KR100304048B1 - Metallocene Catalysts for Polymerization of Styrene and Method of Polymerization Using the Same - Google Patents

Abstract

The metallocene catalyst of the present invention is prepared by reacting a transition metal compound with a compound having two or more functional groups. The half metallocene catalyst is a combination of a cycloalkanedinyl group, which is a main ligand, and an ancillary ligand, to a transition metal. The functional groups of the compounds include hydroxy group (-OH), thiol group (-SH), amine group (-NHR), and popular (-PHR). The catalyst of the present invention can also be prepared by reacting a dianion compound with a transition metal compound. The metallocene catalyst of the present invention has a structure in which an auxiliary ligand of a transition metal compound and a functional group of the compound are bonded to each other. The metallocene catalyst of the present invention may exist in a wide variety of forms depending on the kind of the transition metal compound or the kind of the compound having two or more functional groups and the molar ratio of each reactant. The metallocene catalyst is used together with a promoter to polymerize the styrene system. Cocatalysts are already known in the art and use either organometallic compounds or mixtures of non-coordinated Lewis acids with alkylaluminum. The organometallic compound is an alkyl aluminum oxane or an organoaluminum compound. In the catalyst system consisting of the metallocene catalyst and the cocatalyst according to the present invention, the styrene system is polymerized. Styrene or derivatives thereof may be polymerized alone or two or more monomers may be copolymerized.

Description

Metallocene catalyst for styrene polymerization and polymerization method using the same {Metallocene Catalysts for Polymerization of Styrene and Method of Polymerization Using the Same}

Field of invention

The present invention relates to a metallocene catalyst for producing a styrene polymer and a polymerization method using the same. More specifically, the present invention provides a metallocene catalyst for producing a styrene-based polymer having high activity, excellent stereoregularity and high melting temperature and good molecular weight distribution even with a small amount of promoter and styrene using the same. It relates to a method for producing a polymer.

Background of the Invention

Generally, olefinic or styrene-based polymers are prepared by radical polymerization, ion polymerization or coordination polymerization by Ziegler-Natta Catalysts. By radical polymerization or ionic polymerization, an atactic polymer is obtained. In the case of coordination polymerization with a Ziegler-Natta catalyst, an isotactic polymer is mainly obtained. Polymers are classified into atactic, isotactic and syndiotactic structures according to the position of the benzene ring, the side chain of the molecular chain. The atactic structure means that the arrangement of the side chains is irregular, and the isotactic structure means that the side chain is biased to one side. In this regard, syndiotactic structure means that the side chains are regularly arranged alternately. Synthetic polymers having a syndiotactic structure were known in theory, but the actual production was possible after the metallocene catalyst was applied.

Metallocene catalysts capable of producing polystyrene having stereoregularity are ligands composed of metal compounds, which are compounds of transition metals of Group 4 of the periodic table, and one or two cycloalkanedienyl groups and derivatives thereof. It has a structure combined with (ligand). Transition metals of Group 4 of the periodic table include titanium, zirconium and hafnium, and cycloalkanedienyl groups include cyclopentadienyl groups, indenyl groups, fluorenyl groups and derivatives thereof.

This type of catalyst is used together with a cocatalyst. A Ziegler-Natta catalyst, which is a conventionally used catalyst, consists of a main catalyst of a halogenated titanium compound, which is a transition metal compound, and a cocatalyst of alkylaluminum. Examples of titanium halide compounds include titanium tetrachloride, and examples of alkylaluminum include trimethylaluminum and triethylaluminum. Meanwhile, recently developed metallocene catalysts use alkylaluminum oxane, which is a reaction product of water and an alkylaluminum compound, as cocatalysts, so that stereoregular polystyrenes (syndiotactic polystyrenes and isoforms) have not been produced until now. Tactic polystyrene) has become possible. In particular, syndiotactic polystyrene is a structure in which phenyl groups in the polymer main chain are alternately positioned. Unlike conventional amorphous general purpose atactic polystyrene, syndiotactic polystyrene has a crystalline structure and has a high melting point (Tm) of about 270 ° C., which is excellent in heat resistance and mechanical properties. Has been the subject of interest.

EP 210 615 A2 (1987) discloses syndiotactic polystyrenes having stereoregularity, and cyclopentadienyl titanium trichloride and alkyl-substituted cyclopentadienyl titanium trichloride, ie pentamethyl, for preparing the same Cyclopentadienyl titanium trichloride is disclosed. These catalysts are known to have good catalyst activity, molecular weight and syndiotactic index.

Japanese Patent Laid-Open Nos. 63-191811 and Hei 3-250007 disclose metallocene catalysts having a sulfur bridge bond, but this has the disadvantage of having a very low yield of catalyst production. Also, Japanese Patent Laid-Open Nos. 3-258812, 4-275313 and 5-105712 disclose metallocene catalysts having alkyl bridge bonds. However, these catalysts also have a disadvantage in that it is difficult to commercialize because of low yield of the catalyst production.

U.S. Patent No. 4,544,762 discloses an alpha-olefin system having a higher stereoregularity and a method of preparing a polymer more active than a Ziegler-Natta catalyst using a transition metal catalyst such as a metallocene catalyst and a reaction product of alkylaluminum and a metal hydrate. And a styrene polymer production method.

Japanese Patent Laid-Open Nos. 62-104818 and 62-187708 disclose metallocene catalysts for producing styrene polymers having a syndiotactic structure. This metallocene catalyst is composed of a structure having a group IVB transition metal as a center metal and a cyclopentadienyl group derivative as a ligand, and an alkyl aluminum oxane which is a reaction product of alkyl aluminum and a metal hydrate is used as a promoter.

U. S. Patent No. 5,026, 798 also discloses a process for polymers having high stereoregularity and high molecular weight using metallocene catalysts.

The inventors of the present invention disclose new novel alkyl bimetallic metals for producing syndiotactic polystyrene having excellent stereoregularity, high melting temperature, and good molecular weight distribution in US Patent Application Nos. 08 / 844,109 and 08 / 844,110. Rosene (ABBN), silyl bridge bimetallic metallocene (SBBM), and alkyl-silyl bridge bimetallic metallocene (A-SBBM) catalyst are disclosed.

The present inventors have developed a novel metallocene catalyst and a styrene polymerization method using the same to efficiently produce a styrene polymer.

An object of the present invention is to provide a highly active metallocene catalyst capable of producing polystyrene having excellent stereoregularity, high melting temperature, and good molecular weight distribution.

Another object of the present invention is to provide a highly active metallocene catalyst capable of producing a large amount of polystyrene even with a small amount of promoter.

Still another object of the present invention is to provide a method for preparing the metallocene catalyst and a method for efficiently producing polystyrene using the metallocene catalyst.

The above and other objects of the present invention can be achieved by the present invention described below.

Hereinafter, the content of the present invention will be described in detail.

The metallocene catalyst of the present invention is prepared by reacting a half metallocene catalyst with a compound having two or more functional groups. The half metallocene catalyst is a combination of a cycloalkanedinyl group, which is a main ligand, and an ancillary ligand, to a transition metal. Examples of functional groups of the compound include a hydroxy group (-OH), a thiol group (-SH), an amine group (-NHR, R is hydrogen, an alkyl group, an aryl group, or a cycloalkyl group) or a popular group (phosphorous group). -PHR and R are hydrogen, an alkyl group, an aryl group or a cycloalkyl group), and a diion compound produced by the reaction between a compound containing these functional groups and an alkali metal compound is reacted with a transition metal compound. The catalyst of the invention can be prepared.

The metallocene catalyst of the present invention has a structure in which an auxiliary ligand of a transition metal compound and a functional group of the compound are bonded to each other. The metallocene catalyst of the present invention may exist in a wide variety of forms depending on the kind of the transition metal compound or the kind of the compound having two or more functional groups and the molar ratio of each reactant.

The metallocene catalyst is used together with a promoter to polymerize styrene. Cocatalysts are already known in the art, using organometallic compounds, or mixtures of non-coordinated Lewis acids with alkylaluminum. The organometallic compound is an alkyl aluminum oxane or an organoaluminum compound.

In the catalyst system consisting of the metallocene catalyst and the cocatalyst according to the present invention, the styrene system is polymerized. As the monomer, styrene or a derivative thereof may be polymerized alone or two or more monomers may be copolymerized.

The metallocene catalyst of the present invention reacts a transition metal compound represented by the following structural formula (A) or (B) with a compound having two or more functional groups represented by the following structural formulas (C), (D) and (E). As prepared, it has a structure in which the auxiliary ligand of the half metallocene and the functional group of the compound are linked to each other:

In the formulas (A) and (B), M is a transition metal of Group 4, 5 and 6 of the periodic table, preferably titanium, zirconium or hafnium which is a transition metal of the Periodic Table 4;

Cp is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group; R ¹ , R ² and R ³ are each independently an alkoxy group, an aryloxy group or a substituted aryloxy group; a, b and c are each an integer of 0 to 4; And d and e are each an integer of 0-3.

In formulas (C), (D) and (E), T ¹ , T ² , T ³ and T ⁴ each independently represent a hydrogen atom or an alkali metal such as sodium (Na), lithium (Li), or potassium (K). ego;

Y, Y ', Y' and Y '' are each independently an oxygen atom, a sulfur atom, -Nr ¹⁷ or -Pr ¹⁸ (wherein r ¹⁷ and r ¹⁸ are hydrogen atoms; C _1-30 alkyl group, cycloalkyl group or alkoxy group being an aryl group, an alkylaryl group or an arylalkyl group of C _6~30);

R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently of the formula R ', R'-O-R',-(R'-O-R '')-or Wherein R ', R' R '' and R '' are each independently C _6-30 straight alkyl or branched alkyl group; C _3-30 cycloalkyl group or substituted cycloalkyl group; or C An aryl group, an alkylaryl group, or an arylalkyl group of _{6 to 40} ; r ¹⁹ is a hydrogen atom; an alkyl group, a cycloalkyl group or an alkoxy group of C _1-10 ; or a C _6-20 aryl group, an alkylaryl group or an arylalkyl group );

Q represents a nitrogen atom or -Cr ²⁰ (wherein r ²⁰ is a C _1-10 alkyl group, a cycloalkyl group or an alkoxy group; or a C _6-20 aryl group, an alkylaryl group or an arylalkyl group); And Z is carbon atom, silicon atom, germanium or to be.

Representative examples of the metallocene catalyst according to the present invention are represented by the following structural formulas (I) to (V):

In the structural formulas (I) to (V), M, M ', M' and M '' are each independently a transition metal of Group 4, 5 and 6 of the periodic table, preferably titanium of transition group 4, Zirconium or hafnium;

Cp, Cp ', Cp', and Cp '' each independently represent a cyclopentadienyl group, indenyl group, fluorenyl group or derivative thereof which generates a η ⁵ bond with a transition metal M, M ', M' or M ''. As one of body weight, they are represented by the following structural formulas (a), (b), (c) or (d);

(In the above formulas (a), (b), (c) and (d) r ¹ , r ² , r ³ , r ⁴ , r ⁵ , r ⁶ , r ⁷ , r ⁸ , r ⁹ , r ¹⁰ , r ^{11, r 12, r 13,} r 14, r 15 and r ¹⁶ are independently a hydrogen atom, an alkyl group of C _1~20, a cycloalkyl group or an alkoxy group; or a C _1~20 aryl group, an alkylaryl group or an aryl group Alkyl group; f is an integer of 4 to 8)

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are each independently an alkoxy group or an aryloxy group; Or formula -YR ⁵ Y'R 'one is represented by a (the formula -YR ⁵ Y'R' and Y and Y 'are independently an oxygen atom, a sulfur atom, -Nr ^17, or ¹⁸ in each -Pr, R ⁵ each independently represents a chemical formula R ', R'-O-R'',-(R'-O-R'')-or Wherein R ', R', R '' and R '' are each independently C _6-30 straight alkyl or branched alkyl group; C _3-30 cycloalkyl group or substituted cycloalkyl group; or A C _6-40 aryl group, an alkylaryl group or an arylalkyl group, r ¹⁷ , r ¹⁸ and r ¹⁹ are hydrogen atoms; C _1-10 alkyl group, cycloalkyl group or alkoxy group; or C _6-30 aryl group, Alkylaryl group or arylalkyl group), R 'is independently a hydrogen atom; C _1-10 straight alkyl group or branched alkyl group; A C _3-20 cycloalkyl group or a substituted cycloalkyl group; Or a C _6-20 aryl group, alkylaryl group or arylalkyl group;

G, G 'and G' may be represented by the formula -YR ⁵ Y'- each independently linking one transition metal and the other transition metal (Y and Y 'in the formula -YR ⁵ Y'- are each independently Is an oxygen atom, a sulfur atom, -Nr ¹⁷ or -Pr ¹⁸ , and R ⁵ is each independently represented by the formula R ', R'-O-R',-(R'-O-R '')-or Wherein R ', R', R '' and R '' are each independently C _6-30 straight alkyl or branched alkyl group; C _3-30 cycloalkyl group or substituted cycloalkyl group; or A C _6-40 aryl group, an alkylaryl group or an arylalkyl group, r ¹⁷ , r ¹⁸ and r ¹⁹ are hydrogen atoms; C _1-10 alkyl group, cycloalkyl group or alkoxy group; or C _6-20 aryl group, Alkylaryl group or arylalkyl group;

Y, Y ', Y' and Y '' are each independently an oxygen atom, a sulfur atom, -Nr ¹⁷ or -Pr ¹⁸ (wherein r ¹⁷ and r ¹⁸ are hydrogen atoms; C _1-10 alkyl group, cycloalkyl group, or alkoxy group; or being an aryl group, an alkylaryl group or an arylalkyl group of C _6~30);

Q represents a nitrogen atom or -Cr ²⁰ (r ²⁰ represents a hydrogen atom in the above; Im or an aryl group, an alkylaryl group or an arylalkyl group of C _6~30; alkyl group, a cycloalkyl group or an alkoxy group of C _1~10); And Z is carbon atom, silicon atom, germanium or to be.

Half metallocene compounds used to prepare the metallocene catalysts of the present invention are commercially available. Of course, the half metallocene compound may be prepared and used according to a known method. The half metallocene compound is prepared by reacting a cyclopentadienyl derivative derivative ligand with an alkali metal or an alkali metal compound to prepare a ligand in a salt state containing an alkali metal, and then falls off from the acid well (Si; silicon). Or by introducing a tin (Sn) tin compound and reacting a transition metal compound of Group 4 of the periodic table. If it is desired to replace an ancillary ligand that binds the transition metal of the half metallocene with an alkoxy group, an alkyl group or another compound, an alcohol or an alkali metal compound of a desired equivalent is reacted with a desired substituent. Substituted compounds can be obtained. Methods for preparing such half metallocene compounds can be easily carried out by those skilled in the art.

Examples of the alkali metal or alkali metal compound include potassium, sodium, butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, sodium methoxide and sodium ethoxide.

Transition metal compounds of the Group 4 of the periodic table include titanium tetrachloride (TiCl ₄ ), zirconium tetrachloride (ZrCl ₄ ) and hafnium tetrachloride (HfCl ₄ ).

Representative examples of the transition metal compounds of the structural formulas (A) and (B) include the following ones:

Pentamethylcyclopentadienyltitanium trimethoxide, 1,2,3,4-tetramethylcyclopentadienyltitanium trimethoxide, 1,2,4-trimethylcyclopentadienyltitanium trimethoxide, 1,2- Dimethylcyclopentadienyltitanium trimethoxide, methylcyclopentadienyltitanium trimethoxide and cyclopentadienyltitanium trimethoxide.

Representative examples of compounds having two or more functional groups represented by the structural formulas (C), (D) and (E) that react with the transition metal compound include the following compounds and potassium (K) and sodium (Na) Structural formulas (C), (D) and (E) may also be reacted with alkali metal or alkali metal compounds such as butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, sodium methoxide, sodium ethoxide and the like. It becomes the compound which has two or more functional groups represented by.

Ethylene glycol, 1,2-propanediol, 1,3-propanediol, (s)-(+)-1,2-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1 , 3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, (R)-(-)-1,3-butanediol, (S)-(+)-1,3-butanediol, ( ±) -1,2-butanediol, 2,3-butanediol, meso-2,3-butanediol, (2R, 3R)-(-)-2,3-butanediol, (2S, 3S)-(+)-2 , 3-butanediol, 3,3-dimethyl-1,2-butanediol, pinacol, 1,5-pentanediol, 1,4-pentanediol, 1,2-pentanediol, 2,4-pentanediol, (2R , 4R)-(-)-pentanediol, (2S, 4S)-(+)-pentanediol, 2-methyl-2,4-pentanediol, (R)-(-)-2-methyl-2,4 -Pentanediol, 2,4-dimethyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, (±)- 1,2-hexanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,7-heptanediol, 1,8-octane Diol, 1,2-octanediol, 1,9- Nandiol, 1,10-decanediol, 1,2-decanediol, 1,12-dodecanediol, (±) -1,2-dodecanediol, cis-1,2-cyclopentanediol, trans-1 , 2-cyclopentanediol, 1,3-cyclopentanediol, trans-1,2-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 2,5-dimethylcyclohexane-1 , 4-diol, 2,5-isopropylcyclohexane-1,4-diol, cis-1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, (+)-cis-para-mentan- 3,8-diol, (-)-trans-para-mentan-3,8-diol, (±) -trans-1,2-cycloheptanediol, cis-1,2-cyclooctanediol, trans-1, 2-cyclooctanediol, 1,4-cyclooctanediol, cis-1,5-cyclooctanediol, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] -decane, (1R, 2R, 3S, 5R)-(-)-finandiol, 1,5-decalindiol, 3-cyclohexane-1,1-dimethanol, (±) -trans-2-cyclohexane-1,4-diol, Trans-para-ment-6-ene-2,8-diol, cis-3,5-cyclohexadiene, 5-norbornene-2,2-dimeth Ol, (±)-(2-endo, 3-exo) -bicyclo [2.2.2] -oct-5-ene-2,3-dimethanol, 1,1,1-tris (hydroxymethyl) ethane , (R)-(+)-1,2,4-butanetriol, (S)-(-)-1,2,4-butanetriol, 2-ethyl-2- (hydroxymethyl) -1 , 3-propanediol, (±) -2-amino-1-butanol, 5-amino-1-pentanol, DL-1-amino-2-propanol, 4-amino-1-butanol, (±) -1 , 2,3-trihydroxyhexane, 1,2,6-trihydroxyhexane, ethanolamine, ethanol diamine, 2-hydroxyethylhydrazine, 3-amino-1-propanol, DL-2-amino-1- Pentanol, 6-amino-1-hexanol, 2- (2-aminoethoxy) ethanol, 2- (methylamino) ethanol, 2- (ethylamino) ethanol, 2- (propylamino) ethanol, diethanolamine , Diisopropanolamine, 2- (butylamino) ethanethiol, N-methyldiethanolamine, N-ethyl diethanolamine, N-butyl diethanolamine, triethanolamine, triisopropanolamine, 1- [N, N-bis (2-hydroxyethyl) amino] -2-propanol, catecol, 3-methylcatolol, 4-methylcatolol, 4-tert-butylcatecol, DL-3,4-dihydroxyphenylglycol, 3,5-diisopropylcatecol, 3,5-di-ter Sheryl-butyl catecol, resorcinol, 2-methylresosinol, 4-ethyllesocinol, 4-hexylesocinol, 4-dodecylesosinol, 5-pentylosocinol, 5-pentadedecyl Socinol, 2,5-dimethylresosocinol, hydroquinone, methylhydroquinone, tertiary-butylhydroquinone, 2,3-dimethylhydroquinone, 2,5-di-tertiarybutylhydroquinone, 2,5-bis (1,1 , 3,3-tetramethylbutyl) hydroquinone, trimethylhydroquinone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, bis (2-hydroxyphenyl) methane, (±)- Hydrobenzoin, meso-hydrobenzoin, (R, R)-(+)-hydrobenzoin, (S, S)-(-)-hydrobenzoin, Zopinacol, 1,4-benzenedimethanol, α, α, α ', α'-tetramethyl-1,4-benzenedimethanol, 1,5-dihydroxy-1,2,3,4-tetra Hydronaphthalene, 2,2'-biphenyldimethanol, 3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) -1-propanol, (±) -1-phenyl-1,2- Ethanediol, (S)-(+)-1-phenyl-1,2-ethanediol, (R)-(-)-1-phenyl-1,2-ethanediol, (R)-(+)-1 -Phenyl-1,2-ethanediol, 4,4'-biphenol, phenylhydroquinone, bis (4-hydroxyphenyl) methane, 4,4'-isopropylitratediphenol, 4,4 '-(1, 4-phenylenediisopropyldene) bisphenol, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1,1-tri (4-hydroxyphenyl) ethane, meso-hexerol, 1 , 2-ethanedithiol, 1,3-propanedithiol, 1,2-propanedithiol, 1,4-butanedithiol, 1,3-butanedithiol, 1,5-pentanedithiol, 1,6 -Hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2-mercaptoethanol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, 3-mercapto- 1,2-propanediol, 2,3-dimer Capto-1-propanol, dithiotretol, dithiorethritol, 2-mercaptoethyl ether, 1,4-dithiane-2,5-diol, 2,5-dimethyl-2,5-dihydroxy- 1,4-dithiane, 1,5,9,13-tetrathiacyclohexadecane-3,11-diol, 1,5,9,13,17,21-hexathiacyclocosan-3,11,19- Triol, ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1,2-diamino-2-methylpropane, 1,6-hexanediamine, 1 , 7-diaminoheptane, 1,8-diaminooctane, 2,5-dimethyl-2,5-hexanediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-dia Minododecane, spermidine, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine), 1,4-diaminocyclohexane, 1,3- Cyclohexanebis (methylamine), 1,8-diamino-p-methane, 4,4'-trimethylenedipiperidine, 2-piperidineethanol, 3-piperidineethanol, 4-hydroxypiperidine, 4 , 4'-trimethylenebis (1-piperidineethanol), 2,2,6, 6-tetramethyl-4-piperidinol, piperazine, 2,6-dimethylpiperazine, 1,4-bis (2-hydroxyethyl) piperazine, homopiperazine, 1,4,7-triazacyclo Nonane, 1,5,9-triazacyclodotecan, cyclone, 1,4,8,11-tetraazacyclotetradecane, 1,4,8,12-tetraazacyclotetradecane, 2-anilinoethanol , N-phenyldiethanolamine, 3-aminophenol, 3-aminothiophenol, 4,4'-ethylenedianiline, 3,3'-methylenedianiline, 4,4'-methylenedianiline, 4-aminophenyl Ether, 4-aminophenol, 4-aminophenethyl alcohol, 4,4'-methylenebis (2,6-dimethylaniline), 4,4'-methylenebis (2,6-diethylaniline), 4,4 ' Methylenebis (2,6-diisopropylaniline), 3,3 ', 5,5'-tetramethylbenzidine, 1,4-phenylenediamine, N, N'-diphenyl-1,4-phenylene Diamine, 2,7-diaminofluorene, N, N'-dibenzylethylenediamine, (±) -cinephrine and 4-hydroxy-4-phenylpiperidine, 1,3-bis (phenylphosphino) Propane , 1,2-bis (phosphino) benzene and 1,2-bis (phosphino) ethane.

In the present invention, when the half metallocene compound, which is a transition metal compound, and a compound having two or more functional groups are reacted in an organic solvent, the molar ratio of the transition metal: the compound having two or more functional groups is in the range of from 1: 0.01 to 1: 1000. The reaction temperature is in the range of -80 ° C to 300 ° C, and the weight ratio of the organic solvent to the reactant is prepared by reacting in the range of 0.1: 1 to 1000: 1, more preferably a transition metal: having two or more functional groups. The molar ratio of the compound is in the range of 1: 0.1 to 1:20, the reaction temperature is in the range of 0 ° C to 150 ° C, and the weight ratio of the organic solvent and the reactant is preferably in the range of 1: 1 to 100: 1.

The metallocene catalyst according to the present invention may also be prepared a catalyst represented by the following structural formulas (VI) to (XIV) according to the reaction conditions:

In the above structural formulas (VI) to (XIV), M and M 'are each independently a transition metal of Group 4, 5 and 6 of the periodic table, preferably titanium, zirconium or hafnium, which is a transition metal of Group 4;

Cp and Cp 'are each independently one of a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof, which generates a transition metal M or M' and an η ⁵ bond, which are represented by the following structural formulas (a) and (b) ), (c) or (d):

(In the above formulas (a), (b), (c) and (d) r ¹ , r ² , r ³ , r ⁴ , r ⁵ , r ⁶ , r ⁷ , r ⁸ , r ⁹ , r ¹⁰ , r ^{11, r 12, r 13,} r 14, r 15 and r ¹⁶ are independently a hydrogen atom, an alkyl group of C _1~20, a cycloalkyl group or an alkoxy group; or a C _1~20 aryl group, an alkylaryl group or an aryl group Alkyl group; f is an integer of 4 to 8)

X ⁵ , X ⁶ , X ⁷ and X ¹³ are each independently an alkoxy group or an aryloxy group; Or formula -YR ⁵ Y'R 'one is represented by a (the formula -YR ⁵ Y'R' and Y and Y 'are independently an oxygen atom, a sulfur atom, -Nr ^17, or ¹⁸ in each -Pr, R ⁵ are each independently selected from the general formula R ', R'-O-R ', - (R'-O-R '') - or Wherein R ', R', R '' and R '' are each independently C _6-20 straight alkyl or branched alkyl group; C _3-20 cycloalkyl group or substituted cycloalkyl group; or A C _6-40 aryl group, an alkylaryl group or an arylalkyl group, r ¹⁷ , r ¹⁸ and r ¹⁹ are hydrogen atoms; C _1-10 alkyl group, cycloalkyl group or alkoxy group; or C _6-20 aryl group, Alkylaryl group or arylalkyl group), R 'is independently a hydrogen atom; C _1-10 straight alkyl group or branched alkyl group; A C _3-20 cycloalkyl group or a substituted cycloalkyl group; Or a C _6-20 aryl group, alkylaryl group or arylalkyl group;

G, G 'and G' may be represented by the formula -YR ⁵ Y'- each independently linking one transition metal and the other transition metal (Y and Y 'in the formula -YR ⁵ Y'- are each independently Is an oxygen atom, a sulfur atom, -Nr ¹⁷ or Pr ¹⁸ , and R ⁵ is a chemical formula R ', R'-O-R',-(R'-O-R '')-or (Wherein R ', R', R '' and R '' are each independently C _6-20 straight alkyl or branched alkyl group; C _3-20 cycloalkyl group or substituted cycloalkyl group; or A C _6-40 aryl group, an alkylaryl group or an arylalkyl group, r ¹⁷ , r ¹⁸ and r ¹⁹ are hydrogen atoms; C _1-10 alkyl group, cycloalkyl group or alkoxy group; or C _6-20 aryl group, Alkylaryl group or arylalkyl group;

Y, Y ', Y' and Y '' are each independently an oxygen atom, a sulfur atom, -Nr ¹⁷ or -Pr ¹⁸ (wherein r ¹⁷ and r ¹⁸ are hydrogen atoms; C _1-10 alkyl group, cycloalkyl group or An alkoxy group, or a C _6-20 aryl group, an alkylaryl group, or an arylalkyl group;

Q represents a nitrogen atom or -Cr ²⁰ (wherein r ²⁰ is a hydrogen atom, a C _1-10 alkyl group, a cycloalkyl group or an alkoxy group; or a C _6-20 aryl group, an alkylaryl group or an arylalkyl group); Z is carbon atom, silicon atom, germanium or ego;

(w), (x), (y) and (z) are each independently

or A structure of (wherein M, Cp, X ⁵ , Y, Y ', Y', R ⁵ , R ⁶ and R ⁷ are as defined above);

k and k 'are integers satisfying from 2 to 100;

p and e are integers, e = 0 or 1, and may have a linear or cyclic structure with a relationship of p = 2-e; And

α, β, γ, and δ may each independently have any one of the structural formulas (I) to (?).

The metallocene catalyst of the present invention is used to polymerize styrenic polymers (particularly syndiotactic structures) or copolymers with cocatalysts.

As the cocatalyst, an organometallic compound is used or a mixture of uncoordinated Lewis acid and alkylaluminum is used together. Organometallic compounds that can be used here include alkylaluminum oxane or organoaluminum compounds. Representative examples of the alkylaluminum oxane include methylaluminoxane (MAO) and modified methylaluminiumoxane (MMAO). The alkyl aluminum oxane has a unit represented by the following structural formula (F), and these include a chain-shaped aluminum oxane represented by the following structural formula (G) and a cyclic aluminum oxane represented by the following structural formula (H).

In the structural formulas (F), (G) and (H), R 'is a C _1-6 alkyl group, and q is an integer of 0-100.

In using the novel metallocene catalyst and the cocatalyst described above, the component ratio of the novel metallocene catalyst component of the present invention and the organometallic compound which is the cocatalyst is usually a Group 4 transition metal (e.g., Titanium, zirconium, hafnium) and the molar ratio of aluminum in the cocatalyst component is 1: 1 to 1:10 ⁶ , and more preferably in the range of 1:10 to 1:10 ⁴ .

Non-coordinating Lewis acids in the mixture of non-coordinating Lewis acids and alkylaluminum used as cocatalysts include N, N-dimethyl aniline tetrakis (pentafluorophenyl) borate, triphenyl carbenium tetrakis (pentafluorophenyl) borate , Ferrocerium tetrakis (pentafluorophenyl) borate and tris (pentafluorophenyl) borate; alkylaluminum aluminum includes trimethyl aluminum, triethyl aluminum, dimethylaluminum chloride, diethylaluminum chloride, triisobutyl aluminum, Diisobutylaluminum chloride, tri (n-butyl) aluminum, tri (n-propyl) aluminum and triisopropyl aluminum.

In the catalyst system of the present invention, the molar ratio of transition metal: uncoordinated Lewis acid is preferably in the range of 1: 0.1 to 1:20, and the molar ratio of transition metal to alkylaluminum in the catalyst component is in the range of 1: 1 to 1: 1000. Preferably, the range of 1: 50-1: 500 is more preferable.

0-140 degreeC is preferable and, as for the polymerization temperature for superposing | polymerizing a styrene system using the catalyst system of this invention, 30-100 degreeC is more preferable.

Monomers that are polymerized using the catalyst system of the present invention are styrene or derivatives thereof, and these may be homopolymerized or two or more of the above monomers may be copolymerized.

The structures of the styrene-based and styrene-based derivatives to be polymerized using the catalyst system of the present invention can be represented by the following general formulas (I) and (J):

In Formula (I), J ¹ is a hydrogen atom; Halogen atom; Or a substituent containing at least one carbon atom, oxygen atom, silicon atom, phosphorus atom, sulfur atom, serenium or tin atom, m is an integer satisfying 1 to 3, and m is 2 or 3 days Each may independently have a different substituent.

In Formula (J), J ¹ is the same as defined in Formula (I), J ² is a substituent consisting of C ₂ to ₁₀ having at least one unsaturated bond, m is an integer from 1 to 3, n Is 1 or 2, and when m is 2 or more and n is 2, each may independently have a different substituent.

Specific examples of the compounds having the formula (I) include alkyl styrene, halogenated styrene, halogen substituted alkyl styrene, alkoxy styrene, vinyl biphenyl, vinyl phenyl naphthalene, vinyl phenyl anthracene, vinyl phenylpyrene, trialkyl silyl vinyl biphenyl, trialkyl Stenibiphenyl, alkylsilyl styrene, carboxymethyl styrene, alkyl ester styrene, vinyl benzene sulfonic acid ester, vinyl benzyl dialkoxy phosphide and the like.

Examples of the alkyl styrene include styrene, methyl styrene, ethyl styrene, butyl styrene, para-methyl styrene, para-tertiary-butyl styrene, and dimethyl styrene. Halogenated styrene includes chloro styrene, bromo styrene, and fluoro styrene. Examples of the halogen-substituted alkyl styrene include chloromethyl styrene, bromomethyl styrene, and fluoromethyl styrene. Examples of the alkoxy styrene include methoxy styrene, ethoxy styrene, and butoxy styrene. -Vinylbiphenyl, 3-vinylbiphenyl, 2-vinylbiphenyl, and the like, and examples of vinylphenylnaphthalene include 1- (4-vinylbiphenylnaphthalene), 2- (4-vinylbiphenylnaphthalene), and 1- ( 3-vinyl biphenyl naphthalene), 2- (3-vinyl biphenyl naphthalene), 1- (2-vinyl biphenyl naphthalene), and the like, and examples of vinylphenyl anthracene include 1- (4-vinylphenyl) anthracene and 2- (4-vinylphenyl) anthracene, 9- (4-vinylphenyl) anthracene, 1- (3-vinylphenyl) anthracene, 9- (3-vinylphenyl) anthracene, 1- (2-vinylphenyl) anthracene, and the like. As vinylphenylpyrene, 1- (4-vinylphenyl) pyrene, 2- (4-vinylphenyl) pyrene, 1- (3-vinylphenyl) pyrene, 2- (3-vinylphenyl) pyrene, 1- (2-vinylphenyl) pyrene, 2- (2-vinylphenyl) pyrene And trialkylsilylvinylbiphenyl include 4-vinyl-4-trimethylsilylbiphenyl, and trialkylstenibiphenyl include 4-vinyl-4-trimethylvinylbiphenyl, and as alkylsilylstyrene, p-trimethylsilyl styrene, m-trimethylsilyl styrene, o-trimethylsilyl styrene, p-triethylsilyl styrene, m-triethyl silyl styrene, o-triethyl silyl styrene, and the like.

Specific examples of the compounds having the above formula (J) include divinylbenzene such as p-divinylbenzene, m-divinylbenzene and the like; Trivinylbenzene; And aryl styrene such as p-aryl styrene, m-aryl styrene and the like.

In addition, the unsaturated olefin represented by the following structural formula (K) may be polymerized using the catalyst of the present invention.

Wherein E ¹ , E ² , E ³ and E ⁴ are each independently a hydrogen atom; Halogen atom; Represents a substituent including at least one carbon atom, oxygen atom, silicon atom, phosphorus atom, sulfur atom, serenium or tin atom, and each of E ¹ , E ² , E ³ and E ⁴ independently have a different substituent Can be.

Examples of the structural formula (K) include α-olefin, cyclic olefin, diene, vinyl ketone, acrolein, acrylonitrile, acrylamide, acrylic acid, vinyl acetate, and the like.

α-olefins include ethylene, propylene, 1-butene, 1-hexene, 1-octene and the like, and cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3-methylcyclopentene, 3-methylcyclohexene, Norbornene and the like, dienes include 1,3-butadiene, isoprene, 1-ethoxy-1,3-butadiene, and chloroprene; and vinyl ketones include methyl vinyl ketone, phenyl vinyl ketone, ethyl vinyl ketone, and n. -Propyl vinyl ketone, and the like, and acrolein include acrolein and methacrolein, and acrylonitrile includes vinylidene cyanide, methoxy acrylonitrile, phenyl acrylonitrile, and the like. -Methyl acryl amide, N-ethyl ichryl amide, N-isopropyl acryl amide, and the like, and acrylate acrylate, isopropyl acrylate, ethyl acrylate, acrylic acid chloride, and the like. Bytes, may include vinyl acetate, vinyl thioacetate.

The metallocene catalyst of the present invention may be more clearly understood by the following examples, which are merely illustrative purposes of the present invention and are not intended to limit the scope of the present invention.

Examples 1-9 and Comparative Examples 1-2: Catalyst Synthesis

Comparative Example 1: Cp * TiCl ₃ (Comparative Catalyst 1)

Potassium 126 mmol (4.93 g) was weighed into the flask and then THF (Tetrahydrofuran) (150 ml) was added. After lowering the reaction vessel to 0 ℃, Cp * (1,2,3,4,5-pentamethylcyclopentadiene) (Cp * (1,2,3,4,5-pentamethylcyclopentadiene)) 126 mmol (17.17 g) ) Was added slowly, and the reaction temperature was raised to reflux. As the reaction progressed, a white solid insoluble in the bottom subsided. After refluxing, the reflux was stopped for a further 1 hour, the reflux was stopped, the temperature was lowered to 0 ° C., and 130 mmol (14.12 g) of chlorotrimethylsilane was slowly added using a syringe. After stirring for 2 hours through a celite (filter) to obtain a slightly yellow clear solution, to remove the solvent (THF) under a reduced pressure of about 0.1torr Cp * (1, 2, 3,4,5-pentamethylcyclopentadiene) was obtained in a yield of 90 with a compound having trimethylsilane. 88.9 mmol (18.5 g) of this compound was mixed with toluene (50 ml) and slowly added to a flask containing 88.9 mmol (16.86 g) and toluene (200 ml) TiCl ₄ . The red solution was stirred for 2 hours, then toluene was removed under reduced pressure, washed with pentane or hexane and dried well to produce Cp * TiCl ₃ (1,2,3,4), a type of typical half metallocene. , 5-pentamethylcyclopentadienyl titanium trichloride) was obtained in a yield of 95.

Comparative Example 2: Cp * Ti (OCH ₃ ) ₃ (Comparative Catalyst 2)

20 mmol (5.79 g) of the compound Cp * TiCl ₃ obtained in Comparative Example 1 was placed in a flask, and THF (100 ml) was added thereto to dissolve. Into another flask, 60 mmol (1.92 g) of dried methanol was dissolved in THF (100 ml), and the temperature of the reaction vessel was lowered to -78 ° C. Triethylamine 61mmol (6.1g) was added to the vessel and stirred at that temperature for about 30 minutes. Cp * TiCl ₃ dissolved in 100 ml of THF was dissolved in methanol and triethylamine THF. (100 ml) was added slowly to the solution. After the addition, the temperature of the reaction vessel was gradually raised to room temperature. After reacting at room temperature for about 12 hours, THF was removed under reduced pressure, 100 ml of hexane was added thereto, stirred for 30 minutes, filtered through celite to obtain a yellow solution, and the solvent of the yellow solution was vacuumed. It dried and Cp * Ti (OCH ₃ ) ₃ (1,2,3,4,5-pentamethylcyclopentadienyl titanium trimethoxide) was obtained in the yield of 79.

Example 1 Catalyst 1

7.02 mmol (2.00 g) of Cp * Ti (OCH ₃ ) ₃ prepared in Comparative Example 2 was placed in a 250 ml flask, and 50 ml of toluene was added to dissolve. In another flask, 10.5 mmol (2.41 g) of 4,4'-isopropylidenediphenol was diluted in 50 ml of toluene and stirred for about 10 minutes at room temperature, followed by Cp * Ti (OCH ₃ ) _{3 Add} solution for about 10 minutes. At this time, if about one third of the Cp * Ti (OCH ₃ ) ₃ solution is added, the reaction mixture is free of solids, turns into a complete solution, and has a light yellow color. After stirring at room temperature for 10 hours or more. After completion of the reaction, the methanol and toluene generated in a vacuum were removed, washed with hexane, and filtered. Orange crystal catalyst 1 {Cp * Ti [OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ O] ₃ TiCp * } Was obtained in a yield of 94.

Example 2: Catalyst 2

Catalyst 2 {Cp * Ti (OCH ₃ ) [OC ₆ H ₄ C (CH ₃ ) was prepared in the same manner as in Example 1 except that 7.0 mmol (1.57 g) of 4,4'-isopropylidenediphenol was diluted in 50 ml of toluene. ) ₂ C ₆ H ₄ O] ₂ Ti (OCH ₃ ) Cp *}. A mixture was produced, separated by solubility difference to give catalysts 1, 2 and 3 in yields of 5, 35 and 56, respectively.

Example 3: Catalyst 3

Catalyst 3 {Cp * Ti (OCH ₃ ) ₂ [OC ₆ H ₄ C (CH) was prepared in the same manner as in Example 1 except that 3.45 mmol (4.4 mmol) of 4,4'-isopropylidenediphenol was diluted in 50 ml of toluene. ₃ ) ₂ C ₆ H ₄ O] Ti (OCH ₃ ) ₂ Cp *} was prepared. A mixture was produced, separated by solubility difference to give catalysts 2 and 3 in yields of 85 and 12, respectively.

Example 4: Catalyst 4

Catalytic 4 {Cp * Ti [OC ₆ H ₄ C (CF ₃ ) ₂ C ₆ H ₄ O] ₃ TiCp *} was prepared. Catalyst 4 in orange crystals was obtained in a yield of 92.

Example 5: Catalyst 5

Catalyst 5 {Cp * Ti (OCH ₃ ) [OC ₆ H ₄ C in the same manner as in Example 1, except that 7.00 mmol (2.31 g) of 4,4'-hexafluoroisopropylidenediphenol was diluted in 50 ml of toluene. (CF ₃ ) ₂ C ₆ H ₄ O] ₂ Ti (OCH ₃ ) Cp *} was prepared. A mixture was produced, separated by solubility difference to give catalysts 4, 5 and 6 in yields of 1, 66 and 24, respectively.

Example 6: Catalyst 6

Catalyst 6 {Cp * Ti (OCH ₃ ) ₂ [OC ₆ H _{4] in the} same manner as in Example 1 except that 3.47 mmol (1.15 g) of 4,4'-hexafluoroisopropylidenediphenol was diluted in 50 ml of toluene. C (CF ₃ ) ₂ C ₆ H ₄ O] Ti (OCH ₃ ) ₂ Cp *} was prepared. A mixture was produced, separated by solubility difference to give catalysts 5 and 6 in yields of 4 and 89, respectively.

Example 7: Catalyst 7

Catalyst 7 {Cp * Ti [OC ₆ H _{4) in the} same manner as in Example 1 except that 10.50 mmol (4,4'-dimethylsillylidenediphenol) was diluted in 50 ml of toluene. Si (CH ₃ ) ₂ C ₆ H ₄ O] ₃ Ti (OCH ₃ ) ₂ Cp *}. Catalyst 7 in orange crystals was obtained in a yield of 87.

Example 8 Catalyst 8

Catalyst 8 {Cp * Ti (OCH ₃ ) [] was prepared in the same manner as in Example 1 except that 7.20 mmol (1.76 g) of 4,4'-dimethylsilylidenediphenol was diluted in 50 ml of toluene. OC ₆ H ₄ Si (CH ₃ ) ₂ C ₆ H ₄ O] ₂ Ti (OCH ₃ ) Cp *} was prepared. A mixture was produced, separated by solubility difference to give catalysts 7, 8 and 9 in yields of 9, 48 and 39, respectively.

Example 9: Catalyst 9

Catalyst 9 {Cp * Ti (OCH ₃ ) _{2 in the} same manner as in Example 1 except that 3.50 mmol (0.86 g) of 4,4'-dimethylsilylidenediphenol was diluted in 50 ml of toluene. [OC ₆ H ₄ Si (CH ₃ ) ₂ C ₆ H ₄ O] Ti (OCH ₃ ) ₂ Cp *} was prepared. A mixture was produced, separated by solubility difference to give catalysts 5 and 6 in yields of 7 and 79, respectively.

Examples 10-18: Styrene Polymerization (Solution Polymerization)

Styrene polymerization was carried out using the novel metallocene catalysts (catalysts 1-9) prepared in Examples 1-9. Here, the catalyst concentration (titanium concentration) is 4 × 10 ^-6 mol, the styrene monomer 5 ml, toluene 80 ml, the aluminum concentration contained in the modified methyl aluminum oxane is 1 × 10 ^-3 mol, and the temperature inside the reactor is set at 70 ° C. After aligning, the polymerization was carried out for a certain time until the stirring was stopped.

Styrene polymerization was carried out in a glass reactor equipped with a valve capable of supplying monomers and nitrogen, using an external temperature controller, a magnetic stirrer or a mechanical stirrer. Purified toluene (80 ml) was added to the nitrogen-substituted glass reactor, followed by addition of purified styrene (5 ml), and a modified methyl aluminum oxane (aluminum concentration = 1 × 10 ^-3 mol) as a promoter was added thereto. After sufficient stirring, the required amount of catalyst (concentration of titanium = 4 × 10 ⁻⁶ mol) was injected to initiate polymerization. After some time, a little methanol was added to terminate the polymerization. The obtained mixture was washed with a large amount of methanol added with hydrochloric acid and then filtered, and the physical properties of the polystyrene obtained by drying the polymer thus obtained at 90 ° C. for about 4 hours in a vacuum are shown in Table 1.

Comparative Example 3: Styrene Polymerization (Solution Polymerization)

Styrene polymerization was carried out in the same manner as in Examples 10 to 18 except that pentamethylcyclopentadienyltitanium trimethoxide [Cp * Ti (OCH ₃ ) ₃ ], which is a conventional metallocene catalyst, was used as the catalyst. The physical properties of the polystyrene obtained here are shown in Table 1.

division Polymerization time (minutes) Yield (g) Active KgPS / [Ti] hr SI () Average molecular weight (× 10 ³ ) Molecular weight distribution Melting Point (℃) Example 10 Catalyst 1 24 2.81 1756 99 285 1.98 271 Example 11 Catalyst 2 28 2.49 1334 98 261 2.18 270 Example 12 Catalyst 3 30 2.10 1050 98 243 2.36 270 Example 13 Catalyst 4 18 3.21 2675 99 420 1.89 271 Example 14 Catalyst 5 24 3.05 1906 98 403 2.20 270 Example 15 Catalyst 6 28 2.76 1725 97 372 2.33 269 Example 16 Catalyst 7 24 2.96 1850 99 376 2.06 270 Example 17 Catalyst 8 28 2.61 1398 98 348 2.21 267 Example 18 Catalyst 9 30 2.35 1175 98 330 2.35 266 Comparative Example 3 Comparative Catalyst 2 30 1.65 825 97 230 2.14 271

Examples 19-23 and Comparative Examples 4-9: Styrene Polymerization (Solution Polymerization)

Styrene polymerization was carried out using the metallocene catalysts prepared in Example 1 and Comparative Example 2. Here, the catalyst concentration (titanium concentration) is 4.0 × 10 ^-6 mol, styrene monomer 5 ml, toluene 80 ml, triisobutylaluminum (aluminum concentration = 0-3.2 × 10 ^-3 mol) instead of aluminum oxane modified with cocatalyst. And methylaluminum oxane (aluminum concentration = 1 × 10 ⁻³ mol) for 30 minutes.

Styrene polymerization was carried out in a glass reactor equipped with a valve capable of supplying monomers and nitrogen, using an external temperature controller, a magnetic stirrer or a mechanical stirrer. Purified toluene (80 ml) was added to a nitrogen-substituted glass reactor, and purified styrene (5 ml) was added, followed by triisobutyl aluminum (concentration of aluminum = 0-3.2 x 10 ^-3 mol) and methylaluminum oxane. (Concentration of aluminum = 1 x 10 ^-3 mol) was added and sufficiently stirred, and then a necessary amount of catalyst (concentration of titanium = 4 x 10 ^-6 mol) was injected to initiate polymerization. After a certain time, a little methanol was added to terminate the polymerization, and the obtained mixture was washed with a large amount of methanol added with hydrochloric acid, followed by filtration, and the obtained polymer was dried in vacuo at 90 ° C. for at least 4 hours to obtain physical properties of the polystyrene. Table 2 shows.

division Triisobutylaluminum (mol) MAO (mol) Polymerization time (minutes) Yield (g) Active KgPS / [Ti] hr Example 19 Catalyst 1 2 × 10 ^-4 1 × 10 ^-3 30 2.90 1450 Example 20 4 × 10 ^-4 1 × 10 ^-3 30 3.50 1750 Example 21 8 × 10 ^-4 1 × 10 ^-3 30 2.47 1235 Example 22 1.6 × 10 ^-3 1 × 10 ^-3 30 1.28 640 Example 23 3.2 × 10 ^-3 1 × 10 ^-3 30 0.31 155 Comparative Example 4 Comparative Catalyst 2 2 × 10 ^-4 1 × 10 ^-3 30 2.84 1420 Comparative Example 5 4 × 10 ^-4 1 × 10 ^-3 30 2.40 1200 Comparative Example 6 8 × 10 ^-4 1 × 10 ^-3 30 1.27 635 Comparative Example 7 1.6 × 10 ^-3 1 × 10 ^-3 30 0.67 335 Comparative Example 8 3.2 × 10 ^-3 1 × 10 ^-3 30 0.58 290 Comparative Example 9 - 1 × 10 ^-3 30 0.06 30

Example 24 and Comparative Example 10: styrene polymerization (block polymerization)

Styrene polymerization was carried out using the metallocene catalyst prepared in Example 1. Here, the catalyst concentration (titanium concentration) is 1.5 × 10 ^-5 mol, styrene monomer 200 ml, triisobutylaluminum (aluminum concentration = 1.2 × 10 ^-2 mol) and methyl aluminum oxane (aluminum concentration = 1.5 × 10 ^-3) mol) was used to maintain the reactor internal temperature at 70 ° C. and polymerize for 1 hour.

Styrene polymerization was carried out in a glass reactor equipped with a valve capable of supplying monomers and nitrogen, using an external temperature controller, a magnetic stirrer or a mechanical stirrer. After adding purified styrene (200 ml) to a nitrogen-substituted glass reactor, triisobutyl aluminum (aluminum concentration = 1.2 x 10 ^-2 mol), a promoter, was added, and methyl aluminum oxane (aluminum concentration =) as a promoter. After 1.5 × 10 ⁻³ mol) was added and sufficiently stirred, a necessary amount of catalyst (concentration of titanium = 1.5 × 10 ⁻⁵ mol) was injected to initiate polymerization. After a certain time, a little methanol was added to terminate the polymerization, and the obtained mixture was washed with a large amount of methanol added with hydrochloric acid, followed by filtration, and the obtained polymer was dried in vacuo at 90 ° C. for at least 4 hours to obtain physical properties of the polystyrene. Table 3 shows.

division Yield (g) Active KgPS / [Ti] hr SI () Average molecular weight (× 10 ³ ) Molecular weight distribution Melting Point (℃) Example 24 Catalyst 1 138 9200 99 534 2.21 273 Comparative Example 10 Comparative Catalyst 2 105 7000 95 410 2.54 271

Example 25: Catalyst Preparation and Styrene Solution Polymerization in One Reactor

An external temperature controller, a magnetic stirrer or a mechanical stirrer apparatus was used, and the reaction was carried out in a glass reactor capable of supplying monomers and nitrogen. Purified toluene (40 ml) was added to a nitrogen-substituted glass reactor, and pentamethylcyclopentadienyl titanium trimethoxide [Cp * Ti (OCH ₃ ) ₃ ] 4 × 10 ⁻⁶ mol (1.11 mg) was added to toluene (20 ml). After dilution in), a solution of 4,4'-isopropylidenediphenol diluted in toluene (20 ml) is added thereto. After stirring at room temperature for 1 hour, the temperature was raised to 70 ° C., methylaluminum oxane (Al concentration = 1 × 10 ⁻³ mol) as a promoter was added, and purified styrene (5 ml) was added to initiate polymerization. After a certain time (30 minutes) a little methanol was added to terminate the polymerization. The obtained mixture was poured into a large amount of methanol added with hydrochloric acid to obtain a polymer, washed with methanol and filtered, and the resulting polymer was vacuum dried to obtain 2.04 g of polystyrene. This polymer has a stereoregularity of 96 and has a melting point of 271 ° C.

Example 26 Catalyst Preparation and Styrene Bulk Polymerization in One Reactor

An external thermostat, magnetic stirrer or mechanical stirrer was used and the reaction was carried out in a glass reactor with a valve capable of supplying monomers and nitrogen. Purified toluene (150 ml) was added to a nitrogen-substituted glass reactor, and pentamethylcyclopentadienyl titanium trimethoxide [Cp * Ti (OCH ₃ ) ₃ ] 1.5 × 10 ⁻⁵ mol (4.34 mg) was purified. After diluting in monomer (20 ml), a solution obtained by diluting 4,4'-isopropylidenediphenol in purified styrene monomer (30 ml) is added thereto. After stirring for 1 hour at room temperature, the temperature was raised to 70 ° C., triisobutyl aluminum oxane (aluminum concentration = 1.2 × 10 ⁻² mol) and methylaluminum oxane as a promoter (aluminum concentration = 1.5 × 10 ⁻³ mol) Was added to initiate polymerization. After a certain time (about 1 hour) a little methanol was added to terminate the polymerization. The mixture thus obtained was poured into a large amount of methanol added with hydrochloric acid to obtain a polymer, washed with methanol, filtered and dried in vacuo to obtain 120 g of polystyrene. This polymer had a stereoregularity of 97.

The metallocene catalyst of the present invention can be used to prepare styrene-based polymers (particularly syndiotactic structures) and copolymers having excellent stereoregularity, high melting temperature, and good molecular weight and molecular weight distribution. Not only can the styrene-based polymer and copolymer be prepared using the cocatalyst of the present invention, but also has a very stable effect on air or moisture than a conventionally known catalyst, and the present invention provides a metallocene of the present invention through an easier and simpler process. It has the effect of providing a method for producing a catalyst in high yield.

As can be seen from Tables 1 to 3, in the case of styrene homopolymerization and copolymerization using the metallocene catalyst of the present invention at the time of solution polymerization and bulk polymerization, the polymerization activity of the conventional metallocene It was superior to the catalysts Cp * Ti (OCH ₃ ) ₃ , Cp * Ti (OCH ₃ ) ₂ Cl, Cp * Ti (OCH ₃ ) Cl ₂ , Cp * TiCl ₃ . The polymer can be prepared in a range where the transition temperature (Tg) and melting point (Tm) do not show a significant difference.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims (12)

Transition metal compounds represented by the following structural formulas (A) or (B); And Compounds having two or more functional groups represented by the following structural formulas (C), (D) and (E); A metallocene catalyst for styrene-based polymerization, which is prepared by reacting: M in the formulas (A) and (B) is titanium, zirconium or hafnium, which is a transition metal of the Group 4 of the periodic table; Cp is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group; R ¹ , R ² and R ³ are each independently an alkoxy group, an aryloxy group or a substituted aryloxy group; a, b and c are each an integer of 0 to 4; And d and e are each an integer of 0 to 3; In formulas (C), (D) and (E), T ¹ , T ² , T ³ and T ⁴ each independently represent a hydrogen atom or an alkali metal such as sodium (Na), lithium (Li), or potassium (K). ego; Y, Y ', Y' and Y '' are each independently an oxygen atom, a sulfur atom, -Nr ¹⁷ or -Pr ¹⁸ (wherein r ¹⁷ and r ¹⁸ are hydrogen atoms; C _1-30 alkyl group, cycloalkyl group or alkoxy group being an aryl group, an alkylaryl group or an arylalkyl group of C _6~30); R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently of the formula R ', R'-O-R',-(R'-O-R '')-or Wherein R ', R' R '' and R '' are each independently C _6-30 straight alkyl or branched alkyl group; C _3-30 cycloalkyl group or substituted cycloalkyl group; or C An aryl group, an alkylaryl group, or an arylalkyl group of _{6 to 40} ; r ¹⁹ is a hydrogen atom; an alkyl group, a cycloalkyl group or an alkoxy group of C _1-10 ; or a C _6-20 aryl group, an alkylaryl group or an arylalkyl group ); Q represents a nitrogen atom or -Cr ²⁰ (wherein r ²⁰ is a C _1-10 alkyl group, a cycloalkyl group or an alkoxy group; or a C _6-20 aryl group, an alkylaryl group or an arylalkyl group); And Z is carbon atom, silicon atom, germanium or being. The method of claim 1, wherein the transition metal compound is pentamethylcyclopentadienyl titanium trimethoxide, 1,2,3,4-tetramethylcyclopentadienyl titanium trimethoxide, 1,2,4-trimethylcyclopenta Styrene selected from the group consisting of dienyl titanium trimethoxide, 1,2-dimethylcyclopentadienyl titanium trimethoxide, methylcyclopentadienyl titanium trimethoxide, and cyclopentadienyl titanium trimethoxide Metallocene catalyst for system polymerization. The compound of claim 1, wherein the compound having two or more functional groups is ethylene glycol, 1,3-propanediol, 1,2-propanediol, (s)-(+)-1,2-propanediol, 2-methyl -1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, (R)-(-)-1,3-butanediol, (S)-(+)-1,3-butanediol, (±) -1,2-butanediol, 2,3-butanediol, meso-2,3-butanediol, (2R, 3R)-(-)-2, 3-butanediol, (2S, 3S)-(+)-2,3-butanediol, 3,3-dimethyl-1,2-butanediol, pinacol, 1,5-pentanediol, 1,4-pentanediol, 1 , 2-pentanediol, 2,4-pentanediol, (2R, 4R)-(-)-pentanediol, (2S, 4S)-(+)-pentanediol, 2-methyl-2,4-pentanediol, (R)-(-)-2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6 -Hexanediol, 1,5-hexanediol, (±) -1,2-hexanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl- 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-decanediol, 1 , 12-dodecanediol, (±) -1,2-dodecanediol, cis-1,2-cyclopentanediol, trans-1,2-cyclopentanediol, 1,3-cyclopentanediol, trans-1 , 2-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 2,5-dimethylcyclohexane-1,4-diol, 2,5-isopropylcyclohexane-1,4- Diol, cis-1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, (+)-cis-para-mentan-3,8-diol, (-)-trans-para-mentan-3, 8-diol, (±) -trans-1,2-cycloheptanediol, cis-1,2-cyclooctanediol, trans-1,2-cyclooctanediol, 1,4-cyclooctanediol, cis-1, 5-cyclooctanediol, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.02,6] -decane, (1R, 2R, 3S, 5R)-(-)-finandiol, 1,5-decalin Diol, 3-cyclohexane-1,1-dimethanol, (±) -trans-2-cyclohexane-1,4-diol, trans-para-ment -6-ene-2,8-diol, cis-3,5-cyclohexadiene, 5-norbornene-2,2-dimethanol, (±)-(2-endo, 3-exo) -bicyclo [ 2.2.2] -oct-5-ene-2,3-dimethanol, 1,1,1-tris (hydroxymethyl) ethane, (R)-(+)-1,2,4-butanetriol, (S)-(-)-1,2,4-butanetriol, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, (±) -1,2,3-trihydroxy Hexane, 1,2,6-trihydroxyhexane, ethanolamine, 2-hydroxyethylhydrazine, 3-amino-1-propanol, DL-1-amino-2-propanol, 4-amino-1-butanol, ( ±) -2-amino-1-butanol), 5-amino-1-pentanol, DL-2-amino-1-pentanol, 6-amino-1-hexanol, 2- (2-aminoethoxy) Ethanol), 2- (methylamino) ethanol, 2- (ethylamino) ethanol, 2- (propylamino) ethanol, diethanolamine, diisopropanolamine, 2- (butylamino) ethanethiol, N-methyldiethanolamine , N-ethyldiethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanolamine, 1- [N, N-bis (2- Hydroxyethyl) amino] -2-propanol, catecol, 3-methylcatolol, 4-methylcatolol, 4-tertiary-butylcatecol, DL-3,4-dihydroxyphenylglycol, 3,5 -Diisopropyl catecol, 3,5-di-tertiary-butyl catecol, lesosinol, 2-methyllesosinol, 4-ethylesosinol, 4-hexylesosinol, 4-dodecylesosine Ol, 5-pentylesosinol, 5-pentadesylesinol, 2,5-dimethylresosocinol, hydroquinone, methylhydroquinone, tertiary-butylhydroquinone, 2,3-dimethylhydroquinone, 2,5-di- Tertiarybutylhydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, trimethylhydroquinone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4- Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, Bis (2-hydroxyphenyl) methane, (±) -hydrobenzoin, meso-hydrobenzoin, (R, R)- (+)-Hydrobenzoin, (S, S)-(-)-hydrobenzoin, benzopinacol, 1,4-benzenedimethanol, α, α, α ', α'-tetramethyl-1,4 -Benzenedimethanol, 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, 2,2'-biphenyldimethanol, 3- (3,5-di-tertiary-butyl-4 -Hydroxyphenyl) -1-propanol, (±) -1-phenyl-1,2-ethanediol, (S)-(+)-1-phenyl-1,2-ethanediol, (R)-(- ) -1-phenyl-1,2-ethanediol, (R)-(+)-1,1,2-triphenyl-1,2-ethanediol, 4,4'-biphenol, phenylhydroquinone, bis ( 4-hydroxyphenyl) methane, 4,4'-isopropylitratediphenol, 4,4 '-(1,4-phenylenediisopropylidene) bisphenol, 2,2-bis (4-hydroxy-3- Methylphenyl) propane, 1,1,1-tri (4-hydroxyphenyl) ethane, meso-hexerol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,2-propanedithiol, 1,4-butanedithiol, 1,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2- Mercaptoethanol, 1-mercapto-2-propanol, 3-mer Capto-2-butanol, 3-mercapto-1,2-propanediol, 2,3-dimercapto-1-propanol, dithiotretol, dithiorethritol, 2-mercaptoethyl ether, 1,4 -Dithiane-2,5-diol, 2,5-dimethyl-2,5-dihydroxy-1,4-dithiane, 1,5,9,13-tetrathiacyclohexadecane-3,11-diol , 1,5,9,13,17,21-hexathiacyclocoic acid-3,11,19-triol, ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4- Diaminobutane, 1,2-diamino-2-methylpropane, 1,6-hexanediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 2,5-dimethyl-2,5-hexane Diamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, spermidine, 4,4'-methylenebis (cyclohexylamine), 4,4'- Methylenebis (2-methylcyclohexylamine), 1,4-diaminocyclohexane, 1,3-cyclohexanebis (methylamine), 1,8-diamino-p-methane, 4,4'-trimethylene Dipiperidine, 2-piperidineethanol, 3-piperidineethanol, 4-hydroxypi Lidine, 4,4'-trimethylenebis (1-piperidineethanol), 2,2,6,6-tetramethyl-4-piperidinol, piperazine, 2,6-dimethylpiperazine, 1,4- Bis (2-hydroxyethyl) piperazine, homopiperazine, 1,4,7-triazacyclononane, 1,5,9-triazacyclodotecan, cyclic, 1,4,8,11-tetra Azacyclotetradecane, 1,4,8,12-tetraacyclocyclotedecane, 2-anilinoethanol, N-phenyldiethanolamine, 3-aminophenol, 3-aminothiophenol, 4,4'-ethylenedi Aniline, 3,3'-methylenedianiline, 4,4'-methylenedianiline, 4-aminophenyl ether, 4-aminophenol, 4-aminophenethyl alcohol, 4,4'-methylenebis (2,6-dimethyl Aniline), 4,4'-methylenebis (2,6-diethylaniline), 4,4'-methylenebis (2,6-diisopropylaniline), 3,3 ', 5,5'-tetramethyl Benzidine, 1,4-phenylenediamine, N, N'-diphenyl-1,4-phenylenediamine, 2,7-diaminofluorene, N, N'-dibenzylethylenediamine, (±) -cine Prin, and 4-hi Hydroxy-4-phenylpiperidine, 1,3-bis (phenylphosphinol) propane, 1,2-bis (phosphino) benzene and 1,2-bis (phosphino) ethane A metallocene catalyst for styrene polymerization. The metallocene catalyst for styrene-based polymerization according to claim 1, wherein the metallocene catalyst is represented by any one of the following structural formulas (I) to (V): In the above structural formulas (I) to (V), M, M ', M' and M '' are each independently titanium, zirconium or hafnium, which are transition metals of Group 4 of the periodic table; Cp, Cp ', Cp', and Cp '' each independently represent a cyclopentadienyl group, indenyl group, fluorenyl group or derivative thereof which generates a η ⁵ bond with a transition metal M, M ', M' or M ''. As one of body weight, they are represented by the following structural formulas (a), (b), (c) or (d); (In the above formulas (a), (b), (c) and (d) r ¹ , r ² , r ³ , r ⁴ , r ⁵ , r ⁶ , r ⁷ , r ⁸ , r ⁹ , r ¹⁰ , r ^{11, r 12, r 13,} r 14, r 15 and r ¹⁶ are independently a hydrogen atom, an alkyl group of C _1~20, a cycloalkyl group or an alkoxy group; or a C _1~20 aryl group, an alkylaryl group or an aryl group Alkyl group; and f is an integer of 4 to 8; X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are each independently an alkoxy group or an aryloxy group; Or one of the formula -YR ⁵ Y'R '(wherein Y and Y' are each independently an oxygen atom, a sulfur atom, -Nr ¹⁷ or -Pr ¹⁸ , and each R ⁵ is independently of the formula R ' , R'-O-R '',-(R'-O-R '')-or Wherein R ', R', R '' and R '' are each independently a C _6-30 straight alkyl or branched alkyl group; C _3-20 cycloalkyl group or substituted cycloalkyl group; or A C _6-40 aryl group, an alkylaryl group or an arylalkyl group, r ¹⁷ , r ¹⁸ and r ¹⁹ are hydrogen atoms; C _1-10 alkyl group, cycloalkyl group or alkoxy group; or C _6-30 aryl group, Alkylaryl group or arylalkyl group), R 'is independently a hydrogen atom; C _1-10 straight alkyl group or branched alkyl group; A C _3-20 cycloalkyl group or a substituted cycloalkyl group; Or a C _6-20 aryl group, alkylaryl group or arylalkyl group; G, G 'and G' may be represented by the formula -YR ⁵ Y'- each independently linking one transition metal and the other transition metal (Y and Y 'in the formula -YR ⁵ Y'- are each independently Is an oxygen atom, a sulfur atom, -Nr ¹⁷ or -Pr ¹⁸ , and R ⁵ is each independently represented by the formula R ', R'-O-R',-(R'-O-R '')-or Wherein R ', R', R '' and R '' are each independently C _6-30 straight alkyl or branched alkyl group; C _3-30 cycloalkyl group or substituted cycloalkyl group; or A C _6-40 aryl group, an alkylaryl group or an arylalkyl group, r ¹⁷ , r ¹⁸ and r ¹⁹ are hydrogen atoms; C _1-10 alkyl group, cycloalkyl group or alkoxy group; or C _6-20 aryl group, Alkylaryl group or arylalkyl group; Y, Y ', Y' and Y '' are each independently an oxygen atom, a sulfur atom, -Nr ¹⁷ or -Pr ¹⁸ (wherein r ¹⁷ and r ¹⁸ are hydrogen atoms; C _1-10 alkyl group, cycloalkyl group, or alkoxy group; or being an aryl group, an alkylaryl group or an arylalkyl group of C _6~30); Q represents a nitrogen atom or -Cr ²⁰ (r ²⁰ represents a hydrogen atom in the above; Im or an aryl group, an alkylaryl group or an arylalkyl group of C _6~30; alkyl group, a cycloalkyl group or an alkoxy group of C _1~10); And Z is carbon atom, silicon atom, germanium or being. The process according to claim 1, wherein the transition metal represented by (A) or (B) and a compound having two or more functional groups represented by compounds (C), (D) and (E) are reacted in an organic solvent. Metal: The molar ratio of the compound having two or more functional groups is in the range of 1: 0.1 to 1:20, the reaction temperature is in the range of 0 ° C to 150 ° C, and the weight ratio of the organic solvent to the reactant is 1: 1 to 100: 1. A metallocene catalyst for styrene polymerization, which is prepared by reacting in the range of. Styrene-based polymers and copolymers, which are polymerized in a catalyst system using the metallocene catalyst according to any one of claims 1 to 5 as a main catalyst and using alkylaluminum oxane and alkylaluminum as a promoter. Manufacturing method. The method of claim 6, wherein the alkyl aluminum oxane is methylaluminoxane (MAO) and modified methyl aluminoxane (MAMAO). The styrene-based polymer according to claim 6, wherein the alkyl aluminum oxane has a unit represented by the following structural formula (F) and is a chain or cyclic aluminum oxane represented by the following structural formulas (G) and (H). And a method of preparing the copolymer: In the formulas (F), (G) and (H), R 'is a C _1-6 alkyl group, and q is an integer of 0-100. Claim 6 to claim 8, claim any one of wherein the molar ratio of the aluminum and of the metallocene catalyst component a transition metal and a co-catalyst in the composition is from 1: 10 to 1: styrene, characterized in that in the range of 10 ⁴ based Method of Making Polymers and Copolymers. The method of claim 6, wherein the alkyl aluminum is trimethyl aluminum, triethyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, triisobutyl aluminum, diisobutyl aluminum chloride, tri (n-butyl) aluminum, tri (n-propyl) A method for producing a styrene-based polymer and copolymer, characterized in that it is selected from the group consisting of aluminum and triisopropyl aluminum. The method for producing a styrene-based polymer and copolymer according to claim 10, wherein the molar ratio of the transition metal in the metallocene catalyst component to the alkyl aluminum is in the range of 1: 1 to 1: 1000. The method of claim 6, wherein the styrene is an alkyl styrene type Styrene, methyl styrene, ethyl styrene, butyl styrene, para-methyl styrene, para-t-butyl styrene, dimethyl styrene and the like], halogenated styrene type [example; Chloro styrene, bromostyrene, fluorostyrene, etc.], halogen-substituted alkyl styrene [ex. Chloromethyl styrene, bromomethyl styrene, fluoromethyl styrene, etc.], alkoxy styrene [example; Methoxy styrene, ethoxy styrene, butoxy styrene and the like], vinyl biphenyl-based [example; 4-vinyl biphenyl, 3-vinyl biphenyl, 2-vinyl biphenyl, etc.], vinyl phenyl naphthalene system [eg 1- (4-vinyl biphenyl naphthalene), 2- (4-vinyl biphenyl naphthalene), 1 -(3-vinylbiphenylnaphthalene), 2- (3-vinylbiphenylnaphthalene), 1- (2-vinylbiphenylnaphthalene), etc.], vinylphenylanthracene [1- (4-vinylphenyl) anthracene, 2- (4-vinylphenyl) anthracene, 9- (4-vinylphenyl) anthracene, 1- (3-vinylphenyl) anthracene, 9- (3-vinylphenyl) anthracene, 1- (2-vinylphenyl) anthracene, etc.], Vinylphenylpyrene system [e.g., 1- (4-vinylphenyl) pyrene, 2- (4-vinylphenyl) pyrene, 1- (3-vinylphenyl) pyrene, 2- (3-vinylphenyl) pyrene, 1- ( 2-vinylphenyl) pyrene, 2- (2-vinylphenyl) pyrene and the like], trialkylsilylvinylbiphenyl-based [e.g. 4-vinyl-4-trimethylsilylbiphenyl, etc.], and alkylsilylstyrene-based [e.g. p-trimethylsilylstyrene, m-trimethylsilylstyrene, o-trimethylsilylstyrene, p-triethylsilylstyrene, m-triethylsilylstyrene, o-t Method for producing a silyl ethyl styrene; styrene-based polymers and copolymers, characterized in that one or more selected from the group consisting of.