JP4413848B2 - New half metallocene catalyst and method for producing syndiotactic polystyrene using the same - Google Patents

Description

  The present invention relates to a metallocene catalyst for producing a vinyl aromatic polymer and a styrene polymerization method using the same, and more particularly, high activity, excellent stereoregularity and high melting point even when a small amount of a cocatalyst is used. The present invention relates to a novel transition metal half metallocene catalyst having high activity and capable of producing syndiotactic polystyrene having a good molecular weight distribution and a method for producing a polymer using the same.

  Syndiotactic polystyrene can generally be made with a metallocene catalyst containing one or two cycloalkanedienyl groups on a Group 4 transition metal such as titanium, zirconium or hafnium. Here, as the cycloalkanedienyl group, a cyclopentadienyl, indenyl, fluorenyl group or a derivative thereof may be used.

  As a specific example, Ishihara et al. Of Idemitsu Kosan in 1985 announced that syndiotactic polystyrene can be synthesized in a high yield using a catalyst system in which a titanium compound and an alkylaluminum derivative are combined. This is the metallocene catalyst for syndiotactic polystyrene polymerization synthesized first. Patent Document 1 discloses that syndiotactic polystyrene is produced using a catalyst having various substituents containing an alkyl group or an alkoxy group with a group 4 element as a central metal and a promoter such as an alkylaluminum derivative. The polymerization is described. However, this is because the amount of alkylaluminum derivative used in the reaction is large, and in order to obtain a pure polymer after polymerization, a complicated polymer purification operation is required, and the catalytic activity is 0.8 kg-PS / ( There is a problem that it is less than (mmol-metal) (mol-styrene).

  Patent Document 2 describes a cationic organic metal compound having or not having a group 3 to 10 metal and a cyclopentadienyl group, and stabilizing the cationic organic metal compound, It describes the polymerization of polystyrene having a high degree of alternation (syndiotacticity) by adding a small amount of alkylaluminum using an anionic organometallic compound that does not affect the polymerization activity as a catalyst. Compared to the amount of catalyst used for the polymerization, the amount of styrene used in the reaction ranges from more than 3500 times to as much as 500,000 times, so that there is a problem that a large amount of unreacted styrene remains.

  On the other hand, in Patent Document 3, an organometallic compound having various substituents containing an alkyl group or an alkoxy group with an element of group 3 to 6 as a central metal atom and an alkylaluminum derivative are used, or an organometallic compound is used. A reactor is described that is capable of continuously polymerizing syndiotactic polystyrene utilizing a cation and an anion to stabilize it.

  However, as mentioned earlier, most of the literature studied until recently has sought to introduce changes to the introduction of various forms of substituents into cycloalkanedienyl groups bonded to titanium elements, or other elements of titanium elements. Research has focused on changing the chloro and methoxy groups attached to the position to other simple substitutions.

  For example, the present inventors utilize a half metallocene catalyst system in which a chloro group or a methoxy group is changed to a triethanolamine group or an N-alkyldiethanolamine group having a plurality of binding sites, and thereby have higher activity and alternating sequence than existing ones. Recently, many studies on syndiotactic polystyrene have been reported to international journals ((1) Non-Patent Document 1, (2) Non-Patent Document 2, (3) Non-Patent Document 3, (4) Non-Patent Document 4, (5) Non-patent document 5). At the same time, such a content was also reported to a Korean patent. However, Patent Document 4 has a cycloalkanedienyl group or a derivative thereof and a triethanolamine group or an N-alkyldiethanolamine group with a group 4 element as a central metal. A catalyst system capable of producing a polymer from polystyrene having a high degree of alternating arrangement by using a catalyst and an alkylaluminum or a derivative thereof was reported, and a polymerization method thereof. Patent Document 5 reported that syndiotactic polystyrene having a high alternation degree of synthesis was synthesized by introducing a new novel catalyst by introducing a substituent having very high chirality into triethanolamine. However, the catalyst systems of the two patents mentioned above show a high activity only when a large amount of alkylaluminoxane is used, or a substituent introduced into a triethanolamine group or an N-alkyldiethanolamine group is a steric one. Even with disabilities, there are many disadvantages to commercialization due to the fatal reason of being very expensive.

Therefore, it is required to develop a catalyst having high activity as a catalyst having a cost similar to that of an existing catalyst, being easy to handle as a solid compound, and having excellent stability, and an alkylaluminoxane used as a co-catalyst. Even if it is used in a small amount, a catalyst having high activity is necessary.
U.S. Pat. No. 4,680,353 US Pat. No. 5,206,197 US Pat. No. 5,597,879 Korean Patent No. 0301135 (Youngjo Kim, Min Hyung Lee, Youngkyu Do, Yi-Yeol Lyu, Jin Hyung Lim and Hyun-Joon Kim) Korean Patent No. 0365869 (Youngjo Kim, Min Hyung Lee, Sungjin Park, Youngkyu Do, Sung Woong Yoon, Ki Ho Choi and Bo Geun Song) Youngjo Kim, Eunkee Hong, Min Hyung Lee, Jindong Kim, Yonggyu Han and Youngkyu Do, Organometallics 1999, 18, 36. Youngjo Kim and Youngkyu Do, Macromol.Rapid Comm. 2000, 21, 1148. Youngjo Kim, Yonggyu Han and Youngkyu Do, J. Organomet. Chem. 2001, 634, 19. Youngjo Kim, Yonggyu Han, Jeong-Wook Hwang, Myong Won Kim and Youngkyu Do, Organometallics 2002, 21, 1127. Youngjo Kim and Youngkyu Do, J. Organomet. Chem. 2002, 655, 186.

  The problem to be solved by the present invention is that even if a small amount of a co-catalyst is used, it has excellent stereoregularity, high melting point, and high activity for producing syndiotactic polystyrene with good molecular weight distribution. A novel metallocene catalyst, a styrene homopolymerization method using the catalyst, and a copolymerization method with an olefin are provided.

  Another problem to be solved by the present invention is the use of the metallocene catalyst with syndiotactic styrene polymers and olefins having excellent stereoregularity, high melting points, and various molecular weight distributions. The object is to provide a method capable of producing a styrene polymer such as a copolymer in a high yield.

  In order to achieve the above object, the present inventor has developed a novel catalyst for efficiently producing a high syndiotactic styrene-based polymer as a triethanolamine-based, N-alkyldiethanolamine-based or N-dialkylethanolamine group. It was developed by introducing substituents that give high steric hindrance at low cost.

The new metallocene catalyst according to the present invention has a structure similar to a typical half-metallocene structure, and a cycloalkanedienyl group that forms an η ⁵ bond with one of the transition metals of Groups 3 to 10 of the periodic table or its A triethanolamine, N-alkyldiethanolamine or N-dialkylethanolamine ligand compound having a derivative bonded to the other and having two or more ligands and having a high steric hindrance substituent Has a structure represented by the following chemical formula 1, 2 or 3.

In the above formula, M ¹ , M ² and M ³ are each independently a group 3-10 transition element on the periodic table, and L ¹ , L ² and L ³ are each independently the following chemical formula 4, A cycloalkanedienyl ligand represented by 5, 6, 7 or 8;

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. , Halogen group, alkyl group, cycloalkyl group having 3 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkylsilyl group, haloalkyl group, alkoxy group, alkylsiloxy group, amino group, alkoxyalkyl group, thioalkoxyalkyl Group, alkylsiloxyalkyl group, aminoalkyl group, alkylphosphinoalkyl group, aryl group, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thio Aryloxoalkyl group, aryloxoaryl group, arylsiloxane Group, arylalkylsiloxy group, allylsiloxoalkyl group, arylsiloxoaryl group, arylamino group, arylaminoalkyl group, arylaminoaryl group, or arylphosphinoalkyl group (wherein the alkyl group has 1 to 20 is a linear or branched hydrocarbon group, an aryl group represents an aromatic or heteroaromatic group having 6 to 40 carbon atoms, and m and n are integers of 1 or more,
X ¹ , X ² and X ³ are functional groups of the σ-ligand and each independently represent a hydrogen atom, a halogen group, an alkyl group, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group, a carbon An alkenyl group of 2 to 20, an alkoxy group, an alkenyloxy group, a thioalkoxy group, an alkylsiloxy group, an amide group, an alkoxy alcohol group, an alcohol amine group, an aryl group, an alkylaryl group, an arylalkyl group, an arylsilyl group, a haloaryl Group, aryloxy group, arylalkoxy group, thioaryloxy group, arylalkylsiloxy group, arylamide group, arylalkylamide group, aryloxoalcohol group, alcoholarylamine group or arylaminoaryloxy group (wherein alkyl group Is 1 to 2 carbon atoms Of a linear or branched hydrocarbon group, an aryl group, a represents.) An aromatic or heteroaromatic group having 6 to 40 carbons,
A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are functional groups bonded to the central metal, each independently an oxygen atom or a sulfur atom,
D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are each independently an alkyl group, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 6 to 40 carbon atoms. An aryl group of
E ¹ , E ² , E ³ , E ⁴ , E ⁵ , E ⁶ , E ⁷ , E ⁸ , E ⁹ , E ¹⁰ , E ¹¹ and E ¹² 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 alkylsilyl group, a haloalkyl group, an alkoxy group, an alkylsiloxy group, an amino group, an alkoxyalkyl group, a thioalkoxyalkyl group, an alkylsiloxyalkyl group, Aminoalkyl group, alkylphosphinoalkyl group, aryl group, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryloxoalkyl group, aryloxo Aryl group, arylsiloxy group, arylalkyl Lucyloxy group, allylsiloxoalkyl group, arylsiloxoaryl group, arylamino group, arylaminoalkyl group, arylaminoaryl group or arylphosphinoalkyl group (wherein the alkyl group is a straight chain having 1 to 20 carbon atoms) Or an aryl group represents an aromatic or heteroaromatic group having 6 to 40 carbon atoms).
Q ¹ , Q ² and Q ³ are each independently nitrogen or phosphorus,
Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylsilyl group, a haloalkyl group, an alkoxyalkyl group, Thioalkoxyalkyl group, alkylsiloxyalkyl group, aminoalkyl group, alkylphosphinoalkyl group, aryl group, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryloxoalkyl group, thioaryl Oxoalkyl group, aryloxoaryl group, arylsiloxy group, arylalkylsiloxy group, allylsiloxoalkyl group, arylsiloxoaryl group, arylamino group, arylaminoalkyl group, arylaminoaryl group, or ant All phosphinoalkyl group (wherein the alkyl group is a linear or branched hydrocarbon group having 1 to 20 carbon atoms, and the aryl group is an aromatic or heteroaromatic group having 6 to 40 carbon atoms). It represents.)

In particular, in the above chemical formulas 1 to 3, it is desirable that a coordinated bond-type transannular interaction exists between M ¹ -Q ¹ , M ² -Q ² , and M ³ -Q ³ .

  The metallocene catalyst represented by the chemical formulas 1, 2, and 3 is preferably a metallocene catalyst represented by the following chemical formula 9, 10, 11, 12, 13, 14, 15, 16, or 17. The structure was analyzed with an X-ray single crystal diffractometer, and the structure is shown in FIG.

  Further, the present invention provides a method for producing a styrenic polymer, in which a) a main catalyst of a half metallocene compound represented by the above chemical formula 1, 2 or 3, b) an alkylaluminoxane having a repeating unit of the following chemical formula 18, Homopolymerizing a styrene monomer or styrenic monomer under a catalyst system comprising one or more cocatalysts selected from the group consisting of alkylaluminum of formula 19 and weakly coordinating Lewis acid, or Provided is a method for producing a styrene polymer, which is copolymerized with an olefin monomer.

In the above formula, R ¹⁴ 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 ¹⁵ , R ¹⁶ and R ^17, each independently, a hydrogen atom, a halogen group, an unsubstituted or substituted alkyl group, unsubstituted or substituted cycloalkyl group of 20 3 -C, aryl group, is an alkyl group or an arylalkyl group, At least one of R ¹⁵ , R ¹⁶ and R ¹⁷ is an alkyl group (wherein the alkyl group is a linear or branched hydrocarbon group having 1 to 20 carbon atoms, and the aryl group is Represents an aromatic or heteroaromatic group having 6 to 40 carbon atoms, and n is an integer of 1 to 100.

  The present invention relates to a cyclic rule comprising a cycloalkanedienyl group and a triethanolamine-based, N-alkyldiethanolamine-based or N-dialkylethanolamine-based compound having a plurality of binding sites and having high steric hindrance. Using a transition metal half-metallocene catalyst from Group 3 to Group 10 to form a highly active catalyst system together with a co-catalyst such as alkylaluminoxane, this system is used to provide excellent stereoregularity and high melting point. Thus, syndiotactic styrene polymers having various molecular weight distributions and copolymers with olefins can be produced. The polymer produced according to the present invention is excellent in heat resistance, chemical resistance, chemical resistance and processability, and can be applied to engineering plastics in various ways.

The present invention is described in detail below.
The present invention relates to a half metallocene catalyst satisfying the above formulas 1, 2 and 3 as a main catalyst used when a styrene polymer is produced by polymerization, and production of a styrene polymer using the catalyst as a main catalyst. Is to provide a method.

  The metallocene catalyst satisfying the above formulas 1, 2, and 3 of the present invention includes a triethanolamine system and an N-alkyldiethanolamine system having a high steric hindrance while having a cycloalkanedienyl group and a plurality of binding sites. And an N-dialkylethanolamine-based ligand is a half metallocene compound in which a transition metal from group 3 to group 10 of the periodic table is coordinated. Thus, the metal center creates a cationic polymerization active species during polymerization, and the active species thus generated are stabilized during the polymerization at a high temperature because they are stabilized by a ligand having multiple binding sites. The active species of the catalyst is stabilized, and eventually higher activity than the existing catalyst can be expected at a high polymerization temperature. Therefore, such a catalyst system is expected not only to have high polymerization activity under a high polymerization temperature and low cocatalyst, excellent stereoregularity and high melting point styrene polymer, but also easy to adjust the molecular weight of the polymer. The

  Half metallocene containing triethanolamine, N-alkyldiethanolamine and N-dialkylethanolamine ligands having a plurality of binding sites and having high steric hindrance represented by the above chemical formulas 1 to 3 The compound is prepared by first producing an alkali metal salt of a ligand having a cycloalkadienyl structure, and then reacting with a transition metal compound having a ligand that can be easily substituted and removed, and then triethanol having high steric hindrance. It can be produced by reacting an amine-based, N-alkyldiethanolamine-based or N-dialkylethanolamine-based ligand. In addition, a transition metal compound having a ligand that can be easily replaced and a triethanolamine-based, N-alkyldiethanolamine-based, or N-dialkylethanolamine-based ligand having high steric hindrance are reacted first, It can be produced by reacting an alkali metal salt of a ligand having an alkadienyl structure.

  In the metallocene compound production method, the alkali metal salt of the ligand having a cycloalkanedienyl structure includes a lithium salt, a sodium salt, a potassium salt, and the like. These salts have a configuration having a cycloalkanedienyl structure. Ligand and n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, sodium methoxide, sodium ethoxide, potassium tert-butoxide, potassium hydroxide, methylmagnesium chloride, ethylmagnesium bromide, dimethylmagnesium, It can be produced by reacting lithium, sodium, potassium and the like. The alkali metal salts of cycloalkanedienyl groups that can be synthesized from this include cyclopentadienyl lithium, cyclopentadienyl sodium, cyclopentadienyl potassium, cyclopentadienyl magnesium, methylcyclopentadienyl lithium, methylcyclopentadiene. Sodium sodium, methylcyclopentadienyl potassium, tetramethylcyclopentadienyl lithium, tetramethylcyclopentadienyl sodium, tetramethylcyclopentadienyl potassium, indenyl lithium, indenyl sodium, indenyl potassium, fluorenyl lithium and so on.

  The transition metal compound having a ligand that can be easily removed by substitution includes titanium tetrachloride, titanium tetrachloride ditetrahydrofuran, zirconium tetrachloride, hafnium tetrachloride, vanadium tetrachloride, titanium tetraiodo, titanium tetrabromide, Titanium tetrafluoride, vanadium oxide trichloride, titanium tetraisopropoxide, chlorotitanium triisopropoxide, dichlorotitanium diisopropoxide, trichlorotitanium monoisopropoxide, chlorotitanium triphenoxide, chlorotitanium tributoxide, chlorotitanium Examples include triethoxide.

  The half metallocene compounds include cyclopentadienyl titanium trichloride, cyclopentadienylmethoxy titanium dichloride, cyclopentadienyl dimethoxy titanium monochloride, cyclopentadienyl titanium trimethoxide, and methylcyclopentadienyl trichloride. Titanium, methylcyclopentadienylmethoxy titanium dichloride, methylcyclopentadienyldimethoxy titanium monochloride, methylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium trichloride, pentamethylcyclopentadienylmethoxy 2 Titanium chloride, pentamethylcyclopentadienyldimethoxy titanium monochloride, pentamethylcyclopentadienyl titanium trimethoxide, indenyl titanium trichloride, indenylmethoxy titanium dichloride, indenyl dimethyl Carboxymethyl 1 and titanium chloride and indenyl titanium trimethoxide.

  In addition, triethanolamine-based, N-alkyldiethanolamine-based and N-dialkylethanolamine-based ligands having a plurality of binding sites and having high steric hindrance can be produced through a reaction between ethanolamine and epoxide.

In the above-described triethanolamine-based, N-alkyldiethanolamine-based, and N-dialkylethanolamine compounds having high steric hindrance, the substituent that gives steric hindrance (E ¹ to E ^{12 in} Chemical Formulas 1 to 3) has 1 to It may be a 20 cycloalkyl group, an alkylsilyl group, or an aryl group having 6 to 20 carbon atoms, an arylalkyl group, or an alkylaryl group. Here, the alkyl moiety can be either linear or branched. An example is as follows. 2-dialkyl-2-hydroxyethylamine, 3-dialkyl-3-hydroxypropylamine, 4-dialkyl-4-hydroxybutylamine, 5-dialkyl-5-hydroxypentylamine, 6-dialkyl-6-hydroxyhexylamine, N, N-bis (2-dialkyl-2-hydroxyethyl) amine, N, N-bis (3-dialkyl-3-hydroxypropyl) amine, N, N-bis (4-dialkyl-4-hydroxybutyl) amine, N , N-bis (5-dialkyl-5-hydroxypentyl) amine, N, N-bis (6-dialkyl-6-hydroxyhexyl) amine, N, N, N-tris (2-dialkyl-2-hydroxyethyl) ) Amine, N, N, N-tris (3-dialkyl-3-hydroxypropyl) amine, N, N, N-to (4-dialkyl-4-hydroxybutyl) amine, N, N, N-tris (5-dialkyl-5-hydroxypentyl) amine, N, N, N-tris (6-dialkyl-6-hydroxyhexyl) An alcoholamine compound in which one or more sterically restricted hydroxyalkyl groups are bonded to the nitrogen atom of the amine group, such as an amine, or (2-dialkyl-2-hydroxyethyl) -2-hydroxyethylamine, (3- Dialkyl-3-hydroxypropyl) -3-hydroxypropylamine, (4-dialkyl-4-hydroxybutyl) -4-hydroxybutylamine, (5-dialkyl-5-hydroxypentyl) -5-hydroxypentylamine, (6- Dialkyl-6-hydroxyhexyl) -6-hydroxyhexylamine, (2-dia Kill-2-hydroxyethyl) -bis (2-hydroxyethyl) amine, (3-dialkyl-3-hydroxypropyl) -bis (3-hydroxypropyl) amine, (4-dialkyl-4-hydroxybutyl) -bis ( Such as 4-hydroxybutyl) amine, (5-dialkyl-5-hydroxypentyl) -bis (5-hydroxypentyl) amine, (6-dialkyl-6-hydroxyhexyl) -bis (6-hydroxyhexyl) amine In addition, an alcohol amine compound having an alcohol group which always contains at least one alcohol group having a stereo-restrictive substituent and does not have a stereo-restrictive substituent is applicable.

The M ¹ , M ² or M ³ is preferably a group 4 transition element on the periodic table, more preferably titanium, zirconium or hafnium.

  In addition, the 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, and an iodo group, and the above alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. Group, alkylsilyl group, haloalkyl group, alkoxy group, alkylsiloxy group, amino group, alkoxyalkyl group, thioalkoxyalkyl group, alkylsiloxyalkyl group, aminoalkyl group, alkylphosphinoalkyl group include methyl group, ethyl group 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, trimethylsilyl group Group, ethylsilyl group, diethylsilyl group, triethyl Silyl 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, thiomethoxybutyl group, trimethylsiloxyethyl group, dimethylaminoethyl group, diethylphosphine There is such Inobuchiru group.

  In addition, an aryl group having 6 to 40 carbon atoms, arylalkyl group, alkylaryl group, arylsilyl group, arylalkylsilyl group, haloaryl group, aryloxy group, aryloxoalkyl group, thioaryloxoalkyl group, aryloxoaryl group , Arylsiloxy group, arylalkylsiloxy group, allylsiloxoalkyl group, arylsiloxoaryl group, arylamino group, arylaminoalkyl group, arylaminoaryl group, arylphosphinoalkyl group, preferably phenyl group, biphenyl group Terphenyl, naphthyl, fluorenyl, benzyl, phenylethyl, phenylpropyl, tolyl, xylyl, butylphenyl, phenylsilyl, phenyldimethylsilyl, diphenyl Tylsilyl, triphenylsilyl, chlorophenyl, pentafluorophenyl, phenoxy, naphthoxy, phenoxyethyl, biphenoxybutyl, thiophenoxyethyl, phenoxyphenyl, naphthoxyphenyl, phenylsiloxy, tri Phenylsiloxy group, phenyldimethylsiloxy group, triphenylsiloxoethyl group, diphenylsiloxophenyl group, aniline group, toluidine group, benzylamino group, phenylaminoethyl group, phenylmethylaminophenyl group, diphenylphosphinoethyl group, etc. is there.

  In the present invention, the half metallocene catalyst for producing a styrene polymer represented by the above chemical formulas 1, 2, and 3 can be used for homopolymerization of styrene or copolymerization with olefin together with a co-catalyst using a metallocene catalyst as a main catalyst. Thus, syndiotactic styrene polymers and styrene copolymers having various physical properties can be obtained.

  Co-catalysts used with the half metallocene catalyst include alkylaluminoxanes having a repeating unit of the following chemical formula 18 or weakly coordinated Lewis acids, and these are mainly used together with alkylaluminum represented by the chemical formula 19.

  The compound of Formula 18 can have a linear, cyclic, or network structure, and specifically includes methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane, and decylaluminoxane.

  Specifically, the compound of the chemical formula 19 includes trimethylaluminum, dimethylaluminum chloride, dimethylaluminum methoxide, methylaluminum dichloride, triethylaluminum, diethylaluminum chloride, diethylaluminum methoxide, ethylaluminum dichloride, trialuminum. Examples thereof include normal propyl aluminum, dinormal propyl aluminum chloride, n-propyl aluminum chloride, triisopropyl aluminum, trinormal butyl aluminum, triisobutyl aluminum and diisobutyl aluminum hydride.

  The weakly coordinating Lewis acid cocatalyst can take either ionic or neutral form, specifically, trimethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, Tetramethylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetraphenyl borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenyl borate, pyridinium tetrakis (pentafluorophenyl) borate, silver tetrakis (Pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (Pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, sodium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, tris (pentafluorophenyl) ) Borane, tris (2,3,4,5-tetrafluorophenyl) borane, tris (3,5-bis (trifluoromethyl) phenyl) borane, tris (2,4,6-trifluorophenyl) borane, etc. There is.

  In the implementation of styrene polymerization or copolymerization with olefin using the metallocene catalyst, the amount of the cocatalyst used together is not particularly limited, but may vary depending on the type.

In the case of alkylaluminoxane, the molar ratio with the metallocene catalyst can be mainly used within the range of 1: 1 to 10 ⁶ : 1, preferably 10: 1 to 10 ⁴ : 1. Also, the amount of alkylaluminum that can be used with the alkylaluminoxane can be used in the range of 1: 1 to 10 ⁴ : 1 with respect to the metallocene catalyst.

  In the case of weakly coordinating Lewis acids, the molar ratio with the metallocene catalyst can be used in the range of 0.1: 1 to 50: 1. It is used in the range of 1: 1 to 3000: 1, preferably 50: 1 to 1000: 1.

The polymerization catalyst of the present invention may be used by being supported on an inorganic or organic compound. In this case, the support is not limited to a certain substance, but an inorganic compound having fine pores on the surface and a large surface area is suitable. Examples thereof include silica, alumina, magnesium chloride (MgCl _2), balk site, _{zeolite, CaCl 2, MgO, ZrO 2} , TiO 2, B 2 O 3, CaO, ZnO, and the like BaO or ThO _2. The inorganic compound may be used alone, but a mixture thereof, for example, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —CrO _2. O _3, may be used in the form of _{SiO 2} -TiO 2 -MgO. On the other hand, these compounds may contain a small amount of carbonate, sulfate and nitrate, and organic compounds such as starch, cyclodextrin and synthetic polymers may be used.

  The monomer that can be polymerized with the catalyst system of the present invention can be styrene, a styrene derivative or an olefin, which can be a homopolymer of styrene or a styrene derivative, a copolymer of styrene and a styrene derivative, or a styrene or Styrene derivatives and olefins can be copolymerized.

  The styrene derivative has a substituent on the benzene ring of styrene, and the substituent includes a halogen group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an ester group, a thioalkoxy group, a silyl group, tin Group, amine group, phosphine group, halogenated alkyl group, vinyl group having 2 to 20 carbon atoms, aryl group, vinylaryl group, alkylaryl group, arylalkyl group and the like. Specific examples thereof include chlorostyrene, bromostyrene, fluorostyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, n-butylstyrene, p-tert-butylstyrene, dimethylstyrene, methoxystyrene, ethoxy. Styrene, butoxystyrene, methyl-4-styrenyl ester, thiomethoxystyrene, trimethylsilylstyrene, triethylsilylstyrene, tert-butyldimethylsilylstyrene, trimethyltinstyrene, dimethylaminostyrene, trimethylphosphinostyrene, chloromethylstyrene, bromomethyl Examples include styrene, 4-vinylbiphenyl, p-divinylbenzene, m-divinylbenzene, trivinylbenzene, 4,4'-divinylbiphenyl, and vinylnaphthalene. .

  Examples of olefins that can be mainly used for copolymerization include olefins having 2 to 20 carbon atoms, cycloolefins or cyclodiolefins having 3 to 20 carbon atoms, and diolefins having 4 to 20 carbon atoms. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene, norbornene, methyl-2-norbornene, There are 1,3-butadiene, 1,4-pentadiene, 2-methyl-1,3-butadiene, and 1,5-hexadiene.

  When polymerizing utilizing the polymerization catalyst system of the present invention, the polymerization can be carried out in a slurry phase, a liquid phase, a gas phase and a bulk phase. When the polymerization is carried out in a slurry phase or a liquid phase, a solvent can be used as a polymerization medium, and the solvents used at this time are butane, pentane, hexane, heptane, octane, decane, dodecane, cyclopentane, methylcyclohexane. Alkane or cycloalkane solvents having 4 to 20 carbon atoms such as pentane and cyclohexane, aromatic allene solvents having 6 to 20 carbon atoms such as benzene, toluene, xylene and mesitylene, dichloromethane, chloromethane, chloroform, carbon tetrachloride, C1-C20 halogenated alkanes and halogenated compounds such as chloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene and 1,2,4-trichlorobenzene There are allene solvents. These solvents may be used alone or mixed at a certain ratio. In the solvent-free state, gas phase polymerization is possible under the internal pressure of the reactor of 0.01 to 20 atmospheres.

  In the method for producing a polymer according to the present invention, the polymerization temperature is −80 ° C. to 200 ° C., preferably 0 ° C. to 150 ° C., and the polymerization pressure is a comonomer pressure during styrene homopolymerization or copolymerization with an olefin. 1 to 1000 atmospheres is suitable.

  The process for producing a polymer according to the present invention is large. I) After adding a solvent and a monomer or only a monomer to a reactor and raising the temperature, an alkylaluminum, a cocatalyst, and a metallocene compound as a main catalyst are in this order. Or ii) pre-activate the main catalyst with alkylaluminum and cocatalyst and then inject into the reactor containing the monomer, or iii) add alkylaluminum to the monomer in advance Later, it can be done by injecting the main catalyst activated with the cocatalyst. The reaction for activating the main catalyst by contacting with the cocatalyst is preferably 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 as the main catalyst used in the polymer production process is not particularly limited, but 10 ⁻⁸ to 1.0 M is suitable as the concentration of the central metal in the reaction system, and ideally 10 ^-7 to ^{10 -2} M concentration is suitable.

  The syndiotactic styrene polymer and copolymer obtained from the polymerization reaction using the above catalyst system should adjust the type and amount of main catalyst and cocatalyst, reaction temperature, reaction pressure, and monomer concentration. Can be adjusted in various ways within a molecular weight range of 1,000 to 10,000,000 and a molecular weight distribution range of 1.1 to 100.

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

〔Example〕
Example 1 Synthesis of Cp ^* Ti (OCMe ₂ CH ₂ ) ₃ N (Catalyst 1)
<Production of (HOCMe ₂ CH ₂ ) ₃ N>
10 ml (20 mmol) of ammonia (NH ₃ , 2M solution in MeOH), 4.76 g (66 mmol) of isobutylene oxide and a stirrer are placed in a 20 ml stoppered glass bottle and stirred at room temperature for 12 hours. Was transferred to a 250 ml flask and the glass bottle was washed three times with 20 ml of acetone and the contents were combined. After removing all the solvent with a rotary distiller, each was dissolved in a small amount of hexane, and then left in a refrigerator, a colorless solid was obtained. The solution was filtered and dried under vacuum to give 4.6 g (98% yield) of a white solid (HOCMe ₂ CH ₂ ) ₃ N, the ¹ HNMR result is as follows.
¹ H NMR (300.13MHZ, CDCl ₃ , ppm): δ = 2.55 (s, 6H, CH ₂ ), 1.16 (s, 18H, CMe ₂ ), ¹³ C { ¹ H} NMR (75.4 MHz, CDCl3, ppm) : δ = 69.92 (OCMe2), 61.02 (CH ₂ N), 27.40 (OCMe ₂ ).

<Production of Cp ^* Ti (OCMe ₂ CH ₂ ) ₃ N (Catalyst 1)>
(HOCMe ₂ CH ₂ ) ₃ N 2 mmol (0.47 g) synthesized above was put in a Schlenk flask and well dissolved in 30 ml of toluene. To this, 6 mmol (0.84 ml) of triethylamine was added to make a colorless clean solution. After the temperature of the system was lowered to −78 ° C., 2 mmol (0.578 g) of Cp ^* TiCl ₃ was dissolved in 30 ml of toluene in another Schlenk flask, and the solution was slowly added dropwise to the system. When the addition was complete, the temperature was slowly raised to room temperature and stirred overnight. The next day, the ammonium salt was removed through a celite filter to give a clean yellow solution. The solvent was removed under vacuum, and dried for a long time to obtain 0.8 g (yield 97%) of catalyst 1 of the following chemical formula 9, which is an orange-yellow solid product, and the ¹ HNMR result was as follows. is there.
¹ H NMR (300.13 MHz, CDCl ₃ , ppm): δ = 3.16 (dd, J _1,2 = 6.6 Hz, J _1,3 = 11.9 Hz, 3H, CH ₂ ), 2.81 (dd, J _1,2 = _{7.4Hz, J 1,3 = 11.9Hz, 3H} , CH 2). 1.96 (s, 15H, C ₅ Me ₅ ), 1.20 (s, 9H, CMe ₂ ), 1.11 (s, 9H, CMe ₂ ). ¹³ C { ¹ H} NMR (75.4 MHz, CDCl ₃ , ppm): δ = 125.7 (C ₅ Me ₅ ), 84.34 (OCMe ₂ ), 61.35 (CH ₂ N), 31.17 (OCMe ₂ ), 29.30 (OCMe ₂ ), 11.95 (C ₅ Me ₅ ). EI-MS: m / z = 414.

Example ^{_{2: Cp * Ti (OCMe 2}} CH 2) Synthesis of _{2 N (CH 2 CH 2 O} ) ( catalyst 2)
<Production of (HOCMe ₂ CH ₂ ) ₂ N (CH ₂ CH ₂ O)>
3.05 g (50 mmol) of ethanolamine, 7.93 g (110 mmol) of isobutylene oxide and a stir bar were placed in a 20 ml stoppered glass bottle, stirred at room temperature for 12 hours, and then the colorless sticky contents were transferred to a 250 ml flask. The glass bottle was washed with 20 ml of acetone three times, and the contents were combined. After removing all solvent with a rotary distiller, it was dried under vacuum for a long time to obtain 10 g (yield 97%) of colorless oil (HOCMe ₂ CH ₂ ) ₂ N (CH ₂ CH ₂ OH). The ¹ HNMR results are as follows.
¹ H NMR (300, 13 MHz, CDCl ₃ , ppm): δ = 3.60 (t, J = 5.4 Hz, 2H, CH ₂ CH ₂ N), 2.77 (t, J = 5.4 Hz, 2H, CH ₂ CH ₂ N ), 2.53 (s, 4H, CMe ₂ CH ₂ N), 1.17 (s, 12H, CMe ₂ ). ¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , ppm): δ = 71.03 (OCH ₂ ), 68.81 (OCMe ₂ ), 61.39 (NCH ₂ ), 60.49 (NCH ₂ ), 28.21 (OCMe ₂ ).

<Production of Cp ^* Ti (OCMe ₂ CH ₂ ) ₂ N (CH ₂ CH ₂ O) (Catalyst 2)>
1.45 mmol (0.298 g) of (HOCMe ₂ CH ₂ ) ₂ N (CH ₂ CH ₂ OH) synthesized above was placed in a Schlenk flask and well dissolved in 30 ml of toluene. To this, 4.8 mmol (0.7 ml) of triethylamine was added to make a colorless clean solution. After the temperature of the system was lowered to −78 ° C., 1.45 mmol (0.42 g) of Cp ^* TiCl ₃ was dissolved in 30 ml of toluene in another Schlenk flask, and the solution was slowly added dropwise to the system. When the addition was complete, the temperature was slowly raised to room temperature and stirred overnight. The next day, the ammonium salt was removed through a celite filter to give a clean yellow solution. The solvent was removed under vacuum and dried for a long time to obtain 0.56 g (yield 100%) of catalyst 2 of the following chemical formula 10 as a yellow solid product, and the ¹ HNMR result is as follows. The results of structural analysis of the catalyst by a single crystal X-ray diffractometer are shown in FIG.
¹ H NMR (300, 13 MHz, CDCl ₃ , ppm): δ = 4.10 (t, J = 5.5 Hz, 2H, CH ₂ CH ₂ N), 2.94-2.80 (m, 6H, CH ₂ CH ₂ N and CMe ₂ CH ₂ N), 1.85 (s, 15H, C ₅ Me ₅ ), 0.90 (d, J = 7.4 Hz, 12H, CMe ₂ ), ¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , ppm): δ = 121.4 (C ₅ Me ₅ ), 81.29 (OCH ₂ ), 70.91 (OCMe ₂ ), 70.50 (NCH ₂ ), 63.35 (NCH ₂ ), 31.79 (OCMe ₂ ), 31.14 (OCMe ₂ ), 11.13 (C ₅ Me ₅ ), EI-MS: m / z = 385.

Example 3 Synthesis of Cp ^* Ti (OCMe ₂ CH ₂ ) ₂ N (CH ₂ CH ₂ O) (Catalyst 3)
<Production of (HOCMe ₂ CH ₂ ) N (CH ₂ CH ₂ OH) ₂ >
5.26 g (50 mmol) of diethanolamine, 3.61 g (55 mmol) of isobutylene oxide and a stirrer are placed in a 20 ml stoppered glass bottle and stirred at room temperature for 12 hours, and then the colorless sticky contents are transferred to a 250 ml flask. The glass bottle was washed with 20 ml acetone three times, and the contents were combined. After removing all the solvent with a rotary distiller, it was dried under vacuum for a long time and was 8.6 g (yield 97%) of colorless oil (HOCMe ₂ CH ₂ ) N (CH ₂ CH ₂ OH) ₂ The ¹ HNMR results are as follows.
¹ H NMR (300, 13 MHz, CDCl ₃ , ppm): δ = 4.62 (br s, 3H, OH), 3.58 (t, J = 4.7 Hz, 4H, CH ₂ CH ₂ N), 2.65 (t, J = _{4.7Hz, 2H, CH 2 CH 2} N), 2.42 (s, 2H, CMe 2 CH 2 N), 1.15 (s, 6H, CMe 2). ¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , ppm): δ = 70.73 (OCH ₂ ), 66.85 (OCMe ₂ ), 59.94 (NCH ₂ ), 59.21 (NCH ₂ ), 27.73 (OCMe ₂ ).

<Production of Cp ^* Ti (OCMe ₂ CH ₂ ) N (CH ₂ CH ₂ O) ₂ (Catalyst 3)>
The (HOCMe ₂ CH ₂ ) N (CH ₂ CH ₂ OH) ₂ 1.45 mmol (0.257 g) synthesized above was placed in a Schlenk flask and well dissolved in 30 ml of toluene. To this, 4.8 mmol (0.7 ml) of triethylamine was added to make a colorless clean solution. After the temperature of the system was lowered to −78 ° C., 1.45 mmol (0.42 g) of Cp ^* TiCl ₃ was dissolved in 30 ml of toluene in another Schlenk flask, and the solution was slowly added dropwise to the system. When the addition was complete, the temperature was slowly raised to room temperature and stirred overnight. The next day, the ammonium salt was removed through a celite filter to give a clean yellow solution. The solvent was removed under vacuum and dried for a long time to obtain 0.51 g (yield 98%) of catalyst 3 of the following chemical formula 11 as a yellow solid product, and the ¹ HNMR result is as follows.
¹ H NMR (300, 13 MHz, CDCl ₃ , ppm): δ = 4.17 (t, J = 5.4 Hz, 4H, CH ₂ CH ₂ N), 2.93-2.85 (m, 6H, CH ₂ CH ₂ N and CMe _{2 CH 2 N), 1.86 (s} , 15H, C 5 Me 5), 0.90 (s, 6H, CMe 2). ¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , ppm): δ = 121.9 (C ₅ Me ₅ ), 81.94 (OCH ₂ ), 70.70 (OCMe ₂ ), 67.46 (NCH ₂ ), 59.56 (NCH ₂ ) 32.13 (OCMe ₂ ), 11.07 (C ₅ Me ₅ ), EI-MS: m / z = 357.

[Example 4: Synthesis of Cp ^* Ti (OPh) ₃ N (catalyst 4)]
2 mmol (0.59 g) of tris (2-hydroxyphenyl) amine was placed in a Schlenk flask and well dissolved in 30 ml of toluene. To this, 6 mmol (0.84 ml) of triethylamine was added to make a colorless clean solution. After lowering the temperature of the system to -78 ° C., was dissolved in another Schlenk flask ^Cp * TiCl ₃ 2mmol a (0.578 g) in toluene 30 ml, was added dropwise to the solution slowly the system. When the addition was complete, the temperature was slowly raised to room temperature and stirred overnight. The next day, the ammonium salt was removed through a celite filter to give a clean yellow solution. The solvent was removed under vacuum and dried for a long time to obtain 0.49 g (yield 52%) of catalyst 4 of the following chemical formula 12, which is an orange-yellow solid product, and the ¹ HNMR result was as follows. is there.
¹ H NMR (300, 13 MHz, CDCl ₃ , ppm): δ = 7.43 (d, J = 7.9 Hz, 3H, Ph-H), 7.04 (t, J = 8.0 Hz, 3H, Ph-H), 6.69 ( t, J = 7.9 Hz, 3H, Ph—H), 6.51 (d, J = 8.0 Hz, 3H, Ph—H), 2.15 (s, 15H, C ₅ Me ₅ ). ¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , ppm): δ = 164.0 (Ph), 1 (Ph), 128.9 (Ph), 128.5 (Ph), 126.0 (C ₅ Me ₅ ), 119.2 (Ph ), 116.6 (Ph), 11.56 (C ₅ Me ₅ ). EI-MS: m / z = 473.

Example 5: Synthesis of Cp ^* TiCl {(OCMe ₂ CH ₂ ) ₂ NMe} (Catalyst 5)]
<Production of (HOCMe ₂ CH ₂ ) ₂ NMe>
25 ml (50 mmol) of methylamine (2M solution in MeOH), 7.93 g (110 mmol) of isobutylene oxide and a stir bar were placed in a 20 ml stoppered glass bottle, stirred at 50 ° C. for 12 hours, and then the reaction temperature was lowered to room temperature. The colorless sticky contents were transferred to a 250 ml flask. The glass bottle was washed with 20 ml of acetone three times, and then the contents were combined with the 250 ml flask. After removing all solvent on a rotary evaporator, long and dried under vacuum to give a colorless oil 8.7 g (99% yield) _{(HOCMe 2} CH _{2) 2} NMe ^and, 1 HNMR results It is as follows.
¹ H NMR (300.13 MHz, CDCl ₃ , ppm): δ = 3.86 (s, 2H, OH), 2.46 (s, 4H, CMe ₂ CH ₂ N), 2.42 (s, 3H, NMe), 1.10 (s , 12H, CMe ₂ ). ¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , ppm): δ = 72.05 (OCMe ₂ ), 71.48 (OCMe ₂ ), 61.39 (NCH ₂ ), 60.49 (NMe), 28.21 (OCMe ₂ ).

<Production of Cp ^* TiCl {(OCMe ₂ CH ₂ ) ₂ NMe} (Catalyst 5)>
The (HOCMe ₂ CH ₂ ) ₂ NMe 2.42 mmol (0.424 g) synthesized above was placed in a Schlenk flask and well dissolved in 30 ml of toluene. To this, 5 mmol (0.8 ml) of triethylamine was added to make a colorless clean solution. After the temperature of the system was lowered to −78 ° C., 2.42 mmol (0.7 g) of Cp ^* TiCl ₃ was dissolved in 30 ml of toluene in another Schlenk flask, and then the solution was slowly added dropwise to the system. When the addition was complete, the temperature was slowly raised to room temperature and stirred overnight. The next day, the ammonium salt was removed through a celite filter to give a clean yellow solution. The solvent was removed under vacuum and dried for a long time to obtain 0.85 g (yield 89%) of catalyst 5 of the following chemical formula 13 which is a yellow solid product, and the ¹ HNMR result is as follows.
¹ H NMR (300, 13 MHz, CDCl ₃ , ppm): δ = 2.67 (q, J = 11.6 Hz, 4H, CH ₂ N), 2.58 (s, 3H, NMe), 2.04 (s, 15H, C ₅ Me ₅ ), 1.18 (d, J = 4.4 Hz, 12H, CMe ₂ ). ¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , ppm): δ = 125.1 (C ₅ Me ₅ ), 88.13 (OCMe ₂ ), 73.68 (NCH ₂ ), 50.29 (NMe), 28.59 (OCMe ₂ ), 12.17 (C ₅ Me ₅ ). EI-MS: m / z = 393.

Example 6 Synthesis of Cp ^* Ti (OMe) {(OCMe ₂ CH ₂ ) ₂ NMe} (Catalyst 6)
Ligand (HOCMe ₂ CH ₂ ) ₂ NMe 2.42 mmol (0.424 g) synthesized in Example 5 was placed in a Schlenk flask and well dissolved in 30 ml of toluene. After the temperature of the system was lowered to −78 ° C., 2.42 mmol (0.67 g) of Cp ^* Ti (OMe) ₃ was dissolved in 30 ml of toluene in another Schlenk flask, and the solution was slowly added dropwise to the system. Added. When the addition was complete, the temperature was slowly raised to room temperature and stirred overnight. The solvent was removed under vacuum and dried for a long time to obtain 0.83 g (yield 92%) of catalyst 6 of the following chemical formula 14 which is a yellow solid product, and the ¹ HNMR result is as follows.
¹ H NMR (300, 13 MHz, CDCl ₃ , ppm): δ = 4.01 (s, 3H, OMe), 2.73 (q, J = 12.0 Hz, 4H, CH ₂ N), 2.61 (s, 3H, NMe), _{2.01 (s, 15H, C 5} Me 5), 1.21 (d, J = 5.2Hz, 12H, CMe 2). ¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , ppm): δ = 125.9 (C ₅ Me ₅ ), 87.44 (OCMe ₂ ), 75.15 (NCH ₂ ), 62.32 (OMe), 51.33 (NMe), 29.43 (OCMe ₂ ), 11.29 (C ₅ Me ₅ ).

[Example 7: Synthesis of Cp ^* TiCl {(OCMe ₂ CH ₂ ) NMe (CH ₂ CH ₂ O)} (catalyst 7)]
<Production of (HOCMe ₂ CH ₂ ) NMe (CH ₂ CH ₂ OH)>
7.51 g (100 mmol) of N-methylethanolamine, 7.93 g (110 mmol) of isobutylene oxide and a stirring bar were placed in a 20 ml stoppered glass bottle and stirred at 50 ° C. for 12 hours, and then the reaction temperature was lowered to room temperature. The colorless sticky contents were transferred to a 250 ml flask. The glass bottle was washed with 20 ml of acetone three times, and then the contents were combined with the 250 ml flask. After removing all the solvent with a rotary still, it was dried under vacuum for a long time to give 14.3 g (97% yield) of colorless oil (HOCMe ₂ CH ₂ ) NMe (CH ₂ CH ₂ OH). The obtained ¹ HNMR results are as follows.
¹ H NMR (300, 13 MHz, CDCl ₃ , ppm): δ = 3.56 (t, J = 5.4 Hz, 2H, NCH ₂ CH ₂ ), 3.41 (br, s, 2H, OH), 2.60 (t, J = _{5.5Hz, 2H, NCH 2 CH 2} ), 2.37 (s, 3H, NMe), 2.34 (s, 2H, CMe 2 CH 2 N), 1.12 (s, 6H, CMe 2). ¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , ppm): δ = 70.72 (OCH ₂ ), 68.29 (OCMe ₂ ), 61.75 (NCH ₂ ), 45.46 (NMe), 27.62 (OCMe ₂ ).

<Production of Cp ^* TiCl {(OCMe ₂ CH ₂ ) NMe (CH ₂ CH ₂ O)} (Catalyst 7)>
2.42 mmol (0.356 g) of (HOCMe ₂ CH ₂ ) NMe (CH ₂ CH ₂ OH) synthesized above was placed in a Schlenk flask and well dissolved in 30 ml of toluene. To this, 5 mmol (0.8 ml) of triethylamine was added to make a colorless clean solution. After the temperature of the system was lowered to −78 ° C., 2.42 mmol (0.7 g) of Cp ^* TiCl ₃ was dissolved in 30 ml of toluene in another Schlenk flask, and then the solution was slowly added dropwise to the system. When the addition was complete, the temperature was slowly raised to room temperature and stirred overnight. The next day, the ammonium salt was removed through a celite filter to give a clean yellow solution. The solvent was removed under vacuum and dried for a long time to obtain 0.77 g (yield 88%) of the catalyst 7 of the following chemical formula 15 as a yellow solid product, and the ¹ HNMR result is as follows.
¹ H NMR (300, 13 MHz, CDCl ₃ , ppm): δ = 4.36-4.28 (m, 2H, CH ₂ O), 2.86-2.79 (m, 1H, CH ₂ CH ₂ N), 2.72 (d, J = 3.3Hz, 2H, CMe ₂ CH ₂ N), 2.70-2.61 (m, 1H, CH ₂ CH ₂ N), 2.58 (s, 3H, NMe), 1.97 (s, 15H, C ₅ Me ₅ ), 1.22 ( d, J = 10 Hz, 6H, CMe ₂ ). ¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , ppm): δ = 125.8 (C ₅ Me ₅ ), 85.95 (OCH ₂ ), 72.88 (OCMe ₂ ), 68.29 (CH ₂ CH ₂ N), 61.60 ( CMe ₂ CH ₂ N), 47.79 (NMe), 31.92 (OCMe ₂ ), 31.16 (OCMe ₂ ), 12.00 (C ₅ Me ₅ ). EI-MS: m / z = 363.

[Example 8: Synthesis of Cp ^* Ti (OMe) {(OCMe ₂ CH ₂ ) NMe (CH ₂ CH ₂ O)} (catalyst 8)]
2.42 mmol (0.356 g) of the ligand (HOCMe ₂ CH ₂ ) NMe (CH ₂ CH ₂ O) synthesized in Example 7 was placed in a Schlenk flask and well dissolved in 30 ml of toluene. After the temperature of the system was lowered to −78 ° C., 2.42 mmol (0.67 g) of Cp ^* Ti (OMe) ₃ was dissolved in 30 ml of toluene in another Schlenk flask, and the solution was slowly added dropwise to the system. Added. When the addition was complete, the temperature was slowly raised to room temperature and stirred overnight. The solvent was removed under vacuum and dried for a long time to obtain 0.76 g (yield 91%) of catalyst 8 of the following chemical formula 16, which is a yellow solid product, and the ¹ HNMR result is as follows.
¹ H NMR (300, 13 MHz, CDCl ₃ , ppm): δ = 4.25 (m, 2H, CH ₂ O), 4.01 (s, 3H, OMe), 2.77 (m, 1H, CH ₂ CH ₂ N), 2.65 (d, J = 3.8Hz, 2H, CMe ₂ CH ₂ N), 2.85 (m, 1H, CH ₂ CH ₂ N), 2.51 (s, 3H, NMe), 2.01 (s, 15H, C ₅ Me ₅ ) 1.19 (d, J = 9.1 Hz, 6H, CMe ₂ ). ¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , ppm): δ = 125.3 (C ₅ Me ₅ ), 84.15 (OCH ₂ ), 77.93 (OCMe ₂ ), 65.75 (CH ₂ CH ₂ N), 63.51 ( OMe), 62.58 (CMe ₂ CH ₂ N), 48.94 (NMe), 32.88 (OCMe ₂ ), 30.09 (OCMe ₂ ), 11.79 (C ₅ Me ₅ ).

Example 9 Synthesis of Cp ^* Ti (OMe) ₂ (OCMe ₂ CH ₂ NMe ₂ ) (Catalyst 9)
<Production of HOCMe ₂ CH ₂ NMe ₂ >
20 ml (40 mmol) of dimethylamine (HNMe ₂ , 2M solution in MeOH), 3.17 g (46 mmol) of isobutylene oxide and a stirrer are placed in a 20 ml stoppered glass bottle and stirred at room temperature for 12 hours. The contents were transferred to a 250 ml flask and the glass bottle was washed 3 times with 20 ml acetone before the contents were combined. All solvents were removed by rotary distillation to obtain 2.6 g (yield 55%) of colorless liquid HOCMe ₂ CH ₂ NMe ₂ , and the ¹ HNMR results are as follows.
¹ H NMR (300, 13 MHz, CDCl ₃ , ppm): δ = 3.43 (br s, 1H, OH), 2.33 (s, 6H, NMe ₂ ), 2.24 (s, 2H, CH ₂ N), 1.13 (s , 6H, CMe ₂ ). ¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , ppm): δ = 69.92 (OCMe ₂ ), 61.02 (CH ₂ N), 27.40 (OCMe ₂ ).

<Production of Cp ^* Ti (OMe) ₂ (OCMe ₂ CH ₂ NMe ₂ ) (Catalyst 9)>
HOCMe ₂ CH ₂ NMe ₂ 2.42 mmol (0.284 g) synthesized above was placed in a Schlenk flask and well dissolved in 30 ml of toluene. After the temperature of the system was lowered to −78 ° C., 2.42 mmol (0.67 g) of Cp ^* Ti (OMe) ₃ was dissolved in 30 ml of toluene in another Schlenk flask, and the solution was slowly added dropwise to the system. Added. When the addition was complete, the temperature was slowly raised to room temperature and stirred overnight. The solvent was removed under vacuum and dried for a long time to obtain 0.64 g (yield 88%) of the catalyst 9 of the following chemical formula 17, which is a yellow solid product, and the ¹ HNMR result is as follows.
¹ H NMR (300, 13 MHz, CDCl ₃ , ppm): δ = 4.12 (s, 6H, OMe), 2.68 (s, 2H, CH ₂ N), 2.55 (s, 6H, NMe ₂ ), 1.98 (s, 15H, C ₅ Me ₅ ), 1.12 (d, J = 7.8 Hz, 6H, CMe ₂ ). ¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , ppm): δ = 124.5 (C ₅ Me ₅ ), 76.34 (OCMe ₂ ), 65.29 (OMe), 63.75 (NMe), 47.36 (NMe ₂ ), 34.51 (OCMe ₂ ), 11.33 (C ₅ Me ₅ ).

[Example 10: Production of styrene homopolymer (liquid phase polymerization)]
The half metallocene catalysts of Examples 1 to 9 synthesized above were each subjected to styrene homo-liquid phase polymerization as follows. 70 ml of purified heptane was added to the 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 methylaluminoxane (2.1 M toluene solution, manufactured by Akzo) were sequentially injected. While stirring vigorously, a 0.75 ml (3.75 μmol Ti) toluene solution in which the respective metallocene catalyst was dissolved was added. After stirring for 1 hour, a 10 wt% hydrochloric acid-ethanol solution was added to stop the reaction, followed by filtration to obtain a white solid precipitate. This precipitate was washed with ethanol and dried in a vacuum oven at 50 ° C. overnight to obtain a final styrene polymer. The polymerization results and polymer properties for each catalyst are shown in Table 1 below. In addition, the respective polymers were extracted by refluxing with methyl ethyl ketone for 12 hours to obtain polymers 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. The polymerization results and polymer properties for each catalyst are shown in Table 1 below.

[Comparative Example 1]
Except that the catalyst used in Example 10 above was Cp ^* Ti (OMe) ₃ which is a conventional catalyst, the same procedure as in Example 10 was performed, and the polymerization results and polymer properties for the catalyst were as follows. It showed in Table 1.

[Comparative Example 2]
The catalyst used in Example 10 is the same as Example 10 except that Cp ^* Ti (OCH ₂ CH ₂ ) N, which is a conventional catalyst, is used. The physical properties are shown in Table 1 below.

[Comparative Example 3]
The catalyst used in Example 10 is the same as Example 10 except that the conventional catalyst Cp ^* Ti (OCHMeCH ₂ ) ₃ N is used. The polymerization results and polymer properties for the catalyst are as follows. Is shown in Table 1 below.

[Example 11: Production of styrene homopolymer (bulk phase polymerization)]
Using some of the half metallocene catalysts of Examples 1 to 9 synthesized above, styrene bulk phase polymerization was carried out by the following method.
100 ml of purified styrene was added to the polymerization reactor in a high purity nitrogen atmosphere and the temperature was raised to 50 ° C. Subsequently, 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 strongly stirring it, 5 ml (50 μmol Ti) of toluene solution in which the metallocene was dissolved was added. After stirring for 1 hour, the reaction was stopped by adding a hydrochloric acid-ethanol solution having a concentration of 10% by weight, filtered, washed with ethanol, and dried overnight in a 50 ° C. vacuum oven to obtain the final styrene polymer. Got. The polymerization results and polymer properties for each catalyst are shown in Table 2 below. In addition, the respective polymers were extracted by refluxing with methyl ethyl ketone for 12 hours to obtain polymers that remained undissolved. As a result of analyzing this polymer by carbon nuclear magnetic resonance spectroscopy, it was confirmed that it had a syndiotactic structure. The polymerization results and polymer properties for each catalyst are shown in Table 2 below.

[Comparative Example 4]
Except that the catalyst used in Example 11 above was Cp ^* Ti (OMe) ₃ which is a conventional catalyst, the same procedure as in Example 11 was carried out, and the polymerization results and polymer properties for the catalyst were as follows. Table 2 shows.

[Comparative Example 5]
The catalyst used in Example 11 is the same as Example 11 except that Cp ^* Ti (OCH ₂ CH ₂ ) N, which is a conventional catalyst, is used. The physical properties are shown in Table 2 below.

  Referring to Tables 1 and 2, the styrene homopolymer polymerized using the half metallocene catalyst system according to the present invention has excellent stereoregularity, a high melting point, and various molecular weight distributions. I understand.

  Although the present invention has been described in detail with a focus on the specific examples described above, it will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the present invention and the scope of the technical idea. Of course, it is obvious that such variations and modifications fall within the scope of the claims.

   The present invention is applicable to technical fields related to vinyl aromatic polymers.

1 is an X-ray single crystal structure obtained by an X-ray diffractometer of a half metallocene compound catalyst of Formula 10 according to the present invention.

Claims (18)

A half metallocene catalyst represented by the following chemical formula 1, 2 or 3.

[In the above formula,
M ¹ , M ² and M ³ are each independently a group 3-10 transition element on the periodic table,
L ¹ , L ² and L ³ are each independently a cycloalkanedienyl ligand represented by the following chemical formula 4, 5, 6, 7 or 8;

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. , Halogen group, alkyl group, cycloalkyl group having 3 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkylsilyl group, haloalkyl group, alkoxy group, alkylsiloxy group, amino group, alkoxyalkyl group, thioalkoxyalkyl group, alkyl acyloxyalkyl group, an amino group, an alkyl phosphino alkyl group, aryl group, arylalkyl group, alkylaryl group, aryl silyl group, arylalkyl silyl group, a haloaryl group, an aryloxy group, Ariruo key Soarukiru group, Chioariruo · The Soarukiru group, an aryl oxo aryl group, an aryl Shiroki Group, arylalkylsiloxy group, allylsiloxoalkyl group, arylsiloxoaryl group, arylamino group, arylaminoalkyl group, arylaminoaryl group, or arylphosphinoalkyl group (wherein the alkyl group has 1 carbon atom) Or an aryl group represents an aromatic or heteroaromatic group having 6 to 40 carbon atoms, and m and n are integers of 1 or more. ,
X ¹ , X ² and X ³ are functional groups of the σ-ligand and each independently represent a hydrogen atom, a halogen group, an alkyl group, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group, a carbon An alkenyl group of 2 to 20, an alkoxy group, an alkenyloxy group, a thioalkoxy group, an alkylsiloxy group, an amide group, an alkoxy alcohol group, an alcohol amine group, an aryl group, an alkylaryl group, an arylalkyl group, an arylsilyl group, a haloaryl Group, aryloxy group, arylalkoxy group, thioaryloxy group, arylalkylsiloxy group, arylamide group, arylalkylamide group, aryloxoalcohol group, alcoholarylamine group or arylaminoaryloxy group (wherein alkyl group Has 1 to 0 is a linear or branched hydrocarbon group, the aryl group is a C 6 -C represents an aromatic or heteroaromatic group 40.),
A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are functional groups bonded to the central metal, each independently an oxygen atom or a sulfur atom,
D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are each a carbon atom ;
E ¹ , E ² , E ³ , E ⁴ , E ⁵ , E ⁶ , E ⁷ , E ⁸ , E ⁹ , E ¹⁰ , E ¹¹ and E ¹² 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 alkylsilyl group, a haloalkyl group, an alkoxy group, an alkylsiloxy group, an amino group, an alkoxyalkyl group, a thioalkoxyalkyl group, an alkylsiloxyalkyl group, aminoalkyl group, alkylphosphino alkyl group, aryl group, arylalkyl group, alkylaryl group, aryl silyl group, arylalkyl silyl group, a haloaryl group, an aryloxy group, Ariruo key Soarukiru group, Chioariruo key Soarukiru group, aryl oxo aryl Group, arylsiloxy group, arylalkyl Lucyloxy group, allylsiloxoalkyl group, arylsiloxoaryl group, arylamino group, arylaminoalkyl group, arylaminoaryl group or arylphosphinoalkyl group (wherein the alkyl group is a straight chain having 1 to 20 carbon atoms) Or an aryl group represents an aromatic or heteroaromatic group having 6 to 40 carbon atoms), provided that E ¹ , E ² , E ³ , E ⁴ , E ⁵ , And E ⁶ are not simultaneously hydrogen atoms, E ⁷ , E ⁸ , E ⁹ , and E ¹⁰ are not all hydrogen atoms at the same time , and all E ¹¹ and E ¹² are simultaneously hydrogen atoms. Is not an atom,
Q ¹ , Q ² and Q ³ are each independently nitrogen or phosphorus,
Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylsilyl group, a haloalkyl group, an alkoxyalkyl group, thio alkoxyalkyl group, an alkyl siloxy group, an aminoalkyl group, the alkyl phosphino alkyl group, aryl group, arylalkyl group, alkylaryl group, aryl silyl group, arylalkyl silyl group, a haloaryl group, Ariruo key Soarukiru group, Chioariruo key Soarukiru Group, aryloxoaryl group, arylsiloxy group, arylalkylsiloxy group, allylsiloxoalkyl group, arylsiloxoaryl group, arylamino group, arylaminoalkyl group, arylaminoaryl group or aryl Ruphosphinoalkyl group (wherein the alkyl group is a linear or branched hydrocarbon group having 1 to 20 carbon atoms, and the aryl group represents an aromatic or heteroaromatic group having 6 to 40 carbon atoms. ). ] 2. The half metallocene compound according to claim 1, wherein the half metallocene catalyst is represented by the following chemical formula 9, 10, 11, 12, 13, 14, 15, 16 or 17.

And Hafumetarose down main catalyst of claim 1 wherein,
A styrene monomer or styrene under a catalyst system comprising: an alkylaluminoxane having a repeating unit of formula 18; and one or more promoters selected from the group consisting of an alkylaluminum of formula 19 and a weakly coordinating Lewis acid. A method for producing a styrenic polymer comprising homopolymerizing or copolymerizing a monomer based on copolymerization or copolymerizing with an olefin monomer.

[In the formula, R ¹⁴ is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group 20 3 -C, aryl group, alkylaryl group or arylalkyl group, R ¹⁵ , R ¹⁶ and R ¹⁷ 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 a linear or branched hydrocarbon group having 1 to 20 carbon atoms, and the aryl group represents an aromatic or heteroaromatic group having 6 to 40 carbon atoms). However, at least one of R ¹⁵ , R ¹⁶ and R ¹⁷ includes an alkyl group, and n is an integer of 1 to 100. ] The method for producing a styrenic polymer according to claim 3, wherein the half metallocene catalyst contains a central metal of ^10-8 to 1.0M. The method for producing a styrenic polymer according to claim 3, wherein an equivalence ratio of the alkylaluminoxane and the half metallocene catalyst is 1: 1 to 10 ⁶ : 1. The method for producing a styrenic polymer according to claim 3, wherein the equivalent ratio of the alkylaluminum to the half metallocene catalyst is 1: 1 to 10 ⁴ : 1. The method for producing a styrenic polymer according to claim 3, wherein an equivalence ratio of the weakly coordinating Lewis acid and the half metallocene catalyst is 0.1: 1 to 50: 1. The method for producing a styrenic polymer according to claim 3, wherein the polymerization is carried out at a polymerization temperature of -80 to 200 ° C. The method for producing a styrenic polymer according to claim 3, wherein when the polymerization is styrene homopolymerization, the polymerization is performed under a styrene pressure of 0.01 to 20 atmospheres. The method for producing a styrenic polymer according to claim 3, wherein the polymerization is carried out at a pressure of 1 to 1000 atmospheres including a comonomer pressure. The styrene monomer has 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 carbon number of 2 to 20 on a styrenebenzene ring. One or more substituents selected from the group consisting of a vinyl group, an aryl group, a vinylaryl group, an alkylaryl group and an arylalkyl group (wherein the alkyl group is a linear or branched group having 1 to 10 carbon atoms) 4. The method for producing a styrenic polymer according to claim 3, wherein the aryl group is an aromatic or heteroaromatic group having 4 to 60 carbon atoms. The styrene monomer according to claim 3, wherein the olefin monomer is selected from the group consisting of a cycloolefin having 2 to 20 carbon atoms, a cyclodiolefin, and a diolefin having 4 to 20 carbon atoms. Manufacturing method of coalescence. The polymer is a styrene homopolymer, a styrene derivative homopolymer, a copolymer of styrene and a styrene derivative, a copolymer of styrene and an olefin, or a copolymer of a styrene derivative and an olefin. The method for producing a styrenic polymer according to claim 3. The method for producing a styrenic polymer according to claim 3, wherein the polymerization is performed by slurry phase polymerization, liquid phase polymerization, gas phase polymerization, or bulk phase polymerization. The styrene polymer according to claim 3, wherein the polymerization is performed by injecting a solvent, a styrenic monomer, an alkylaluminum, a cocatalyst, and a half metallocene catalyst into the reactor in this order. Method. The main catalyst is activated in advance with a co-catalyst selected from the group consisting of the alkylaluminoxane of the chemical formula 18, the alkylaluminum of the chemical formula 19 and a weakly coordinating Lewis acid, and the activated main catalyst includes a monomer. 4. The method for producing a styrenic polymer according to claim 3, wherein the reaction is carried out by pouring into a reactor that has been used. The polymerization process is
i) adding alkylaluminum to the styrenic monomer;
ii) activating the half-metallocene catalyst of the main catalyst by contacting with a co-catalyst;
and iii) injecting the activated catalyst of ii) into a reactor filled with the styrenic monomer and alkylaluminum of i) and carrying out a polymerization reaction. The manufacturing method of the styrenic polymer of Claim 3. The method for producing a styrenic polymer according to claim 3, wherein the activation reaction of the main catalyst is advanced at 0 to 150 ° C for 0.1 to 240 minutes.

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