KR100425250B1 - Styrene polymerization process using new multinuclear half metallocene catalyst - Google Patents

Abstract

The present invention relates to a catalyst for producing a vinyl aromatic polymer and a styrene polymerization method using the same, in particular, a transition of a novel structure for preparing a syndiotactic styrene polymer having high activity, excellent stereoregularity, high melting temperature, and various molecular weight distributions. A metal half metallocene catalyst and a method for producing a styrenic polymer using the same.

The present invention provides a multinuclear half metallocene compound in which at least two transition metals of Group 3 to Group 10 of the periodic table are linked through a bridge ligand containing a cycloalkanedinyl group, which is a π- ligand, and a functional group, which is an σ- ligand, at the same time. A method and a method for producing a styrene polymer using this compound as a catalyst are provided.

The multinuclear half metallocene catalyst of the present invention can be used to produce vinyl aromatic polymers having a superior syndiotactic structure with high activity, as well as polymers of various molecular weight distributions.

Description

STYRENE POLYMERIZATION PROCESS USING NEW MULTINUCLEAR HALF METALLOCENE CATALYST}

The present invention relates to a catalyst for producing a vinyl aromatic polymer and a styrene polymerization method using the same, in particular, a transition of a novel structure for preparing a syndiotactic styrene polymer having high activity, excellent stereoregularity, high melting temperature, and various molecular weight distributions. A metal half metallocene catalyst and a method for producing a polymer using the same.

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.

Such syndiotactic styrene polymers can generally be prepared with metallocene catalysts, which are Group 4 transition metal compounds with π-ligand and σ-ligand. Here, as the π-ligand, cyclopentadienyl, indenyl, fluorenyl group or derivatives thereof may be used, and as σ-ligand, alkyl group, aryl group, allyl group, alkoxy group, aryloxy group, thioalkoxy group, A thioaryloxy group, an amino group, an amido group, a carboxyl group, an alkyl silyl group, a halogen, etc. can be used.

EP 210,615 discloses a method for synthesizing syndiotactic styrene polymers in high yield by combining a metallocene catalyst of the above structure as a main catalyst and an alkylaluminoxane as a cocatalyst. More specifically, main catalysts such as cyclopentadienyl titanium trichloride and pentamethylcyclopentadienyl titanium trichloride are activated with methylaluminoxane cocatalysts and used for syndiotactic styrene polymerization with excellent stereoregularity.

In addition, Japanese Patent Application Laid-open No. Hei 4-314,709 discloses that when a secondary ligand of a metallocene catalyst having the above structure is substituted with a chlorine to an alkoxy group, that is, a pentamethylcyclopentadienyl titanium trimethoxide main catalyst and a methylaluminoxane cocatalyst It has been described that using can yield syndiotactic styrene polymers in much higher yields.

On the other hand, Canadian Patent Publication No. CA 2,026,552 discloses a method for producing a syndiotactic styrene polymer having a wide molecular weight distribution by using together two or more of the metallocene catalysts when polymerizing. This makes it possible to vary the narrow molecular weight distribution obtained when only one type of catalyst is present. However, in this case, since the catalysts introduced are separately involved in the polymerization, the resulting styrene polymers are also independent of each other, so that they are difficult to mix uniformly in the molecular unit.

U. S. Patent No. 6,010, 974 discloses the preparation of a binuclear half metallocene catalyst having two cycloalkanedienyl groups linked to both via alkylene or silylene bridges and styrene polymerization using the same. Styrene polymerization showed high polymerization activity, good stereoregularity and narrow molecular weight distribution, as in the case of mononuclear metallocenes, even though the presence of two or more metal centers in a molecule did not inhibit the polymerization reaction. However, according to the method of preparing the ligand used in this case, since both cycloalkanedienyl groups are the same, the narrow molecular weight distribution of the resulting styrene polymer provides various styrene polymers, which is one of the advantages of the multinuclear metallocene catalyst. There is a problem that is not effective.

In addition, EP 964,004 discloses the preparation of a multinuclear metallocene catalyst in which two or more half metallocenes are linked through an auxiliary ligand bridge having a dialkoxy group or a diaryloxy group and styrene polymerization using the same. . Also in this case, styrene polymerization provides high polymerization activity, excellent stereoregularity and narrow molecular weight distribution. However, since the secondary ligand used has a symmetrical structure and also acts as a leaving group during polymerization, the resulting styrene polymer does not show much difference with the mononuclear metallocene catalyst.

The present invention, in consideration of the problems of the prior art, a new multinuclear metallocene catalyst and a method for producing a syndiotactic styrene polymer having a high stereoregularity and at the same time having a high molecular weight distribution with high activity It is an object to provide a styrene homopolymerization method using this catalyst and a copolymerization method with olefins.

Another object of the present invention is to provide a multinuclear half metallocene catalyst comprising at least two transition metal compounds of Groups 3 to 10 of the Periodic Table having a cycloalkanedienyl group.

It is still another object of the present invention to provide a method for preparing a multinuclear half metallocene catalyst using a bridging ligand simultaneously containing a cycloalkanedinyl group, which is a?-Ligand, and a functional group, which is a?-Ligand.

Still another object of the present invention is to provide a high yield of styrene-based polymers such as syndiotactic styrene polymers and copolymers with olefins having excellent stereoregularity, high melting temperature, and various molecular weight distributions using the metallocene catalyst. It is to provide a method that can be produced by.

The present invention provides a multinuclear half metallocene compound represented by the following Chemical Formulas 1, 2, or 3 in order to achieve the above object.

[Formula 1] [Formula 2]

[Formula 3]

In the formula 1, 2, and 3,

M ¹ , M ² , M ³ , and M ⁴ are each independently or simultaneously a transition element of Groups 3 to 10 on the periodic table in the same formula,

Cp ¹ , Cp ² , Cp ³ , and Cp ⁴ are cycloalkanedinyl ligands represented by the following general formulas (4), (5), (6), (7), or (8) independently or simultaneously in the same formula:

[Formula 4] [Formula 5] [Formula 6]

[Formula 7] [Formula 8]

R ₁ , r ₂ , r ₃ , r ₄ , r ₅ , r ₆ , r ₇ , r ₈ , r ₉ , r ₁₀ , r ₁₁ , r _{12 of} Formula 4, 5, 6, 7, or 8, and r ₁₃ is each independently or simultaneously in the same formula, a hydrogen atom, a halogen group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an alkylsilyl group, a haloalkyl group, an alkoxy group, an alkylsiloxy group, an amino group, Alkoxyalkyl group, thioalkoxyalkyl group, alkylsiloxyalkyl group, aminoalkyl group, alkylphosphinoalkyl group, aryl group having 6 to 40 carbon atoms, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryl jade Period, aryl oxo alkyl group, thioaryl oxo alkyl group, aryl oxo aryl group, aryl siloxy group, aryl alkyl siloxy group, aryl siloxane alkyl group, aryl siloxane aryl group, arylamino group, arylamino alkyl group, arylaminoaryl group, or aryl force A pinoalkyl group, each m and n are an integer of 1 or more,

X _a , X _b , X _c , X _d , X _e , X _f , X _g , X _h , and X _i are functional groups that are σ- ligands, each independently or simultaneously in the same formula, a hydrogen atom, a halogen group , Hydroxy group, alkyl group having 1 to 20 carbon atoms, cycloalkyl group, alkylsilyl group, alkenyl group, alkoxy group, alkenyloxy group, thioalkoxy group, alkylsiloxy group, amide group, alkoxyalcohol group, alcoholamine group, carboxyl group, sulfonyl group Aryl group, alkylaryl group, arylalkyl group, arylsilyl group, haloaryl group, aryloxy group, arylalkoxy group, thioaryloxy group, arylsiloxy group, arylalkylsiloxy group, arylamide group having 6 to 40 carbon atoms, An arylalkylamide group, an aryl oxo alcohol group, an alcohol aryl amine group, or an arylamino aryloxy group,

R ¹ , R ² , R ³ , and R ⁴ represent M ¹ , M ² , M ³ , or M ⁴ , which is the transition metal, and Cp ¹ , Cp ² , Cp ³ , or Cp ^4, which are the cycloalkanedinyl ligands. As a bridging linking group, each independently or simultaneously in the same formula, an alkyl group, cycloalkyl group, alkenyl group, alkylsilyl group, haloalkyl group, alkoxy group, alkylsiloxy group, amino group, dialkyl ether group, Dialkylthioether group, alkylsiloxyalkyl group, alkylaminoalkyl group, alkylphosphinoalkyl group, aryl group having 6 to 40 carbon atoms, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryljade Period, aryl oxo alkyl group, thioaryl oxo alkyl group, aryl oxo aryl group, aryl siloxy group, aryl alkyl siloxy group, aryl siloxane alkyl group, aryl siloxane aryl group, arylamino group, arylamino alkyl group, arylaminoaryl group, or aryl force It is a pinoalkyl group,

Z is carbon, silicon, or germanium,

Q is nitrogen, phosphorus, Cr ₁₄ , Si-r ₁₅ , or Ge-r ₁₆ ,

Y ¹ , Y ² , and Y ³ are functional groups that are σ-ligands, each independently or simultaneously in the same formula, oxygen, sulfur, carboxyl group, sulfonyl group, Nr ₁₇ and Pr ₁₈ ,

R ₁₄ , r ₁₅ , r ₁₆ , r ₁₇ , and r ₁₈ of Cr ₁₄ , Si-r ₁₅ , Ge-r ₁₆ , Nr ₁₇ , and Pr ₁₈ each represent a hydrogen atom, a halogen group, 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, aryl group, arylalkyl group, Alkyl aryl group, aryl silyl group, aryl alkyl silyl group, haloaryl group, aryloxy group, aryl oxoalkyl group, thioaryl oxoalkyl group, aryl oxoaryl group, arylsiloxy group, arylalkyl siloxy group, aryl siloxane alkyl group, aryl Selected from the group consisting of a siloxanearyl group, an arylamino group, an arylaminoalkyl group, an arylaminoaryl group, or an arylphosphinoalkyl group,

p is an integer from 1 to 3, q is an integer from 0 to 2,

p + q = 3 is satisfied.

In addition, the present invention is a method for producing a styrene polymer,

Styrene monomer

a) the multinuclear half metallocene represented by Formula 1, 2 or 3

Catalysts of compounds; And

b) alkylaluminoxanes

Ii) mixtures of alkylaluminoxanes, and alkylaluminums; And

Viii) a mixture of coordinating Lewis acid and alkylaluminum

Promoter selected from the group consisting of

Polymerizing under a catalyst system comprising a

It provides a method for producing a styrene-based polymer comprising a.

Hereinafter, the present invention will be described in detail.

The present invention provides a multinuclear half-metallocene catalyst satisfying the formula (1), (2) or (3), and a method for preparing the styrene-based polymer by polymerization, and using the catalyst as a main catalyst. It is to provide a method for producing a styrenic polymer.

The metallocene catalyst that satisfies the formula (1), (2), or (3) of the present invention has two or more transition metals of Group 3 to Group 10 of the periodic table through a bridge containing a cycloalkanedinyl group and at least one functional group at the same time. Linked multinuclear half metallocene compounds. Therefore, each metal center generates a different type of cationic polymerization active species during polymerization, so that not only styrene polymers having high polymerization activity, excellent stereoregularity, and high melting temperature, which are various advantages of the conventional mononuclear metallocene, Since the polymers of various molecular weights are uniformly mixed in the molecular unit, it is easy to control the molecular weight of the polymer. This overcomes the difficulty of polymer processability due to the narrow molecular weight distribution which is a disadvantage of the metallocene catalyst system and can also provide polymers of various physical properties.

The multinuclear half-metallocene catalyst introduces a functional group of a ligand into a transition metal by first reacting a ligand containing a cycloalkanedienyl group and at least one functional group with a half-metallocene compound having a leaving group, and then i) cycloalkane. It may be prepared by converting a dienyl group to an alkali metal salt to react with a transition metal compound having another leaving group, or ii) introducing an alkylsilyl group or an alkyl tin group into a cycloalkanedienyl group and then reacting with a transition metal compound.

In addition, a ligand containing a cycloalkanedienyl group and at least one functional group at the same time may include i) reaction with an alkali metal salt of the cycloalkanedinyl group and an organic compound containing a leaving group and a functional group, or ii) an organic compound containing a functional group. It may be prepared through the reaction of an alkali metal salt with a ketone compound which may have a cycloalkanedienyl skeleton.

In the method for producing the multinuclear half metallocene catalyst, examples of the alkali metal salt of the cycloalkanedinyl group include cyclopentadienyl lithium, cyclopentadienyl sodium, cyclopentadienyl potassium, cyclopentadienyl magnesium, and methylcyclo Pentadienyl 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, organic compounds containing both leaving groups and functional groups include 2-bromo-1-ethanol, 4-bromo-1-butanol, 5-bromo-1-pentanol, 6-bromo-1-hexanol, 9-bromo-1-nonanol, 10-bromo-1-decanol, 4-hydroxybenzylbromide, (2-bromoethyl) -methyl-N-ethanolamine, (2-bromoethyl) -N, N-diethanolamine 4-bromophenol, 4-bromo-2,6-dimethylphenol, 4- (4-bromophenyl) phenol, 4-bromobenzyl alcohol, 4-bromoaniline, 4-bromobenzylamine, 4-bromobutyl acid, 6-bromohexyl acid, 4-bromobenzoic acid, and the like.

In addition, ketone compounds which may have a cycloalkanedienyl skeleton include 2-cyclopenten-l-one, 3-methyl-2-cyclopenten-l-one, and 3,4-dimethyl-2-cyclopenten-l-one. , 2,3,4-trimethyl-2-cyclopenten-l-one, 2,3,4,5-tetramethyl-2-cyclopenten-l-one, 3-ethyl-2-cyclopenten-l-one , 3-tert-butyl-2-cyclopenten-l-one, 3,4-diphenyl-2-cyclopenten-l-one, 1-indanone, 2-indanone, 4,5,6,7- Tetrahydro-1-indanon, 4,5,6,7-tetrahydro-2-indanon 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 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, chlorotitanium triphenoxide, chlorotitanium tributoxide, chlorotitanium triethoxide and the like.

Alkylsilyl or alkyl tin groups which may be substituted with a cycloalkanedienyl group include trimethylsilyl, triethylsilyl, butyldimethylsilyl, phenyldimethylsilyl, trimethyltin, triethyltin, tributyltin and the like.

In the multinuclear half metallocene catalyst for producing a styrene-based polymer represented by Chemical Formulas 1, 2, or 3 of the present invention prepared by the above method, n and m are ideally 1 ≦ n or m ≦ 10 This is preferred.

In addition, the M ¹ to M ⁴ 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, 2,3,4,5,6,7,8,9 -Octahydrofluorenyl group, and the like.

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 is a syndiotactic styrene polymer when the multinuclear half metallocene catalyst for preparing a styrene polymer represented by Formula 1, 2, or 3 is used as a main catalyst for styrene homopolymerization or copolymerization with an olefin. And styrene copolymers of various physical properties can be obtained.

Cocatalysts used with the multinuclear half metallocene catalyst include alkylaluminoxanes represented by the following formula (9), or weakly coordinated Lewis acids, which are mainly used with alkylaluminum represented by the formula (10).

[Formula 9]

In the formula (9),

R ₅ 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.

[Formula 10]

In the formula of Formula 10,

R ₆ , R ₇ , and R ₈ 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, 6 carbon atoms An aryl group, an alkylaryl group, or an arylalkyl group of 40 to 40, wherein at least one of R ₆ , R ₇ , and R ₈ includes an alkyl group.

The compound of Formula 9 may be linear, cyclic, or a net structure, specifically, methyl aluminoxane, modified methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane, hexyl aluminoxane, decyl aluminoxane and the like.

The compound of Formula 10 may specifically include 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 polymerization or copolymerization with an olefin 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 molar ratio with the metallocene catalyst is mainly usable within the range of 1: 1 to 10 ⁶ : 1, preferably between 10: 1 and 10 ⁴ : 1. In addition, the amount of alkylaluminum that can be used with the alkylaluminoxane can be used within the range of 1: 1 to 10 ⁴ : 1 for the metallocene catalyst.

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

Monomers capable of polymerizing with the catalyst system of the present invention may be styrene or styrene derivatives or olefins, and these may be polymerized styrene or styrene derivatives alone, or copolymerization of styrene and styrene derivatives, or styrene or styrene derivatives may be copolymerized with olefins. have.

Styrene derivatives have substituents on the benzene ring of styrene, and the substituents include halogen groups, alkyl groups having 1 to 10 carbon atoms, alkoxy groups, ester groups, thioalkoxy groups, silyl groups, tin groups, amine groups, phosphine groups, and halogenated alkyl groups. , 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, ethyl styrene, normal butyl styrene, p-tertiary butyl styrene, dimethyl styrene, methoxy styrene and ethoxy styrene. , Butoxy styrene, methyl-4- styrenyl ester, thiomethoxy styrene, trimethylsilyl styrene, triethyl silyl styrene, tertiary butyl dimethyl silyl styrene, trimethyl tin styrene, dimethylamino styrene, trimethyl phosphino styrene, chloromethyl styrene , Bromomethylstyrene, 4-vinylbiphenyl, p-divinylbenzene, m-divinylbenzene, trivinylbenzene, 4,4'- divinyl biphenyl, vinyl naphthalene, etc. are mentioned.

In addition, olefins mainly used for copolymerization may be olefins having 2 to 20 carbon atoms, cycloolefins or cyclodiolefins having 3 to 20 carbon atoms, diolefins having 4 to 20 carbon atoms, and the like. Specifically, ethylene, propylene, 1 -Butene, 1-pentene, 1-hexene, 1-octene, 1-decene, cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene, norbornene, methyl-2-norbornene, 1,3-butadiene, 1 , 4-pentadiene, 2-methyl-1,3-butadiene, 1,5-hexadiene and the like.

When the polymerization is carried out using the polymerization catalyst system of the present invention, the polymerization may be carried out in a slurry phase, a liquid phase, a gaseous phase, or 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, and cyclohexane. 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 the solvent-free state, gas phase polymerization is possible under a reactor internal pressure of 0.01 to 20 atmospheres.

In the polymer production method according to the invention, the polymerization temperature is -80 to 200 ℃, preferably 0 to 150 ℃, the polymerization pressure is 1 to 1, including the pressure of the comonomer, when styrene homopolymerization or copolymerization with olefins 1000 atm is adequate.

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 compound, which is the main catalyst used in the polymer manufacturing process, is not particularly limited, but 10 ^-8 to 1.0 M is suitable as the concentration of the central metal in the reaction system, 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 10 to 10 million, 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

Example 1

(O ⁱ Pr) ₃ Ti [Cp (CH ₂ ) ₆ O] TiCp ^* (OMe) ₂ Synthesis of Catalyst

(Preparation of (C ₅ H ₄ ) (CH ₂ ) ₆ OH)

30 ml of tetrahydrofuran (THF) was added to a 250 ml Schlenk flask containing 1.81 g (10 mmol) of Br (CH ₂ ) ₆ OH to dissolve the temperature of the reaction vessel in dry ice / acetone. It was lowered to -78 ℃ using a mixed refrigerant. Next, 1.2 equivalents of NaCp THF solution was slowly injected using a syringe. The reaction solution was stirred at this temperature for 30 minutes, and then slowly heated up to maintain room temperature. It was stirred overnight to give a pale violet solution.

30 ml of saturated aqueous ammonium chloride (NH ₄ Cl) solution was poured into the reaction mixture to terminate the reaction, and then the organic solution portion was extracted twice with 50 ml of diethyl ether. The obtained organic solution was treated with anhydrous magnesium sulfate (MgSO ₄ ) to remove moisture, and then the solution was filtered and the solvent was removed from a rotary evaporator. It was dried under vacuum to obtain 1.41 g (yield 85%) of (C ₅ H ₄ ) (CH ₂ ) ₆ OH.

(Preparation of (C ₅ H ₄ ) (CH ₂ ) ₆ OTiCp ^* (OMe) ₂ )

0.831 g (5 mmol) of (C ₅ H ₄ ) (CH ₂ ) ₆ OH obtained above was dissolved in 30 mL of carbon dichloride (CH ₂ Cl ₂ ) and 1.1 equivalent of triethylamine (0.767 mL) was added thereto. Then, after lowering the temperature of the reaction vessel to -78 ℃, the same equivalent Cp * Ti (OMe) ₂ Cl (1.40 g) carbon dichloride solution dissolved in another flask prepared in advance was slowly added dropwise to the cannula. From here, a white precipitate could be observed.

The temperature of the reaction mixture was raised to room temperature, followed by stirring overnight to obtain a light yellow reaction solution. After the solvent was removed under reduced pressure, the orange-yellow product obtained was extracted with 30 ml of normal hexane. Filter through a Celite 545 filter, triethylamine hydrogen chloride salt and the solution was separated to give a clear yellow solution. The solvent was again removed in vacuo and dried for a long time to obtain 1.64 g (yield 80%) of an orange-yellow product ((C ₅ H ₄ ) (CH ₂ ) ₆ OTiCp ^* (OMe) ₂ ).

(Preparation of (O ⁱ Pr) ₃ Ti [Cp (CH ₂ ) ₆ O] TiCp ^* (OMe) ₂ catalyst)

0.821 g (2 mmol) of (C ₅ H ₄ ) (CH ₂ ) ₆ OTiCp ^* (OMe) ₂ synthesized above was dissolved in 30 mL of diethyl ether, and the temperature of the reaction vessel was lowered to -78 ° 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 pale yellow precipitate. After stirring overnight, the temperature of the reaction vessel was lowered to −78 ° C. and the same equivalent ClTi (O ⁱ Pr) ₃ (0.521 g) diethyl ether solution dissolved in a 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. The reaction was carried out at this temperature for one day.

All solvents of the reaction were removed under vacuum and extracted again with 20 mL of normal hexane. This was filtered through a Celite 545 filter to separate the solution from LiCl to obtain a clean lime green solution. The solvent was removed again under vacuum and dried for a long time to obtain 0.888 g (yield 70%) of (O ⁱ Pr) ₃ Ti [Cp (CH ₂ ) ₆ O] TiCp ^* (OMe) ₂ .

Example 2

(O ⁱ Pr) ₃ Ti [Cp (CH ₂ ) ₉ O] TiCp ^* (OMe) ₂ Synthesis of Catalyst

Br (CH _{2) 6} in OH instead of Br (CH ₂₎ and the (O ⁱ Pr) in the same manner as in Example 1 except for the use of _{9 OH 3 Ti [Cp (CH} 2) 9 O] TiCp * ( OMe) ₂ catalyst was prepared.

Example 3

(O ⁱ Pr) ₃ Ti [Cp (CH ₂ ) ₁₂ O] TiCp ^* (OMe) ₂ Synthesis of Catalyst

Br (CH _{2) 6} in OH instead of Br (CH ₂₎ and the (O ⁱ Pr) in the same manner as in Example 1 except for using _{12 OH 3 Ti [Cp (CH} 2) 12 O] TiCp * ( OMe) ₂ catalyst was prepared.

Example 4

(O ⁱ Pr) ₃ Ti [Cp (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ Synthesis of Catalyst

(Preparation of (C ₅ H ₄ ) (C ₆ H ₄ ) ₂ OH)

30 mL of diethyl ether was dissolved in a 250 mL Schlenk flask containing 2.49 g (10 mmol) of 4-Br (C ₆ H ₄ ) ₂ OH, and the temperature of the reaction vessel was reduced to -78 ° C. Lowered. Next, 2 equivalents 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 20 ml of 1 equivalent of 2-cyclopenten-1-one (0.821 g) THF solution prepared in advance to another flask was added dropwise using a cannula. After stirring at this temperature for 30 minutes, the reaction mixture was warmed to room temperature and stirred overnight. 30 ml of saturated aqueous ammonium chloride (NH ₄ Cl) solution was poured into the reaction mixture to terminate the reaction, and then the organic solution portion was extracted twice with 50 ml of diethyl ether.

The solvent of the obtained organic solution was all removed using the rotary evaporator, and the obtained oily compound was dissolved in 20 ml of carbon dichloride solvent again. A catalytic amount (0.1 g) of paratoluenesulfonic acid was added to the solution as a solid and stirred at room temperature for 1 hour. The reaction mixture was washed with water, and then the organic solution portion was extracted with 30 ml of carbon dichloride, and the water was removed with anhydrous magnesium sulfate (MgSO ₄ ). After filtering the solution, the solvent was removed from the rotary evaporator and dried under vacuum to obtain a yellow solid compound.

The obtained compound was re-dissolved in 20 ml of normal hexane and cooled overnight at -20 ° C to obtain 1.76 g (yield 75%) of (C ₅ H ₄ ) (C ₆ H ₄ ) ₂ OH as an ivory solid compound.

(Preparation of (C ₅ H ₄ ) (C ₆ H ₄ ) ₂ OTiCp ^* (OMe) ₂ )

(C ₅ H ₄ ) (C ₆ H ₄ ) ₂ OH obtained above was reacted with the same equivalent of Cp * Ti (OMe) ₂ Cl by the method of Example 1 to give an orange product ((C ₅ H ₄ ) (C ₆ H ₄ ) ₂ OTiCp ^* (OMe) ₂ ) was obtained.

(Preparation of (O ⁱ Pr) ₃ Ti [Cp (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ catalyst)

The synthesized (C ₅ H ₄ ) (C ₆ H ₄ ) ₂ OTiCp ^* (OMe) ₂ was reacted with the same equivalent of ClTi (O ⁱ Pr) ₃ by the method of Example 1 to give (O ⁱ Pr) ₃ Ti [ Cp (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ was obtained.

Example 5

(O ⁱ Pr) ₃ Ti [(C ₅ Me ₄ ) (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ Synthesis of Catalyst

Except for using 2,3,4,5-tetramethylcyclopent-2-enone instead of 2-cyclopenten-1-one in the same manner as in Example 4 (O ⁱ Pr) ₃ Ti [(C ₅ Me ₄ ) (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ catalyst was prepared.

Example 6

(O ⁱ Pr) ₃ Ti [CpC] ₆ H ₄ O] TiCp ^* (OMe) ₂ Synthesis of Catalyst

(O ⁱ Pr) ₃ Ti [CpC ₆ H ₄ O] TiCp in the same manner as in Example 4 except for using 4-BrC ₆ H ₄ OH instead of 4-Br (C ₆ H ₄ ) ₂ OH ^* (OMe) ₂ catalyst was prepared.

Example 7

(O ⁱ Pr) ₃ Ti [Cp (2,6-Me ₂ C ₆ H ₂ ) O] TiCp ^* (OMe) ₂ Synthesis of Catalyst

(O ⁱ Pr) _{3 in the} same manner as in Example 4, except that 4-Br (2,6-Me ₂ C ₆ H ₂ ) OH is used instead of 4-Br (C ₆ H ₄ ) ₂ OH. Ti [Cp (2,6-Me ₂ C ₆ H ₂ ) O] TiCp ^* (OMe) ₂ catalyst was prepared.

Example 8

(O ⁱ Pr) ₃ Ti [CpC] ₆ H ₄ S] TiCp ^* (OMe) ₂ Synthesis of Catalyst

(O ⁱ Pr) ₃ Ti [CpC ₆ H ₄ S] TiCp in the same manner as in Example 4 except for using 4-BrC ₆ H ₄ SH instead of 4-Br (C ₆ H ₄ ) ₂ OH ^* (OMe) ₂ catalyst was prepared.

Example 9

(O ⁱ Pr) ₃ Ti [CpC] ₆ H ₄ CH ₂ O] TiCp ^* (OMe) ₂ Synthesis of Catalyst

_{4-Br (C 6 H 4} ) 2 4-BrC 6 H 4 CH and the (O ⁱ Pr) in the same manner as in Example 4 except for the use of _{2 OH 3 Ti [CpC 6 H} 4 CH a OH instead of ₂ O] TiCp ^* (OMe) ₂ catalyst was prepared.

Example 10

Preparation of Styrene Homopolymers (Liquid Polymerization)

The multinuclear half metallocene catalysts of Examples 1 to 9 synthesized above 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) Activity (kgPS / molTi · h) Shift Arrangement (%) Molecular Weight (x10 ³ ) Molecular weight distribution Melting Point (℃) Catalyst of Example 1 (O ⁱ Pr) ₃ Ti [Cp (CH ₂ ) ₆ O] TiCp ^* (OMe) ₂ 19.2 1456 92 205 14.5 269 Catalyst of Example 2 (O ⁱ Pr) ₃ Ti [Cp (CH ₂ ) ₉ O] TiCp ^* (OMe) ₂ 22.0 1760 93 220 15.6 270 Catalyst of Example 3 (O ⁱ Pr) ₃ Ti [Cp (CH ₂ ) ₁₂ O] TiCp ^* (OMe) ₂ 22.5 1800 93 225 15.2 270 Catalyst of Example 4 (O ⁱ Pr) ₃ Ti [Cp (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ 22.7 1816 94 240 16.8 271 Catalyst of Example 5 (O ⁱ Pr) ₃ Ti [(C ₅ Me ₄ ) (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ 26.5 2120 97 310 11.5 272 Catalyst of Example 6 (O ⁱ Pr) ₃ Ti [CpC ₆ H ₄ O] TiCp ^* (OMe) ₂ 20.3 1624 94 250 15.7 271 Example 7 Catalyst (O ⁱ Pr) ₃ Ti [Cp (2,6-Me ₂ C ₆ H ₂ ) O] TiCp ^* (OMe) ₂ 21.1 1688 95 274 15.3 272 Catalyst of Example 8 (O ⁱ Pr) ₃ Ti [CpC ₆ H ₄ S] TiCp ^* (OMe) ₂ 14.6 1168 93 210 17.8 269 Catalyst of Example 9 (O ⁱ Pr) ₃ Ti [CpC ₆ H ₄ CH ₂ O] TiCp ^* (OMe) ₂ 19.8 1584 94 238 16.2 270

Example 11

Preparation of Styrene Homopolymers (Block Polymerization)

Among the multinuclear half metallocene catalysts of Examples 1 to 9 synthesized above, styrene was selected in the following manner using the catalysts of Examples 3, 4, 5, and 7 having high liquid phase polymerization activity as in Example 10. Bulk polymerization was performed.

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 mol 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) Activity (kgPS / molTi · h) Shift Arrangement (%) Molecular Weight (x10 ³ ) Molecular weight distribution Melting Point (℃) Catalyst of Example 3 (O ⁱ Pr) ₃ Ti [Cp (CH ₂ ) ₁₂ O] TiCp ^* (OMe) ₂ 52.2 1044 91 280 21.5 268 Catalyst of Example 4 (O ⁱ Pr) ₃ Ti [Cp (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ 56.8 1136 92 340 18.4 270 Catalyst of Example 5 (O ⁱ Pr) ₃ Ti [(C ₅ Me ₄ ) (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ 67.6 1352 94 478 15.9 271 Example 7 Catalyst (O ⁱ Pr) ₃ Ti [Cp (2,6-Me ₂ C ₆ H ₂ ) O] TiCp ^* (OMe) ₂ 51.0 1020 92 325 19.6 270

Example 12

Preparation of Styrene / Ethylene Copolymer

Styrene / ethylene copolymerization was carried out in the following manner using a catalyst of Examples 3, 4, and 5 having high styrene homopolymerization activity among the multinuclear half metallocene catalysts of Examples 1 to 9 synthesized above. .

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, 2 atmospheres of ethylene were added and saturated, and 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 mol of Ti) toluene solution in which the metallocene was dissolved was added. After stirring for 2 hours, 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 / ethylene copolymer.

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

Styrene / Ethylene Copolymerization Results division Yield (g) Activity (kgPS / molTi · h) Ethylene Content (mol%) Glass transition temperature (℃) Melting Point (℃) Catalyst of Example 3 (O ⁱ Pr) ₃ Ti [Cp (CH ₂ ) ₁₂ O] TiCp ^* (OMe) ₂ 22.2 222 8.2 82 256 Catalyst of Example 4 (O ⁱ Pr) ₃ Ti [Cp (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ 21.5 215 10 80 240 Catalyst of Example 5 (O ⁱ Pr) ₃ Ti [(C ₅ Me ₄ ) (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ 18.6 186 6.4 93 260

Example 13

Preparation of Styrene / p-Methylstyrene Copolymer

Styrene / p-methylstyrene copolymerization was carried out in the following manner using a catalyst of Examples 3, 4, and 5 having high styrene homopolymerization activity among the multinuclear half metallocene catalysts of Examples 1 to 9 synthesized above. Was carried out.

100 ml of purified styrene and 5 ml of p-methylstyrene were added to a polymerization reactor in a high purity nitrogen atmosphere, and the temperature was raised 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 mol 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) Activity (kgPS / molTi · h) p-methylstyrene content (mol%) Glass transition temperature (℃) Melting Point (℃) Catalyst of Example 3 (O ⁱ Pr) ₃ Ti [Cp (CH ₂ ) ₁₂ O] TiCp ^* (OMe) ₂ 50.5 1010 7.4 101 246 Catalyst of Example 4 (O ⁱ Pr) ₃ Ti [Cp (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ 52.2 1044 8.0 100 244 Catalyst of Example 5 (O ⁱ Pr) ₃ Ti [(C ₅ Me ₄ ) (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ 64.8 1296 9.2 98 240

Example 14

Preparation of Styrene / 1,3-Butadiene Copolymer

Among the multinuclear half metallocene catalysts of Examples 1 to 9 synthesized above, styrene / 1,3-butadiene was selected using the catalysts of Examples 3, 4, and 5 having high styrene homopolymerization activity. Copolymerization was carried out.

50 ml of purified styrene and 50 ml of 1,3-butadiene were added to a polymerization reactor in a high purity nitrogen atmosphere, and the reaction temperature was adjusted to 25 ° 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 2 hours, the reaction was stopped by adding a 10% by weight hydrochloric acid-ethanol solution, filtered, washed with ethanol and dried in a vacuum oven at 50 ° C. overnight to obtain a final styrene / 1,3-butadiene copolymer. .

Polymerization results and polymer properties for each catalyst are shown in Table 5 below.

Styrene / 1,3-butadiene copolymerization result division Yield (g) Activity (kgPS / molTi · h) 1,3-butadiene content (mol%) Glass transition temperature (℃) Melting Point (℃) Catalyst of Example 3 (O ⁱ Pr) ₃ Ti [Cp (CH ₂ ) ₁₂ O] TiCp ^* (OMe) ₂ 19.8 198 55 83 265 Catalyst of Example 4 (O ⁱ Pr) ₃ Ti [Cp (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ 21.2 212 41 84 267 Catalyst of Example 5 (O ⁱ Pr) ₃ Ti [(C ₅ Me ₄ ) (C ₆ H ₄ ) ₂ O] TiCp ^* (OMe) ₂ 23.5 235 46 86 269

Comparative Example 1

CpTi (OMe) ₃ With Cp ^* Ti (OMe) ₃ Of Styrene Homopolymer Using

Except for using CpTi (OMe) ₃ 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 11.

Polymerization results and polymer properties for each catalyst are shown in Table 6 below.

Styrene homopolymerization results using CpTi (OMe) ₃ and Cp ^* Ti (OMe) ₃ as catalysts division Yield (g) Activity (kgPS / molTi · h) Shift Arrangement (%) Molecular Weight (x 10 ³ ) Molecular weight distribution Melting Point (℃) CpTi (OMe) ₃ 37.2 744 88 105 2.3 265 Cp ^* Ti (OMe) ₃ 64.0 1280 93 298 2.5 269

The transition metal multinuclear half-metallocene catalyst of the periodic table group 3 to group 10 using a bridge ligand containing both a pi- ligand, a cycloalkanedienyl group and a σ- ligand functional group at the same time, is a cocatalyst such as alkylaluminoxane. And a high activity catalyst system, by using it can be prepared a copolymer of syndiotactic styrene polymer and olefin having excellent stereoregularity, high melting temperature and showing various molecular weight distribution. 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 (3)

In the method for producing a styrene polymer, Styrene monomer a) a multinuclear half metallocene compound represented by the following formula (1), (2) or (3) Catalyst of; And b) alkylaluminoxanes Ii) mixtures of alkylaluminoxanes, and alkylaluminums; And Viii) a mixture of coordinating Lewis acid and alkylaluminum Promoter selected from the group consisting of Polymerizing under a catalyst system comprising a Method for producing a styrene-based polymer comprising: [Formula 1] [Formula 2] [Formula 3] In the formula 1, 2, and 3, M ¹ , M ² , M ³ , and M ⁴ are each independently or simultaneously a transition element of Groups 3 to 10 on the periodic table in the same formula, Cp ¹ , Cp ² , Cp ³ , and Cp ⁴ are cycloalkanedinyl ligands represented by the following general formulas (4), (5), (6), (7), or (8) independently or simultaneously in the same formula: [Formula 4] [Formula 5] [Formula 6] [Formula 7] [Formula 8] R ₁ , r ₂ , r ₃ , r ₄ , r ₅ , r ₆ , r ₇ , r ₈ , r ₉ , r ₁₀ , r ₁₁ , r _{12 of} Formula 4, 5, 6, 7, or 8, and r ₁₃ is each independently or simultaneously in the same formula, a hydrogen atom, a halogen group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an alkylsilyl group, a haloalkyl group, an alkoxy group, an alkylsiloxy group, an amino group, Alkoxyalkyl group, thioalkoxyalkyl group, alkylsiloxyalkyl group, aminoalkyl group, alkylphosphinoalkyl group, aryl group having 6 to 40 carbon atoms, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryl jade Period, aryl oxo alkyl group, thioaryl oxo alkyl group, aryl oxo aryl group, aryl siloxy group, aryl alkyl siloxy group, aryl siloxane alkyl group, aryl siloxane aryl group, arylamino group, arylamino alkyl group, arylaminoaryl group, or aryl force A pinoalkyl group, each m and n are an integer of 1 or more, X _a , X _b , X _c , X _d , X _e , X _f , X _g , X _h , and X _i are functional groups that are σ- ligands, each independently or simultaneously in the same formula, a hydrogen atom, a halogen group , Hydroxy group, alkyl group having 1 to 20 carbon atoms, cycloalkyl group, alkylsilyl group, alkenyl group, alkoxy group, alkenyloxy group, thioalkoxy group, alkylsiloxy group, amide group, alkoxyalcohol group, alcoholamine group, carboxyl group, sulfonyl group Aryl group, alkylaryl group, arylalkyl group, arylsilyl group, haloaryl group, aryloxy group, arylalkoxy group, thioaryloxy group, arylsiloxy group, arylalkylsiloxy group, arylamide group having 6 to 40 carbon atoms, An arylalkylamide group, an aryl oxo alcohol group, an alcohol aryl amine group, or an arylamino aryloxy group, R ¹ , R ² , R ³ , and R ⁴ represent M ¹ , M ² , M ³ , or M ⁴ , which is the transition metal, and Cp ¹ , Cp ² , Cp ³ , or Cp ^4, which are the cycloalkanedinyl ligands. As a bridging linking group, each independently or simultaneously in the same formula, an alkyl group, cycloalkyl group, alkenyl group, alkylsilyl group, haloalkyl group, alkoxy group, alkylsiloxy group, amino group, dialkyl ether group, Dialkylthioether group, alkylsiloxyalkyl group, alkylaminoalkyl group, alkylphosphinoalkyl group, aryl group having 6 to 40 carbon atoms, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryljade Period, aryl oxo alkyl group, thioaryl oxo alkyl group, aryl oxo aryl group, aryl siloxy group, aryl alkyl siloxy group, aryl siloxane alkyl group, aryl siloxane aryl group, arylamino group, arylamino alkyl group, arylaminoaryl group, or aryl force It is a pinoalkyl group, Z is carbon, silicon, or germanium, Q is nitrogen, phosphorus, Cr ₁₄ , Si-r ₁₅ , or Ge-r ₁₆ , Y ¹ , Y ² , and Y ³ are functional groups that are σ-ligands, each independently or simultaneously in the same formula, oxygen, sulfur, carboxyl group, sulfonyl group, Nr ₁₇ and Pr ₁₈ , R ₁₄ , r ₁₅ , r ₁₆ , r ₁₇ , and r ₁₈ of Cr ₁₄ , Si-r ₁₅ , Ge-r ₁₆ , Nr ₁₇ , and Pr ₁₈ each represent a hydrogen atom, a halogen group, 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, aryl group, arylalkyl group, Alkyl aryl group, aryl silyl group, aryl alkyl silyl group, haloaryl group, aryloxy group, aryl oxoalkyl group, thioaryl oxoalkyl group, aryl oxoaryl group, arylsiloxy group, arylalkyl siloxy group, aryl siloxane alkyl group, aryl Selected from the group consisting of a siloxanearyl group, an arylamino group, an arylaminoalkyl group, an arylaminoaryl group, or an arylphosphinoalkyl group, p is an integer of 1 to 3, q is an integer of 0 to 2, and satisfies p + q = 3. The method of claim 1, The styrene monomer is a styrene, a styrene derivative, a mixture of styrene and styrene derivatives, a mixture of styrene and olefins, or a mixture of styrene derivatives and olefins. The method of claim 1, The styrene polymer is a styrene homopolymer, a styrene derivative homopolymer, a copolymer of styrene and a styrene derivative, a copolymer of styrene and an olefin, or a copolymer of a styrene derivative and an olefin.