts is required.

US Patent No. 5,064,802 US Patent No. 6,548,686

Chem. Rev. 2003, 103, 283 Organometallics 1997, 16, 5958 Organometallics 2004, 23, 540 Chem. Commun. 2003, 1034 Organometallics 1999, 18, 348 Organometallics 1998, 17, 1652 J. Organomet. Chem. 2000, 608, 71

A problem to be solved by the present invention is to provide a novel transition metal compound.

Another object of the present invention is to provide a method for producing the transition metal compound.

Another object of the present invention is to provide a catalyst composition comprising the transition metal compound.

Another object of the present invention is to provide a method for producing a polymer using the catalyst composition, and a polymer produced using the catalyst composition.

In order to solve the above problems,

There is provided a transition metal compound represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₁₃ are each independently hydrogen, halogen, silyl, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, ≪ / RTI >

X and Y are each independently C (R _14), N, O, or S, wherein said R ₁₄ is hydrogen, halogen, silyl, alkenyl having 1 to 20 carbon alkyl, having 2 to 20, C 6 -C An aryl of 20 to 20 carbon atoms, an alkylaryl of 7 to 20 carbon atoms, or an arylalkyl of 7 to 20 carbon atoms;

n is 0 or 1;

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 , Alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;

M is Ti, Zr or Hf.

Further, in order to solve the above-mentioned other problems,

(1) reacting a compound of formula (2) with a compound of formula (3) to produce a compound of formula (4); And

(2) reacting a compound of the following formula (4) with a compound of the following formula (5) to prepare a compound of the formula

≪ / RTI > wherein: < RTI ID = 0.0 >

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas,

R ₁ to R ₁₃ , X, Y, n, Q _1, and Q ₂ are as defined in Formula 1, respectively.

Further, in order to solve the above-mentioned problems, the present invention provides a catalyst composition comprising a transition metal compound.

According to another aspect of the present invention, there is provided a method for producing a polymer using the catalyst composition, and a polymer produced using the catalyst composition, wherein the polymer has an MI of 0.01 to 0.4 and a Mw of 100,000 to 1,000,000 And provides a polymer having a density of less than 0.91 g / cc.

The novel transition metal compound according to the present invention can be used as a catalyst of a polymerization reaction because a polymer having excellent physical properties can be prepared by controlling the steric effect of a heteroatom ligand.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The transition metal compound of the present invention is represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₁₃ are each independently hydrogen, halogen, silyl, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, ≪ / RTI >

X and Y are each independently C (R _14), N, O, or S, wherein said R ₁₄ is hydrogen, halogen, silyl, alkenyl having 1 to 20 carbon alkyl, having 2 to 20, C 6 -C An aryl of 20 to 20 carbon atoms, an alkylaryl of 7 to 20 carbon atoms, or an arylalkyl of 7 to 20 carbon atoms;

n is 0 or 1;

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 , Alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;

M is Ti, Zr or Hf.

In Formula 1, Q ₁ and Q ₂ are each independently selected from the group consisting of hydrogen, halogen, alkyl having 1 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 Lt; / RTI >

Each of R ₁ to R ₈ and R ₁₄ 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;

Each of R ₉ to R ₁₃ 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.

In one embodiment of the present invention, the transition metal compound of Formula 1 may be any one of the following compounds:

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

[Formula 1g]

.

.

Each of the substituents defined in the present specification will be described in detail as follows.

The term " halogen ", as used herein, unless otherwise indicated, means fluorine, chlorine, bromine or iodine.

The term " alkyl ", as used herein, unless otherwise indicated, means a linear or branched hydrocarbon residue.

The term " alkenyl ", as used herein, unless otherwise indicated, means a straight chain or branched chain alkenyl group.

Wherein the branched chain is selected from the group consisting of alkyl of 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.

According to one embodiment of the present invention, the silyl group is selected from the group consisting of trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, Silyl) silyl, and the like, but are not limited to these examples.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like.

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 (or heterocyclic group) means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 carbon atoms and containing at least one hetero atom, and may be a single ring or a condensed ring of two or more rings. The heterocyclic group may be substituted or unsubstituted with an alkyl group. Examples thereof include indoline, tetrahydroquinoline and the like, but the present invention is not limited thereto.

The alkylamino group means an amino group substituted by the alkyl group, and includes, but is not limited to, dimethylamino group, diethylamino group, and the like.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl and the like, no.

The transition metal compound of the present invention may be prepared by reacting a compound of the following formula (2) with a compound of the following formula (3) 4 < / RTI >; And (2) reacting a compound of the following formula (4) with a compound of the following formula (5) to prepare a compound of the formula (1).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas,

R ₁ to R ₁₃ , X, Y, n, Q _1, and Q ₂ are as defined in Formula 1, respectively.

(1) reacting a compound of formula (2) with a compound of formula (3) to prepare a compound of formula

The reaction of step (1) may be carried out by gradually adding the compound of formula (3) to the compound of formula (2) and then stirring.

The compound of formula (2) may be first mixed in a separate solvent, wherein the solvent may be an organic solvent such as toluene.

The temperature at which the compound of Formula 3 is added may be -120 ° C to 0 ° C, specifically, -80 ° C to -20 ° C. When the compound of Formula 3 is added to the compound of Formula 2 in the temperature range The reaction may be carried out by slowly raising the temperature to room temperature and then stirring the mixture for 1 to 24 hours, specifically 6 to 18 hours.

When the reaction is completed, quenching can be performed with NH ₄ Cl or the like.

(2) reacting the compound of formula (4) with the compound of formula (5) to produce a compound of formula

In the step (2), the transition metal compound of Formula 1 is prepared by reacting the compound of Formula 4 and the compound of Formula 5, which are the ligands prepared through the above step (1).

The reaction of step (2) may be carried out by gradually adding the compound of formula (5) to the compound of formula (4) and then stirring.

The compound of formula (4) and the compound of formula (5) may each be preferentially mixed in a separate solvent, wherein the solvent may be an organic solvent such as toluene.

The temperature at which the compound of Formula 5 is added may be -120 ° C to 0 ° C, specifically, -80 ° C to -20 ° C. After the process of adding the compound of Formula 5 to the compound of Formula 4 is completed in the temperature range The reaction may be carried out by slowly raising the temperature to room temperature and then stirring the mixture for 1 to 24 hours, specifically 6 to 18 hours.

When the reaction is completed, the solvent may be removed by evaporation or the like.

In this case, the compound of formula (5) can be prepared by the following method.

The present invention also provides a catalyst composition comprising the transition metal compound.

The transition metal compound according to the present invention may be used alone or in the form of a composition further comprising at least one of the promoter compounds represented by the following general formulas (6), (7) and (8) Can be used.

[Chemical Formula 6]

- [Al (R ₁₅ ) -O] _a -

In Formula (6), R ₁₅ is independently selected from the group consisting of a halogen radical; A hydrocarbyl radical having from 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;

(7)

D (R _{15) 3}

In Formula 7, D is aluminum or boron; R ₁₅ are each independently a halogen radical; A hydrocarbyl radical having from 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;

[Chemical Formula 8]

^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

Wherein L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is independently an aryl having 6 to 20 carbon atoms or an alkyl having 1 to 20 carbon atoms in which at least one hydrogen atom may be substituted with a substituent; The substituent is halogen, hydrocarbyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, or aryloxy of 6 to 20 carbon atoms.

Examples of the compound represented by the formula (6) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like. A more preferred compound is methyl aluminoxane.

Examples of the compound represented by Formula 7 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, 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 8 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (p-dimethylphenyl) boron, tributylammonium tetra (ptrifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N -Diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, dimethyl Anilinium tetrakis (pentafluorophenyl) borate, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, Trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributyl (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (ptrifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylaniliniumtetraphenylaluminum, N, N - diethyl anilinium tetrapentafluorophenyl aluminum, diethyl ammonium tetrapentatetraprapaluminum aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) boron, triethyl Ammonium tetra (o, p-dimethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron or triphenylcarbamoyl Tetra-pentafluoropropane, and the like phenylboronic.

Specifically, aluminoxane can be used, and more specifically, methylaluminoxane (MAO), which is an alkylaluminoxane, can be used.

The catalyst composition comprises, as a first method, 1) contacting a transition metal compound represented by Formula 1 and a compound represented by Formula 6 or 7 to obtain a mixture; And 2) adding the compound represented by Formula 8 to the mixture.

Also, the catalyst composition may be prepared by a method of contacting the transition metal compound represented by Formula 1 and the compound represented by Formula 6 as a second method.

In the first method of the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 6 or Formula 7 is preferably 1 / 5,000 to 1/2, Preferably 1 / 1,000 to 1/10, and most preferably 1/500 to 1/20. When the molar ratio of the transition metal compound represented by the formula (1) / the compound represented by the formula (6) or the formula (7) is more than 1/2, the amount of the alkylating agent is so small that the alkylation of the metal compound can not proceed completely If the molar ratio is less than 1 / 5,000, alkylation of the metal compound occurs, but there is a problem that the alkylated metal compound can not be completely activated due to the side reaction between the remaining excess alkylating agent and the activating agent, . The molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 8 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1/5 Lt; / RTI > When the molar ratio of the transition metal compound represented by the formula (1) / the compound represented by the formula (8) is more than 1, the activation of the metal compound is not completely achieved due to the relatively small amount of the activator, If the molar ratio is less than 1/25, the activation of the metal compound is completely performed. However, there is a problem that the unit cost of the catalyst composition is not economical due to the excess activator remaining or the purity of the produced polymer is low.

In the second method of the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 6 is preferably 1 / 10,000 to 1/10, more preferably 1 / 5,000 to 1/100, and most preferably 1/3000 to 1/500. When the molar ratio is more than 1/10, the amount of the activator is relatively small and the activation of the metal compound is not achieved completely. Therefore, there is a problem in that the activity of the catalyst composition is decreased. Although the activation is completely performed, there is a problem that the unit cost of the catalyst composition is not economical due to the excess activator remaining or the purity of the produced polymer is low.

The catalyst composition may further include a reaction solvent. As the reaction solvent, a hydrocarbon-based solvent such as pentane, hexane, heptane or the like, or an aromatic solvent such as benzene, toluene or the like may be used.

In addition, the catalyst composition may contain the transition metal compound and the cocatalyst compound in the form of being carried on a carrier.

The present invention also provides a process for producing a polymer using the catalyst composition.

Specifically, the polymerization reaction for polymerizing olefinic monomers in the presence of the catalyst composition comprising the transition metal compound can be carried out by a solution polymerization process, a continuous polymerization process, a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor, Slurry process or gas phase process. Further, homopolymerization with one olefin monomer or copolymerization with two or more kinds of monomers can be carried out.

The polymerization of the polyolefin may be carried out by reacting at a temperature of from about 25 ° C to about 500 ° C and from about 1 to about 100 kgf / cm ² .

In particular, the polymerization of the polyolefin may be carried out at a temperature of from about 25 to about 500 캜, preferably from about 25 to 200 캜, more preferably from about 50 to 100 캜. The reaction pressure can also be carried out at from about 1 to about 100 kgf / cm ² , preferably from about 1 to about 50 kgf / cm ² , and more preferably from about 5 to about 40 kgf / cm ² .

Examples of the polymerizable olefin-based monomer using the transition metal compound and the cocatalyst according to an embodiment of the present invention include ethylene, alpha-olefin, cyclic olefin, etc., and diene olefins having two or more double bonds Based monomers or triene olefin-based monomers can also be polymerized.

Specific examples of the olefin-based monomer in the polyolefin produced according to the present invention include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-undecene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aidocene and the like, or a copolymer obtained by copolymerizing two or more of these.

The polyolefin may be a propylene polymer, but is not limited thereto.

The polymer may be either a homopolymer or a copolymer. When the olefin polymer is a copolymer of ethylene and other comonomers, the monomers constituting the copolymer are preferably selected from the group consisting of ethylene and propylene, 1-butene, 1-hexene, and 4-methyl- Is at least one comonomer selected from the group consisting of < RTI ID = 0.0 >

The polymer produced by the process of the present invention may have a density of less than 0.91 g / cc, specifically less than 0.89 g / cc, and more specifically less than 0.885 g / cc.

In addition, the polymer prepared by the production method of the present invention may have Mw of 100,000 or more, specifically 100,000 to 1,000,000.

Meanwhile, the polymer produced by the production method of the present invention may have a melt index (Melt Index) (MI) of 0.4 or less, specifically 0.01 to 0.3, and more specifically 0.01 to 0.2.

Polymers prepared according to one example of the present invention may have a MI of 0.01 to 0.4, Mw of 100,000 to 1,000,000, and a density of less than 0.91 g / cc.

In addition, the polymer produced by the production process of the present invention may have two melting temperatures (Tm) obtained from the DSC curve (Tm1 and Tm2), and in this case, since the crystals melt and crystallize at different temperatures, The mechanical strength can be increased.

At this time, the polymer produced by the production method according to an example of the present invention has a Tm1 in the range of -30 to 90 占 폚 in the range of the density of 0.85 to 0.91 g / cc and a Tm2 in the range of -10 to 120 占 폚 .

Tm used herein means the temperature at the peak of each peak in the temperature-heat flow graph of a differential scanning calorimeter (DSC).

In addition, the polymer produced by the production method according to an example of the present invention may have two crystallization temperatures (Tc) obtained in the DSC curve (Tc1 and Tc2), and in this case, the crystals melt and crystallize at different temperatures Thermal stability and mechanical strength can be increased.

In the present specification, the crystallization temperature means a temperature at which crystallization occurs in which the arrangement of the material structure irregularly changes in a regular manner by the attraction between molecules / atoms, and can be analyzed through, for example, differential scanning calorimetry (DSC) .

The polymer produced by the production method according to an example of the present invention may have a Tc1 ranging from 20 to 75 占 폚 and a Tc2 ranging from 50 to 95 占 폚 in the range of density of 0.85 to 0.91 g / cc.

Hereinafter, preferred embodiments of the present invention will be described to facilitate understanding of the present invention. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

Synthesis of ligands and transition metal compounds

Organic reagents and solvents were purchased from Aldrich unless otherwise noted and purified by standard methods. At every stage of the synthesis, the contact between air and moisture was blocked to improve the reproducibility of the experiment. Spectra and schematics were obtained using 500 MHz nuclear magnetic resonance (NMR) to verify the structure of the compounds.

≪ Preparation Example : Preparation of ligand >

Manufacturing example  One : Phenyl (4-methylpyridin-2-yl) methanimine  Produce

PhMgBr (4.6 mmol, 1.1 eq) was slowly added dropwise to a solution of 2-cyano-4-methylpyridine (500 mg, 4.23 mmol) in 10 mL of toluene at -40 ° C. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. 20 mL of an aqueous solution of NH ₄ Cl / H ₂ O was poured, the organic solvent was extracted, and water was removed with Na ₂ SO ₄ . Yellow oil was obtained in a yield of 490 mg, 60% through a silica gel column.

^{_{1 H NMR (C 6 D 6}} ): δ 1.73 (S, 3H CH3), 6.51 ~ 6.52 (d, 1H aromatic), 7.15 (s, 3H aromatic), 7.79 (s, 1H aromatic), 8.26 ~ 8.27 (d , 1H aromatic), 8.36-8.38 (d, 2H aromatic).

Manufacturing example  2: Preparation of phenyl (3,5-difluoropyridin-2-yl) methanimine

PhMgBr (3.69 mmol, 1.0 eq) was slowly added dropwise at -40 ° C to a solution of 3,5-difluoropyridine-2-carbonitrile (517 mg, 3.69 mmol) in 10 mL of toluene. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. 20 mL of an aqueous solution of NH ₄ Cl / H ₂ O was poured, the organic solvent was extracted, and water was removed with Na ₂ SO ₄ . A yellow oil was obtained through a silica gel column at a yield of 439 mg, 60%.

^{_{1 H NMR (C 6 D 6}} ): δ 6.20 ~ 6.24 (t, 1H aromatic), 7.01 ~ 7.04 (t, 2H aromatic), 7.09 ~ 7.12 (t, 2H aromatic), 7.78 (s, 1H aromatic), 7.89 ~ 7.91 (d, 2H aromatic).

Manufacturing example  3: Phenyl (pyrimidin-2-yl) methanimine  Produce

PhMgBr (4.73 mmol, 1.0 eq) was slowly added dropwise to a solution of 2-pyrimidinecarbonitrile (498 mg, 4.73 mmol) in 10 mL of toluene at -40 ° C. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. 20 mL of an aqueous solution of NH ₄ Cl / H ₂ O was poured, the organic solvent was extracted, and water was removed with Na ₂ SO ₄ . A yellow oil was obtained through a silica gel column at a yield of 519 mg, 60%.

^{_{1 H NMR (C 6 D 6}} ): δ 6.08 (s, 1H aromatic), 7.19 ~ 7.22 (t, 3H aromatic), 8.01 ~ 8.02 (d, 2H aromatic), 8.22 (s, 2H aromatic), 12.06 (s , 1H aromatic).

Manufacturing example  4 : Phenyl (3,5-dichloropyridin-2-yl) methanimine  Produce

PhMgBr (3.69 mmol, 1.0 eq) was slowly added dropwise at -40 ° C to a solution of 3,5-difluoropyridine-2-carbonitrile (517 mg, 3.69 mmol) in 10 mL of toluene. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. 20 mL of an aqueous solution of NH ₄ Cl / H ₂ O was poured, the organic solvent was extracted, and water was removed with Na ₂ SO ₄ . A yellow oil was obtained through a silica gel column at a yield of 519 mg, 60%.

^{_{1 H NMR (C 6 D 6}} ): δ 6.20 ~ 6.24 (t, 1H aromatic), 7.01 ~ 7.04 (t, 2H aromatic), 7.09 ~ 7.12 (t, 2H aromatic), 7.78 (s, 1H aromatic), 7.89 ~ 7.91 (d, 2H aromatic).

Manufacturing example  5: Phenyl (4-phenylpyridin-2-yl) methanimine  Produce

PhMgBr (5.82 mmol, 1.05 eq) was slowly added dropwise to a solution of 4-phenylpyridine-2-carbonitrile (1.0 g, 5.54 mmol) in 10 mL of toluene at -40 ° C. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. 20 mL of an aqueous solution of NH ₄ Cl / H ₂ O was poured, the organic solvent was extracted, and water was removed with Na ₂ SO ₄ . A yellow oil was obtained through silica gel column at 857 mg, 60% yield.

^{_{1 H NMR (C 6 D 6}} ): δ 7.01 ~ 7.02 (d, 1H aromatic), 7.08 ~ 7.09 (t, 3H aromatic), 7.13 ~ 7.15 (m, 3H aromatic), 7.21 ~ 7.22 (m, 2H aromatic) , 8.30-8.31 (s, 1H aromatic), 8.34-8.36 (t, 3H aromatic).

Manufacturing example  6: Phenyl (thiophen-2-yl) methanimine  Produce

PhMgBr (13.74 mmol, 1.5 eq) was slowly added dropwise to a solution of 2-cyanothiophene (1 g, 9.16 mmol) in 4 mL of toluene at -78 ° C. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. 50 mL of an aqueous NH ₄ Cl / H ₂ O solution was injected, and then the organic solvent was extracted and the water was removed with Na ₂ SO ₄ . A yellow solid was obtained via silica gel column with 1.16 g, 68% yield.

^{_{1 H NMR (C 6 D 6}} ): δ 6.53 (S, 1H aromatic), 6.91 ~ 6.92 (d, 1H aromatic), 7.00 ~ 7.03 (t, 2H aromatic), 7.09 ~ 7.12 (t, 1H aromatic), 7.21 (s, 1H aromatic), 7.69-7.70 (d, 2H aromatic).

Manufacturing example  7: (3,4- Dichlorophenyl ) ( Furan -2 days) Methane-imine  Produce

3,4-Dichloro PhMgBr (2 mmol, 1 eq) was slowly added dropwise to a solution of 2-cyanofuran (186.16 mg, 2 mmol) in 2 mL of toluene at -78 ° C. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. 50 mL of an aqueous NH ₄ Cl / H ₂ O solution was injected, and then the organic solvent was extracted and the water was removed with Na ₂ SO ₄ . A white solid was obtained through a silica gel column with a yield of 240 Mg, 98%.

^{_{1 H NMR (C 6 D 6}} ): δ 5.81 ~ 5.82 (d, 1H aromatic), 6.79 ~ 6.80 (d, 1H aromatic), 6.84 ~ 6.85 (d, 1H aromatic), 6.91 ~ 6.92 (d, 1H aromatic) , 7.42-7.44 (d, 1H aromatic), 7.90-7.91 (d, 1H aromatic).

< Example  : Preparation of transition metal compound &gt;

Example  One

To a solution of phenyl (4-methylpyridin-2-yl) methanimine (86 mg, 0.438 mmol), which is the ligand prepared in Preparation Example 1, in 5 mL of toluene was added Cp ^* TiMe ₃ (100 mg, 0.438 mmol) in 5 mL of toluene was slowly added dropwise. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. The toluene was evaporated, filtered through a celite filter, and then vacuum dried to obtain 160 mg of a brown solid (0.39 mmol).

^{_{1 H NMR (C 6 D 6}} ): δ 0.67 (s, 3H, Ti-CH 3), 0.84 (s, 3H, Ti-CH 3), 1.89 (s, 15H, Cp (CH 3) 5), 6.27 1H aromatic, 6.92 (s, 1H aromatic), 7.08-7.55 (t, 1H aromatic), 7.24-7.21 (t, 2H aromatic), 7.76-7.75 (d, 2H aromatic).

Example  2

To a solution of the ligand prepared in Preparation Example 2, phenyl (3,5-difluoropyridin-2-yl) methanimine (143 mg, 0.657 mmol) in 5 mL of toluene was added Cp ^* TiMe ₃ 150 mg, 0.657 mmol) dissolved in 5 mL of toluene was slowly added dropwise. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. The toluene was evaporated, then filtered through a celite filter and then vacuum dried to obtain 250 mg of a brown solid (90% yield).

^{_{1 H NMR (C 6 D 6}} ): δ 0.57 (s, 3H, Ti-CH 3), 0.71 (s, 3H, Ti-CH 3), 1.74 (s, 15H, Cp (CH 3) 5), 6.17 1H aromatic, 7.08-7.11 (t, 1H aromatic), 7.22-7.25 (t, 2H aromatic), 7.79-7.81 (d, 2H aromatic), 7.85 (s, 1H aromatic).

Example  3

Cp ^* TiMe ₃ (100 mg, 0.438 mmol) was added to a solution of phenyl (pyrimidin-2-yl) methanimine (80 mg, 0.438 mmol) prepared in Preparation Example 3 in 5 mL of toluene at- In 5 mL of toluene was slowly added dropwise. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. The toluene was evaporated, filtered through a celite filter and then vacuum dried to give 155 mg (90% yield) of a brown solid.

^{_{1 H NMR (C 6 D 6}} ): δ 0.99 (s, 6H, Ti-CH 3), 1.78 (s, 15H, Cp- (CH 3) 5), 5.90 (s, 1H, aromatic), 6.98 ~ 6.99 (d, 1H aromatic), 7.27-7.30 (t, 2H aromatic), 7.81-7.82 (d, 2H aromatic), 8.41-8.42 (d, 2H aromatic).

Example  4

To a solution of the ligand prepared in Preparation Example 4, phenyl (3,5-dichloropyridin-2-yl) methanimine (117 mg, 0.47 mmol) in 5 mL of toluene was added Cp ^* TiMe ₃ , 0.438 mmol) in 5 mL of toluene was slowly added dropwise. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. The toluene was evaporated, filtered through a celite filter and then vacuum dried to give 195 mg (90% yield) of a brown solid.

^{_{1 H NMR (C 6 D 6}} ): δ 0.63 ~ 0.65 (d, 6H, Ti-CH 3), 1.72 (s, 15H, Cp (CH 3) 5), 6.90 ~ 6.20 (s, 1H aromatic), 7.09 1H aromatic, 7.21-7.24 (t, 2H aromatic), 7.67-7.69 (d, 2H aromatic), 8.08 (s, 1H aromatic).

Example  5

Cp ^* TiMe ₃ (100 mg, 0.438 mmol) was added to a solution of the ligand prepared in Preparation Example 5, phenyl (4-phenylpyridin-2-yl) methanimine (117 mg, 0.47 mmol) mmol) in 5 mL of toluene was slowly added dropwise. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. The toluene was evaporated, filtered through a celite filter and then vacuum dried to give 195 mg (90% yield) of a brown solid.

^{_{1 H NMR (C 6 D 6}} ): δ 0.70 (s, 3H, Ti-CH 3), 0.84 (s, 3H, Ti-CH 3), 1.87 (s, 15H, Cp (CH 3) 5), 6.77 7.39 (d, 1H aromatic), 7.09-7.10 (d, 1H aromatic), 7.19-7.21 (m, 3H aromatic), 7.60 (s, 1H aromatic), 7.87-7.89 (d, 2H aromatic), 7.93-7.94 (d, 2H aromatic).

Example  6

Cp ^* TiMe ₃ (243 mg, 1.07 mmol) was added to a solution of the ligand prepared in Preparation Example 6, phenyl (thiophen-2-yl) methanimine (200 mg, 1.07 mmol) in 5 mL of toluene at- In 5 mL of toluene was slowly added dropwise. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. The toluene was evaporated, filtered through a celite filter, and then vacuum-dried to obtain 180 mg of a yellow solid (0.45 mmol).

^{_{1 H NMR (C 6 D 6}} ): δ 0.63 (s, 3H, Ti-CH 3), 0.64 (s, 3H, Ti-CH 3), 1.72 (s, 15H, Cp (CH 3) 5), 6.68 2H aromatic, 7.71-7.73 (t, 1H aromatic), 6.84 (t, 1H aromatic), 6.68 (d, 2H aromatic).

Example  7

To a solution of the ligand (3,4-dichlorophenyl) (furan-2-yl) methanimine (50 mg, 0.21 mmol) prepared in Preparation Example 7 in 2 mL of toluene was added Cp ^* TiMe ₃ 48 mg, 0.21 mmol) dissolved in 2 mL of toluene was slowly added dropwise. The mixture was slowly warmed to room temperature and stirred at room temperature for 12 hours. The toluene was evaporated, filtered through a celite filter, and then vacuum-dried to obtain a yellow solid (40 mg, 0.09 mmol).

^{_{1 H NMR (C 6 D 6}} ): δ 0.52 (s, 3H, Ti-CH 3), 0.54 (s, 3H, Ti-CH 3), 1.71 (s, 15H, Cp (Me 3) 5), 5.97 2H), 6.93 (s, 1H aromatic), 7.02-7.04 (d, 1H aromatic), 7.12 (d, 1H aromatic), 7.88-7.89 (d, 1H aromatic).

Example  8

&Lt; Preparation of ethylene-octene copolymer >

A hexane solvent (1.0 L), octene (280 mL) and ethylene (35 bar) were added to the 2 L autoclave reactor, and the pressure was adjusted to 500 psi under high pressure argon pressure and the reactor temperature was preheated to 80 ° C. (2 μmol) of the above Example 1, which had been treated with triisobutylaluminum compound (1.0M, manufactured by Aldrich), and dimethylanilinium tetrakis (pentafluorophenyl) borate AB) co-catalyst were added in turn to the reactor under high-pressure argon pressure (molar ratio of Al: Ti = 10: 1). Subsequently, the copolymerization reaction was carried out for 8 minutes. Next, the remaining ethylene gas was removed and the polymer solution was added to excess ethanol to induce precipitation. The precipitated polymer was washed with ethanol and acetone two to three times, respectively, and then dried in a vacuum oven at 80 캜 for 12 hours or more, and then the physical properties thereof were measured.

Example  9

&Lt; Preparation of ethylene-octene copolymer >

The procedure of Example 8 was repeated except that the transition metal compound of Example 2, which was treated with triisobutyl aluminum compound, was used instead of the transition metal compound of Example 1, which was treated with triisobutyl aluminum compound in Example 8, Ethylene-octene copolymer was prepared in the same manner as in Example 1.

Comparative Example  One

&Lt; Preparation of ethylene-octene copolymer >

In the above Example 8 treated with triisobutyl aluminum compound in Example 8

Ethylene-octene copolymer was prepared in the same manner as in Example 8, except that Cp ^* TiCl ₃ treated with triisobutyl aluminum compound was used instead of the transition metal compound of the formula (1).

Experimental Example  : Measurement of physical properties

The properties of the copolymers prepared in Examples 8 and 9 and Comparative Example 1 were evaluated according to the following methods.

The density of the polymer; ASTM D-792.

The melt index (MI) of the polymer was measured by ASTM D-1238 (condition E, 190 ° C, 2.16 Kg load).

The crystallization temperature (Tc) and the melting temperature (Tm) were measured using a Differential Scanning Calorimeter (DSC) manufactured by PerKinElmer. Specifically, the temperature of the copolymer was increased to 200 ° C in a nitrogen atmosphere using a DSC, maintained at that temperature for 5 minutes, cooled to 30 ° C, and then the temperature was increased and the DSC curve was observed. At this time, the heating rate and the cooling rate were set at 10 ° C / min.

C ₈
(mL) density
(g / cc) MI
(g / 10 min) Tc1
(° C) Tc2
(° C) Tm1
(° C) Tm2
(° C) Example 8 210 0.895 0.12 67.9 84.4 85.9 104.2 Example 9 210 0.898 0.03 - 82.4 - 100.3 Comparative Example 1 210 0.895 0.49 71.5 81.6 86.7 102.1

Claims (11)

A transition metal compound represented by the following general formula (1)
[Chemical Formula 1]

In Formula 1,
R ₁ to R ₁₃ are each independently hydrogen, halogen, silyl, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, &Lt; / RTI &gt;
X and Y are each independently C (R _14), N, O, or S, wherein said R ₁₄ is hydrogen, halogen, silyl, alkenyl having 1 to 20 carbon alkyl, having 2 to 20, C 6 -C An aryl of 20 to 20 carbon atoms, an alkylaryl of 7 to 20 carbon atoms, or an arylalkyl of 7 to 20 carbon atoms;
n is 0 or 1;
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 , Alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;
M is Ti, Zr or Hf.
The method according to claim 1,
Wherein 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. Transition metal compound.
The method according to claim 1,
Each of R ₁ to R ₈ and R ₁₄ is 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;
Each of R ₉ to R ₁₃ is independently hydrogen, an alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, an alkylaryl having 7 to 20 carbon atoms, or an arylalkyl having 7 to 20 carbon atoms.
The method according to claim 1,
Wherein the compound of Formula 1 is any one of the following compounds:
[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

&Lt; RTI ID = 0.0 &

[Formula 1e]

(1f)

[Formula 1g]

(1) reacting a compound of formula (2) with a compound of formula (3) to produce a compound of formula (4); And
(2) reacting a compound of the following formula (4) with a compound of the following formula (5) to prepare a compound of the formula
&Lt; / RTI &gt; wherein the transition metal compound is a transition metal compound.
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas,
R ₁ to R ₁₃ are each independently hydrogen, halogen, silyl, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, &Lt; / RTI &gt;
X and Y are each independently C (R _14), N, O, or S, wherein said R ₁₄ is hydrogen, halogen, silyl, alkenyl having 1 to 20 carbon alkyl, having 2 to 20, C 6 -C An aryl of 20 to 20 carbon atoms, an alkylaryl of 7 to 20 carbon atoms, or an arylalkyl of 7 to 20 carbon atoms;
n is 0 or 1;
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 , Alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms;
M is Ti, Zr or Hf.
A catalyst composition comprising the transition metal compound according to claim 1.
The method according to claim 6,
Wherein the catalyst composition further comprises at least one cocatalyst,
Wherein the cocatalyst comprises at least one selected from the following formulas (6) to (8):
[Chemical Formula 6]
- [Al (R ₁₅ ) -O] _a -
In Formula (6), R ₁₅ is independently selected from the group consisting of a halogen radical; A hydrocarbyl radical having from 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;
(7)
D (R _{15) 3}
In Formula 7, D is aluminum or boron; R ₁₅ are each independently a halogen radical; A hydrocarbyl radical having from 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;
[Chemical Formula 8]
^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -
Wherein L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is independently an aryl having 6 to 20 carbon atoms or an alkyl having 1 to 20 carbon atoms in which at least one hydrogen atom may be substituted with a substituent; The substituent is halogen, hydrocarbyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, or aryloxy of 6 to 20 carbon atoms.
The method according to claim 6,
Wherein the catalyst composition further comprises a reaction solvent.
A process for producing a polymer using the catalyst composition according to claim 6.
10. The method of claim 9,
Wherein the polymer is a homopolymer or copolymer of a polyolefin.
A polymer produced using the catalyst composition according to claim 6,
The polymer is a polymer having a melt index (MI) of 0.4 or less.