JP5577197B2 - Process for producing aromatic vinyl compound polymer - Google Patents

Description

  The present invention relates to a method for producing an aromatic vinyl compound polymer, and more specifically, an aromatic vinyl compound using an aromatic vinyl compound polymerization catalyst obtained by using a specific catalyst component and a specific aromatic vinyl compound. The present invention relates to a method for producing a polymer.

  In recent years, olefin polymers are important as molding materials and the like, and many technical developments have been made on the polymers and their production methods. For example, regarding the production method, technical development has been conducted on solid catalysts such as Ziegler-Natta catalysts and catalysts using metal complexes, and the results have been reported. In particular, catalysts that use metal complexes have been found to have high homogeneity, and that the reactivity can be changed by changing the central metal or ligand of the metal complex. Has been continued.

Examples of the metal complex include a metallocene complex, and so far, a metal complex having two cyclic ligands such as a cyclopentadienyl group and an indenyl group, and a metal including a bridging group that binds the cyclic ligand. Complexes (crosslinked metallocene complexes), metal complexes having one cyclic ligand (half metallocene complex), and the like have been reported (hereinafter, a catalyst using a metallocene complex may be abbreviated as a metallocene catalyst).
In a metallocene catalyst, the positional relationship between a monomer and a growing polymer chain during polymerization can be controlled by selecting a cyclic ligand, introducing a substituent, and the like. A polymer having properties (isotacticity, syndiotacticity, etc.) can be produced.
As for the central metal in the metallocene complex, group 4 transition metals such as titanium, zirconium and hafnium were conventionally used, but in recent years, group 3 transition metals such as scandium, yttrium and lanthanum and lanthanoid metals are used. A polymerization reaction using a metallocene complex has been reported.

By the way, a polymer of an aromatic vinyl compound having a syndiotactic structure (hereinafter sometimes abbreviated as “syndiotactic polymer”) is excellent in mechanical strength, heat resistance, appearance, solvent resistance, and the like. And is used in various applications.
Regarding the catalyst for producing a syndiotactic polymer, there is a report on a metallocene catalyst using a metal other than the Group 4 transition metal. For example, Patent Document 1 discloses a half-group containing a Group 3 metal atom or a lanthanoid metal atom. Disclosed are a polymerization catalyst composition containing a metallocene complex and a polymer having high syndiotacticity obtained using the same. However, this catalyst has a problem that it is easily deactivated, and there is a problem in terms of productivity.
In the polymerization method using a titanium compound or the like as a catalyst, Patent Documents 2 and 3 are known as techniques using a purified styrene-based monomer, but a description regarding the case of using a complex of a Group 3 transition metal or a lanthanoid metal is described. not exist.

International Publication No. 2006/004068 Pamphlet Japanese National Patent Publication No. 11-508272 JP-A-7-233213

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing an aromatic vinyl compound polymer in which a decrease in the activity of the catalyst is suppressed when a polymerization catalyst using a half metallocene complex is used. It is what.

As a result of intensive studies, the present inventors have used a specific catalyst component containing a Group 3 or lanthanoid series transition metal of the periodic table and an aromatic vinyl compound with a reduced content of the specific compound. It has been found that the above object can be achieved by inhibiting the poisoning of the catalyst by the method for producing an aromatic vinyl compound polymer. The present invention has been completed based on such findings.
That is, the present invention
1. A process for producing an aromatic vinyl compound polymer that polymerizes an aromatic vinyl compound in the presence of a polymerization catalyst using a half metallocene complex containing a transition metal of Group 3 of the periodic table or a lanthanoid series, A method for producing an aromatic vinyl compound polymer, wherein the indene content of the vinyl compound is 0.8 mass ppm or less,
2. 2. The method for producing an aromatic vinyl compound polymer according to the above 1, wherein the polymerization catalyst is formed using an organoaluminum compound in addition to the half metallocene complex,
3. The method for producing an aromatic vinyl compound polymer according to the above 1 or 2, wherein the polymerization catalyst comprises an ionic compound comprising a non-coordinating anion and a cation in addition to the half metallocene complex,
4). The method for producing an aromatic vinyl compound polymer according to any one of 1 to 3 above, wherein the indene content of the aromatic vinyl compound is 0.5 mass ppm or less,
5. The method for producing an aromatic vinyl compound polymer according to any one of the above 1 to 4, wherein the acetophenone content of the aromatic vinyl compound is 0.8 mass ppm or less,
6). The method for producing an aromatic vinyl compound polymer according to 5 above, wherein the aromatic vinyl compound has an acetophenone content of 0.5 ppm by mass or less,
7). The method for producing an aromatic vinyl compound polymer according to any one of 1 to 6, wherein the benzaldehyde content of the aromatic vinyl compound is 20 mass ppm or less,
8). The method for producing an aromatic vinyl compound polymer according to 7 above, wherein the benzaldehyde content of the aromatic vinyl compound is 15 mass ppm or less,
9. The method for producing an aromatic vinyl compound polymer according to any one of 1 to 8 above, wherein the half metallocene complex is represented by the following formula (II):
RMX _a-1 Y _b (II)
[In the formula (II), R represents a fused polycyclic cyclopentadienyl π ligand, at least one of which is a saturated ring, M represents a group 3 or lanthanoid series transition metal in the periodic table, and X represents represents a sigma ligand, and Y represents a Lewis base. a represents the valence of M, and b represents 0, 1 or 2. ]
10. The method for producing an aromatic vinyl compound polymer according to any one of 2 to 9 above, wherein the organoaluminum compound is represented by the following formula (VII):
R'R''R '''Al (VII)
[In the formula (VII), R ′, R ″ and R ′ ″ each independently represents an alkyl group having 3 to 5 carbon atoms. ]
11. The ionic compound is an ionic compound comprising a cation selected from substituted or unsubstituted triarylcarbenium or substituted or unsubstituted anilinium and a non-coordinating anion represented by the general formula (X). The method for producing an aromatic vinyl compound polymer according to any one of 3 to 10 above,
(BZ ¹ Z ² Z ³ Z ⁴ ) ^- (X)
[Wherein, Z ^{1 to} Z ⁴ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms (including a halogen-substituted aryl group). ), An alkylaryl group, an arylalkyl group, a substituted alkyl group and an organic metalloid group or a halogen atom. ]
12 The method for producing an aromatic vinyl compound polymer according to any one of the above 1 to 11, wherein the polymerization is performed in the presence of an inert solvent selected from an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent,
13. 13. A method for producing an aromatic vinyl compound polymer according to any one of 1 to 12 above, wherein the stereoregularity of a repeating unit chain composed of an aromatic vinyl compound, comprising a step of polymerizing the aromatic vinyl compound [ rrrr] is 80 mol% or more, and a method for producing an aromatic vinyl compound polymer, and14. 13. A method for producing an aromatic vinyl compound polymer according to any one of the above 1 to 12, comprising a step of polymerizing an aromatic vinyl compound and an olefin monomer, wherein the repeating unit chain is composed of an aromatic vinyl compound. A method for producing an aromatic vinyl compound polymer having a stereoregularity [rrrr] of 80 mol% or more,
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, when using the polymerization catalyst which uses a half metallocene complex, the manufacturing method of the aromatic vinyl compound polymer by which the activity fall of the catalyst was suppressed is provided.

  The present invention relates to a method for producing an aromatic vinyl compound polymer, and relates to an aromatic polymer for polymerizing an aromatic vinyl compound in the presence of a polymerization catalyst using a half metallocene complex containing a group 3 transition metal or a lanthanoid series transition metal. A method for producing a vinyl compound polymer, wherein the indene content of the aromatic vinyl compound is 0.8 mass ppm or less.

  In the present specification, the “aromatic vinyl compound polymer” refers to a polymer in which the aromatic vinyl compound monomer unit is 1 mol% or more, specifically, a single compound composed of one kind of aromatic vinyl compound. Polymers, copolymers comprising two or more aromatic vinyl compounds, and copolymers comprising aromatic vinyl compounds and other monomers (olefins) are included.

As the aromatic vinyl compound in the method for producing an aromatic vinyl compound polymer of the present invention, those having an indene content of 0.8 mass ppm or less, preferably 0.5 mass ppm or less are used. When the indene content in the aromatic vinyl compound exceeds the above range, the polymerization catalyst is extremely poisoned, and efficient polymerization cannot be performed.
As a method for reducing the indene content of the aromatic vinyl compound, purification by distillation may be mentioned. As pressure conditions, distillation under reduced pressure is preferable to normal pressure, specifically 10 kPaA or less is preferable, and 4 kPaA or less is more preferable.

The aromatic vinyl compound preferably has an acetophenone content of 0.8 mass ppm or less, and more preferably 0.5 mass ppm or less.
Further, the aromatic vinyl compound preferably has a benzaldehyde content of 20 mass ppm or less, more preferably 15 mass ppm or less, further preferably 12 mass ppm or less, and particularly preferably 5 mass ppm or less. .
When the acetophenone content or the benzaldehyde content is within the above range, poisoning of the catalyst can be effectively suppressed.
Examples of the method for reducing the acetophenone content and the benzaldehyde content of the aromatic vinyl compound include an alumina treatment in which the aromatic vinyl compound is treated with alumina or activated alumina (hereinafter sometimes abbreviated as alumina or the like). Alumina treatment can be performed under various conditions, but usually, alumina or the like and an aromatic vinyl compound may be contacted at a temperature of about 0 to 50 ° C. for about 10 minutes to 2 hours.

  As the polymerization catalyst in the present invention, a catalyst obtained by reacting the half metallocene complex, the organoaluminum compound, and an ionic compound comprising a non-coordinating anion and a cation is preferably used.

In the preparation of the polymerization catalyst, it is preferable to contact the half metallocene complex and the organoaluminum compound, and then contact the contact product with the ionic compound.
In this invention, it is preferable that the said organoaluminum compound of the quantity used as the molar ratio with respect to the said half metallocene complex is 20-500. When the molar ratio is 20 or more, the polymerization activity is hardly lowered in the polymerization reaction after storing the catalyst. For economic reasons, the molar ratio is preferably 500 or less. From this viewpoint, the molar ratio is preferably 50 to 400, more preferably 100 to 300.
In the present invention, preferably, the ionic compound is used in an amount such that the molar ratio to the half metallocene complex is 0.5 to 3.0. When the molar ratio is 0.5 or more, high polymerization activity is obtained. For economic reasons, the molar ratio is preferably 3.0 or less. From this viewpoint, the molar ratio is preferably 0.5 to 2.5, more preferably 0.5 to 2.0.

  When preparing a polymerization catalyst, it is desirable to perform the contact operation in an inert gas atmosphere such as nitrogen gas. And what was prepared beforehand in the catalyst preparation tank may be used for a catalyst, and what was prepared in the polymerization reactor which superposes | polymerizes an aromatic vinyl compound may be used as it is.

  In the method for producing an aromatic vinyl compound polymer of the present invention, polymerization is carried out using an aromatic vinyl compound as a raw material in the presence of the polymerization catalyst.

  In the method for producing an aromatic vinyl compound polymer of the present invention, preliminary polymerization can be performed using the polymerization catalyst. There is no restriction | limiting in particular in the method, It can carry out by a well-known method. There is no restriction | limiting in particular about the aromatic vinyl compound used for prepolymerization, What was mentioned above can be used. The prepolymerization temperature is usually from -20 to 200 ° C, preferably from -1 to 130 ° C. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent.

  Although there is no restriction | limiting in particular as a polymerization system used in the manufacturing method of the aromatic vinyl compound polymer of this invention, Bulk polymerization, solution polymerization, etc. can be employ | adopted suitably. In the case of the bulk polymerization method, there is no solvent, and as the solvent used in the case of the solution polymerization method, an inert solvent is suitable. Examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclohexane, and aliphatic hydrocarbons such as pentane, hexane, and heptane. The polymerization temperature is usually in the range of 0 to 200 ° C, preferably 0 to 120 ° C. Moreover, the pressure at the time of superposition | polymerization is 0.01-30 Mpa normally, Preferably it is the range of 0.01-3 Mpa.

  There are various types of aromatic vinyl compounds, but those represented by the following general formula (I) are preferred.

(In the formula, R represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 20 or less carbon atoms, and m represents an integer of 1 to 3. When m is plural, each R is the same or different. May be good.)

  Specific examples of the aromatic vinyl compound include, for example, styrene, p-methylstyrene, p-ethylstyrene, pn-propylstyrene, p-isopropylstyrene, pn-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, on-propylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, mn-propylstyrene, m-isopropylstyrene, m -Alkyl styrene such as n-butyl styrene, mesityl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, 3,5-dimethyl styrene, 4-butenyl styrene, p-chlorostyrene, m-chlorostyrene , O-chlorostyrene, p-bromostyrene, m-bromostyrene Halogenated styrene such as o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene, p-methoxystyrene, o-methoxystyrene, m-methoxystyrene, etc. Examples include alkoxystyrene and vinyl benzoate. The said aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the method for producing an aromatic vinyl compound polymer of the present invention, it is preferable to use only an aromatic vinyl compound as a raw material, but copolymerization may be performed by combining an aromatic vinyl compound and an olefin monomer.

  Examples of the olefin monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-phenyl-1-butene, 6 -Phenyl-1-hexene, 3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-hexene, 4-methyl -1-hexene, 5-methyl-1-hexene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclohexane, hexafluoropropene, Tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene, , 4-dichloro-1-butene, butadiene, isoprene, dicyclopentadiene, norbornene, acetylene and the like. Among these, ethylene, propylene, 1-hexene, 1-octene. These may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the method of carrying out copolymerization using an aromatic vinyl compound and an olefin monomer as raw materials, the content of the aromatic vinyl compound unit in the resulting copolymer is 1 mol% or more, preferably 5 to 99 mol%. More preferably, it is 40-95 mol%. That is, the content of the olefin monomer unit is 99 mol% or less, preferably 1 to 95 mol%, more preferably 5 to 60 mol%. When the content of the olefin monomer unit is within the above range, the physical properties of the aromatic vinyl compound polymer are improved.

In the preparation of the polymerization catalyst, those represented by the following formula (II) are preferably used as the half metallocene complex.
RMX _a-1 Y _b (II)
[In the formula (II), R represents a condensed polycyclic cyclopentadienyl π ligand, at least one of which is a saturated ring, M represents a group 3 or lanthanoid series transition metal in the periodic table, and X represents In the case where a σ ligand is present and a plurality of Xs are present, the plurality of Xs may be the same or different, and may be bonded to each other via an arbitrary group. Y represents a Lewis base and may be cross-linked with X. a represents the valence of M, and b represents 0, 1 or 2. ]

  Examples of the σ ligand represented by X include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, Examples thereof include an amide group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. Examples of the Lewis base represented by Y include amines, ethers, phosphines, thioethers, and the like.

  Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-hexyl group, and n-decyl group. Alkenyl groups such as alkyl groups, allyl groups, isopropenyl groups, aryl groups such as phenyl groups, 1-naphthyl groups, 2-naphthyl groups, aralkyl groups such as benzyl groups, N, N-dimethylaminobenzyl groups, etc. Can be mentioned. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, and n-pentyloxy. Group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group and the like.

  Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group. Examples of the amide group having 1 to 20 carbon atoms include N-methylamide group and N, N-dimethylamide group. Examples of the silyl group having 1 to 20 carbon atoms include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a trimethylsilylmethyl group, and a bis (trimethylsilyl) methyl group. Examples of the phosphide group having 1 to 20 carbon atoms include a diphenyl phosphide group. As a C1-C20 sulfide group, a phenyl sulfide group etc. are mentioned, for example. As a C1-C20 acyl group, an acetyl group, a propionyl group, a butyryl group etc. are mentioned, for example.

M is preferably a metal of Group 3 of the periodic table, more preferably scandium.
R in the general formula (II) is preferably any condensed polycyclic cyclopentadienyl π ligand represented by any one of the following formulas (III), (IV) and (V). .

[In the formulas (III) to (V), R ^{1 to} R ³³ are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a carbon number. An alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an amino group, an amide group, a carboxyl group or an alkylsilyl group; R ^{1 to} R ³³ may be the same as or different from each other, and c, d, e, and f represent an integer of 1 or more.
c, d, e and f are preferably integers of 1 to 3, more preferably 2.

  In the formulas (III) to (V), examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a pentyl group, a hexyl group, and a cyclohexyl group. Groups, alkyl groups such as octyl group; alkenyl groups such as vinyl group, propenyl group and cyclohexenyl group. Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include aralkyl groups such as benzyl group, phenethyl group and phenylpropyl group; tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, butyl Examples include alkyl-substituted phenyl groups such as phenyl group and tri-t-butylphenyl group; phenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, phenanthonyl group and the like. Examples of the thioalkoxy group having 1 to 20 carbon atoms include a thiomethoxy group. Examples of the thioaryloxy group having 6 to 20 carbon atoms include a thiophenoxy group. Specific examples of the halogen atom, the alkoxy group having 1 to 20 carbon atoms, the aryloxy group having 6 to 20 carbon atoms, and the alkylsilyl group are the same as those given in the general formula (I).

  Specific examples of the condensed polycyclic cyclopentadienyl π ligand of the formula (III) include 4,5,6,7-tetrahydroindenyl group, 1-methyl-4,5,6,7-tetrahydroindene. Nyl group, 1,2-dimethyl-4,5,6,7-tetrahydroindenyl group, 1,3-dimethyl-4,5,6,7-tetrahydroindenyl group, 1,2,3-trimethyl-4 , 5,6,7-tetrahydroindenyl group, 2-methyl-4,5,6,7-tetrahydroindenyl group, 1-ethyl-4,5,6,7-tetrahydroindenyl group, 1-ethyl- 2-methyl-4,5,6,7-tetrahydroindenyl group, 1-ethyl-3-methyl-4,5,6,7-tetrahydroindenyl group, 1-ethyl-2,3-dimethyl-4, 5,6,7-tetrahydroindenyl group, 1 2-diethyl-4,5,6,7-tetrahydroindenyl group, 1,2-diethyl-3-methyl-4,5,6,7-tetrahydroindenyl group, 1,3-diethyl-4,5, 6,7-tetrahydroindenyl group, 1,3-diethyl-2-methyl-4,5,6,7-tetrahydroindenyl group, 1,2,3-triethyl-4,5,6,7-tetrahydroindene Nyl group, 2-ethyl-4,5,6,7-tetrahydroindenyl group, 1-methyl-2-ethyl-4,5,6,7-tetrahydroindenyl group, 1,3-dimethyl-2-ethyl -4,5,6,7-tetrahydroindenyl group, tetrahydropentalenyl group, 1-methyltetrahydropentalenyl group, 2-methyltetrahydropentalenyl group, 1,2-dimethyltetrahydropentalenyl group, 1,3-dimethyltetrahydropentalenyl group, 1,2,3-trimethyltetrahydropentalenyl group, hexahydroazurenyl group, 1-methylhexahydroazurenyl group, 2-methylhexahydroazurenyl group, 1, Examples include 2-dimethylhexahydroazurenyl group, 1,3-dimethylhexahydroazurenyl group, 1,2,3-trimethylhexahydroazurenyl group and the like.

  Specific examples of the condensed polycyclic cyclopentadienyl π ligand of the formula (IV) include tricyclo [6,4,0,0] dodecadienyl group, 2-methyltricyclo [6,4,0,0]. A dodecadienyl group etc. are mentioned.

  Specific examples of the condensed polycyclic cyclopentadienyl π ligand of the formula (V) include 1,2,3,4-tetrahydrofluorenyl group, 9-methyl-1,2,3,4-tetrahydro -1-fluorenyl group, 9-ethyl-1,2,3,4-tetrahydro-1-fluorenyl group, 9-npropyl-1,2,3,4-tetrahydro-1-fluorenyl group, 1,2,3 , 8-tetrahydrocyclopenta [α] indene, 8-methyl-1,2,3,8-tetrahydrocyclopenta [α] indene, 8-ethyl-1,2,3,8-tetrahydrocyclopenta [α] indene 8-n-propyl-1,2,3,8-tetrahydrocyclopenta [α] indene, 8-phenyl-1,2,3,8-tetrahydrocyclopenta [α] indene, 8-trimethylsilyl-1,2 , 3, -Tetrahydrocyclopenta [α] indene, 4a, 5,6,7,8,9-hexahydrobenzo [α] azurenyl group, 10-methyl-4a, 5,6,7,8,9-hexahydrobenzo [ α] azurenyl group, 10-ethyl-4a, 5,6,7,8,9-hexahydrobenzo [α] azurenyl group, 10-n-propyl-4a, 5,6,7,8,9-hexahydro Benzo [α] azurenyl group, 10-phenyl-4a, 5,6,7,8,9-hexahydrobenzo [α] azurenyl group, 10-trimethylsilyl-4a, 5,6,7,8,9-hexahydro A benzo [α] azulenyl group and the like can be mentioned.

Among the condensed polycyclic cyclopentadienyl π ligands, a ligand represented by the formula (V) is particularly preferable, and a ligand having an alicyclic 6-membered ring structure, that is, the following formula (VI ) Is most preferable in terms of activity, stability of the complex, and production cost.

[In the formula (VI), R ^{34 to} R ⁴⁶ are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. an alkoxy group, an aryloxy group having 6 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, a thioaryloxy group, an amino group having 6 to 20 carbon atoms, an amide group, a carboxyl group or an alkylsilyl group, R ³⁴ R ⁴⁶ may be the same as or different from each other. ]
Specific examples of these substituents include those exemplified with respect to formulas (III) to (V).

  Specific examples of the half metallocene complex represented by the formula (II) include (1,3-dimethyltetrahydropentalenyl) bis (N, N-dimethylaminobenzyl) scandium, (tricyclo [6,4,0,0 ] Dodecadienylbis (N, N-dimethylaminobenzyl) scandium, (1,2,3,8-tetrahydrocyclopenta [α] indenyl) bis (N, N-dimethylaminobenzyl) scandium, (8-methyl- 1,2,3,8-tetrahydrocyclopenta [α] indenyl) bis (N, N-dimethylaminobenzyl) scandium, (1,2,3,4-tetrahydro-1-fluorenyl) bis (N, N-dimethyl) Aminobenzyl) scandium, (9-methyl-1,2,3,4-tetrahydro-1-fluorenyl) bis (N, N-dimethyl) Minobenzyl) scandium, (9-ethyl-1,2,3,4-tetrahydro-1-fluorenyl) bis (N, N-dimethylaminobenzyl) scandium, (9-n-propyl-1,2,3,4) (Tetrahydro-1-fluorenyl) bis (N, N-dimethylaminobenzyl) scandium, (9-trimethylsilyl-1,2,3,4-tetrahydro-1-fluorenyl) bis (N, N-dimethylaminobenzyl) scandium, 4a, 5,6,7,8,9-hexahydrobenzo [α] azulenyl) bis (N, N-dimethylaminobenzyl) scandium, (9-methyl-1,2,3,4-tetrahydro-1-fluorenyl) ) Bis (trimethylsilylmethyl) scandium, (9-ethyl-1,2,3,4-tetrahydro-1-fluorenyl) Bis (trimethylsilylmethyl) scandium, (9-n-propyl-1,2,3,4-tetrahydro-1-fluorenyl) bis (trimethylsilylmethyl) scandium, (9-trimethylsilyl-1,2,3,4-tetrahydro- 1-fluorenyl) bis (trimethylsilylmethyl) scandium, (9-methyl-1,2,3,4-tetrahydro-1-fluorenyl) bis (allyl) scandium, (9-ethyl-1,2,3,4-tetrahydro) -1-fluorenyl) bis (allyl) scandium, (9-n-propyl-1,2,3,4-tetrahydro-1-fluorenyl) bis (allyl) scandium, (9-trimethylsilyl-1,2,3,4) -Tetrahydro-1-fluorenyl) bis (allyl) scandium and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

In the preparation of the polymerization catalyst, an organic aluminum compound represented by the formula (VII) is preferably used.
R'R''R '''Al (VII)
[In the formula (VII), R ′, R ″ and R ′ ″ each independently represents an alkyl group having 3 to 5 carbon atoms. ]
When the number of carbon atoms of the alkyl group is 2 or less, the catalytic activity is lowered, and when it is 6 or more, the catalytic activity is also lowered.

  Examples of the alkyl group having 3 to 5 carbon atoms in the formula (VII) include various propyl groups, various butyl groups, and various pentyl groups.

Examples of the organoaluminum compound include tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tri-n-pentylaluminum. Among these, an organoaluminum compound having only a substituent having 4 carbon atoms is preferable because excellent activity is obtained, and tri-n-butylaluminum and triisobutylaluminum are more preferable.
In this invention, these organoaluminum compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the preparation of the polymerization catalyst, as the ionic compound, a non-coordinating anion and cation capable of forming an ionic complex by reacting with the above half metallocene complex or a contact product of the above half metallocene complex and an organoaluminum compound. An ionic compound consisting of Examples of the compound include an ionic compound composed of a non-coordinating anion and a substituted or unsubstituted triarylcarbenium, and an ionic compound composed of a non-coordinating anion and a substituted or unsubstituted anilinium.

Examples of the substituted or unsubstituted triarylcarbenium include, for example, the general formula (VIII)
[CR ⁴⁷ R ⁴⁸ R ⁴⁹ ] ⁺ (VIII)
[Wherein R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are each an aryl group such as a phenyl group, a substituted phenyl group, a naphthyl group and an anthracenyl group, and they may be the same as or different from each other. ]
And triarylcarbenium represented by the formula:
The substituted phenyl group is, for example, the formula (IX)
C ₆ H _5-k R ⁵⁰ _k (IX)
[Wherein, R ⁵⁰ represents a hydrocarbyl group having 1 to 10 carbon atoms, an alkoxy group, an aryloxy group, a thioalkoxy group, a thioaryloxy group, an amino group, an amide group, a carboxyl group, or a halogen atom, It is an integer of 5. When k is 2 or more, the plurality of R ⁵⁰ may be the same or different. ]
It can be expressed as

Specific examples of the substituted or unsubstituted triarylcarbenium represented by the formula (VIII) include tri (phenyl) carbenium, tri (toluyl) carbenium, tri (methoxyphenyl) carbenium, tri (chlorophenyl) carbenium, tri ( Fluorophenyl) carbenium, tri (xylyl) carbenium, [di (toluyl), phenyl] carbenium, [di (methoxyphenyl), phenyl] carbenium, [di (chlorophenyl), phenyl] carbenium, [toluyl, di (phenyl)] Carbenium, [methoxyphenyl, di (phenyl)] carbenium, [chlorophenyl, di (phenyl)] carbenium and the like can be mentioned.
Specific examples of substituted or unsubstituted anilinium include N, N-dimethylanilinium.

Non-coordinating anions include, for example, formula (X)
(BZ ¹ Z ² Z ³ Z ⁴ ) ^- (X)
[Wherein, Z ^{1 to} Z ⁴ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms (including a halogen-substituted aryl group). ), An alkylaryl group, an arylalkyl group, a substituted alkyl group and an organic metalloid group or a halogen atom. ]
The non-coordinating anion represented by these can be mentioned.

  Specific examples of the non-coordinating anion represented by the formula (X) include tetrakis (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (Pentafluorophenyl) borate, tetrakis (trifluoromethylphenyl) borate, tetra (toluyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, Examples include tridecahydride-7,8-dicarboundeborate.

Specific examples of the ionic compound comprising the non-coordinating anion and cation used in the present invention include tri (phenyl) carbenium tetrakis (pentafluorophenyl) borate, tri (4-methylphenyl) carbenium tetrakis (pentafluorophenyl). ) Borate, tri (4-methoxyphenyl) carbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, etc. Is mentioned.
In this invention, the ionic compound which consists of a non-coordinating anion and a cation may be used individually by 1 type, and may be used in combination of 2 or more type.

The aromatic vinyl compound polymer obtained in the present invention preferably has a syndiotactic structure. That is, when repeating units composed of an aromatic vinyl compound contained in the polymer are continuous, the aromatic rings of the repeating units are alternately arranged with respect to the plane formed by the polymer main chain. It is preferable that the ratio (syndiotacticity) is high. Syndiotacticity can be expressed by stereoregularity [rrrr] of a repeating unit chain composed of an aromatic vinyl compound. In the polymer of the present invention, the stereoregularity [rrrr] is usually 80 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more. When it is less than 80 mol%, the heat resistance, which is a characteristic of the syndiotactic structure, is lowered.
The stereoregularity [rrrr] is a racemic fraction (mol%) of pentad (five-chain) units in the aromatic vinyl compound polymer, and is an index representing the stereoregularity distribution. This stereoregularity [rrrr] can be calculated by measuring a ¹³ C-NMR spectrum in accordance with the method proposed in “Macromolecules, 6,925 (1973)” by A. Zambelli et al. it can. Specifically, it is represented by the fraction of the peak excluding noise (satellite peak and spinning side band) in the phenyl C1 carbon region (146.3 ppm to 144.5 ppm) of the styrene chain in the copolymer.

The aromatic vinyl compound polymer of the present invention has a molecular weight distribution (Mw / Mn) measured by GPC method of usually 1.7 or more, preferably 2.0 to 5.0, more preferably 2.0 to 3. 5.
The molecular weight distribution is given by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). GPC can be measured, for example, using a GPC column Shodex UT806L (manufactured by GL Science) under conditions of a temperature of 145 ° C., a solvent 1,2,4-trichlorobenzene, and a flow rate of 1.0 ml / min.
Further, the weight average molecular weight of the aromatic vinyl compound polymer obtained by the production method of the present invention is not particularly limited, but from the viewpoint of impact resistance, it is a weight average molecular weight in terms of polystyrene, usually 10,000 to 3,000. , Preferably in the range of 50,000 to 900,000.
The weight average molecular weight can be determined by measuring intrinsic viscosity [η], which is an index of molecular weight. In the examples, the intrinsic viscosity [η] is a viscometer (VMR-053U-PC · F01) manufactured by Rouai Co., Ltd., an Ubbelohde viscometer (time volume of bulb: 2-3 ml, capillary diameter: 0.44- 0.48 mm), and a solution of 0.02 to 0.16 g / dL was measured at 145 ° C. using 1,2,4-trichlorobenzene as a solvent. When the aromatic vinyl compound polymer of the present invention is represented by intrinsic viscosity [η], it is usually 0.1 to 16 dl / g (10,000 to 3,000,000 in weight average molecular weight), preferably 0.2 to It is in the range of 5.0 dl / g (50,000 to 900,000 in weight average molecular weight).

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Production Example 1 Synthesis of dimethylaminobenzyllithium N, N-dimethyl-o-toluidine (162 ml, 1.11 mmol) in hexane (437 ml) -diethyl ether (140 ml) in n-BuLi in hexane (2.6 mol / L , 440 ml) was added dropwise over 100 minutes. After stirring for 45 hours, the precipitate was separated by filtration. The obtained solid was washed with hexane (200 ml × 3 times) and then dried under reduced pressure to obtain 130 g (yield 83%) of dimethylaminobenzyllithium.

Production Example 2 Synthesis of Tris (dimethylaminobenzyl) scandium A suspension of anhydrous ScCl ₃ (20.7 g, 0.14 mol) in tetrahydrofuran (THF) (160 ml) was stirred at room temperature for 1 hour, and synthesized here in Production Example 1. A solution of dimethylaminobenzyllithium (57.9 g, 0.41 mol) in THF (250 ml) was added dropwise and stirred for 40 hours. The solvent was distilled off, followed by extraction with toluene, and further purification by recrystallization to obtain 49 g of tris (dimethylaminobenzyl) scandium as pale yellow crystals. The yield was 80%.

Production Example 3 Synthesis of 9-ethyl-1,2,3,4-tetrahydrofluorene Fluorene (60 g, 0.36 mol) was dissolved in a mixed solution of ethylenediamine 350 ml-THF 350 ml. To this solution, lithium metal (11.3 g, 1.62 mol) was charged at 10 ° C. or less over 4 hours. After completion of the reaction, water was added, extracted with diethyl ether, and washed with an aqueous sodium chloride solution. Magnesium sulfate was added to the diethyl ether layer and dried overnight in a refrigerator. Magnesium sulfate was filtered off and diethyl ether was distilled off to obtain 58.7 g of 1,2,3,4-tetrahydrofluorene. The yield was 96%. This 1,2,3,4-tetrahydrofluorene (55.0 g, 0.32 mol) was dissolved in 400 ml of THF. The solution was cooled to −78 ° C., and a hexane solution of n-BuLi (2.6 mol / L, 141 ml) was added dropwise over 90 minutes. The mixture was warmed to room temperature and stirred for 40 hours. The mixture was cooled again to 0 ° C., ethyl bromide (24.2 ml, 0.32 mol) was added, and the mixture was further stirred at room temperature for 24 hours. After completion of the reaction, the reaction was stopped by adding water, extracted with ether, and dried with magnesium sulfate to obtain 50.4 g of 9-ethyl-1,2,3,4-tetrahydrofluorene. The yield was 79%.

Production Example 4 Synthesis of (9-ethyl-1,2,3,4-tetrahydro-1-fluorenyl) bis (N, N-dimethylaminobenzyl) scandium Tris (dimethylaminobenzyl) scandium obtained in Production Example 2 ( 35 g, 78 mmol) in THF (100 ml) was charged with 60 ml of 9-ethyl-1,2,3,4-tetrahydrofluorene (18.6 g, 94 mmol) obtained in Preparation Example 3 at 70 ° C. for 12 hours. Stir. After completion of the reaction, the solvent was removed, washed with 150 ml of hexane three times, extracted with toluene, purified by recrystallization, and (9-ethyl-1,2,3,4-tetrahydro-1-fluorenyl) bis ( 19.6 g of N, N-dimethylaminobenzyl) scandium was obtained as pale yellow crystals. The yield was 49%.

Production Example 5 Purification of Styrene Crude styrene containing 12 mass ppm of indene, 50 mass ppm of acetophenone, 50 mass ppm of benzaldehyde and 130 mass ppm of moisture as impurities was degassed under reduced pressure to make 2 mass ppm of moisture. It was also confirmed that a similar change can be achieved even if inert gas is vented. After the crude styrene subjected to such pretreatment was distilled, it was processed through a column packed with 50 g of alumina obtained by calcining 100 ml.
According to gas chromatography analysis, the indene (ID) content is 0.09 mass ppm, the acetophenone (AP) content is 0.01 mass ppm, and the benzaldehyde (BA) content is 0.18 mass ppm. , It was confirmed that each decreased.

Example 1
5 mL of the purified styrene obtained in Production Example 5 and 0.79 μmol of triisobutylaluminum (TIBA) were added to a 30 mL wine bottle vial that had been dried by heating at room temperature in a nitrogen atmosphere, and sealed with an inner cap and an aluminum seal. . The wine bottle type vial was placed in a water bath at 60 ° C.
In another container, 40 μl (0.5 mM) of a toluene solution of (9-ethyl-1,2,3,4-tetrahydro-1-fluorenyl) bis (N, N-dimethylaminobenzyl) scandium obtained in Production Example 4 was used. ) And 25 μL (0.0313 M) of tri-n-butylaluminum at 25 ° C., and 30 minutes later, 0.024 μmol of dimethylanilinium tetrakispentafluorophenylborate was contacted at 25 ° C. to prepare a catalyst. The said catalyst was preserve | saved at 25 degreeC, the catalyst was added to the said vial container with which impurity containing styrene was prepared after progress for a predetermined time, and polymerization reaction was performed.
After 30 minutes, methanol was added to the reaction system to stop the polymerization, and the resulting polymer was dried at 200 ° C. for 3 hours.
The conversion rate was 76.9% by mass. Moreover, the stereoregularity [rrrr] of the obtained polystyrene was 99%.

Examples 2 to 7 and Comparative Example 1
Impurity-containing styrene was prepared by adding predetermined amounts of commercially available reagents, indene (ID), acetophenone (AP), and benzaldehyde (BA), to the purified styrene obtained in Production Example 5. Except for changing the styrene to be used, the polymerization reaction of the impurity-containing styrene was carried out in the same manner as in Example 1. The result was evaluated by the relative value with respect to the conversion rate of Example 1.

The results of Examples 1 to 7 and Comparative Example 1 are shown below.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the aromatic vinyl compound polymer with high activity and the activity fall after catalyst preparation was suppressed is provided. By the production method of the present invention, the productivity of the aromatic vinyl compound polymer is improved. The production method of the present invention is particularly preferably used when polymerization is carried out on a mass production scale.

Claims (12)

1) a half metallocene complex containing a Group 3 or lanthanoid series transition metal in the periodic table , 2) an ionic compound comprising a non-coordinating anion and a cation, and 3) an organoaluminum compound represented by the following formula (VII) A method for producing an aromatic vinyl compound polymer in which an aromatic vinyl compound is polymerized in the presence of a polymerization catalyst, wherein the indene content of the aromatic vinyl compound is 0.8 mass ppm or less. A method for producing an aromatic vinyl compound polymer.
R'R''R '''Al (VII)
[In the formula (VII), R ′, R ″ and R ′ ″ each independently represents an alkyl group having 3 to 5 carbon atoms. ] The method for producing an aromatic vinyl compound polymer according to claim 1 , wherein an indene content of the aromatic vinyl compound is 0.5 mass ppm or less. The method for producing an aromatic vinyl compound polymer according to claim 1 or 2, wherein the aromatic vinyl compound contains indene . The method for producing an aromatic vinyl compound polymer according to any one of claims 1 to 3, wherein an acetophenone content of the aromatic vinyl compound is 0.8 mass ppm or less. The method for producing an aromatic vinyl compound polymer according to claim 4 , wherein an acetophenone content of the aromatic vinyl compound is 0.5 mass ppm or less. The method for producing an aromatic vinyl compound polymer according to any one of claims 1 to 5 , wherein the aromatic vinyl compound has a benzaldehyde content of 20 mass ppm or less. The method for producing an aromatic vinyl compound polymer according to claim 6 , wherein the benzaldehyde content of the aromatic vinyl compound is 15 mass ppm or less. The method for producing an aromatic vinyl compound polymer according to any one of claims 1 to 7 , wherein the half metallocene complex is represented by the following formula (II).
RMX _a-1 Y _b (II)
[In the formula (II), R represents a fused polycyclic cyclopentadienyl π ligand, at least one of which is a saturated ring, M represents a group 3 or lanthanoid series transition metal in the periodic table, and X represents represents a sigma ligand, and Y represents a Lewis base. a represents the valence of M, and b represents 0, 1 or 2. ] The ionic compound is an ionic compound comprising a cation selected from substituted or unsubstituted triarylcarbenium or substituted or unsubstituted anilinium and a non-coordinating anion represented by the general formula (X). The method for producing an aromatic vinyl compound polymer according to any one of claims 1 to 8 .
(BZ ¹ Z ² Z ³ Z ⁴ ) ^- (X)
[Wherein, Z ^{1 to} Z ⁴ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms (including a halogen-substituted aryl group). ), An alkylaryl group, an arylalkyl group, a substituted alkyl group and an organic metalloid group or a halogen atom. ] The method for producing an aromatic vinyl compound polymer according to any one of claims 1 to 9 , wherein the polymerization is carried out in the presence of an inert solvent selected from an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent. It is a manufacturing method of the aromatic vinyl compound polymer in any one of Claims 1-10 , Comprising: The stereoregularity of the repeating unit chain comprised from an aromatic vinyl compound including the process of superposing | polymerizing an aromatic vinyl compound The manufacturing method of the aromatic vinyl compound polymer whose [rrrr] is 80 mol% or more. It is a manufacturing method of the aromatic vinyl compound polymer in any one of Claims 1-10 , Comprising: The repeating unit chain comprised from an aromatic vinyl compound including the process of superposing | polymerizing an aromatic vinyl compound and an olefin type monomer A method for producing an aromatic vinyl compound polymer having a stereoregularity [rrrr] of 80 mol% or more.