KR100782278B1 - Novel Halophenoxy or Halobenzyloxy Half Metallocene Catalysts and Method for Preparing Syndiotactic Polystyrenes - Google Patents

Abstract

The present invention provides novel halogen phenolic or halogen benzyl alcohol based half metals for the production of syndiotactic styrene polymers with high activity, good stereoregularity, high melting temperature and various molecular weight distributions even with a small amount of promoter. The present invention relates to a sen catalyst and a method for producing syndiotactic polystyrene using the same, wherein the novel metallocene catalyst according to the present invention is a cycloalkanedienyl group which generates a five coordination bond on one side of transition metals of Groups 3 to 10 of the periodic table. Or a derivative thereof is bonded and has a half metallocene structure in which a plurality of halogen-based phenols or halogen-based benzyl alcohols are introduced on the other side, and by using this, a vinyl aromatic polymer having a superior syndiotactic structure can be produced with high activity. In addition, polymers of various molecular weight distributions can be prepared.

Half metallocene catalyst, halogenated phenol, halogenated benzyl alcohol, phenol, benzyl alcohol, syndiotactic polystyrene, alkylaluminum oxane

Description

Novel Halophenoxy or Halobenzyloxy Half Metallocene Catalysts and Method for Preparing Syndiotactic Polystyrenes

1 is an X-ray single crystal structure obtained by a single-crystal X-ray diffractometer of a half metallocene catalyst of Chemical Formula 12 according to the present invention.

2 is an X-ray single crystal structure obtained by an X-ray diffractometer of the half metallocene catalyst of Chemical Formula 13 according to the present invention.

3 is an X-ray single crystal structure obtained by an X-ray diffractometer of the half metallocene catalyst of Chemical Formula 21 according to the present invention.

The present invention relates to a metallocene catalyst for producing vinyl aromatic polymer and a styrene polymerization method using the same. More specifically, the present invention has high activity, excellent stereoregularity and high melting temperature even with a small amount of promoter, and has a molecular weight distribution. A high activity novel transition metal half metallocene catalyst capable of producing good syndiotactic polystyrene and a process for producing a polymer using the same.

Syndiotactic polystyrene is generally prepared using a metallocene catalyst containing one or two cycloalkanedienyl groups in a Group 4 transition metal such as titanium, zirconium or hafnium. Can be. As the cycloalkanedienyl group, cyclopentadienyl, indenyl, fluorenyl group or derivatives thereof may be used. This type of metallocene catalyst is syndiotactic polystyrene having high activity and alternating arrangement when used together with alkylaluminum oxane (eg, methylaluminum oxane), which is a reaction product of water as alkyl catalyst and alkylaluminum compound. Can be obtained. Such a method is disclosed in Japanese Patent Laid-Open Nos. 1983-19309, 1984-95292 and 1985-135408, European Patent EP210615, US Patent No. 4,680,353 and PCT Patent Publication No. WO8,810,275.

However, these metallocene catalyst systems have a disadvantage in that they are very expensive in terms of production cost or do not have sufficient activity compared to existing catalysts, and also show high activity only when alkylaluminoxane used as a cocatalyst is used a lot. There are many disadvantages to commercialization due to the fatal reasons for the poor stability of the product. Therefore, it is necessary to develop a catalyst having high activity as a catalyst having a similar price to that of the existing catalyst, easy to handle with a solid compound, and excellent stability, and also using less alkyl aluminum oxane as a promoter. There is a need for a catalyst having a.

In addition, before the present study, the electron donor groups such as OMe, O- i- Pr, and the like were most commonly used as substituents introduced into the syndiotactic polystyrene polymerization catalyst. No compound was used for syndiotactic polystyrene polymerization using the compound introduced with trifluoromethanesulfonate group reported in US0904018. However, recently, in the case of the FI catalyst developed by Mitsui Chemicals as a catalyst for polyethylene polymerization, the literature introduced that the catalyst system to which the fluorine-based benzene group, which is an electron withdrawing group, is very excellent as a catalyst for polyethylene polymerization ( J. Am. Chem. Soc . 2003, 125 , 4293; Chem. Eur. J. 2003, 9 , 2396; Adv. Synth. Catal . 2002, 344 , 477; Angew. Chem. Int. Ed. 2001, 40 , 2918). As can be seen, the development of half-metallocene catalysts for syndiotactic polystyrene incorporating halogen-based benzene groups not only breaks the structural interest of the catalyst itself, but also breaks that the conventional stereotype ligand must be an electron donor group unconditionally. Has considerable appeal. In addition, these electron attracting groups are applied to various types of promoters (borate-type promoters all have electron attracting groups), but studies on the use of low promoters in the case where the catalyst itself contains an electron attracting group There is no situation.

An object of the present invention is a novel metallocene having high activity for producing syndiotactic polystyrene having high stereoregularity, high melting temperature and good molecular weight distribution even with a small amount of a promoter. It is for providing a catalyst, a styrene homopolymerization method using this catalyst, and a copolymerization method with an olefin.

The above object of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present inventor more actively overcomes the problems of the prior art using low activity, expensive manufacturing cost and many promoters, and also combines the idea of introducing the above-mentioned electron attracting group with the problems. In order to achieve this, a novel catalyst incorporating the following halogen-based phenol or halogen-based benzyl alcohol is developed, and the catalyst system has a higher molecular weight, a better molecular weight distribution, a smaller amount of promoter, and a higher shift. It is intended to synthesize arrayed polystyrene.

The novel metallocene catalyst according to the present invention has a structure similar to a typical half metallocene structure, in which a cycloalkanedienyl group or a derivative thereof, which generates η ⁵ bonds, is bonded to one side of the transition metal of Group 4 of the periodic table, and the other Has a structure represented by the following formula (1), (2), (3) or (4) in which a plurality of halogen-based phenols or halogen-based benzyl alcohol compounds are introduced.

In the above formulas,

M ¹ , M ² , M ³ , M ⁴ and M ⁵ are each independently a group 4 transition element on the periodic table,

L ¹ , L ² , L ³ , L ⁴ and L ⁵ are each independently a cycloalkanedienyl ligand represented by the following chemical formulas 5, 6, 7, 8 or 9,

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group, A C3-20 cycloalkyl group or an aryl group, m and n are integers of 1 or more,

X ¹ and X ² are functional groups which are γ-ligands, each independently a hydroxy group, an alkoxy group, a thioalkoxy group or an arylalkoxy group,

A ¹ , A ² , A ³ , A ⁴ and A ⁵ are functional groups that are γ-ligands, each independently oxygen, sulfur, NR ¹⁴ or PR ¹⁵ ,

D ¹ , D ² , D ³ and D ⁴ are each independently a single bond or an alkylene group or a cycloalkylene group having 3 to 20 carbon atoms,

E ¹ , E ² , E ³ , E ⁴ , E ⁵ , E ⁶ , E ⁷ , E ⁸ , E ⁹ , E ¹⁰ , E ¹¹ , E ¹² , E ¹³ , E ¹⁴ , E ¹⁵ , E ¹⁶ , E ¹⁷ , E ¹⁸ , E ¹⁹ and E ²⁰ are each independently a hydrogen atom, a halogen group, an alkyl group or a haloalkyl group, at least one of the groups must be a halogen group or a haloalkyl group,

R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a halogen group, an alkyl group, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group or an aryl group.

The metallocene catalyst of Formula 1, 2, 3 or 4 is the following Formula 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 Metallocene catalysts are preferred.

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

a) the main catalyst of the half metallocene compound represented by Formula 1, 2, 3 or 4 and

b) at least one cocatalyst selected from the group consisting of alkylaluminum oxanes having repeating units of formula 26, alkylaluminum of formula 27 and weakly coordinated Lewis acids;

It provides a method for producing a styrene-based polymer, characterized in that the styrene monomer or a styrene-based monomer homopolymerized or copolymerized or copolymerized with an olefin monomer under a catalyst system comprising a.

Wherein R ¹⁶ is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group, and R ¹⁷ , R ¹⁸ and R ¹⁹ are Each independently a hydrogen atom, a halogen group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms, an aryl group, an alkylaryl group, or an arylalkyl group, wherein the alkyl group is linear having 1 to 20 carbon atoms Or an aryl group represents an aromatic or heteroaromatic group having 6 to 40 carbon atoms, wherein at least one of R ¹⁷ , R ^18, and R ¹⁹ includes an alkyl group, and n is an integer of 1 to 100. .

Hereinafter, the present invention will be described in detail.

The present invention provides a half metallocene catalyst that satisfies the formula (1), (2), (3) or (4), and a styrene-based polymer using the catalyst as a main catalyst. To provide a way.

Metallocene catalysts satisfying the formulas of Formulas 1, 2, 3, and 4 of the present invention include cycloalkanedienyl groups and one or more halogen-based phenol groups or halogen-based benzyl alcohol groups in transition metals of Groups 3 to 10 of the periodic table. Half metallocene compound contained. Therefore, the metal center forms a cationic polymerization active species at the time of polymerization, and thus the active species is deficient in electrons by a halogen-based phenol group or a halogen-based benzyl alcohol group, which is an electron withdrawing group, and thus has a higher activity than the conventional catalyst. Can be expected. Therefore, such a catalyst system is expected to facilitate molecular weight control of the polymer as well as styrene polymer of high polymerization activity, excellent stereoregularity and high melting temperature.

The half metallocene catalyst containing the halogen-based phenol group or the halogen-based benzyl alcohol group is first introduced into a transition metal compound having a cycloalkanedienyl group as a leaving group, and then i) a halogen-based phenol or a halogen-based benzyl alcohol ligand is alkali metal. Converted to a salt and reacted with a half metallocene compound having a cycloalkanedienyl group previously synthesized, or ii) a half metal with a cycloalkanedienyl group having a neutral halogen-phenol or halogen-benzyl alcohol ligand synthesized above. It can be prepared by reacting with a rosene compound.

In the method for preparing a half metallocene catalyst containing the halogen-based phenol group or the halogen-based benzyl alcohol group, examples of the alkali metal salt of the cycloalkanedinyl group include cyclopentadienyl lithium and cyclopentadienyl sodium. sodium, cyclopentadienyl potassium, cyclopentadienyl magnesium, methylcyclopentadienyl lithium, methylcyclopentadienyl sodium, methylcyclopentadienyl sodium Potassium (methylcyclopentadienyl potassium), tetramethylcyclopentadienyl lithium, tetramethylcyclopentadienyl sodium, tetramethylcyclopentadienyl potassium, indenyl lithium, Indenyl sodium, indenyl Potassium (indenyl potassium), fluorenyl lithium (fluorenyl lithium) and the like. These salts include a ligand having a cycloalkanedienyl structure, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, and methyl lithium. ), Sodium methoxide, sodium ethoxide, potassium tert-butoxide, potassium hydroxide, methylmagnesium chloride, ethylmagnesium bromide Bromide), dimethylmagnesium (dimethylmagnesium), lithium (lithium), sodium (sodium), potassium (potassium) and the like can be prepared by the reaction.

In addition, halogen-based phenol or halogen-based benzyl alcohol compounds include 2-fluorophenol, 2-chlorophenol, 2-bromophenol, and 3-fluorophenol ( 3-fluorophenol, 3-bromophenol, 3-chlorophenol, 4-fluorophenol, 4-chlorophenol, 4-bro 4-phenolic, 4-iodophenol, 2,3-dichlorophenol, 2,6-difluorophenol, 2 , 3-difluorophenol (2,3-difluorophenol), 2,6-dichlorophenol (2,6-dichlorophenol), 2,6-dibromophenol (3,5-di) Fluorophenol (3,5-difluorophenol), 3,5-dichlorophenol (3,5-dichlorophenol), α, α, α-trifluoro-orthocresol (α, α, α-trifluoro-o-cresol ), 3-chloro-5-methoxyphenol, α, α, α-trifluoro-methcresol, α-α, α-trifluoro-m-cresol, 2-di Fluoro-6-methoxyphenol (2-fl uoro-6-methoxyphenol), 3,5-bis (trifluoromethyl) phenol (3,5-bis (trifluoromethyl) phenol), 4-chloro-3-methylphenol, 3 -(Trifluoromethoxy) phenol (3- (trifluoromethoxy) phenol), 4-fluoro-2-methylphenol, 4-trifluoromethoxyphenol (4- (trifluoromethoxy) phenol ), 4-fluoro-3-methylphenol, 2-chloro-4-methylphenol, 2-chloro-5-methylphenol (2- chloro-5-methylphenol), 4-chloro-2-methylphenol, 2-bromo-4-methylphenol, 4-iodo-2 -Methylphenol (4-iodo-2-methylphenol), 4-chloro-2-fluorophenol (4-chloro-2-fluorophenol), 2,4-difluorophenol (2,4-difluorophenol), 2, 5-difluorophenol (2,5-difluorophenol), 3,4-difluorophenol (3,4-difluorophenol), 2-chloro-5- (trifluoromethyl) phenol (2-chloro-5- (trifluoromethyl) phenol), 3-chloro-4-fluorophenol ol), 4-chloro-3-fluorophenol, 2-bromo-4-fluorophenol, 4-bromo-2-fluoro Chlorophenol (4-bromo-2-fluorophenol), 2-bromo-5-fluorophenol, 2,4-dichlorophenol, 3,4- Dichlorophenol (3,4-dichlorophenol), 2,5-dichlorophenol (2,5-dichlorophenol), 2-bromo-4-chlorophenol (2-bromo-4-chlorophenol), 2-chloro-4-fluoro Chlorophenol (2-chloro-4-fluorophenol), 2,4-dibromophenol (2,4-dibromophenol), 2,4-dichloro-3-methylphenol, 2,3,4-trifluorophenol (2,3,4-trifluorophenol), 2,3,6-trifluorophenol (2,3,6-trifluorophenol), 2,3,4-trichlorophenol ( 2,3,4-trichlorophenol), 4-chloro-3,5-dimethylphenol, 4-bromo-3,5-dimethylphenol (4-bromo-3,5 -dimethylphenol), 2,4,5-trifluorophenol, 2-chloro-3,5-difluorophenol, 2, 4,6-trichlorophenol (2,4,6-trichlorophenol), 4,4'-isopropylidenebis (2,6-dichlorophenol (4,4'-isopropylidenebis (2,6-dichlorophenol)), 2 -Chloro-4,5-dimethylphenol (2-chloro-4,5-dimethylphenol), 2,3,5-trichlorophenol (2,3,5-trichlorophenol), 4-bromo-2,6-dimethyl Phenol (4-bromo-2,6-dimethylphenol), 4-bromo-6-chloro-o-cresol, 2,6-dibromo-4-methyl Phenol (2,6-dibromo-4-methylphenol), 2,4,6-tribromophenol (2,4,6-tribromophenol), 2,6-dichloro-4-fluorophenol (2,6-dichloro -4-fluorophenol), 2,6-dibromo-4-fluorophenol, 4-chloro-2-isopropyl-5-methylphenol (4-chloro-2 -isopropyl-5-methylphenol), 2-bromo-4,5-difluorophenol, 2,4,5-trichlorophenol (2,4,5-trichlorophenol ), 2,3,5,6-tetrafluorophenol (2,3,5,6-tetrafluorophenol), 3,4,5,6-tetrabromo-orthocresol (3,4,5,6- tetrabromo-o-cresol), pentabro Pentabromophenol, pentafluorophenol, 3-fluorocatechol, tetrachlorocatechol, tetrabromocatechol, 4-chloro-1-naphthol 4-chloro-1-naphthol), tetrafluorohydroquinone, 2,4-dichloro-1-naphthol, 1-bromo-2-naphthol (1- bromo-2-naphthol), 6-bromo-2-naphthol, 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol ( 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol), 1,6-dibromo-2-naphthol, 2,3, 5,6-tetrafluoro-4- (pentafluorophenyl) phenol (2,3,5,6-tetrafluoro-4- (pentafluorophenyl) phenol), 4- (4-bromophenyl) phenol (4- ( 4-bromophenyl) phenol), 2,4-dibromo-6-phenylphenol, 2,2 ', 3,3', 5,5 ', 6,6' Octafluoro-4,4'-biphenol (2,2 ', 3,3', 5,5 ', 6,6'-octafluoro-4,4'-biphenol), 2,5-dichlorobenzyl alcohol (2,5-dichl orobenzyl alcohol), 4,4 '-(hexafluoroisopropylidene) diphenol (4,4'-(hexafluoroisopropylidene) diphenol), 4,4'-isopropylidenebis (2,6-dibromophenol) (4,4'-isopropylidenebis (2,6-dibromophenol)), α- (trifluoromethyl) benzyl alcohol, α- (trifluoromethyl) benzylalcohol, 2-fluorobenzyl alcohol, 2- (Trifluoromethyl) benzyl alcohol (2- (trifluoromethyl) benzyl alcohol), 2-chlorobenzyl alcohol, 2-bromobenzyl alcohol, 2-iodobenzyl alcohol ( 2-iodobenzyl alcohol, α-methyl-2- (trifluoromethyl) benzyl alcohol, α-methyl-2- (trifluoromethyl) benzyl alcohol, 3-fluorobenzyl alcohol, 3- ( Trifluoromethyl) benzyl alcohol (3- (trifluoromethyl) benzyl alcohol), 3-chlorobenzyl alcohol, 3-bromobenzyl alcohol, α-methyl-3- (tri Fluoromethyl) benzyl alcohol (α-methyl-3- (trifluoromethyl) benzyl alcohol), 3,3 ', 3 '', 3 '' '-tetrakis (trifluoromethyl) benzyl alcohol (3,3', 3 '', 3 '' '-tetrakis (trifluoromethyl) benzyl alcohol), 3-iodobenzyl alcohol (3 -iodobenzyl alcohol), 4-fluorobenzyl alcohol, 4- (trifluoromethyl) benzyl alcohol, 4-chlorobenzyl alcohol, 4-chlorobenzyl alcohol, 4-bromobenzyl alcohol, 4-fluoro-alpha-methylbenzyl alcohol, 1- (4-chlorophenyl) ethanol (1- (4-chlorophenyl) ) ethanol), 4,4'-difluorobenzhydrol, 4,4'-dichlorobenzhydrol, 4,4'-dichlorobenzhydrol, 4,4'-dichlorobenzhydrol -Methylbenzhydrol (4,4'-dichloro-α-methylbenzhydrol), 4-bromo-α-methylbenzyl alcohol (4-bromo-α-methylbenzyl alcohol), 2,6-difluorobenzyl alcohol (2 , 6-difluorobenzyl alcohol), 2,3-difluorobenzyl alcohol, 2-chloro-6-fluorobenzyl alcohol hol), 2,6-dichlorobenzyl alcohol, 3,4-difluorobenzyl alcohol, 2,4-difluorobenzyl alcohol (2,4 -difluorobenzyl alcohol), 2,5-difluorobenzyl alcohol, 2,4-dichlorobenzyl alcohol, 3,4-dichlorobenzyl alcohol (3,4 -dichlorobenzyl alcohol), α- (chloromethyl) -2,4-dichlorobenzyl alcohol (α- (chloromethyl) -2,4-dichlorobenzyl alcohol), 3,5-bis (trifluoromethyl) benzyl alcohol (3, 5-bis (trifluoromethyl) benzyl alcohol), 3,5-difluorobenzyl alcohol, 1- (pentafluorophenyl) ethanol, 2,3, 4,5,6-pentafluorobenzyl alcohol (2,3,4,5,6-pentafluorobenzyl alcohol), 2,4,5,6-meth-xylene-α, α'-diol (2,4, 5,6-tetrachloro-m-xylene-α, α'-diol), 2-bromothiophenol, 2-bromo-1-indanol, deca Fluorobenzhydrol, 2,3,4,5,6 -Pentafluorobenzhydrol (2,3,4,5,6-pentafluorobenzhydrol), 3-chlorothiophenol (3-chlorothiophenol), 4-chlorothiophenol (4-chlorothiophenol), 3-chlorophenethyl alcohol ( 3-chlorophenethyl alcohol), 3-bromothiophenol, 4-fluorothiophenol, 2- (2,3,6-trifluorophenoxy) ethanol (2- ( 2,3,6-trifluorophenoxy) ethanol), 4-chlorophenethyl alcohol, 2- (trifluoromethyl) phenethyl alcohol, 2- (trifluoromethyl) phenethyl alcohol, 4-chlorothiophenol (4-chlorothiophenol), 4-fluorophenethyl alcohol, 4- (trifluoromethyl) phenethyl alcohol, 3- (trifluoromethyl) phenethyl alcohol, 4-bromophenethyl alcohol (4- bromophenethyl alcohol), 2- (4-bromophenoxy) ethanol, 4-chloro-α, α-dimethylphenethyl alcohol (4-chloro-α, α-dimethylphenethyl alcohol) , 2,3,5,6-tetrafluorothiophenol (2,3,5,6-tetrafluorothiophenol), 2-cle Lobenzyl mercaptan (2-chlorobenzyl mercaptan), 2,2-bis (4-chlorophenyl) ethanol (2,2-bis (4-chlorophenyl) ethanol), 3,4-dichlorobenzenethiol , 4-bromothiophenol or pentafluorothiophenol.

In addition, the half metallocene compound is cyclopentadienyltitanium trichloride, (η ⁵ -C ₅ H ₅ ) TiCl ₃ ), cyclopentadienylmethoxytitanium dichloride, (η ⁵ -C ₅ H ₅ ) TiCl ₂ (OMe)), cyclopentadienyldimethoxytitanium monochloride, (η ⁵ -C ₅ H ₅ ) TiCl (OMe) ₂ ), cyclopentadienyl titanium trimethoxide (cyclopentadienyltitanium trimethoxide) , (η ⁵ -C ₅ H ₅ ) Ti (OMe) ₃ ), methylcyclopentadienyltitanium trichloride, (η ⁵ -C ₅ H ₄ Me) TiCl ₃ ), methylcyclopentadienylmethoxytitanium dichloride ^{(methylcyclopentadienylmethoxytitanium dichloride, (η 5 -C} 5 H 4 Me) TiCl 2 (OMe)), methylcyclopentadienyl titanium dimethoxy monochloride ^{(methylcyclopentadienyldimethoxytitanium monochloride, (η 5 -C} 5 H 4 Me) TiCl (OMe) ₂ ), methylcyclopentadienyltitanium trimethoxide, (η ⁵ -C ₅ H ₄ Me) Ti (OMe) ₃ ), pentamethylcyclopentadienyltitanium trichloride (pentamethylcyclopentadienyltitainium trichloride, (η ⁵ -C ₅ Me ₅ ) TiCl ₃ ), pentamethylcyclopentadienylmethoxytitanium dichloride, (η ⁵ -C ₅ Me ₅ ) TiCl ₂ (OMe), pentamethylcyclopentadiene Pentamethylcyclopentadienyldimethoxytitainium monochloride, (η ⁵ -C ₅ Me ₅ ) TiCl (OMe) ₂ ), pentamethylcyclopentadienyltitanium trimethoxide, (η ⁵ -C ₅ Me ₅ ) Ti (OMe) ₃ ), indenyltitanium trichloride (η ⁵ -C ₉ H ₇ ) TiCl ₃ ), indenylmethoxytitanium dichloride, (η ⁵ -C ₉ H ₇ ) TiCl ₂ ( OMe)) Indenyldimethoxytitanium monochloride, (η ⁵ -C ₉ H ₇ ) TiCl (OMe) ₂ and indenyltitanium trimethoxide, (η ⁵ -C ₉ H ₇ ) Ti (OMe) ₃ ).

In addition, transition metal compounds having leaving groups include titanium tetrachloride (tetrachlorotitanium), titanium tetrachloride tetra tetrafurfuran (tetrachlorotitanium ditetrahydrofuran), zirconium tetrachloride (tetrachlorozirconium), tetrachlorohafnium (tetrachlorohafnium), and titanium tetraiodine (titachlorochlorovanadium) ), Titanium tetrabromide, titanium tetrafluoride, oxovanadium trichloride, titanium tetraisopropoxide, chlorotitanium triisopropoxide , Dichlorotitanium diisopropoxide, trichlorotitanium isopropoxide, chlorotitanium triphenoxide, chlorotitanium tributoxide itanium tributoxide and chlorotitanium triethoxide.

In the half metallocene catalyst for producing a styrene-based polymer represented by Formula 1, 2, 3 or 4 of the present invention prepared by the above methods, M ¹ , M ² , M ³ or M ⁴ on the periodic table Group 4 transition elements are preferred, 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 and the like, and an alkyl group, cycloalkyl group, alkenyl group, alkylsilyl group, haloalkyl group, alkoxy group, alkylsiloxy group, amino group, The alkoxyalkyl group, the thioalkoxyalkyl group, the alkylsiloxyalkyl group, the aminoalkyl group, and the alkyl phosphinoalkyl group are methyl groups 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 Rokso there is a phenyl group, an aniline group, a toluidine group, a benzyl group, a phenyl amino group, phenyl-methyl-amino group, a diphenylphosphino group.

The present invention uses the half metallocene catalyst for preparing a styrene-based polymer represented by the following Chemical Formulas 1, 2, 3 or 4 as a main catalyst for the polymerization of styrene homopolymerization or olefin together with a cocatalyst. If the syndiotactic styrene polymer and a styrene copolymer of various physical properties can be obtained.

The cocatalyst used with the half metallocene catalyst includes alkylaluminum oxane or weakly coordinating Lewis acid represented by the following Formula 26, and these are mainly used together with alkylaluminum represented by the Formula 27.

The compound of Formula 26 may be linear, cyclic or reticulated, specifically methylaluminum oxane, modified methylaluminum oxane, ethylaluminum oxane, butylaluminium oxane), hexylaluminium oxane, and decylaluminium oxane.

Specifically, the compound of Formula 27 is trimethylaluminum, dimethylaluminum chloride, dimethylaluminum methoxide, dimethylaluminum chloride, triethylaluminum, triethylaluminium, and diethylaluminum. Diethylaluminium chloride, diethylaluminum methoxide, ethylaluminum dichloride, tri-n-propylaluminium, di-n-propylaluminium chloride , N-propylaluminium chloride, triisopropylaluminum, tri-n-butylaluminium, diisobutylaluminum hydride, and triisobutylaluminium Etc There is this.

In addition, weakly coordinating Lewis acid can take both ionic and neutral forms, specifically trimethylammonium tetraphenylborate, tributylammonium tetraphenylborate , Pyridium tetraphenylborate, tetramethylammonium tetrakis (pentafluorophenyl) borate, trimethylammonium triphenylborate, tris (pentafluoro) borane , Tetramethylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetraphenylborate, dimethylanilinium tetrakis (pentafluorophenyl) borate (dimethylanilinium tetrakis (pentafluorophenyl) borate), pyridinium tetrakis (penta Pyridium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate (ferrocerium tetrakis (pentafluorophenyl) borate borate), triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate (triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate), triphenylcarbenium tetrakis (pentafluor Triphenylcarbenium tetrakis (pentafluorophenyl) borate), tris (2,3,4,5-tetrafluorophenyl) borane, tris (2, 4,6-trifluorophenyl) borane (tris (2,4,6-trifluorophenyl) borane), tris (3,5-bis (trifluoromethyl) phenyl) borane (tris (3,5-bis) (trifluoromethyl) phenyl) borane), and sodium tetrakis (3,5-bis (trifluoromethyl) p henyl) borate).

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 alkylaluminum oxane, the molar ratio with the metallocene catalyst is mainly usable within the range of 1: 1 to 10 ⁶ : 1, and preferably used between 10: 1 and 10 ⁴ : 1. In addition, the amount of alkylaluminum that can be used with the alkylaluminum oxane 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.

The monomers that can be polymerized by the catalyst system of the present invention may be styrene, styrene derivatives or olefins, and these may polymerize styrene or styrene derivatives alone, or copolymerize styrene and styrene derivatives or copolymerize styrene or styrene derivatives 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, and ethyl styrene. , n-butylstyrene, p-tert-butylstyrene, dimethylstyrene, methoxystyrene, ethoxystyrene, ethoxystyrene, butoxystyrene ), Methyl-4-styrenylester, thiomethoxystyrene, trimethylsilylstyrene, triethylsilylstyrene, tert-butylmethylsilylstyrene ), Trimethyltin styrene, dimethylaminostyrene, chloromethylstyrene, trimethylphosphinostyrene, 4-vinyl biphenyl (4-vinylstyrene), bromome Styrene (bromomethylstyrene), p-divinylbenzene, m-divinylbenzene, trivinylbenzene, 4,4'-divinylbiphenyl ) And vinylnaphthalene.

In addition, olefins mainly used for copolymerization may include 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, methyl-2-norbornene, 1,3- Butadiene (1,3-butadiene), 1,4-pentadiene (1,4-pentadiene), 2-methyl-1,3-butadiene (2-methyl-1,3-butadiene) and 1,5-hexadiene (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, and a block. When the polymerization is carried out in a slurry or liquid phase, a solvent may be used as a polymerization medium, and the solvent used may include butane, pentane, hexane, heptane, octane, and decane. alkanes and cycloalkane solvents having 4 to 20 carbon atoms such as (decane), dodecane, cyclopentane, methylcyclopentane, and cyclohexane; Aromatic arylene solvents having 6 to 20 carbon atoms such as benzene, toluene, xylene and mesitylene; Dichloromethane, chloromethane, chloroform, tetrachloromethane, chloroethane, 1,2-dichloroethane, 1,1,2,2, Tetrachloroethane (1,1,2,2, tetrachloroethane), chlorobenzene, 1,2-dichlorobenzene and 1,2,4-trichlorobenzene (1,2 Halogen alkanes having 1 to 20 carbon atoms, halogen arene solvents, and the like, and 4-trichlorobenzene). 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 present invention, the polymerization temperature is -80 ℃ to 200 ℃, preferably 0 ℃ to 150 ℃, the polymerization pressure including the pressure of the comonomer when styrene homopolymerization or copolymerization with olefins 1 to 1000 atm is suitable, and in the case of styrene homopolymerization, it is carried out under styrene at 0.01 to 20 atm.

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) a main catalyst 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 of activating the main catalyst by bringing it into contact with the cocatalyst may be carried out between 0 ° C. and 150 ° C. for 0.1 to 240 minutes, preferably 0.1 to 60 minutes.

The amount of the metallocene compound, which is the main catalyst used in the polymer manufacturing process, is not particularly limited, but the concentration of the central metal in the reaction system is preferably 10 ^-8 to 1.0M, 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 are in the range of 10 to 10 million molecular weight, molecular weight distribution by controlling 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 1.1 to 100.

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 Preparation of Cp ^* Ti (OMe) ₂ (OC ₆ F ₅ ) (Catalyst 1)

Method 1: A solution of 0.666 g (3.62 mmol) of pentafluorophenol in 30 ml of toluene was dissolved in 1.00 g (3.62 mmol) of pentamethylcyclopentadienyltitanium trimethoxide (Cp * Ti (OMe) ₃ ). To a solution dissolved in 30 ml of toluene (C ₆ H ₅ CH ₃ , toluene) was slowly added dropwise at room temperature. The color of the solution turned dark yellow every drop, and the vessel was stirred for 12 hours at room temperature. After 12 hours, the solvent was removed under reduced pressure, and the resulting orange-yellow product was extracted with 30 ml of normal hexane. Filtering through a Celite filter gave a clear yellow solution. The solvent was removed again in vacuo and dried for a long time to obtain a catalyst 1 of Formula 10, a yellow solid product, in a yield of 78% (g).

Method 2: 3.9 g (100 mmol) of potassium was added to the flask, and then 100 mL of THF was added and the reaction vessel was lowered to 0 ° C. 13.6 g (100 mmol) of pentamethylcyclopentadiene was slowly added thereto, and the reaction temperature was raised to reflux. As the reaction proceeded, a white powder insoluble at the bottom was formed. After 3 hours of reflux, the reaction temperature was lowered to 0 ° C. 100 mmol of chlorotrimethylsilane was slowly added thereto using a syringe, followed by stirring for 2 hours. The solid produced through Celite was filtered off and the resulting weak yellow clear solution was removed under reduced pressure with all solvents. The solution containing 92 mmol (19.1 g) and 50 ml of toluene was slowly added dropwise to the solution containing 93 mmol (17.6 g) of titanium tetrachloride and 100 ml of toluene. After 6 hours, toluene was removed under reduced pressure, and the solid obtained as pentane was washed well and dried well to obtain desired pentamethylcyclopentadienyltitanium trichloride (Cp ^* TiCl ₃ ) in a yield of 95% or more. 5 mmol (1.44 g) of this compound pentamethylcyclopentadienyltitanium trichloride was added to a flask, dissolved well with 20 mL of dichloromethane, and the temperature of the reaction vessel was lowered to -78 ° C. Into another flask was added 10 mmol of methanol, 10 mmol of triethylamine (1.4 mL), and 20 mL of dichloromethane, and slowly added dropwise to the previous flask. Immediately after the addition, the temperature of the reaction vessel was raised to room temperature, stirred well for 3 hours, and then the temperature of the flask was lowered to -78 ° C. In another flask, a solution containing 5 mmol (pentafluorophenol) 5 mmol (0.92 g), triethylamine 5 mmol (0.7 mL) and 20 mL dichloromethane was slowly added to the previous vessel. Immediately after the addition, the temperature of the reaction vessel was raised to room temperature, reacted at room temperature for 12 hours, all solvents were removed under reduced pressure, 50 ml of toluene was added, stirred for 30 minutes, filtered through celite, and very clear. A yellow solution is obtained. When the solvent is removed again under reduced pressure, this solution can be obtained in a yield of 51% as a catalyst 1 of Formula 10, a yellow solid product. Since Method 1 is a more effective synthesis method in terms of the efficiency of the reaction (short reaction path and yield), the following synthesis method was all chosen.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): δ = 4.05 (s, 6H), 2.08 (s, 15H).

[Formula 10]

Example 2: Preparation of Cp ^* Ti (OMe) (OC ₆ F ₅ ) ₂ (Catalyst 2)

Catalyst 2 of Chemical Formula 11 was prepared in the same manner as in Example 1, except that 2 equivalents of pentafluorophenol was used instead of 1 equivalent of pentafluorophenol.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): δ = 4.12 (s, 3H), 2.14 (s, 15H).

[Formula 11]

Example 3: Preparation of Cp ^* Ti (OC ₆ F ₅ ) ₃ (Catalyst 3)

Catalyst 3 of Chemical Formula 12 was prepared in the same manner as in Example 1 except that 3 equivalents of pentafluorophenol was used instead of 1 equivalent of pentafluorophenol. The result of analyzing the half metallocene catalyst of Formula 12 by X-ray single crystal is shown in FIG. 1.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): δ = 2.19 (s, 15H).

[Formula 12]

Example 4: Preparation of [Cp ^* Ti (OC ₆ F ₅ ) ₂ ] ₂ (μ-O) (catalyst 4)

Catalyst 4 of Chemical Formula 13 was prepared in the same manner as in Example 1, except that 2 equivalents of pentafluorophenol and 1/2 equivalents of water were used instead of 1 equivalent of pentafluorophenol. The result of analyzing the half metallocene catalyst of Formula 13 by X-ray single crystal is shown in FIG. 2.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): δ = 2.22 (s, 30H).

[Formula 13]

Example 5 Preparation of Cp ^* Ti (OMe) ₂ (OC ₆ H ₃ F ₂ ) (Catalyst 5)

Except for using 1 equivalent of 2,6-difluorophenol (2,6-difluorophenol) instead of 1 equivalent of pentafluorophenol (pentafluorophenol) in the same manner as in Example 1 Prepared.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): δ = 6.97 (m, 1H), 6.74 (m, 2H), 4.01 (s, 6H), 2.01 (s, 15H).

[Formula 14]

Example 6: Preparation of Cp ^* Ti (OMe) (OC ₆ H ₃ F ₂ ) ₂ (Catalyst 6)

Except for using 2 equivalents of 2,6-difluorophenol (2,6-difluorophenol) instead of 1 equivalent of pentafluorophenol (pentafluorophenol) was carried out in the same manner as in Example 1 to give a catalyst 6 of Formula 15 Prepared.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): delta = 7.01 (m, 2H), 6.84 (m, 4H), 4.06 (s, 3H), 2.04 (s, 15H).

[Formula 15]

Example 7: Preparation of Cp ^* Ti (OC ₆ H ₃ F ₂ ) ₃ (Catalyst 7)

Except for using 3 equivalents of 2,6-difluorophenol (2,6-difluorophenol) instead of 1 equivalent of pentafluorophenol (pentafluorophenol) in the same manner as in Example 1 Prepared.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): delta = 7.03 (m, 3H), 6.88 (m, 6H), 2.10 (s, 15H).

[Formula 16]

Example 8 Preparation of [Cp ^* Ti (OC ₆ H ₃ F ₂ ) ₂ ] ₂ (μ-O) (Catalyst 8)

Catalyst 8 of Chemical Formula 17 was prepared by the same method as Example 1 except for using 2 equivalents of pentafluorophenol and 1/2 equivalents of water instead of 1 equivalent of pentafluorophenol. It was.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): δ = 7.03 (m, 4H), 6.86 (m, 8H), 2.09 (s, 30H).

[Formula 17]

Example 9 Preparation of Cp ^* Ti (OMe) ₂ (OCH ₂ C ₆ F ₅ ) (Catalyst 9)

Catalyst 9 of Chemical Formula 18 was prepared in the same manner as in Example 1 except that 1 equivalent of pentafluorobenzyl alcohol was used instead of 1 equivalent of pentafluorophenol.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): delta = 4.79 (m, 2H), 3.95 (s, 6H), 1.97 (s, 15H).

 [Formula 18]

Example 10 Preparation of Cp ^* Ti (OMe) (OCH ₂ C ₆ F ₅ ) ₂ (Catalyst 10)

Catalyst 10 of Chemical Formula 19 was prepared in the same manner as in Example 1, except that 2 equivalents of pentafluorobenzyl alcohol was used instead of 1 equivalent of pentafluorophenol.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): delta = 4.84 (m, 4H), 4.00 (s, 3H), 2.01 (s, 15H).

[Formula 19]

Example 11: Preparation of Cp ^* Ti (OCH ₂ C ₆ F ₅ ) ₃ (Catalyst 11)

Catalyst 11 of Chemical Formula 20 was prepared in the same manner as in Example 1, except that 3 equivalents of pentafluorobenzyl alcohol was used instead of 1 equivalent of pentafluorophenol.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): δ = 4.88 (m, 6H), 2.11 (s, 15H).

[Formula 20]

Example 12 Preparation of [Cp ^* Ti (OCH ₂ C ₆ F ₅ ) ₂ ] ₂ (μ-O) (Catalyst 12)

Catalyst 12 of Chemical Formula 21 was carried out in the same manner as in Example 1 except that 2 equivalents of pentafluorobenzyl alcohol and 1/2 equivalents of water were used instead of 1 equivalent of pentafluorophenol. Was prepared. The result of analyzing the half metallocene catalyst of Chemical Formula 21 by X-ray single crystal is shown in FIG. 3.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): δ = 4.92 (m, 8H), 2.15 (s, 30H).

[Formula 21]

Example 13: Cp ^* Ti (OMe) ₂ (OCH ₂ C ₆ H ₃ F ₂ ) Preparation of Catalyst 13

The catalyst of Chemical Formula 22 was carried out in the same manner as in Example 1 except that 1 equivalent of 2,6-difluorobenzyl alcohol was used instead of 1 equivalent of pentafluorophenol. 13 was prepared.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): δ = 6.93 (m, 1H), 6.76 (m, 2H), 4.63 (m, 2H), 3.95 (s, 6H), 1.97 (s, 15H).

[Formula 22]

Example 14 Preparation of Cp ^* Ti (OMe) (OCH ₂ C ₆ H ₃ F ₂ ) ₂ (Catalyst 14)

Except for using 2 equivalents of 2,6-difluorobenzyl alcohol instead of 1 equivalent of pentafluorophenol (2,6-difluorobenzyl alcohol) was carried out in the same manner as in Example 1 to the catalyst of formula 23 14 was prepared.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): delta = 6.98 (m, 2H), 6.81 (m, 4H), 4.66 (m, 4H), 4.03 (s, 3H), 2.04 (s, 15H).

[Formula 23]

Example 15 Preparation of Cp ^* Ti (OCH ₂ C ₆ H ₃ F ₂ ) ₃ (Catalyst 15)

Except for using 3 equivalents of 2,6-difluorobenzyl alcohol instead of 1 equivalent of pentafluorophenol (2,6-difluorobenzyl alcohol) was carried out in the same manner as in Example 1 to the catalyst of formula 15 was prepared.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): delta = 7.01 (m, 3H), 6.84 (m, 6H), 4.70 (m, 6H), 2.09 (s, 15H).

[Formula 24]

Example 16: Preparation of [Cp ^* Ti (OCH ₂ C ₆ F ₅ ) ₂ ] ₂ (μ-O) (catalyst 12)]

In the same manner as in Example 1, except that 2 equivalents of 2,6-difluorobenzyl alcohol and 1/2 equivalents of water were used instead of 1 equivalent of pentafluorophenol. The catalyst 16 of Chemical Formula 25 was prepared.

¹ H NMR (300.13 MHz, CDCl ₃ , ppm): delta = 7.05 (m, 4H), 6.88 (m, 8H), 4.73 (m, 8H), 2.15 (s, 30H).

[Formula 25]

Example 17 Preparation of Styrene Homopolymer (Liquid Polymerization)

Using the half metallocene catalyst of Examples 1 to 16 synthesized above, styrene homopolymerization was carried out as follows. 70 mL of purified heptane was added to a polymerization reactor in a high purity nitrogen atmosphere, and the temperature was raised to 50 ° C. 30 ml of styrene, 0.5 ml of triisobutylaluminum (1.0 M toluene solution) and 0.44 ml of methylaluminum oxane (2.1 M toluene solution, manufactured by Akzo) were sequentially injected. While stirring it vigorously, 0.75 mL (3.75 mol of Ti) toluene solution to which the respective metallocene catalyst was dissolved was added. After stirring for 1 hour, 10 wt% hydrochloric acid-ethanol solution was added to stop the reaction, and a white solid precipitate was obtained by filtration. 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. Polymerization results and polymer properties for each catalyst are shown in Table 1 below.

Comparative Example 1

The catalyst used in Example 17 was carried out in the same manner as in Example 17, except that Cp ^* Ti (OMe) ₃ , which is a known catalyst, was used.

Styrene homopolymerization result catalyst Yield (%) Active (kg PS / molTi hr) SI (%) Molecular Weight (Mw) Molecular Weight Distribution (Mw / Mn) Melting point (℃) One 27.7 1010 93 291,000 2.2 272 2 14.4 530 92 287,000 2.3 271 3 24.8 900 91 297,000 2.1 273 4 11.3 410 90 292,000 2.3 272 5 32.5 1180 92 292,000 2.1 271 6 17.3 630 93 298,000 2.2 270 7 29.4 1070 92 292,000 2.1 271 8 14.7 530 93 299,000 2.0 272 9 34.2 1240 93 301,000 2.1 271 10 19.6 710 91 302,000 2.2 270 11 27.5 1000 93 310,000 2.3 272 12 12.5 450 92 299,000 2.1 271 13 35.1 1270 91 297,000 2.2 272 14 18.5 670 92 296,000 2.3 271 15 31.2 1130 91 301,000 2.1 270 16 15.3 560 92 302,000 2.3 271 Comparative Example 1 Cp ^* Ti (OMe) ₃ 34.1 1240 91 297,000 2.5 269

Example 18 Preparation of Styrene Homopolymer (Block Polymerization)

Some of the half metallocene catalysts of Examples 1 to 16 synthesized above were selected and subjected to styrene bulk polymerization in the following manner. 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 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, the respective polymers were extracted by refluxing in methyl ethyl ketone for 12 hours to obtain a polymer that remained unmelted. As a result of analyzing this polymer by carbon element nuclear magnetic resonance spectroscopy, it was confirmed that it had a syndiotactic structure. Polymerization results and polymer properties for each catalyst are shown in Table 2 below.

Comparative Example 2

The catalyst used in Example 18 was carried out in the same manner as in Example 18, except that Cp ^* Ti (OMe) ₃ , which is a known catalyst, was used.

Styrene homopolymerization result catalyst Yield (g) Activation (kg polymer / molTi hr) Molecular Weight (Mw) Molecular Weight Distribution (Mw / Mn) Melting point (℃) One 58.2 1160 330,000 2.7 270 5 62.1 1240 310,000 2.5 271 9 64.3 1290 309,000 2.6 269 13 64.9 1300 311,000 2.5 270 Comparative Example 2 Cp ^* Ti (OMe) ₃ 64.0 1280 298,000 2.5 269

Referring to Tables 1 and 2, it can be seen that the styrene homopolymer polymerized using the half metallocene catalyst system according to the present invention has excellent stereoregularity, high melting temperature, and various molecular weight distributions.

The transition metal half metallocene catalyst of the Group 3 to Group 10 of the periodic table using a bridge ligand containing a π- ligand, a cycloalkanedienyl group and a s- ligand functional group, together with a promoter such as alkylaluminum oxane A high activity catalyst system can be used to prepare copolymers of syndiotactic styrene polymers and olefins having excellent stereoregularity, high melting temperature and various molecular weight distributions. 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.

Although the present invention has been described in detail with reference to the embodiments described, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the present invention, and such modifications and variations are included in the appended claims. It is natural to belong.

Claims (18)

Half metallocene compound represented by the following formula (1), (2), (3) or (4). [Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In the above formulas, M ¹ , M ² , M ³ , M ⁴ and M ⁵ are each independently a group 4 transition element on the periodic table, L ¹ , L ² , L ³ , L ⁴ and L ⁵ are each independently a cycloalkanedienyl ligand represented by the following chemical formulas 5, 6, 7, 8 or 9, [Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group , A cycloalkyl group or aryl group having 3 to 20 carbon atoms, m and n are 1, X ¹ and X ² are functional groups which are γ-ligands, each independently a hydroxy group, an alkoxy group, a thioalkoxy group or an arylalkoxy group, A ¹ , A ² , A ³ , A ⁴ and A ⁵ are functional groups that are γ-ligands, each independently oxygen, sulfur, NR ¹⁴ or PR ¹⁵ , D ¹ , D ² , D ³ and D ⁴ are each independently a single bond or an alkylene group or a cycloalkylene group having 3 to 20 carbon atoms, E ¹ , E ² , E ³ , E ⁴ , E ⁵ , E ⁶ , E ⁷ , E ⁸ , E ⁹ , E ¹⁰ , E ¹¹ , E ¹² , E ¹³ , E ¹⁴ , E ¹⁵ , E ¹⁶ , E ¹⁷ , E ¹⁸ , E ¹⁹ and E ²⁰ are each independently a hydrogen atom, a halogen group, an alkyl group or a haloalkyl group, at least one of the groups must be a halogen group or a haloalkyl group, R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a halogen group, an alkyl group, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group or an aryl group. The method of claim 1, The half metallocene catalyst is a half metallocene compound, characterized in that the following formula 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 . [Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

The main catalyst of the half metallocene compound of claim 1; And At least one cocatalyst selected from the group consisting of an alkyl aluminum oxane having a repeating unit of formula 26, an alkyl aluminum of formula 27 and a weakly coordinated Lewis acid; Method for producing a styrene-based polymer, characterized in that the styrene monomer or a styrene-based monomer homopolymerized or copolymerized or copolymerized with an olefin monomer under a catalyst system comprising a. [Formula 26]

[Formula 27]

Wherein R ¹⁶ is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group, and R ¹⁷ , R ¹⁸ and R ¹⁹ are Each independently a hydrogen atom, a halogen group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms, an aryl group, an alkylaryl group, or an arylalkyl group, wherein the alkyl group is linear having 1 to 20 carbon atoms Or an aryl group represents an aromatic or heteroaromatic group having 6 to 40 carbon atoms, wherein at least one of R ¹⁷ , R ^18, and R ¹⁹ includes an alkyl group, and n is an integer of 1 to 100. . The method of claim 3, wherein The half metallocene compound is a method for producing a styrenic polymer, characterized in that it comprises a central metal of 10 ^-8 to 1.0M. The method of claim 3, wherein A method of producing a styrene-based polymer, characterized in that the equivalent ratio of the alkyl aluminum oxane and the half metallocene compound is 1: 1 to 10 ⁶ : 1. The method of claim 3, wherein A method of producing a styrene-based polymer, characterized in that the equivalent ratio of the alkylaluminum and the half metallocene compound is 1: 1 to 10 ⁴ : 1. The method of claim 3, wherein The equivalent ratio of the coordinating Lewis acid and the half metallocene compound is 0.1: 1 to 50: 1. The method of claim 3, wherein Method for producing a styrene-based polymer, characterized in that the polymerization is carried out at a polymerization temperature of -80 to 200 ℃. The method of claim 3, wherein Method for producing a styrene-based polymer, characterized in that the polymerization is carried out under a styrene pressure of 0.01 to 20 atm when the polymerization is styrene homopolymerization. The method of claim 3, wherein Method for producing a styrene-based polymer, characterized in that the polymerization is carried out at 1 to 1000 atm including the pressure of the comonomer. The method of claim 3, wherein The styrene monomer is a halogen group, an alkyl group, an alkoxy group, an ester group, a thioalkoxy group, a silyl group, a tin group, an amine group, a phosphine group, a halogenated alkyl group, a C2-C20 vinyl group, an aryl group, One or more substituents selected from the group consisting of a vinylaryl group, an alkylaryl group and an arylalkyl group, wherein the alkyl group is a straight or crushed hydrocarbon group having 1 to 10 carbon atoms, and the aryl group is aromatic or hetero having 4 to 60 carbon atoms Aromatic group). The method of claim 3, wherein The olefin monomer is a method for producing a styrene polymer, characterized in that selected from the group consisting of a cycloolefin having 2 to 20 carbon atoms, a cyclodiolefin having 3 to 20 carbon atoms and a diolefin having 4 to 20 carbon atoms. The method of claim 3, wherein The polymer is a styrene homopolymer, a styrene derivative homopolymer, a copolymer of styrene and styrene derivative, a copolymer of styrene and olefin or a copolymer of styrene derivative and olefin. The method of claim 3, wherein The polymerization is a method for producing a styrene polymer, characterized in that carried out by slurry polymerization, liquid phase polymerization, gas phase polymerization or bulk polymerization. The method of claim 3, wherein And the polymerization is carried out by injecting a solvent, a styrene monomer, an alkylaluminum, a cocatalyst, and a half metallocene compound into the reactor in this order. The method of claim 3, wherein The main catalyst is pre-activated with a cocatalyst selected from the group consisting of alkyl aluminum oxane of Formula 26, alkyl aluminum of Formula 27 and weakly coordinating Lewis acid, and the activated main catalyst is injected into a reactor containing a monomer and reacted. Method for producing a styrene-based polymer, characterized in that. The method of claim 3, wherein (I) adding alkyl aluminum to the styrene monomer; Ii) activating the half metallocene compound as the main catalyst by contacting with the promoter; And Iii) injecting the activated catalyst of ii) into a reactor filled with the styrene-based monomer and alkylaluminum of iii) and conducting a polymerization reaction; Method for producing a styrene-based polymer comprising a. The method of claim 17, Activation reaction of the main catalyst is a method for producing a styrene polymer, characterized in that for 0.1 to 240 minutes at 0 to 150 ℃.

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