KR100503359B1 - Metallocene catalyst for styrene polymerization and polymerization process using the same - Google Patents

Abstract

The present invention relates to a metallocene catalyst for producing a styrene polymer and a method for producing a styrene polymer using the same, and more particularly, to a metallocene catalyst for producing a styrene-based polymer of Formula 1 and a method for producing a styrene polymer using the same.

[Formula 1]

L _a MX _b

When the styrene polymer is prepared using the metallocene catalyst for preparing the styrene polymer of the present invention, a syndiotactic styrene polymer having high activity, excellent stereoregularity, and high melting temperature can be produced in high yield.

Description

Metallocene catalyst for the production of styrene polymer and method for producing the styrene polymer using the same {METALLOCENE CATALYST FOR STYRENE POLYMERIZATION AND POLYMERIZATION PROCESS USING THE SAME}

[TECHNICAL FIELD OF THE INVENTION]

The present invention relates to a metallocene catalyst for producing a styrene polymer and a method for producing a styrene polymer using the same, wherein a styrene capable of producing a syndiotactic styrene polymer having high activity, excellent stereoregularity, and a high melting temperature in high yield It relates to a metallocene catalyst for producing a polymer and a method for producing a styrene polymer using the same.

[Prior art in the field]

Styrene polymers are largely divided into three types of polymers: atactic, isotactic and syndiotactic polystyrene, depending on the arrangement of the benzene rings suspended in the polymer backbone.

Amorphous atactic styrene polymers are thermoplastic polymers obtained by general radical or ionic polymerization. They are manufactured by various processing methods, such as injection molding, extrusion molding, or vacuum molding, and are used for packaging materials, household goods, toys, electrical and electronic housing materials, and the like. Among these, isotactic styrene polymers having stereoregularity are mainly obtained using heterogeneous Ziegler-Natta catalysts but are not widely used due to low productivity and slow crystallization rate.

On the other hand, syndiotactic styrene polymers have good mechanical properties such as heat resistance, chemical resistance and fast crystallization, which are characteristics of crystalline polymers due to high stereoregularity, while maintaining the process formability and electrical properties of general amorphous styrene polymers. Because of its properties, it is used more in engineering plastics than general purpose resins.

Therefore, syndiotactic styrene polymer is suitable for electronic parts and automotive engine parts, and is used for mobile phones and microwave oven parts using excellent high frequency characteristics. EP 210,615 discloses such syndiotactic styrene polymers by using a metallocene catalyst, a Group 4 transition metal compound having π-ligand and σ-ligand as a main catalyst, and combining alkylaluminoxane as a promoter. A method that can be prepared in yield is disclosed.

More specifically, the half metallocene main catalyst such as cyclopentadienyl titanium trichloride or pentamethylcyclopentadienyl titanium trichloride is activated with methylaluminoxane cocatalyst to be used for syndiotactic styrene polymerization of excellent stereoregularity. Doing. In this case, the highly active catalyst structure consists of one cycloalkanedienyl π-ligand and three bicycloalkanedenyl σ-ligands.

In addition, Ishihara et al. Et al., Unlike the metallocene of the half of the structure described above, a metallocene type catalyst structure containing two cycloalkanedienyl π-ligands can also be used for syndiotactic styrene polymerization. Reported ( Macromolecules , 1988, 21 , 3356). However, the polymerization activity of these metallocene catalysts was very low, unlike the highly active half metallocenes, because the two π-ligands provided a strong steric hindrance during the polymerization reaction.

On the other hand, European Patent Publication EP 492,282 has reported styrene polymerization using ansa-metallocene in which two π-ligand cycloalkanedinyl groups are linked by a bridge bond. However, the low proportion of syndiotactic polystyrene in the obtained polystyrene was found to be ineffective for high activity syndiotactic styrene polymerization.

From the previous studies, the metallocene compound in which two cycloalkanedienyl groups are linked to a metal by π-bonding does not act as a good catalyst for syndiotactic styrene polymerization.

The present invention has been invented in view of the problems of the prior art, and an object of the present invention is to produce a styrene polymer for producing a high yield, syndiotactic styrene polymer having high stereoregularity and high melting temperature in high yield It is to provide a Rosene catalyst.

It is also an object of the present invention to provide a method for producing a styrene polymer using a metallocene catalyst for producing a styrene polymer capable of producing syndiotactic styrene polymer having high activity, excellent stereoregularity, and high melting temperature in high yield. It is.

The present invention provides a metallocene catalyst for producing a styrene-based polymer of the general formula (1) to achieve the above object.

[Formula 1]

L _a MX _b

The present invention also provides a method for preparing a metallocene catalyst for preparing a styrene-based polymer of Chemical Formula 1, comprising the steps of: a) converting a cycloalkanedienyl group to an alkali metal salt; And b) directly reacting the alkali metal salt of the cycloalkanedienyl group of a) with a transition metal compound having a leaving group, or ii) reacting with a half metallocene compound having a leaving group. Provided is a method for preparing a metallocene catalyst.

The present invention also provides a method for producing a styrenic polymer, the styrene monomer comprising a) a metallocene catalyst of the formula (1); And b) polymerizing under a catalyst system comprising a promoter selected from the group consisting of alkylaluminoxanes, alkylaluminum and weakly coordinated Lewis acids.

Hereinafter, the present invention will be described in more detail.

The present invention is characterized by using a metallocene catalyst of the formula (1) as the main catalyst used in the production of styrene polymer.

[Formula 1]

L _a MX _b

(In Formula 1,

L is a cycloalkanedienyl group represented by the following Chemical Formulas 2 to 6 bonded to a metal through one π-configuration and one or more σ-configuration independently or simultaneously in the same formula,

M is a transition element of Groups 3 to 10 on the periodic table,

X is a functional group that is an σ- ligand, each independently or simultaneously in the same formula, hydrogen atom, halogen group, hydroxy group, alkyl group having 1 to 20 carbon atoms, cycloalkyl group, alkylsilyl group, alkenyl group, alkoxy group, alkenyloxy group, thio Alkoxy group, alkylsiloxy group, amide group, alkoxyalcohol group, alcoholamine group, carboxyl group, sulfonyl group, aryl group having 6 to 40 carbon atoms, alkylaryl group, arylalkyl group, arylsilyl group, haloaryl group, aryloxy group, Arylalkoxy group, thioaryloxy group, arylsiloxy group, arylalkylsiloxy group, arylamide group, arylalkylamide group, aryloxo alcohol group, alcohol arylamine group, or arylaminoaryloxy group,

a is an integer from 2 to 4, b is an integer from 0 to 2, and a + b = 4.

[Formula 2] [Formula 3] [Formula 4]

[Formula 5] [Formula 6]

In Formulas 2 to 6, r ₁ , r ₂ , r ₃ , r ₄ , r ₅ , r ₆ , r ₇ , r ₈ , r ₉ , r ₁₀ , r ₁₁ , r ₁₂ , and r ₁₃ are the same formulas, respectively. Each independently or simultaneously hydrogen atom, halogen group, alkyl group of 1 to 20 carbon atoms, cycloalkyl group, alkenyl group, alkylsilyl group, haloalkyl group, alkoxy group, alkylsiloxy group, amino group, alkoxyalkyl group, thioalkoxyalkyl group, alkyl Siloxyalkyl group, aminoalkyl group, alkylphosphinoalkyl group, aryl group having 6 to 40 carbon atoms, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryl Oxoalkyl group, aryloxoaryl group, arylsiloxy group, arylalkylsiloxy group, arylsiloxanealkyl group, arylsiloxanearyl group, arylamino group, arylaminoalkyl group, arylaminoaryl group, or arylphosphinoalkyl group,

m and n are integers of 1 or more.)

Specifically, the metallocene catalyst of formula (I) is (η ⁵ -2- methylbenzamide [e] indene) (η ¹ -2- methylbenzamide [e] _{indene) Ti (OiPr) 2, (} η 5 -Cp *) Preference is given to metallocene catalysts which are (η ¹ -9-fluorenyl) Ti (OiPr) ₂ or [η ⁵ : η ¹ -ethylenebis (9-pulluenyl)] Ti (OiPr) ₂ .

The metallocene catalyst of Chemical Formula 1 of the present invention is a metallocene compound in which two or more cycloalkanedienyl groups and transition metals of Groups 3 to 10 of the periodic table are bonded.

In particular, two or more cycloalkanedinyl groups bind to the central metal via one π-coordination and one or more σ-coordination. Therefore, the cycloalkanedienyl group linked in the σ-coordination at the time of polymerization is easily activated by the cocatalyst or has little steric hindrance to the polymerization reaction. And styrene polymers of high melting temperature.

The metallocene catalyst may be prepared by converting a cycloalkanedienyl group into an alkali metal salt to react directly with a transition metal compound having i) a leaving group or ii) with a half metallocene compound having a leaving group.

In the method for producing the metallocene catalyst, examples of the alkali metal salt of the cycloalkanedinyl group include cyclopentadienyl lithium, cyclopentadienyl sodium, cyclopentadienyl potassium, cyclopentadienyl magnesium, and methylcyclopentadienyl. Lithium, methylcyclopentadienyl sodium, methylcyclopentadienyl potassium, tetramethylcyclopentadienyl lithium, tetramethylcyclopentadienyl sodium, tetramethylcyclopentadienyl potassium, indenyl lithium, indenyl sodium, indenyl Potassium, fluorenyl lithium and the like.

These salts include a ligand having a cycloalkanedinyl structure, normal butyl lithium, secondary butyl lithium, tertiary butyl lithium, methyl lithium, sodium methoxide, sodium ethoxide, potassium tert-butoxide, potassium hydroxide, methyl magnesium chloride, and ethyl. It can be prepared by reacting magnesium bromide, dimethyl magnesium, lithium, sodium, potassium and the like.

In addition, transition metal compounds having leaving groups include titanium tetrachloride, titanium tetrachloride ditetrahydrofuran, zirconium tetrachloride, hafnium tetrachloride, vanadium tetrachloride, titanium tetraiodine, titanium tetrabromide, titanium tetrafluoride, vanadium trichloride, and titanium tetraiso. Propoxide, chlorotitanium triisopropoxide, dichlorotitanium diisopropoxide, trichlorotitanium monoisopropoxide, titanium tetrabutylbutoxide, chlorotitanium tributarybutoxide, dichlorotitanium butoxide, Trichlorotitanium monobutyoxide, chlorotitanium triphenoxide, chlorotitanium triethoxide and the like.

As the half metallocene compound having a leaving group, cyclopentadienyl titanium trichloride, cyclopentadienyl methoxy titanium dichloride, cyclopentadienyl dimethoxy titanium monochloride, cyclopentadienyl titanium trimethoxide, and methyl cyclopenta Dienyltitanium trichloride, methylcyclopentadienylmethoxytitanium dichloride, methylcyclopentadienyldimethoxytitanium monochloride, methylcyclopentadienyltitanium trimethoxide, pentamethylcyclopentadienyltitanium trichloride, pentamethylcyclo Pentadienylmethoxytitanium dichloride, pentamethylcyclopentadienyldimethoxytitanium monochloride, pentamethylcyclopentadienyltitanium trimethoxide, indenyltitanium trichloride, indenylmethoxytitanium dichloride, indenyldimethoxytitanium And the like furnace chloride, indenyl titanium methoxide tree.

In the metallocene catalyst for preparing the styrene-based polymer of Chemical Formula 1 of the present invention prepared by the above methods, n and m are preferably 1 ≦ n or m ≦ 10.

In addition, M is preferably a Group 4 transition element on the periodic table, more preferably titanium, zirconium, or hafnium.

In addition, a ligand having a cycloalkanedienyl skeleton includes a cyclopentadienyl group, an indenyl group, a fluorenyl group, 4,5,6,7-tetrahydroindenyl group, 2,3,4,5,6,7,8, And 9-octahydrofluorenyl groups.

In addition, the halogen group includes a fluoro group, a chloro group, a bromo group, an iodine group,

In addition, the alkyl group, cycloalkyl group, alkenyl group, alkylsilyl group, haloalkyl group, alkoxy group, alkylsiloxy group, amino group, alkoxyalkyl group, thioalkoxyalkyl group, alkylsiloxyalkyl group, aminoalkyl group, alkylphosphinoalkyl group of 1 to 20 carbon atoms Methyl and ethyl groups. Propyl group, butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 2-pentenyl group, methylsilyl group, dimethylsilyl group, trimethyl Silyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, propylsilyl group, dipropylsilyl group, tripropylsilyl group, butylsilyl group, dibutylsilyl group, tributylsilyl group, butyldimethylsilyl group, Trifluoromethyl group, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, methylsiloxy group, dimethylsiloxy group, trimethylsiloxy group, ethylsiloxy group, diethylsiloxy group, triethylsiloxy group , Butyldimethylsiloxy group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, pyrrolidine group, piperidine group, methoxyethyl group, methoxypropyl group, methoxybutyl group, thiomethoxyethyl group, thiometh Oxybutyl group, trimethylsiloxy Ethyl group, dimethylaminoethyl group, diethylphosphinobutyl group and the like.

In addition, an aryl group, arylalkyl group, arylalkyl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryloxoalkyl group, aryloxoaryl group, arylsiloxy group having 6 to 40 carbon atoms , Arylalkylsiloxy group, arylsiloxanealkyl group, arylsiloxanearyl group, arylamino group, arylaminoalkyl group, arylaminoaryl group, arylphosphinoalkyl group include phenyl group, biphenyl group, terphenyl group, naphthyl group, fluorenyl group, benzyl group , Phenylethyl group, phenylpropyl group, tolyl group, xylyl group, butylphenyl group, phenylsilyl group, phenyldimethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, chlorophenyl group, pentafluorophenyl group, phenoxy group, naphthoxy Period, phenoxyethyl group, biphenoxybutyl group, thiophenoxyethyl group, phenoxyphenyl group, naphthoxyphenyl group, phenylsiloxy group, triphenylsiloxy group, phenyldimethylsiloxy group, triphenylsiloxane ethyl group, diphenyl Siloxanephenyl group, aniline group, toluidine group, benzylamino group, phenylaminoethyl group, phenylmethylaminophenyl group, diphenylphosphinoethyl group and the like.

The present invention provides a syndiotactic styrene polymer and a styrene copolymer of various physical properties by using the metallocene catalyst for preparing a styrene-based polymer of Chemical Formula 1 as a main catalyst and co-polymerizing with styrene homopolymerization or styrene derivative. Can be.

Cocatalysts used with the metallocene catalyst of Chemical Formula 1 include various types such as alkylaluminoxane, alkylaluminum, weakly coordinated Lewis acid, or mixtures thereof. Among them, a cocatalyst of a mixture of alkylaluminoxane and alkylaluminum or a cocatalyst of a mixture of weakly coordinated Lewis acid and alkylaluminum may be preferably used.

As the alkylaluminoxane, a compound represented by the following Chemical Formula 7 may be preferably used.

[Formula 7]

(In Chemical Formula 7,

R ₁ is a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkylaryl group, or an arylalkyl group,

n is an integer from 1 to 100.)

The compound of Formula 7 may be linear, cyclic or reticulated, specifically, methyl aluminoxane, modified methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane, hexyl aluminoxane, decyl aluminoxane and the like.

In addition, as the alkyl aluminum, a compound of Formula 8 may be preferably used.

[Formula 8]

(In Formula 8,

R ₂ , R ₃ , and R ₄ are each independently or simultaneously a hydrogen atom, a halogen group, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms, and 6 to C carbon atoms. An aryl group, an alkylaryl group, or an arylalkyl group of 40, wherein at least one of R ₂ , R ₃ , and R ₄ includes an alkyl group.)

The compound of Formula 8 is specifically trimethylaluminum, dimethylaluminum chloride, dimethylaluminum methoxide, methylaluminum dichloride, triethylaluminum, diethylaluminum chloride, diethylaluminum methoxide, ethylaluminum dichloride, trinormal propylaluminum, Dinormal propyl aluminum chloride, normal propyl aluminum chloride, triisopropyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, diisobutyl aluminum hydride and the like.

In addition, the coordinating Lewis acid cocatalyst can take both ionic or neutral forms, specifically trimethylammonium tetrafetylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, tetra Methylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetraphenylborate, dimethylanilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluoro Phenyl) borate, silver tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, sodium tetrakis (3,5-bis (trifluoromethyl) phene ) Borate, Tris (pentafluorophenyl) borane, Tris (2,3,4,5-tetrafluorophenyl) borane, Tris (3,5-bis (trifluoromethyl) phenyl) borane, tris (2,4,6-trifluorophenyl) borane and the like.

In carrying out styrene homopolymerization or copolymerization using the metallocene catalyst, the amount of the cocatalyst used together is not particularly limited but may be different depending on the type thereof.

In the case of alkylaluminoxanes, the equivalent ratio with the metallocene catalyst is mainly usable in the range of 1: 1 to 10 ⁶ : 1, and is preferably used between 10: 1 and 10 ⁴ : 1.

In addition, the equivalent ratio of alkylaluminum which may be used with the alkylaluminoxane may be used in the range of 1: 1 to 10 ⁴ : 1 relative to the metallocene catalyst.

In the case of weakly coordinating Lewis acid, the equivalent ratio with the metallocene catalyst may be used in the range of 0.1: 1 to 50: 1, wherein the amount of the alkyl aluminum used together may be 1: 1 to 3000: 1, Preferably it is used within the range of 50: 1 to 1000: 1.

As the monomer which can be polymerized by the catalyst system of the present invention, styrene or a styrene derivative may be used, and these may polymerize or copolymerize styrene or a styrene derivative alone.

The styrene derivative includes a substituent on the benzene ring of styrene, and the substituent includes a halogen group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkoxy group, an ester group, a thioalkoxy group, a silyl group, a tin group, an amine group, and a phosphine group. , A halogenated alkyl group, a vinyl group having 2 to 20 carbon atoms, an aryl group, a vinylaryl group, an alkylaryl group, an arylalkyl group, and the like.

Specific examples thereof include chlorostyrene, bromostyrene, fluorostyrene, p-methylstyrene, m-methylstyrene, p-ethylstyrene, p-normal butyl styrene, p-tertiary butyl styrene, p-normal hexyl styrene, p-cyclohexyl styrene, dimethyl styrene, methoxy styrene, ethoxy styrene, butoxy styrene, methyl-4- styrenyl ester, thiomethoxy styrene, trimethylsilyl styrene, triethyl silyl styrene, tertiary butyl dimethyl silyl styrene, Trimethyltin styrene, dimethylaminostyrene, trimethylphosphinostyrene, chloromethylstyrene, bromomethylstyrene, 4-vinylbiphenyl, p-divinylbenzene, m-divinylbenzene, trivinylbenzene, 4,4'-di Vinyl biphenyl, vinyl naphthalene, and the like.

When the polymerization is carried out using the catalyst system for polymerization of the present invention, the polymerization can be carried out in a slurry phase, a liquid phase, a gaseous phase, and a block. When the polymerization is carried out in a slurry or liquid phase, a solvent may be used as a polymerization medium, and the solvent used may include butane, pentane, hexane, heptane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, and the like. Alkanes or cycloalkane solvents having 4 to 20 carbon atoms; Aromatic arene solvents having 6 to 20 carbon atoms such as benzene, toluene, xylene, and mesitylene; Dichloromethane, chloromethane, chloroform, carbon tetrachloride, chloroethane, 1,2-dichloroethane, 1,1,2,2, -tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichloro C1-C20 halogen alkanes, such as robenzene, a halogen arene solvent, etc. are mentioned.

These solvents may be used alone or in combination at a constant ratio. In addition, in the solvent-free state, gas phase polymerization is possible under styrene pressure in the reactor of 0.01 to 20 atm.

In the polymer production process according to the invention, the polymerization temperature is -80 to 200 ° C, preferably 0 to 150 ° C.

The polymerization pressure is suitably 1 to 1000 atm, including the pressure of the comonomer, when styrene homopolymerization or copolymerization.

The process for producing a polymer according to the present invention is largely performed by i) adding only a solvent and a monomer or monomer to a reactor and raising the temperature, and then injecting an alkylaluminum, a promoter and a metallocene compound as a main catalyst, or ii) After activating with the cocatalyst in advance, it can be made by injecting into the reactor containing the monomer, or iii) pre-adding alkylaluminum to the monomer, and then injecting the main catalyst activated with the cocatalyst.

In addition, the reaction for activating the main catalyst by bringing it into contact with the cocatalyst is preferably performed for 0.1 to 60 minutes between 0 and 150 ° C.

The amount of the metallocene catalyst, which is the main catalyst used in the polymer production process, is not particularly limited, but a suitable concentration of the central metal in the reaction system is 10 ^-8 to 1.0 M, ideally 10 ^-7 to 10 ^-2 M The concentration is appropriate.

Syndiotactic styrene polymers and copolymers obtained from the polymerization reaction using the catalyst system have a molecular weight of 1,000 to 10,000,000, molecular weight distribution 1.1 by adjusting the type and amount of the main catalyst and the cocatalyst, the reaction temperature, the reaction pressure and the concentration of the monomer. It can be variously adjusted in the range of 100 to.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.

[Example 1] (η ⁵ -2- methylbenzamide [e] indene), the synthesis of (η ¹ -2- methylbenzamide [e] indene), Ti (OiPr) ₂ catalyst

(TiCl ₂ (OiPr) ₂  Manufacture)

71.0 g (0.25 mol) of Ti (OiPr) ₄ (titanium tetraisopropoxide) was dissolved in 350 mL of diethyl ether, and then the same equivalent of TiCl ₄ (47.5 g) was slowly added dropwise at 0 ° C. . After stirring for 1 hour at this temperature, diethyl ether was added to adjust the total volume to 0.5 L. The resulting 1M TiCl ₂ (OiPr) ₂ diethyl ether solution was refrigerated and used without purification in the next reaction.

(η ⁵ -2-methylbenz [ e ] Inden) (η ^One -2-methylbenz [ e Inden) Ti (OiPr) ₂  Manufacture)

1.80 g (10 mmol) of 2-methylbenz [ e ] indene ( Organometallics, 1994, 13 , 964) was dissolved in 30 mL of diethyl ether and the temperature of the reaction vessel was lowered to 0 ° C. Next, 1 equivalent of normal butyllithium hexane solution was slowly injected using a syringe, and the reaction mixture was slowly heated up to room temperature. After stirring for 4 hours, the reaction vessel was lowered to −78 ° C., and 5 mL (5 mmol) of the equivalent of TiCl ₂ (OiPr) ₂ diethylether solution prepared above was added dropwise using a syringe. After raising the temperature of the reaction mixture to room temperature, the mixture was stirred overnight to obtain a red reaction mixture. After removing the solvent under reduced pressure, the obtained solid product was extracted with 30 mL of dichloromethane. Filtered through celite 545 filter, concentrated again, and the solvent partially removed under vacuum to separate the solution was added an appropriate amount of n-hexane after overnight cooling at -20 ℃ when the solid product is of red color (η ⁵ -2- methyl 1.45 g (yield 55%) of benz [ e ] indene) (η ^1-2 -methylbenz [ e ] indene) -Ti (OiPr) ₂ was obtained.

Example 2 Synthesis of (η ⁵ -Cp ^* ) (η ¹ -9-fluorenyl) Ti (OiPr) ₂ Catalyst

5 mmol (0.83 g) of fluorene was dissolved in 30 mL of diethyl ether, and then the temperature of the reaction vessel was lowered to 0 ° C. The same equivalent amount of normal butyllithium hexane solution was slowly injected into the syringe. Gradually raising the temperature of the reaction vessel to room temperature was confirmed to produce a dark orange solution. After stirring for 2 hours, the temperature of the reaction vessel was lowered to -78 ° C, and the same equivalent Cp ^* TiCl (OiPr) ₂ (1.68 g) diethyl ether solution dissolved in the flask prepared in advance was slowly added dropwise to the cannula. After the cooling vessel was removed, the temperature of the reaction mixture was gradually raised to maintain room temperature. After stirring at this temperature overnight, the solvents were all removed under vacuum and extracted again with 50 mL of normal hexane. This was filtered through a Celite 545 filter to separate the LiCl and the red solution to obtain a clean solution. The solution was concentrated again by removing the solvent under vacuum, and then cooled overnight at -20 ° C. to give 1.42 g of orange colored solid product (η ⁵ -Cp ^* ) (η ¹ -9-puluorenyl) Ti (OiPr) _2. (Yield 61%) was obtained.

Example 3 Synthesis of [η ⁵ : η ¹ -ethylenebis (9-puluorenyl)] Ti (OiPr) ₂ Catalyst 1,2-bis (9-fluorenyl) ethyl ( J.Organomet.Chem. 1994, 472 , 113) 5 mmol (1.79 g) was dissolved in 30 mL of diethyl ether, and then the temperature of the reaction vessel was lowered to 0 ° C. Two equivalents of normal butyllithium hexane solution was slowly injected into the syringe. When the temperature of the reaction vessel was gradually raised to room temperature, a dark orange solution and crystalline precipitates were confirmed. After stirring overnight, the temperature of the reaction vessel was lowered to −78 ° C. and the same equivalent amount of TiCl ₂ (OiPr) ₂ (5 mL) diethyl ether solution dissolved in the flask prepared beforehand was slowly added dropwise to the cannula. After the cooling vessel was removed, the temperature of the reaction mixture was gradually raised to maintain room temperature. After stirring for 6 hours at this temperature, the solution part is filtered off, and the red solid product is washed twice with 10 mL of diethyl ether. The obtained solid compound is again dissolved in dichloromethane solvent and filtered to separate LiCl. The solution was concentrated by removing the solvent under vacuum, followed by normal hexane addition and cooling at -20 ° C. overnight to give a red solid product [η ⁵ : η ¹ -ethylenebis (9-fluorenyl)] Ti (OiPr). ₂ 1.36 g (yield 52%) was obtained.

Example 4 Preparation of Styrene Homopolymer (Liquid Polymerization)

The metallocene catalysts synthesized in Examples 1 to 3 were each subjected to styrene homopolymerization as follows.

50 mL of purified heptane was added to a polymerization reactor in a high purity nitrogen atmosphere, and the temperature was raised to 50 ° C. 50 mL of styrene, 2.5 mL of triisobutylaluminum (1.0 M toluene solution), and 2.5 mL of methylaluminoxane (2.1 M toluene solution, manufactured by Akzo) were sequentially injected.

While stirring it vigorously, 5 mL (25 μmol of Ti) toluene solution in which the respective metallocene catalyst was dissolved was added. After stirring for 30 minutes, the reaction was stopped by addition of a 10% by weight hydrochloric acid-ethanol solution, which was filtered to give a white solid precipitate. This precipitate was washed with ethanol and dried overnight in a vacuum oven at 50 ° C. to obtain the final styrene polymer. Polymerization results and polymer properties for each catalyst are shown in Table 1 below. In addition, each of the polymers were extracted by refluxing in methyl ethyl ketone for 12 hours to obtain a polymer that remained undissolved. As a result of analyzing this polymer by carbon element nuclear magnetic resonance spectroscopy, it was confirmed that it had a syndiotactic structure.

Styrene homopolymerization result division Yield (g) Active (KgPS / molTih) Shift Arrangement (%) Molecular Weight (× 10 ³ ) Molecular weight distribution Melting Point (℃) Catalyst of Example 1 18.5 1403 93 320 2.5 265 Catalyst of Example 2 25.7 2056 95 374 2.3 270 Catalyst of Example 3 16.2 1296 96 273 2.7 271

Example 5 Preparation of Styrene Homopolymer (Block Polymerization)

Styrene bulk polymerization was carried out using the metallocene catalyst synthesized in Examples 1 to 3 as described below.

100 mL of purified styrene was added to a polymerization reactor in a high purity nitrogen atmosphere, and the temperature was raised to 50 ° C. Next, 5 mL of triisobutylaluminum (1.0 M toluene solution) and 5 mL of methylaluminoxane (2.1 M toluene solution, manufactured by Akzo) were sequentially injected.

While stirring it vigorously, 5 mL (50 μmol of Ti) toluene solution in which the metallocene was dissolved was added. After stirring for 1 hour, the reaction was stopped by adding a 10 wt% hydrochloric acid-ethanol solution, filtered off, washed with ethanol and dried overnight in a vacuum oven at 50 ° C. to obtain a final styrene polymer.

Polymerization results and polymer properties for each catalyst are shown in Table 2 below. In addition, each of the polymers were extracted by refluxing in methyl ethyl ketone for 12 hours to obtain a polymer that remained undissolved. As a result of analyzing this polymer by carbon element nuclear magnetic resonance spectroscopy, it was confirmed that it had a syndiotactic structure.

Styrene homopolymerization result division Yield (g) Active (KgPS / molTih) Shift Arrangement (%) Molecular Weight (× 10 ³ ) Molecular weight distribution Melting Point (℃) Catalyst of Example 1 45.3 906 90 370 2.7 262 Catalyst of Example 2 68.5 1370 93 476 2.5 268 Catalyst of Example 3 53.0 1060 94 373 2.8 269

Comparative Example 1 Preparation of Styrene Homopolymer Using Cp ₂ TiCl ₂ and Cp ^* Ti (OMe) ₃

Except for using Cp ₂ TiCl ₂ and Cp ^* Ti (OMe) _3, which are well known catalysts, respectively, a single block polymerization of styrene was carried out by the same polymerization method as in Example 5.

Polymerization results and polymer properties for each catalyst are shown in Table 3 below.

Results of styrene homopolymerization using Cp ₂ TiCl ₂ and Cp ^* Ti (OMe) ₃ as catalyst division Yield (g) Active (KgPS / molTih) Shift Arrangement (%) Molecular Weight (× 10 ³ ) Molecular weight distribution Melting Point (℃) Cp ₂ TiCl ₂ 45.3 906 90 370 2.7 262 Cp ^* Ti (OMe) ₃ 68.5 1370 93 476 2.5 268

As shown in Tables 2 and 3, the bulk polymerization of the styrene homopolymer using the metallocene catalyst synthesized in Examples 1 to 3 of the present invention is excellent in terms of yield, activity, alternating arrangement and molecular weight distribution. It can be seen that the molecular weight and melting point of the prepared styrene polymer are also high.

Example 6 Preparation of Styrene / p-Methylstyrene Copolymer

Styrene / p-methylstyrene copolymerization was carried out using the metallocene catalyst synthesized in Examples 1 to 3 in the following manner. 100 mL of styrene purified in a polymerization reactor in a high purity nitrogen atmosphere and p-methylstyrene 5 mL was added and heated to 50 ° C. 5 mL of triisobutylaluminum (1.0 M toluene solution) and 5 mL of methylaluminoxane (2.1 M toluene solution, manufactured by Akzo) were sequentially injected.

While stirring it vigorously, 5 mL (50 μmol of Ti) toluene solution in which the metallocene was dissolved was added. After stirring for 1 hour, the reaction was stopped by adding a 10 wt% hydrochloric acid-ethanol solution, filtered off, washed with ethanol and dried in a vacuum oven at 50 ° C. overnight to obtain a final styrene / p-methylstyrene copolymer.

Polymerization results and polymer properties for each catalyst are shown in Table 4 below.

Styrene / p-methylstyrene copolymerization result division Yield (g) Active (KgPS / molTih) p-methylstyrene content (mol%) Glass transition temperature (℃) Melting Point (℃) Catalyst of Example 1 40.0 800 5.3 101 248 Catalyst of Example 2 62.7 1254 7.5 99 240 Catalyst of Example 3 49.4 988 5.5 101 245

The transition metal metallocene catalyst of the Group 3 to Group 10 of the periodic table containing two or more cycloalkanedienyl groups of the present invention forms a highly active catalyst system together with a promoter such as alkylaluminoxane. It is possible to prepare syndiotactic styrene polymers and copolymers with styrene derivatives having excellent and high melting temperatures. The polymer prepared according to the present invention is excellent in heat resistance, chemical resistance, chemical resistance, and processability, and thus may be variously applied to engineering plastics.

Claims (20)

A metallocene catalyst for preparing a styrene-based polymer of Formula 1 [Formula 1] L _a MX _b (In Formula 1, L is a cycloalkanedienyl group represented by the following Chemical Formulas 2 to 6 bonded to a metal through one π-configuration and one or more σ-configuration independently or simultaneously in the same formula, M is a transition element of Groups 3 to 10 on the periodic table, X is a functional group that is an σ- ligand, each independently or simultaneously in the same formula, hydrogen atom, halogen group, hydroxy group, alkyl group having 1 to 20 carbon atoms, cycloalkyl group, alkylsilyl group, alkenyl group, alkoxy group, alkenyloxy group, thio Alkoxy group, alkylsiloxy group, amide group, alkoxyalcohol group, alcoholamine group, carboxyl group, sulfonyl group, aryl group having 6 to 40 carbon atoms, alkylaryl group, arylalkyl group, arylsilyl group, haloaryl group, aryloxy group, Arylalkoxy group, thioaryloxy group, arylsiloxy group, arylalkylsiloxy group, arylamide group, arylalkylamide group, aryloxo alcohol group, alcohol arylamine group, or arylaminoaryloxy group, a is an integer from 2 to 4, b is an integer from 0 to 2, and a + b = 4. [Formula 2] [Formula 3] [Formula 4] [Formula 5] [Formula 6] In Formulas 2 to 6, r ₁ , r ₂ , r ₃ , r ₄ , r ₅ , r ₆ , r ₇ , r ₈ , r ₉ , r ₁₀ , r ₁₁ , r ₁₂ , and r ₁₃ are the same formulas, respectively. Each independently or simultaneously hydrogen atom, halogen group, alkyl group of 1 to 20 carbon atoms, cycloalkyl group, alkenyl group, alkylsilyl group, haloalkyl group, alkoxy group, alkylsiloxy group, amino group, alkoxyalkyl group, thioalkoxyalkyl group, alkyl Siloxyalkyl group, aminoalkyl group, alkylphosphinoalkyl group, aryl group having 6 to 40 carbon atoms, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryl Oxoalkyl group, aryloxoaryl group, arylsiloxy group, arylalkylsiloxy group, arylsiloxanealkyl group, arylsiloxanearyl group, arylamino group, arylaminoalkyl group, arylaminoaryl group, or arylphosphinoalkyl group, m and n are integers of 1 or more.) The method of claim 1 wherein the metallocene catalyst of formula (I) is (η ⁵ -2- methylbenzamide [e] indene) (η ¹ -2- methylbenzamide [e] _{indene) Ti (OiPr) 2, (} η 5 -Cp ^* ) (η ¹ -9-fluorenyl) Ti (OiPr) ₂ or [η ⁵ : η ¹ -ethylenebis (9-puluorenyl)] Ti (OiPr) ₂ Metallocene for the production of styrenic polymers catalyst. a) converting a cycloalkanedienyl group to an alkali metal salt; And b) Alkali metal salt of the cycloalkanedienyl group of said a) Iii) directly reacting with a transition metal compound having a leaving group or ii) preparing by reacting with a half metallocene compound having a leaving group Method for producing a metallocene catalyst for producing a styrenic polymer of claim 1 comprising a. Styrene monomer a) the metallocene catalyst of claim 1; And b) a promoter selected from the group consisting of alkylaluminoxanes, alkylaluminum and weakly coordinated Lewis acids Polymerizing under a catalyst system comprising a Method for producing a styrene-based polymer comprising: The method of claim 4, wherein Method for producing a styrene-based polymer wherein the alkyl aluminoxane of b) is a compound of formula: [Formula 7] (In Chemical Formula 7, R ₁ is a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkylaryl group, or an arylalkyl group, n is an integer from 1 to 100.) The method of claim 4, wherein Method for producing a styrene-based polymer wherein the alkyl aluminum of b) is a compound of formula (8): [Formula 8] (In Formula 8, R ₂ , R ₃ , and R ₄ are each independently or simultaneously a hydrogen atom, a halogen group, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms, and 6 to C carbon atoms. An aryl group, an alkylaryl group, or an arylalkyl group of 40, wherein at least one of R ₂ , R ₃ , and R ₄ includes an alkyl group.) The method of claim 4, wherein The coordination Lewis acid of b) is trimethylammonium tetrafetylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, tetramethylammonium tetrakis (pentafluorophenyl) borate, N, N- Dimethylanilinium tetraphenylborate, dimethylanilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, ferro Cernium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, sodium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, tris (pentafluorophenyl) borane, tris (2,3,4,5-tetra Styrene-based polymers selected from the group consisting of fluorophenyl) borane, tris (3,5-bis (trifluoromethyl) phenyl) borane, and tris (2,4,6-trifluorophenyl) borane Manufacturing method. The method of claim 4, wherein ^Wherein said polymerization is carried out under a catalyst core metal concentration of a) of 10 ^-8 to 1.0 M. The method of claim 4, wherein B) a method for producing a styrene polymer having an equivalent ratio of alkylaluminoxane to a catalyst of a) of 1: 1 to 10 ⁶ : 1. The method of claim 4, wherein B) a method of producing a styrene-based polymer having an equivalent ratio of alkyl aluminum to the catalyst of a) of 1: 1 to 10 ⁴ : 1. The method of claim 4, wherein The equivalent ratio of b) the coordinating Lewis acid to the catalyst of a) is 0.1: 1 to 50: 1, and the equivalent ratio of b) the alkyl aluminum to the catalyst of a) is 1: 1 to 3000: 1. Manufacturing method. The method of claim 4, wherein The styrene-based monomer is a styrene-based polymer manufacturing method of styrene, a styrene derivative or a mixture of styrene and styrene derivatives. The method of claim 4, wherein A method for producing a styrene polymer wherein the polymer of the polymerization is a styrene homopolymer, a styrene derivative homopolymer, or a copolymer of styrene and a styrene derivative. The method of claim 4, wherein The polymerization method of producing a styrene-based polymer is carried out at a temperature of -80 to 200 ℃. The method of claim 4, wherein The polymerization is a method for producing a styrene polymer, which is slurry polymerization, liquid phase polymerization, gas phase polymerization, or bulk polymerization. The method of claim 4, wherein The polymerization method of producing a styrene-based polymer is a styrene monomer is carried out under styrene pressure of 0.01 to 20 atm of styrene alone. The method of claim 4, wherein The polymerization method of the styrene-based polymer is carried out under 1 to 1000 atm including the pressure of the comonomer. The method of claim 4, wherein A method for producing a styrene polymer, wherein the polymerization is carried out by injecting a solvent, a styrene monomer, a cocatalyst of b), and a catalyst of a) into a reactor. The method of claim 4, wherein The polymerization Iii) activating the catalyst of a) by contacting with the cocatalyst of b); And Ii) injecting the activated i) catalyst into a reactor filled with a styrene monomer and carrying out a polymerization reaction Method for producing a styrene-based polymer comprising a. The method of claim 4, wherein The polymerization Iii) adding alkyl aluminum to the styrene monomer; Ii) activating the catalyst of a) by contacting with the cocatalyst of b); And Iii) injecting the activated catalyst of ii) into a reactor filled with the styrene monomer and alkylaluminum of iii) and performing a polymerization reaction. Method for producing a styrene-based polymer comprising a.