Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F112/02—Monomers containing only one unsaturated aliphatic radical
  • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F112/06—Hydrocarbons
  • C08F112/08—Styrene

Definitions

• the present invention relates to a method for producing an aromatic vinyl compound polymer having a syndiotactic structure having a high syndiotacticity, and more specifically, using a powder bed continuous polymerization apparatus in the presence of a group 3 transition metal complex.
• the present invention relates to a method for producing an aromatic vinyl compound polymer having a tic structure.
• olefin polymers are important as molding materials and the like, and many technical developments have been made on the polymers and their production methods.
• solid catalysts such as Ziegler-Natta catalysts and catalysts using metal complexes, and the results have been reported.
• 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.
• the metal complex examples 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
• metalocene catalyst a catalyst using a metallocene complex
• 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.
• 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 half metallocene complex has been reported.
• an aromatic vinyl compound polymer having a syndiotactic structure (hereinafter sometimes abbreviated as “syndiotactic polymer”) is characterized by excellent mechanical strength, heat resistance, appearance, solvent resistance, and the like. Are used in various applications.
• 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.
• Patent Document 1 contains a Group 3 metal atom or a lanthanoid metal atom.
• a polymerization catalyst composition containing a half metallocene complex and a polymer having high syndiotacticity obtained using the same are disclosed.
• a syndiotactic polymer having a narrow molecular weight distribution can be produced regardless of the polymerization mode.
• a metallocene catalyst containing a group 3 transition metal atom as described above a polymer having a narrow molecular weight distribution can be obtained by solution polymerization or bulk polymerization using a batch polymerization apparatus.
• a powder bed continuous polymerization apparatus suitable for the production of is used, there is a problem that the molecular weight distribution becomes wide.
• the problem to be solved by the present invention is a method for producing an aromatic vinyl compound polymer having a syndiotactic structure with a narrow molecular weight distribution in the presence of a group 3 transition metal complex using a powder bed continuous polymerization apparatus. It is to provide.
• this invention provides the manufacturing method of the following aromatic vinyl compound polymers.
• a method for producing an aromatic vinyl compound polymer having a syndiotactic structure using a powder bed continuous polymerization apparatus comprising (A) a group 3 transition metal complex and (B) a catalyst composition And (C) hydrogen is added to the reaction system when the aromatic vinyl compound polymer is produced by polymerizing the aromatic vinyl monomer in the presence of the above.
• an aromatic vinyl compound polymer having a syndiotactic structure with a narrow molecular weight distribution is efficiently produced in the presence of a group 3 transition metal complex using a powder bed continuous polymerization apparatus. Can do.
• the method for producing an aromatic vinyl compound polymer of the present invention is a method for producing an aromatic vinyl compound polymer having a syndiotactic structure using a powder bed continuous polymerization apparatus, and comprises (A) a group 3 transition metal complex And (B) (C) adding hydrogen to the reaction system when producing the aromatic vinyl compound polymer by polymerizing an aromatic vinyl monomer in the presence of a catalyst composition containing a cocatalyst. .
• the concentration of hydrogen acting as a chain transfer agent during polymerization in order to control the molecular weight of the polymer.
• the molecular weight distribution becomes wider when the hydrogen concentration is increased (for example, JP 2000-1506 A, JP 6-316606 A, etc.).
• the present invention can be obtained by adding hydrogen to the reaction system when polymerizing an aromatic vinyl monomer in the presence of a group 3 transition metal complex using a powder bed continuous polymerization apparatus.
• the molecular weight distribution of the aromatic vinyl compound polymer becomes unexpectedly narrow. Although this mechanism of action is not clear, it is estimated as follows.
• the catalyst composition used in the present invention contains (A) a group 3 transition metal complex and (B) a cocatalyst, and further contains (D) an organoaluminum compound as necessary.
• the group 3 transition metal complex used as the component (A) is a complex having a group 3 transition metal or a lanthanoid series transition metal, and is preferably a complex represented by the following general formula (I).
• RMX a-1 Y b (I) [Wherein, R represents a cyclopentadienyl-based ⁇ ligand, M represents a group 3 or lanthanoid series transition metal in the periodic table, X represents a monoanionic ligand, and Y represents a Lewis base. Show. a represents the valence of M, and b represents 0, 1 or 2. ]
• Examples of the monoanionic 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, and an aryloxy group having 6 to 20 carbon atoms. And 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.
• halogen atom examples include fluorine, chlorine, bromine, iodine and the like.
• hydrocarbon group having 1 to 20 carbon atoms examples 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.
• 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.
• 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.
• Examples of the sulfide group having 1 to 20 carbon atoms include a phenyl sulfide group.
• Examples of the acyl group having 1 to 20 carbon atoms include acetyl group, propionyl group, butyryl group and the like.
• X is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably an aralkyl group, and particularly preferably a benzyl group or N, N-dimethylaminobenzyl group.
• M is preferably a Group 3 metal, more preferably scandium or yttrium, and still more preferably scandium.
• R in the general formula (I) is represented by a substituted cyclopentadienyl ⁇ ligand, a substituted indenyl ⁇ ligand, or any one of the following general formulas (II), (III), or (IV).
• a condensed polycyclic cyclopentadienyl ⁇ ligand is preferred.
• 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, carbon 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 or different from each other, and c, d, e and f each represent an integer of 1 or more, preferably an integer of 1 to 3, more preferably 2.
• 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, and a hexyl group.
• Alkyl groups such as cyclohexyl group and octyl group; alkenyl groups such as vinyl group, propenyl group and cyclohexenyl group.
• aromatic hydrocarbon group having 6 to 20 carbon atoms examples include aralkyl groups such as benzyl group, phenethyl group and phenylpropyl group; tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, butyl Examples thereof 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 described in the general formula (I).
• condensed polycyclic cyclopentadienyl ⁇ ligand of the general formula (II) include 4,5,6,7-tetrahydroindenyl group, 1-methyl-4,5,6,7- Tetrahydroindenyl 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-tetrahydroindeni
• condensed polycyclic cyclopentadienyl ⁇ ligand of the general formula (III) include tricyclo [6,4,0,0] dodecadienyl group, 2-methyltricyclo [6,4,0, 0] dodecadienyl group and the like.
• condensed polycyclic cyclopentadienyl ⁇ ligand of the general formula (IV) 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-n-propyl-1,2,3,4-tetrahydro-1-fluorenyl group, 9- Isopropyl-1,2,3,4-tetrahydro-1-fluorenyl group, 1,2,3,8-tetrahydrocyclopenta [ ⁇ ] indene, 8-methyl-1,2,3,8-tetrahydrocyclopenta [ ⁇ Indene, 8-ethyl-1,2,3,8-tetrahydrocyclopenta [ ⁇ ] indene, 8-n-propyl-1,2,3,8-tetrahydrocyclopenta [ ⁇ ] indene
• a ligand represented by the general formula (IV) is particularly preferable, and a ligand having an alicyclic 6-membered ring structure, that is, the following general formula
• the ligand represented by the formula (V) is most preferable in view of polymerization activity, complex stability, and production cost.
• 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 1 to 20 carbon atoms.
• substituents include those exemplified with respect to the general formulas (II) to (IV).
• half metallocene type scandium complex represented by the general formula (I) include (pentamethylcyclopentadienyl) bis (N, N-dimethylaminobenzyl) scandium, (2,3,4,5- Tetramethyl-1-trimethylsilylcyclopentadienyl) bis (N, N-dimethylaminobenzyl) scandium, (1,3-dimethyltetrahydropentalenyl) bis (N, N-dimethylaminobenzyl) scandium, (tricyclo [6 , 4,0,0] dodecadienyl) bis (N, N-dimethylaminobenzyl) scandium, (1,2,3,4-tetrahydroindenyl) bis (N, N-dimethylaminobenzyl) scandium, (1,2 , 3,8-Tetrahydrocyclopenta [ ⁇ ] indenyl) bis (N, N-dimethyla Nobenzyl) scandium, (8-methylmethylcyclopen
• the promoter used as the component (B) includes (B-1) a non-coordinating ionic compound or (B-2) an organoaluminum oxy compound, and (B-1) a non-coordinated compound.
• a coordinated ionic compound is preferably used.
• Non-coordinating ionic compound used as the (B) cocatalyst can react with the contact product of the component (A) and the component (D) to form an ionic complex.
• An ionic compound composed of a non-coordinating anion and a cation is used. 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.
• An ionic compound comprising a non-coordinating anion and a substituted or unsubstituted anilinium is preferred.
• non-coordinating anion examples include a non-coordinating anion represented by the following general formula (VI).
• 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, or an aryl group having 6 to 20 carbon atoms (halogen substitution).
• non-coordinating anion represented by the general formula (VI) include tetrakis (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, and tetrakis (tetrafluorophenyl) borate.
• Tetrakis (pentafluorophenyl) borate Tetrakis (pentafluorophenyl) borate, tetrakis (trifluoromethylphenyl) borate, tetra (toluyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl]
• Examples thereof include borates and tridecahydride-7,8-dicarbaoundecaborate.
• Examples of the substituted or unsubstituted triarylcarbenium include triarylcarbenium represented by the following general formula (VII). [CR 47 R 48 R 49 ] + (VII)
• 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 or different from each other. May be.
• the substituted phenyl group can be represented, for example, by the following general formula (VIII).
• 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.
• K is an integer of 1 to 5.
• the plurality of R 50 may be the same or different.
• substituted or unsubstituted triarylcarbenium represented by the general formula (VII) 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.
• substituted or unsubstituted anilinium include N, N-dimethylanilinium.
• the ionic compound comprising a non-coordinating anion and a cation include tri (phenyl) carbenium tetrakis (pentafluorophenyl) borate, tri (4-methylphenyl) carbenium tetrakis (pentafluorophenyl) borate, And tri (4-methoxyphenyl) carbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate and the like. .
• N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate is preferable.
• the ionic compound comprising the non-coordinating anion and cation of the component (B-1) may be used alone or in combination of two or more.
• Examples of the (B-2) organoaluminum oxy compound used as the (B) promoter include aluminoxane.
• the aluminoxane is preferably an alkylaluminoxane, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane.
• MAO methylaluminoxane
• modified methylaluminoxane MMAO-3A (trade name, manufactured by Tosoh Finechem Co., Ltd.) and the like can be preferably used.
• organoaluminum compound (D) used as necessary examples include an organoaluminum compound represented by the following general formula (IX).
• R ′, R ′′ and R ′ ′′ each independently represents an alkyl group having 3 to 5 carbon atoms. It is preferable that the alkyl group has 3 to 5 carbon atoms because sufficient polymerization activity can be obtained. Examples of the alkyl group having 3 to 5 carbon atoms include various propyl groups, various butyl groups, and various pentyl groups.
• organoaluminum compound of component (D) examples include tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tri-n-pentylaluminum. Can be mentioned. Among these, an aluminum 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.
• the component (A) is brought into contact with the component (B).
• the amount of component (B-1) used is preferably in the range of 1.0 to 1.5 molar ratio to component (A) from the viewpoint of catalyst activity.
• the amount is preferably in the range of 5 to 1000 in molar ratio to the component (A).
• the contact time when the component (A) and the component (B) are contacted is usually about 1 minute to 60 minutes, and the temperature condition is usually 0 to 50 ° C.
• the component (D) is used, the component (A) and the component (D) are contacted so that the component (D) / (A) component (molar ratio) is 5 or more, and then the component (B) is added.
• the component (D) / component (A) (molar ratio) is preferably 5 to 300, more preferably 10 to 300, from the viewpoints of catalyst activity and storage stability of the catalyst.
• the contact time when the component (A) and the component (D) are contacted is usually about 1 minute to 60 minutes, and the temperature condition is usually 0 to 50 ° C.
• the catalyst composition When preparing the catalyst composition, it is desirable to perform the contact operation in an inert gas atmosphere such as nitrogen gas. And as for each of these catalyst components, those prepared in advance in a catalyst preparation tank may be used, or those prepared in a polymerization reactor for polymerizing aromatic vinyl monomers may be used as they are.
• an aromatic vinyl compound in an amount such that the molar ratio to the component (A) is 0.5 to 500 may be used. When the molar ratio is 0.5 or more, a sufficiently high polymerization activity can be obtained even in the polymerization reaction after storing the catalyst.
• the polymerization reaction may proceed during storage of the catalyst and the product may be precipitated, but this precipitation can be suppressed by the molar ratio being 500 or less.
• the catalyst can be charged to the reactor without adverse effects. From this viewpoint, the molar ratio is preferably 1 to 200, more preferably 1 to 50.
• an aromatic vinyl compound polymer is produced by polymerizing an aromatic vinyl monomer in the presence of the catalyst composition using a powder bed continuous polymerization apparatus.
• the “aromatic vinyl compound polymer” refers to a polymer in which the aromatic vinyl compound monomer unit is 1 mol% or more, specifically, from one kind of aromatic vinyl compound.
• Aromatic vinyl monomer There are various types of aromatic vinyl compounds used as the monomer for polymerization, but those represented by the following formula (X) are preferred.
• 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 may be the same or different.
• examples of the aromatic vinyl monomer used as a raw material include styrene, alkyl styrene, aryl styrene, halogenated styrene, alkoxy styrene, and vinyl benzoate.
• alkyl styrene include o-methyl styrene, m-methyl styrene, p-methyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, on-propyl styrene, mn-propyl.
• Styrene pn-propyl styrene, o-isopropyl styrene, m-isopropyl styrene, p-isopropyl styrene, mn-butyl styrene, pn-butyl styrene, p-tert-butyl styrene, 4-butenyl styrene 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, mesitylstyrene and the like.
• arylstyrene include p-phenylstyrene.
• halogenated styrene examples include o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p -Bromostyrene, o-methyl-p-fluorostyrene and the like.
• alkoxystyrene include o-methoxystyrene, m-methoxystyrene, p-methoxystyrene and the like. Of these, styrene is particularly preferred.
• the said vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.
• the aromatic vinyl monomer and the olefin monomer may be combined and copolymerized.
• the olefin monomer is preferably a substituted or unsubstituted olefin having 2 to 12 carbon atoms.
• 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, 3,4-dichloro-1- Ten, butadiene, isoprene, dicyclopropene
• the content of the aromatic vinyl compound unit in the obtained copolymer is 1 mol% or more, preferably 5 to 99 mol%. More preferably, it is 40 to 95 mol%. That is, the content of the olefin monomer unit is 99 mol% or less, preferably 1 to 95 mol%, more preferably 3 to 60 mol%.
• the content of the olefin monomer unit is within the above range, the physical properties of the syndiotactic polystyrene are improved.
• a powder bed continuous polymerization apparatus is used from the viewpoint of production on an industrial scale.
• the polymerization temperature is usually in the range of 0 to 200 ° C, preferably 0 to 120 ° C.
• the pressure during the polymerization is usually in the range of 0.01 to 30 MPa, preferably 0.01 to 3 MPa.
• an aromatic vinyl monomer is polymerized in the presence of the catalyst composition using a powder bed continuous polymerization apparatus, and the hydrogen partial pressure is preferably about 1 kPa to 1.0 MPa, more preferably.
• Hydrogen is supplied to the reaction system so as to be 10 kPa to 0.5 MPa, more preferably 20 to 30 kPa.
• the molecular weight distribution (Mw / Mn) of the resulting syndiotactic polymer can be narrowed to preferably 3 or less, more preferably 2.0 to 2.5.
• the aromatic vinyl compound polymer obtained by the method of the present invention is characterized by having 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 characterized by a high ratio (syndiotacticity).
• the syndiotacticity can be expressed by stereoregularity [rrrr] (racemic pentad fraction) of a repeating unit chain composed of an aromatic vinyl compound.
• the stereoregularity [rrrr] is 80 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, still more preferably 99 mol% or more, preferably 100 mol%. It is as follows. 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 a method proposed by A. Zambelli et al. In “Macromolecules, 6, 925 (1973)”. it can. Specifically, it is expressed as a fraction of a 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 preferably 3 or less, more preferably 2.0 to 2.6, and still more preferably 2.0 to 2. 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 gel permeation chromatography
• the GPC is measured using, for example, a GPC column Shodex UT806L (trade name, manufactured by GL Sciences Inc.), a temperature of 145 ° C., a solvent 1,2,4-trichlorobenzene, a flow rate of 1.0 ml / min. Can be performed under the following conditions.
• the weight average molecular weight of the aromatic vinyl compound polymer of the present invention is not particularly limited, but from the viewpoint of impact resistance, the weight average molecular weight in terms of polystyrene is usually 10,000 to 3,000,000, preferably 50,000 to 90. It is 10,000, more preferably in the range of 100,000 to 300,000.
• the weight average molecular weight can be determined by measuring intrinsic viscosity [ ⁇ ], which is an index of molecular weight.
• the intrinsic viscosity [ ⁇ ] is a viscometer (trade name: “VMR-053U-PC • F01”, manufactured by Kogyo Co., Ltd.), Ubbelohde type viscosity tube (timepiece volume: 2 to 3 ml, capillary tube) (Diameter: 0.44 to 0.48 mm) A solution of 0.02 to 0.16 g / dL was measured at 145 ° C. using 1,2,4-trichlorobenzene as a solvent.
• aromatic vinyl compound polymer of the present invention is expressed in terms of intrinsic viscosity [ ⁇ ], it is usually 0.1 to 16 dl / g (10,000 to 3 million in weight average molecular weight), preferably 0.2 to 5.0 dl / g. g (weight average molecular weight 50,000 to 900,000).
• styrene monomer (SM) 8 L / h was used as a raw material, and a TNBA (tri-normal butyl aluminum) solution was used so that n (mol-Sc / 350 kmol-SM) was a set value shown in Table 1.
• TNBA tri-normal butyl aluminum
• Al / SM (mol / 350 kmol) was supplied so as to have a set value shown in Table 1.
• the supply amount of the TNBA solution was adjusted in consideration of the amount of TNBA brought from the catalyst solution.
• Example 5 SPS powder was produced in the same manner as in Example 1 except that the catalyst adjustment conditions and reaction conditions were changed as shown in Table 2. The results are shown in Table 2.
• Comparative Examples 1 and 2 SPS powder was produced in the same manner as in Example 1 except that the hydrogen supply was not performed and the reaction conditions were changed as shown in Table 3. The results are shown in Table 3.
• an aromatic vinyl compound polymer having a syndiotactic structure having a narrow molecular weight distribution in the presence of a Group 3 transition metal complex is obtained using a powder bed continuous polymerization apparatus. It turns out that it can manufacture efficiently.
• an aromatic vinyl compound polymer having a syndiotactic structure with a narrow molecular weight distribution can be efficiently produced on an industrial scale.

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