JP2003119222A - Process for producing syndiotactic substituted hydroxystyrene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly efficient process for producing a highly syndiotactic aromatic vinyl polymer. SOLUTION: The process for producing a syndiotactic aromatic vinyl polymer comprises polymerizing a substituted hydroxystyrene monomer represented by general formula (1) in the presence of a catalyst component comprising a reaction product of (A) transition metal compounds represented by general formula (3): MR<2> R<3> a X3-a and/or the general formula (4): MR<2> R<3> b X2-b with (B) a modified methylaluminoxane.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a highly syndiotactic substituted hydroxystyrene polymer which is a precursor of a hydroxystyrene polymer.

[0002]

2. Description of the Related Art In recent years, hydroxystyrene polymers have been
For example, it is known to be useful as a material for a printed wiring board, an offset PS printing plate, a photoresist, etc., and also as a flame-retardant adhesive or a metal surface treatment agent.
On the other hand, the styrene-based polymer having a syndiotactic structure is
It is known that it has superior heat resistance, chemical resistance and electrical characteristics compared to those with an atactic structure.
It is considered that the hydroxystyrene polymer having a syndiotactic structure is also excellent in the above properties.

An alkoxy-substituted styrene polymer having a syndiotactic structure is used as a precursor of a hydroxystyrene polymer having a syndiotactic structure, and (A) a specific titanium-containing compound and (B) (a) transition are used as a catalyst. A production method characterized by polymerizing an alkoxy-substituted styrene, the main component of which is a compound capable of reacting with a metal compound to form an ionic complex and / or (b) an organoaluminum and a contact product of a condensing agent. JP-A-5-3108
No. 34 publication. However, the examples disclosed in the patent publications are disclosed only when p-methoxystyrene is used as a monomer, and other substituted hydroxystyrene-based monomers, especially other than alkoxy-substituted styrene. It was not known at all what kind of structure a polymer of the above monomer could be obtained.

It is generally known that alkoxy-substituted phenols are easily converted into phenols [Sy
nthesis, page 417 (1977), Tetrahedron Lett.,
Volume 21, Pages 3731 (1980), Tetrahedron, 24
Volume, p. 2289 (1968)]. However, deprotection of p-methoxystyrene is extremely difficult, and there is a problem in industrial implementation such as an increase in cost.
In addition, as disclosed in the comparative example of the patent publication,
Pt which is an alkoxy-substituted styrene that is easily deprotected
In the polymerization using butoxystyrene, only a polymer having an atactic structure was obtained. Furthermore, specific examples of the monomer disclosed in the publication include p-
Alkoxy-substituted styrenes such as methoxystyrene, m-methoxystyrene, p-ethoxystyrene, pn-propoxystyrene, pn-butoxystyrene, etc., but no mention of trialkylsilyloxystyrenes. .

Further, the aluminoxane used in the examples of the patent publication was methylaluminoxane obtained by condensing trimethylaluminum to prepare it. Therefore, from the patent publication, a modified methylaluminoxane obtained by reacting a tetraalkyldialuminoxane and / or a polyalkylaluminoxane having an alkyl group of C2 or more with trimethylaluminum is represented by the general formula (3) and / or In combination with the transition metal compound represented by the general formula (4), in the polymerization of a substituted hydroxystyrene-based monomer,
It was unimaginable to give a polymer having a completely different structure from the methylaluminoxane obtained by condensing trimethylaluminum to prepare it.

On the other hand, there is a report on the polymerization of p-methoxystyrene or m-methoxystyrene using methylaluminoxane obtained by condensing tetrabenzyl titanium and trimethylaluminum, but [Macromol
ecules, Vol. 22, p. 104 (1989)], this method has only yielded atactic structures. Also, Macromolecular Rapid Communicati
ons, vol. 21, p. 1148 (2000), using (pentamethylcyclopentadienyl) titanatran and triisobutylaluminum modified methylaluminoxane,
It has been reported that poly (t-butyldimethylsilyloxystyrene) having a syndiotactic structure can be obtained. However, the (pentamethylcyclopentadienyl) titanatran used in this method is not only an extremely expensive catalyst, but also has insufficient polymerization activity and has a problem in industrial implementation. in this way,
Regarding the method for producing a substituted hydroxystyrene polymer having a high degree of syndiotactic structure, no satisfactory production method has been known so far in terms of cost and versatility in industrial practice.

[0007]

Under these circumstances, the present invention is used as a material for printed wiring boards, offset PS printing plates, photoresists, or as a flame-retardant adhesive or metal surface treatment agent. The main object of the present invention is to provide a general-purpose method for producing a syndiotactic substituted hydroxystyrene polymer that is a precursor of a useful hydroxystyrene polymer having a syndiotactic structure.

[0008]

The inventors of the present invention have conducted extensive studies to develop a method for producing a substituted hydroxystyrene polymer having a high syndiotactic structure, and as a result, as a result, a specific transition metal compound and a modified It was found that a highly syndiotactic substituted hydroxystyrene-based polymer can be obtained by polymerizing a substituted hydroxystyrene-based monomer such as trialkylsilyloxystyrene in the presence of a reaction product with methylaluminoxane. Has been completed.

That is, the present invention provides the following general formula (1)

[Chemical 3] (In the formula, R ¹ is a trialkylsilyloxy group having 3 to 30 carbon atoms or a trialkylgermaniumoxy group having 3 to 30 carbon atoms, m is an integer of 1 to 3, and when m is plural, R 1
¹ may be the same or different. ) From a substituted hydroxystyrene-based monomer represented by the following general formula (2)

[Chemical 4] (In the formula, R ¹ is a trialkylsilyloxy group having 3 to 30 carbon atoms or a trialkylgermaniumoxy group having 3 to 30 carbon atoms, m is an integer of 1 to 3, and when m is plural, R 1
¹ may be the same or different) and has a tacticity of ¹³
A method for producing a substituted hydroxystyrene polymer having a syndiotactic structure, which is 30% or more in racemic pentad by C-NMR,

As the catalyst component, (A) the following general formula (3)
And / or general formula (4) MR ² R ³ _a X _3-a (3) MR ² R ³ _b X _2-b (4) (wherein M represents a transition metal element of Group 4 of the periodic table) , R
² represents a π ligand. R ³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms.
20 alkylaryl group, C7-20 arylalkyl group, C1-20 acyloxy group, C1-20 alkoxy group, C1-20 thioalkoxy group, C6-20 Represents a thioaryloxy group,
They may be the same or different. X
Represents a halogen atom. a shows the integer of 0-3, b shows the integer of 0-2. ) A transition metal compound represented by
(B) a tetraalkyldialuminoxane and / or polyalkylaluminoxane the reaction product of modified methylaluminoxane obtained by reacting trimethylaluminum with alkyl group having 2 or more carbon atoms having alkyl group having 2 or more carbon atoms The present invention provides a method for producing a syndiotactic substituted hydroxystyrene-based polymer, which comprises polymerizing the substituted hydroxystyrene-based monomer in the presence.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The highly syndiotactic substituted hydroxystyrene polymer of the present invention can be produced extremely efficiently by using the following specific catalyst system. That is, in the method of the present invention, as the catalyst component, at least one transition metal compound selected from the compounds represented by the general formula (3) and the general formula (4) of the component (A) described above, The number of carbon atoms in the (B) component was 2
Containing a reaction product with a modified methylaluminoxane obtained by reacting trimethylaluminum with a tetraalkyldialuminoxane having an alkyl group and / or a polyalkylaluminoxane having an alkyl group having 2 or more carbon atoms as a main catalyst component Use what you do.

The transition metal compound as the component (A) is at least one compound selected from the group consisting of the transition metal compounds represented by the general formula (3) and / or the general formula (4). M in the above general formula (3) or (4) represents a transition metal element of Group 4 of the periodic table, and specifically, titanium (Ti), zirconium (Zr) or hafnium (H
f) is shown. R ² represents a π ligand. Π here
The ligand refers to one having a cyclopentadienyl structure in which an aromatic structure may be condensed and bonded, and specifically, a cyclopentadienyl group, a methylcyclopentadienyl group,
Examples thereof include a substituted cyclopentadienyl group such as a 1,2-dimethylcyclopentadienyl group and a pentamethylcyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group and a substituted fluorenyl group.

R ³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms (phenyl group, naphthyl group, etc.), an alkylaryl group having 7 to 20 carbon atoms (tolyl group, xylyl group). Etc.), arylalkyl group having 7 to 20 carbon atoms (benzyl group, etc.), acyloxy group having 1 to 20 carbon atoms (heptadecylcarbonyloxy group, etc.), alkoxy group having 1 to 20 carbon atoms, 1 to 20 carbon atoms A thioalkoxy group (thiomethoxy group, etc.), a thioaryloxy group having 6 to 20 carbon atoms (thiophenoxy group), etc. are shown. R ³ may be the same or different.

X represents a halogen atom. Furthermore, a
Represents an integer of 0 to 3, and b represents an integer of 0 to 2. Among these transition metal compounds, the titanium compound is most preferably used in terms of polymerization activity. A more preferable titanium compound is a transition metal compound represented by the general formula (5). TiR ² R ³ _a X _3-a (5) (In the formula, R ² represents a π ligand. R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
Alkylaryl group having 7 to 20 carbon atoms, 7 to 20 carbon atoms
Of arylalkyl group, acyloxy group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms, and thioaryloxy group having 6 to 20 carbon atoms. It may be different or different. X represents a halogen atom. a shows the integer of 0-3, b shows the integer of 0-2. )

Specific examples of the titanium compound represented by the general formula (5) include cyclopentadienyl trimethyl titanium; cyclopentadienyl triethyl titanium;
Cyclopentadienyl tripropyl titanium; Cyclopentadienyl tributyl titanium; Methyl cyclopentadienyl trimethyl titanium; 1,2-Dimethyl cyclopentadienyl trimethyl titanium; 1,2,4-Trimethyl cyclopentadienyl trimethyl titanium; 1 , 2, 3, 4
-Tetramethylcyclopentadienyltrimethyltitanium; pentamethylcyclopentadienyltrimethyltitanium; pentamethylcyclopentadienyltriethyltitanium;

Pentamethylcyclopentadienyltripropyltitanium; Pentamethylcyclopentadienyltributyltitanium; Cyclopentadienylmethyltitanium dichloride; Cyclopentadienylethyltitanium dichloride; Pentamethylcyclopentadienylmethyltitanium dichloride; Pentamethyl Cyclopentadienyl ethyl titanium dichloride; cyclopentadienyl dimethyl titanium monochloride; cyclopentadienyl diethyl titanium monochloride; cyclopentadienyl titanium trimethoxide; cyclopentadienyl titanium triethoxide;

Cyclopentadienyl titanium tripropoxide; cyclopentadienyl titanium triphenoxide;
Pentamethylcyclopentadienyl titanium trimethoxide; Pentamethylcyclopentadienyl titanium triethoxide; Pentamethylcyclopentadienyl titanium tripropoxide; Pentamethylcyclopentadienyl titanium tributoxide; Pentamethylcyclopentadienyl titanium Triphenoxide;

Cyclopentadienyl titanium trichloride; pentamethylcyclopentadienyl titanium trichloride; cyclopentadienyl methoxy titanium dichloride; cyclopentadienyl dimethoxy titanium chloride;
Pentamethylcyclopentadienylmethoxytitanium dichloride; Cyclopentadienyltribenzyltitanium; Pentamethylcyclopentadienylmethyldiethoxytitanium; Indenyltitanium trichloride; Cyclopentadienyltitanium trifluoride; Pentamethylcyclopentadienyltitanium Trifluoride; indenyl titanium trifluoride; indenyl titanium trimethoxide; indenyl titanium triethoxide; indenyl trimethyl titanium; indenyl tribenzyl titanium; pentamethylcyclopentadienyl titanium trithiomethoxide; pentamethylcyclopenta Examples thereof include dienyl titanium trithiophenoxide.

Among these titanium compounds, cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride and indenyl titanium trichloride are preferable in terms of availability, cost and polymerization activity. is there. Furthermore, pentamethylcyclopentadienyl titanium trichloride and indenyl titanium trichloride are particularly preferable in terms of stereoregularity of the obtained polymer. In the polymerization catalyst used in the present invention, one kind of the transition metal compound as the component (A) may be used, or two or more kinds thereof may be used in combination. The transition metal compound containing the above-mentioned titanium compound may be one which is further complexed with an ester or ether.

The catalyst component in the present invention contains as a main catalyst component a reaction product of the above-mentioned transition metal compound which is the component (A) and modified methylaluminoxane which is the component (B). As the component (B), a modified methylaluminoxane obtained by reacting tetraalkyldialuminoxane having an alkyl group having 2 or more carbon atoms and / or polyalkylaluminoxane having an alkyl group having 2 or more carbon atoms with trimethylaluminum Contains as an essential component.

The tetraalkyldialuminoxane having an alkyl group having 2 or more carbon atoms, which is a raw material of the modified methylaluminoxane used in the present invention, is represented by the general formula (6).

[Chemical 5] (In the formula, R ⁴ represents an alkyl group having 2 or more carbon atoms) In the general formula (6), R ⁴ is an alkyl group having 2 or more carbon atoms, preferably 2 to 20 carbon atoms, and is linear Alternatively, a branched or cyclic one can be used. Examples of suitable alkyl groups include n-propyl, isopropyl, n
-Butyl, isobutyl, n-hexyl, cyclohexyl and the like can be mentioned.

The polyalkylaluminoxane having an alkyl group having 2 or more carbon atoms is represented by the general formula (7).

[Chemical 6] (In the formula, R ⁵ represents an alkyl group having 2 or more carbon atoms. N is an integer of 1 to 50.) R ⁵ in the general formula (7) has 2 or more carbon atoms, preferably 2 to 2 carbon atoms. The 20 alkyl groups which may be linear, branched or cyclic may be used. Examples of suitable alkyl groups include n-propyl, isopropyl, n
-Butyl, isobutyl, n-hexyl, cyclohexyl and the like can be mentioned.

Trimethylaluminum, which is another raw material of the modified methylaluminoxane used in the present invention, is
Commercially available products can be used as they are, or can be purified as necessary before use. A tetraalkyldialuminoxane having an alkyl group having 2 or more carbon atoms and / or a polyalkylaluminoxane having an alkyl group having 2 or more carbon atoms and trimethylaluminum represented by the general formula (6) and / or (7), The modified methylaluminoxane used in the present invention can be obtained by reacting in the presence of water added at any time. Here, the modified methylaluminoxane means various structures (linear and cage) in which a part of the alkyl group having 2 or more carbon atoms represented by the general formula (6) and / or (7) is substituted with a methyl group. It is a mixture of a few to a dodecameric oligomer containing a mixture of molds and the like, and some unreacted trimethylaluminum remains.

The content of the alkane having 2 or more carbon atoms is 5 to 80 mol, which represents the modified amount of the modified methylaluminoxane obtained by analyzing the methane produced by hydrolyzing the modified methylaluminoxane and the alkane having 2 or more carbon atoms. It is preferably within the range of%. It is more preferably 10 to 65 mol%, and most preferably 1
It is 5 to 50 mol%. When the alkane content having 2 or more carbon atoms is less than 5 mol%, the stereoregularity of the obtained polymer is lowered, which is not preferable. Further, if the content of alkane having 2 or more carbon atoms is more than 80 mol%, the polymerization activity remarkably decreases, which is not preferable.

In the present invention, the transition metal compound represented by the general formula (3) and / or the general formula (4) or the modified methylaluminoxane can be used by supporting it on a carrier. Examples of the carrier include inorganic compounds and organic polymer compounds. The inorganic compound is preferably an inorganic oxide, an inorganic chloride, an inorganic hydroxide or the like, and may contain a small amount of carbonate or sulfate. Preferred are inorganic oxides such as silica, alumina, magnesia, titania, zirconia, calcia, and inorganic chlorides such as magnesium chloride. These inorganic compounds have an average particle size of 5 to 150 μm and a specific surface area of ² to 800 m ² /
g of porous fine particles are preferable, for example, 100 to 800
It can be heat-treated at ° C and used.

The organic polymer compound preferably has an aromatic ring, a substituted aromatic ring or a functional group such as a hydroxy group, a carboxyl group, an ester group or a halogen atom in its side chain. Specific examples of the organic polymer compound include α having a functional group obtained by chemically modifying a polymer having a unit such as ethylene, propylene or butene.
-Olefin homopolymers, α-olefin copolymers, polymers having units such as acrylic acid, methacrylic acid, vinyl chloride, vinyl alcohol, styrene, divinylbenzene, and their chemical modifications. These organic polymer compounds have an average particle size of 5 to 2
Spherical fine particles of 50 μm are used. Transition metal compounds,
By supporting the co-catalyst as a simple substance, it is possible to prevent contamination due to the adhesion of the catalyst to the polymerization reactor.

In the present invention, the above-mentioned general formula (1) is used in the presence of the catalyst in which the transition metal compound of the component (A) is contacted with the modified aluminoxane of the component (B) which is the cocatalyst. The substituted hydroxystyrene-based monomer shown is polymerized. Specifically, the following method (I)-
Polymerization may be carried out in (VII). In the following description, the component (A) represents a transition metal compound and the component (B) represents a cocatalyst.

The components (I), (A) and (B) are contacted in advance and then further contacted with a monomer component such as a substituted hydroxystyrene-based monomer to carry out polymerization. (II) The component (A), the component (B) and a small amount of the substituted hydroxystyrene-based monomer component are brought into contact with each other in advance and then further contacted with a monomer component such as the substituted hydroxystyrene-based monomer to carry out polymerization. To do. (III) Component (A) and component (B) are mixed, brought into contact with a carrier, the resulting supported catalyst is separated, and the supported catalyst is brought into contact with a monomer component such as a substituted hydroxystyrene monomer. To polymerize. (IV) After contacting the component (A) with the carrier, (B)
The supported catalyst thus produced is separated, and the supported catalyst is brought into contact with a monomer component such as a substituted hydroxystyrene-based monomer to carry out polymerization.

After bringing the components (V) and (B) into contact with the carrier,
Further, it is brought into contact with the component (A), the generated supported catalyst is separated, and the supported catalyst is brought into contact with a monomer component such as a substituted hydroxystyrene-based monomer to carry out polymerization. (VI) After mixing the component (A) and a monomer component such as a substituted hydroxystyrene-based monomer, the component (B) is brought into contact with each other to carry out polymerization. (VII) After mixing the component (B) and a monomer component such as a substituted hydroxystyrene-based monomer, the component (A) is brought into contact with each other to carry out polymerization.

Among the methods (I) to (VII), since the efficiency of the initiator and the polymerization activity are improved and the molecular weight distribution of the obtained polymer can be further narrowed, (I) and (I)
Method I) is preferred.

The component (A) and the component (B) can be used either in the form of solution or slurry, but the form of solution is preferable in order to obtain higher polymerization activity. The solvent used for preparing the solution or slurry is a hydrocarbon solvent such as butane, pentane, hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, xylene, or chloroform, methylene chloride, dichloroethane, chlorobenzene, etc. It is a halogenated hydrocarbon solvent. Preferred solvents are aromatic hydrocarbons such as toluene and benzene. Further, two or more kinds of solvents may be mixed and used.

In the present invention, in the presence of the catalyst,
The substituted hydroxystyrene-based monomer is polymerized, and as the polymerization method, any of bulk polymerization, solution polymerization and suspension polymerization can be used. In this polymerization reaction, the polymerization temperature is generally -100 ° C to 250 ° C, preferably -50 ° C to 120 ° C, particularly preferably -30 ° C to
It is in the range of 100 ° C. Typical polymerization time is 30 seconds to 3
It is 6 hours, preferably 1 minute to 20 hours, and more preferably 5 minutes to 10 hours. The optimum time required to produce the desired polymer will vary with the temperature used, solvent and other polymerization conditions. Also, the polymerization can be carried out at pressures below atmospheric pressure as well as above atmospheric pressure. It is also performed under reduced pressure until the lowest component of the polymerization mixture has vaporized. However, it is preferred to use pressures near atmospheric pressure. As a polymerization method, a solution polymerization method in an inert solvent, a slurry polymerization method, or a bulk polymerization method using a monomer as a diluent is usually used. Among these methods, the solution polymerization method and the bulk polymerization method are preferable.

Inert solvents used in the polymerization include aliphatic, cycloaliphatic, aromatic and halogenated aromatic hydrocarbons, and mixtures thereof. Preferred inert solvents for the polymerization are C4-C26 alkanes, especially branched alkanes, toluene, ethylbenzene, and mixtures thereof. A suitable solvent is used to provide a monomer concentration of 0.5-100% by weight. Further, a small amount of polar compounds such as ethers such as anisole, diphenyl ether, ethyl ether, diglyme, tetrahydrofuran and dioxane, triethylamine and amines such as tetramethylethylenediamine are added in a range not impairing the effect of the present invention to carry out a polymerization reaction May be. In order to control the molecular weight of the polymer, a chain transfer agent may be added within a range that does not impair the effects of the present invention. As the chain transfer agent, arenes such as 1,2-butadiene,
Cyclic dienes such as cyclooctadiene and hydrogen are preferably used.

The substituted hydroxystyrene polymer obtained by the production method of the present invention has a high degree of syndiotactic structure, but is usually represented by the following general formula (2).

[Chemical 7] (In the formula, R ¹ is a trialkylsilyloxy group having 3 to 30 carbon atoms or a trialkylgermaniumoxy group having 3 to 30 carbon atoms, m is an integer of 1 to 3, and when m is plural, R 1
¹ may be the same or different. ) And having a tacticity of 3 in the racemic pentad by ¹³ C-NMR.
It preferably has a syndiotactic structure of 0% or more.

The syndiotactic structure referred to here is
The stereochemical structure is a syndiotactic structure, that is, it has a stereostructure in which a phenyl group or a substituted phenyl group, which is a side chain with respect to the main chain formed from carbon-carbon bonds, is alternately located in opposite directions. Tacticity is quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon. ^The tacticity measured by the ¹³ C-NMR method is the proportion of a plurality of continuous structural units, for example, two are diads, three are triads, 5
Individual cases can be indicated by pen duds.

The substituted hydroxystyrene polymer having a high degree of syndiotactic structure referred to in the present invention means a chain of repeating units of substituted hydroxystyrenes.
Racemic pentad is 30% or more, preferably 50% or more, more preferably 70% or more, further preferably 80%.
% Or more, or preferably 75% in racemic diad
% Or more, more preferably 85% or more, even more preferably 90% or more of syndiotacticity. However, the degree of syndiotacticity varies slightly depending on the type of substituent.

In the substituted hydroxystyrene-based polymer having a syndiotactic structure produced by the production method of the present invention, the repeating units bonded are not limited to one type of structural unit but also to two or more types of both. Each of the structural units has a syndiotactic structure (co-syndiotactic structure). Further, the copolymer composed of these structural units has various aspects such as block copolymerization, random copolymerization and alternating copolymerization. The substituted hydroxystyrene polymer mainly having a syndiotactic structure in the present invention does not necessarily have to be a single polymer. As long as the syndiotacticity is in the above range, even if a mixture with a substituted hydroxystyrene polymer having an isotactic or atactic structure or a substituted hydroxystyrene polymer having an atactic structure is incorporated in the polymer chain. Good.

Further, the substituted hydroxystyrene polymer of the present invention has a number average molecular weight of 800 or more, preferably 1000 to 2,000,000, more preferably 2000 to.
It is desirable to be in the range of 1,000,000, particularly preferably 3000 to 500,000. If the molecular weight is too small, the physical properties of the polymer such as low mechanical strength will be insufficient, and if the molecular weight is too large, molding will be difficult. The molecular weight distribution is not particularly limited, but the preferable range of the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the syndiotactic substituted hydroxystyrene polymer, is , 15 or less, more preferably 10 or less, further preferably 3.0 or less, and particularly preferably 2.0 or less. If the molecular weight distribution is too wide, there is a problem of deterioration of physical properties, which is not preferable. The weight average molecular weight of the syndiotactic substituted hydroxystyrene-based polymer (M
w), number average molecular weight (Mn) and molecular weight distribution (Mw / M
n) means the molecular weight and the molecular weight distribution obtained by measuring with a differential refractometer as a detector, using gel permeation chromatography calibrated with standard polystyrene having a monodisperse molecular weight distribution as a standard sample. That is.

As the styrene-based monomer used in the method for producing a substituted hydroxystyrene-based polymer of the present invention, one or more substituted hydroxystyrene-based monomers represented by the following general formula (1) are preferably used. To be done.

[Chemical 8] (In the formula, R ¹ is a trialkylsilyloxy group having 3 to 30 carbon atoms or a trialkylgermaniumoxy group having 3 to 30 carbon atoms, m is an integer of 1 to 3, and when m is plural, R 1
¹ may be the same or different. )

Specific examples of the monomer represented by the general formula (1) include p-triisopropylsilyloxystyrene, m-triisopropylsilyloxystyrene and p.
-Tri-n-propylsilyloxystyrene, m-tri-n-propylsilyloxystyrene, p-tert-butyldimethylsilyloxystyrene, m-t-butyldimethylsilyloxystyrene, p-isopropyldimethylsilyloxystyrene, m -Isopropyldimethylsilyloxystyrene,

P-Triisopropylgermanium oxystyrene, m-triisopropylgermanium oxystyrene, p-tri-n-propylgermanium oxystyrene, m-tri-n-propylgermanium oxystyrene, p-tert-butyldimethylgermanium oxystyrene. , M-tert-butyldimethylgermanium oxystyrene, p-isopropyldimethylgermanium oxystyrene, m-isopropyldimethylgermanium oxystyrene,

3,5-bis (triisopropylsilyloxy) styrene, 3,5-bis (tri-n-propylsilyloxy) styrene, 3,5-bis (t-butyldimethylsilyloxy) styrene, 3,5 -Bis (isopropyldimethylsilyloxy) styrene, 3,5-bis (triisopropylgermaniumoxy) styrene,
Examples thereof include 3,5-bis (tri-n-propylgermaniumoxy) styrene, 3,5-bis (tert-butyldimethylgermaniumoxy) styrene and 3,5-bis (isopropyldimethylgermaniumoxy) styrene. The monomer represented by the general formula (1) may be used alone or in combination of two or more.

Further, together with the monomer represented by the general formula (1), another styrene-based monomer different from the above may be copolymerized within a range not impairing the effects of the present invention.
Examples of the styrene-based monomer in this case include styrene, p-methylstyrene, m-methylstyrene, 3,4-
Alkyl styrene such as dimethyl styrene, 3,5-dimethyl styrene, p-tertiary butyl styrene, p-
Examples thereof include halogenated styrenes such as chlorostyrene, m-chlorostyrene, p-bromostyrene, m-bromostyrene, p-fluorostyrene, and m-fluorostyrene, and may be a copolymer containing these units. .

The amount of these other styrenic monomers that can be used together with the monomer represented by the general formula (1) varies depending on the use of the polymer of the present invention and is not uniquely determined. In the monomer, it is preferably 45 mol% or less, particularly preferably 0.1 to 30 mol%. Most preferably, it is 0.5 to 10 mol%. Further, in the method for producing a syndiotactic substituted hydroxystyrene-based polymer of the present invention, other monomers copolymerizable with the substituted hydroxystyrene-based monomer within the range that does not impair the effects of the present invention, if necessary. Can be copolymerized.

In this case, the other monomer copolymerizable with the substituted hydroxystyrene monomer is ethylene,
Propylene, olefins such as 1-butene, cyclopentene, cyclic olefins such as 2-norbornene, 1,3
-Butadiene, 2-methyl-1,3-butadiene, 2,
3-dimethyl-1,3-butadiene, 2-chloro-1,
Conjugated dienes such as 3-butadiene, 1,3-pentadiene and 1,3-hexadiene, 1,5-hexadiene,
Non-conjugated dienes such as 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and (meth) acrylic acid esters such as methyl methacrylate and methyl acrylate are included. The amount of the other monomer that can be used together with the monomer represented by the general formula (1) varies depending on the use of the polymer of the present invention and is not uniquely determined, but it is preferable that all monomers are used. Is 45 mol% or less, particularly preferably 0.1
~ 30 mol%. Most preferably, it is 0.5 to 10 mol%.

The substituted hydroxystyrene-based polymer having a high degree of syndiotactic structure obtained in the present invention is a precursor of the hydroxystyrene-based polymer.
In order to obtain a hydroxystyrene-based polymer having a syndiotactic structure, it can be produced extremely efficiently by bringing it into contact with an acid or a base to carry out a deprotecting group-forming reaction. The applications of the hydroxystyrene polymer having a high syndiotactic structure thus obtained include, for example, printed wiring boards, offset PS printing plates, photoresists, color filters, sliding materials, brake materials, ion exchange resin raw materials, adsorption. As raw materials for agents, synthetic carriers, packing materials for chromatograms, separation membranes, flame retardant raw materials, sealing materials, coating materials, flocculants, C
It is useful as a B-containing film resistor, a magnetic tape binder, an adhesive and a metal surface treatment agent.

[0047]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

First, each evaluation used in the examples of the present invention,
The measurement method will be described. 1) Catalytic activity Catalyst metal 1 mmol It was represented by the polymer production amount (gram) per hour. 2) Molecular weight and molecular weight distribution of polymer Using Tosoh 8020 gel permeation chromatography, measurement was carried out by mounting a differential refractometer as a detector. 3)% syndiotacticity using JEOL LA600 type nuclear magnetic resonance spectrometer, ¹³
Determined by measuring pentad (racemic pentad) by C-NMR analysis. ¹³ C-NMR measurement conditions 74.2 ppm standard measurement temperature of heavy tetrachloroethane: 50 ° C.

Reference Example 1 (modified methylaluminoxane-1
Preparation) Triisobutylaluminum (TIBAL) in 25% toluene solution was charged into a 300 ml flask under a nitrogen atmosphere. Water was added dropwise over 3 hours with vigorous stirring at a temperature of 0 to 15 ° C. After completing the dropping of water,
The solution was heated to 70-80 ° C. to complete the reaction. The dissolved isobutane was removed to prepare a colorless and transparent isobutylaluminoxane (IBAO) solution. Trimethyl aluminum (TMAL) diluted with toluene was added to the obtained IBAO solution, and the mixture was heated at 60 to 85 ° C. for 1 hour to obtain a toluene solution of modified methylaluminoxane-1. As a result of analyzing a toluene solution of modified methylaluminoxane-1, the aluminum content was 5.
7% by weight, the hydrolyzed gas composition was 29% isobutane and 70% methane.

Reference Example 2 (modified methylaluminoxane-2
Preparation of triisobutylaluminum (TIBAL) in 25% toluene solution (solution containing 3.40% Al 246.
4 g) was charged into a 500 ml flask under a nitrogen atmosphere. With vigorous stirring at a temperature of 0 to 5 ° C., 3.92 g of water (H ₂ 0 / Al = 0.70) was added dropwise over 30 minutes. After the addition of water is complete, heat to 70-80 ° C,
The reaction was completed. Remove dissolved isobutane,
A colorless transparent isobutylaluminoxane (IBAO) solution was prepared. The obtained IBAO solution (3.7% Al) 9
TMAL (8.80 g) was added to 0.0 g, and the mixture was heated under reflux for 60 minutes. Then, to 86.5 g of the obtained TMAL / IBAO toluene solution, the temperature of 0 to 12 ° C. was maintained, and H ₂ O was added to 6.1 while stirring vigorously for 40 minutes.
g (H ₂ O / TMAL = 0.31) was added. Subsequently, the product was heated under reflux for 1 hour to obtain a toluene solution of modified methylaluminoxane-2. As a result of analyzing a toluene solution of modified methylaluminoxane-2, the aluminum content was 6.9 wt%, and the hydrolyzed gas composition was 30% isobutane and 65% methane.

Example 1 A polymerization reaction was carried out in a nitrogen atmosphere using a glass three-necked flask having an inner volume of 100 ml which had been dried and purged with nitrogen.
32.0 ml of toluene and 5.4 ml of a toluene solution of modified methylaluminoxane-1 obtained in Reference Example 1 (aluminum concentration: 5.7 wt%) were placed in a glass three-necked flask and aged at room temperature for 10 minutes.
0.01 mmol of pentamethylcyclopentadienyltitanium trichloride was charged therein and aged at 30 ° C. for 2 minutes. Next, the temperature was kept constant at 0 ° C. and aging was performed for 5 minutes. Further, 0.01 mmol of 4-tert-butyldimethylsilyloxystyrene was charged to obtain 10
Aged for minutes. Finally, a toluene solution of 4.0 mmol of 4-tert-butyldimethylsilyloxystyrene and 0.1 mmol of triisobutylaluminum was charged, and a polymerization reaction was carried out at 0 ° C. for 30 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The resulting polymer was redissolved in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. The polymer was washed, filtered, dried and weighed to obtain 0.873 g of a polymer (yield: 92.7 wt%). The weight average molecular weight (Mw) of the obtained polymer was 274,000, the number average molecular weight (Mn) was 132000, and the molecular weight distribution (Mw / Mn) was 2.
It was 07. The syndiotacticity determined by ¹³ C-NMR measurement is 95% for racemic pentad.
% Or more.

Example 2 A polymerization reaction was carried out in a nitrogen atmosphere by using a glass three-necked flask having an inner volume of 100 ml which had been dried and purged with nitrogen.
25.1 ml of toluene and 5.4 ml of a modified methylaluminoxane-1 toluene solution (aluminum concentration: 5.7 wt%) obtained in Reference Example 1 were placed in a glass three-necked flask and aged at 0 ° C. for 10 minutes. . 0.02 mmol of pentamethylcyclopentadienyl titanium trichloride was added to this, and further,
4-tert-butyldimethylsilyloxystyrene 0.02
After mmol was charged, aging was performed for 10 minutes. Finally, 4.0 mmol of 4-tert-butyldimethylsilyloxystyrene and 0.1 m of triisobutylaluminum
A mol toluene solution was charged and a polymerization reaction was carried out at 0 ° C. for 30 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The resulting polymer was redissolved in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. The polymer was washed, filtered, dried and weighed to obtain 0.796 g of a polymer (yield: 84.4 wt%). The weight average molecular weight (Mw) of the obtained polymer was 160000, the number average molecular weight (Mn) was 75,000, and the molecular weight distribution (Mw / Mn) was 2.1.
It was 3. The syndiotacticity determined by ¹³ C-NMR measurement is 95% for racemic pentad.
% Or more.

Example 3 A glass three-necked flask having an internal volume of 100 ml which had been dried and purged with nitrogen was used to carry out a polymerization reaction in a nitrogen atmosphere.
21.56 ml of toluene 14.1 ml and a toluene solution of modified methylaluminoxane-1 obtained in Reference Example 1 (aluminum concentration: 5.7 wt%) were placed in a glass three-necked flask and aged at 0 ° C. for 10 minutes. . Cyclopentadienyl titanium trichloride (0.04 mmol) was charged therein, and further 4-tert-butyldimethylsilyloxystyrene (0.04 mmol) was charged therein, followed by aging for 10 minutes. Finally, 4-te
rt-Butyldimethylsilyloxystyrene 4.0mmo
1 and a toluene solution of 0.1 mmol of triisobutylaluminum were charged, and a polymerization reaction was performed at 0 ° C. for 30 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The resulting polymer was redissolved in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. The polymer was washed, filtered, dried and weighed to obtain 0.383 g of polymer (yield: 40.4 wt%). The obtained polymer had a weight average molecular weight (Mw) of 8070, a number average molecular weight (Mn) of 6360 and a molecular weight distribution (Mw / Mn) of 1.27.
Met. The syndiotacticity determined by ¹³ C-NMR measurement is 95% for racemic pentad.
That was all.

Example 4 A polymerization reaction was carried out in a nitrogen atmosphere using a glass three-necked flask having an inner volume of 100 ml which was dried and purged with nitrogen.
21.56 ml of toluene (14.8 ml) and a toluene solution of modified methylaluminoxane-1 obtained in Reference Example 1 (aluminum concentration: 5.7 wt%) were placed in a glass three-necked flask and aged at 0 ° C. for 10 minutes. . Here, indenyl titanium trichloride 0.
04 mmol was charged, and further 4-tert-butyldimethylsilyloxystyrene 0.04 mmol was charged,
Aged for 10 minutes. Finally, a toluene solution of 4.0 mmol of 4-tert-butyldimethylsilyloxystyrene and 0.1 mmol of triisobutylaluminum was charged, and a polymerization reaction was carried out at 0 ° C. for 30 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The resulting polymer was redissolved in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. The polymer was washed, filtered, dried and weighed to obtain 0.802 g of a polymer (yield: 84.7 wt%). The weight average molecular weight (Mw) of the obtained polymer was 39,900, the number average molecular weight (Mn) was 22,400, and the molecular weight distribution (Mw / Mn) was 1.7.
Was eight. The syndiotacticity determined by ¹³ C-NMR measurement is 95% for racemic pentad.
% Or more.

Example 5 A polymerization reaction was carried out in a nitrogen atmosphere using a glass three-necked flask having an inner volume of 100 ml which had been dried and purged with nitrogen.
21.56 ml of a toluene solution (aluminum concentration: 5.7 wt%) of modified methylaluminoxane-1 obtained in Reference Example 1 with 14.3 ml of toluene was placed in a glass three-necked flask and aged at 0 ° C. for 10 minutes. . 0.04 mmol of pentamethylcyclopentadienyltitanium trichloride was added to the mixture, and further 4-tert-butyldimethylsilyloxystyrene was added.
04 mmol was charged and aging was performed for 10 minutes. Finally, 4-tert-butyldimethylsilyloxystyrene (4.0 mmol) and triisobutylaluminum (0.2 mmol).
A 1 mmol toluene solution was charged and a polymerization reaction was carried out at 0 ° C. for 30 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The resulting polymer was redissolved in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. The polymer was washed, filtered, dried and weighed to obtain 0.889 g of a polymer (yield: 93.8 wt%). The weight average molecular weight (Mw) of the obtained polymer was 107,000, the number average molecular weight (Mn) was 53400, and the molecular weight distribution (Mw / Mn) was 2.0.
It was 1. The syndiotacticity determined by ¹³ C-NMR measurement is 95% for racemic pentad.
% Or more.

Example 6 Polymerization reaction was carried out in a nitrogen atmosphere using a glass three-necked flask having an internal volume of 100 ml which was dried and purged with nitrogen.
21.56 ml of a toluene solution of 15.3 ml of toluene and a modified methylaluminoxane-1 obtained in Reference Example 1 (aluminum concentration: 5.7 wt%) was charged into a glass three-necked flask and aged at 50 ° C. for 10 minutes. . 0.04 mmol of indenyl titanium trichloride was charged therein, and 0.04 mmol of 4-tert-butyldimethylsilyloxystyrene was further charged therein, followed by aging for 5 minutes. Finally, a toluene solution of 4.0 mmol of 4-tert-butyldimethylsilyloxystyrene and 0.1 mmol of triisobutylaluminum was charged, and a polymerization reaction was carried out at 50 ° C. for 30 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The resulting polymer was redissolved in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. The polymer was washed, filtered, dried and weighed to obtain 0.941 g of polymer (yield: 99.3 wt%). The obtained polymer had a weight average molecular weight (Mw) of 8830, a number average molecular weight (Mn) of 5410, and a molecular weight distribution (Mw / Mn) of 1.63.
Met. The syndiotacticity determined by ¹³ C-NMR measurement is 95% for racemic pentad.
That was all.

Example 7 A glass three-necked flask having an inner volume of 100 ml which had been dried and purged with nitrogen was used to carry out a polymerization reaction in a nitrogen atmosphere.
21.56 ml of a toluene solution (aluminum concentration: 5.7 wt%) of modified methylaluminoxane-1 obtained in Reference Example 1 with 14.3 ml of toluene was placed in a three-necked glass flask and aged at 50 ° C. for 10 minutes. . 0.04 mmol of pentamethylcyclopentadienyltitanium trichloride was added to the mixture, and further 4-tert-butyldimethylsilyloxystyrene was added.
04 mmol was charged and aging was performed for 5 minutes.
Finally, 4.0 mmol of 4-tert-butyldimethylsilyloxystyrene and 0.1 m of triisobutylaluminum
A mol toluene solution was charged and a polymerization reaction was carried out at 50 ° C. for 30 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The resulting polymer was redissolved in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. The polymer was washed, filtered, dried and weighed to obtain 0.859 g of a polymer (yield: 90.7 wt%). The weight average molecular weight (Mw) of the obtained polymer was 48500, the number average molecular weight (Mn) was 17100, and the molecular weight distribution (Mw / Mn) was 2.8.
It was 3. The syndiotacticity determined by ¹³ C-NMR measurement is 95% for racemic pentad.
% Or more.

Comparative Example 1 A glass three-necked flask having an inner volume of 100 ml which had been dried and purged with nitrogen was used to carry out a polymerization reaction in a nitrogen atmosphere.
22.2 ml of toluene was charged into a three-necked flask. Next, 13.7 ml of a toluene solution of methylaluminoxane (aluminum concentration: 8.9 wt%) synthesized by bringing trimethylaluminum and water into contact with each other was placed in a three-neck glass flask and aged at 0 ° C. for 10 minutes. It was 0.04 mmol of pentamethylcyclopentadienyl titanium trichloride was charged therein, and 0.04 mmol of 4-tert-butyldimethylsilyloxystyrene was further charged therein, followed by aging for 10 minutes. Finally, a toluene solution of 4.0 mmol of 4-tert-butyldimethylsilyloxystyrene and 0.1 mmol of triisobutylaluminum was charged, and a polymerization reaction was carried out at 0 ° C. for 30 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The obtained polymer was redissolved in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. The polymer was washed, filtered, dried and weighed to obtain 0.069 g of polymer (yield: 7.24 wt%). The obtained polymer has a weight average molecular weight (Mw) of 22,500, a number average molecular weight (Mn) of 12,200 and a molecular weight distribution (Mw / Mn) of 1.8.
It was 4. The stereo structure of the polymer determined by ¹³ C-NMR measurement was an atactic structure.

Example 8 Using a glass three-necked flask having an internal volume of 100 ml which had been dried and purged with nitrogen, a polymerization reaction was carried out under a nitrogen atmosphere.
33.2 ml of toluene and 4.5 ml of a toluene solution of the modified methylaluminoxane-2 obtained in Reference Example 2 (aluminum concentration: 6.9 wt%) were placed in a glass three-necked flask and aged for 10 minutes at room temperature.
0.01 mmol of pentamethylcyclopentadienyltitanium trimethoxide was charged therein and aged at 30 ° C. for 2 minutes. Next, the temperature was kept constant at 0 ° C. and aging was performed for 5 minutes. Further, 0.01 mmol of 4-triisopropylsilyloxystyrene was charged and aging was performed for 10 minutes. Finally, a toluene solution of 4.0 mmol of 4-triisopropylsilyloxystyrene and 0.1 mmol of triisobutylaluminum was charged,
A polymerization reaction was carried out at 0 ° C. for 60 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The resulting polymer was redissolved in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. The polymer was washed, filtered, dried and weighed to obtain 1.058 g of a polymer (yield: 94.7 wt%). The weight average molecular weight (Mw) of the obtained polymer was 326,000, the number average molecular weight (Mn) was 155,000, and the molecular weight distribution (Mw / Mn) was 2.
It was 10. The syndiotacticity determined by ¹³ C-NMR measurement is 95% for racemic pentad.
% Or more.

Example 9 Using a glass three-necked flask having an inner volume of 100 ml which had been dried and purged with nitrogen, a polymerization reaction was carried out under a nitrogen atmosphere.
25.1 ml of toluene and 5.4 ml of a modified methylaluminoxane-1 toluene solution (aluminum concentration: 5.7 wt%) obtained in Reference Example 1 were placed in a glass three-necked flask and aged at 0 ° C. for 10 minutes. . Trimethyl (pentamethylcyclopentadienyl titanium) 0.02 mmol was charged therein, and further 4-tert-butyldimethylgermanium oxystyrene 0.02 mmol was charged therein, and aging was performed for 10 minutes. Finally, a toluene solution of 4.0 mmol of 4-tert-butyldimethylgermanium oxystyrene and 0.1 mmol of triisobutylaluminum was charged, and the mixture was heated to 0 ° C.
Polymerization reaction was carried out for 30 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The obtained polymer was redissolved in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. The polymer was washed, filtered, dried and weighed to obtain 0.931 g of polymer (yield: 82.6 wt%). The weight average molecular weight (Mw) of the obtained polymer was 187,000, the number average molecular weight (Mn) was 90800, and the molecular weight distribution (Mw / Mn) was 2.0.
It was 6. The syndiotacticity determined by ¹³ C-NMR measurement is 95% for racemic pentad.
% Or more.

Example 10 The polymerization reaction was carried out in a nitrogen atmosphere using a glass three-necked flask having an internal volume of 100 ml which was dried and purged with nitrogen.
21.56 ml of toluene (14.8 ml) and a toluene solution of modified methylaluminoxane-1 obtained in Reference Example 1 (aluminum concentration: 5.7 wt%) were placed in a glass three-necked flask and aged at 0 ° C. for 10 minutes. . Where indenyl titanium dichloride 0.0
Charge 4 mmol and then 0.04 mmol of 4-tert-butyldimethylsilyloxystyrene to obtain 1
Aged for 0 minutes. Finally, a toluene solution of 4.0 mmol of 4-tert-butyldimethylsilyloxystyrene and 0.1 mmol of triisobutylaluminum was charged, and a polymerization reaction was carried out at 0 ° C. for 30 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The resulting polymer was redissolved in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. The polymer was washed, filtered, dried and weighed to obtain 0.760 g of a polymer (yield: 80.2 wt%). The weight average molecular weight (Mw) of the obtained polymer was 36800, the number average molecular weight (Mn) was 19600, and the molecular weight distribution (Mw / Mn) was 1.8.
Was eight. The syndiotacticity determined by ¹³ C-NMR measurement is 95% for racemic pentad.
% Or more.

Example 11 Polymerization reaction was carried out in a nitrogen atmosphere by using a glass three-necked flask having an inner volume of 100 ml, which was dried and purged with nitrogen.
21.56 ml of toluene (14.8 ml) and a toluene solution of modified methylaluminoxane-1 obtained in Reference Example 1 (aluminum concentration: 5.7 wt%) were placed in a glass three-necked flask and aged at 0 ° C. for 10 minutes. . 0.04 mmol of indenyl titanium trifluoride was charged therein, and 0.04 mmol of 4-tert-butyldimethylsilyloxystyrene was further charged therein, followed by aging for 10 minutes. Finally, a toluene solution of 4.0 mmol of 4-tert-butyldimethylsilyloxystyrene and 0.1 mmol of triisobutylaluminum was charged and a polymerization reaction was carried out at 0 ° C. for 30 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The resulting polymer was redissolved in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. The polymer was washed, filtered, dried and weighed to obtain 0.913 g of a polymer (yield: 96.4 wt%). The weight average molecular weight (Mw) of the obtained polymer was 42300, the number average molecular weight (Mn) was 23400, and the molecular weight distribution (Mw / Mn) was 1.81.
Met. The syndiotacticity determined by ¹³ C-NMR measurement is 95% for racemic pentad.
That was all.

Example 12 Polymerization reaction was carried out in a nitrogen atmosphere by using a three-neck flask made of glass, which was dried and purged with nitrogen and which had an internal volume of 100 ml.
25.1 ml of toluene and 5.4 ml of a toluene solution of modified methylaluminoxane-1 obtained in Reference Example 1 (aluminum concentration: 5.7 wt%) were placed in a glass three-necked flask and aged at 0 ° C. for 10 minutes. .
0.02 mmol of pentamethylcyclopentadienyltitanium trichloride was added to this, and 3-te
rt-Butyldimethylsilyloxystyrene 0.02mm
ol was charged and aging was performed for 10 minutes. Finally, 3-tert-butyldimethylsilyloxystyrene 4.
0 mmol and triisobutylaluminum 0.1 mmo
A toluene solution of 1 was charged and a polymerization reaction was carried out at 0 ° C. for 30 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The resulting polymer was redissolved in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. The polymer was washed, filtered, dried and weighed to obtain 0.865 g of a polymer (yield: 91.3 wt%). The obtained polymer has a weight average molecular weight (Mw) of 135,000, a number average molecular weight (Mn) of 64700, and a molecular weight distribution (Mw / Mn) of 2.0.
Was eight. The syndiotacticity determined by ¹³ C-NMR measurement is 95% for racemic pentad.
% Or more.

[0077]

According to the method for producing a syndiotactic substituted hydroxystyrene polymer of the present invention, a printed wiring board, an offset PS printing plate, a photoresist, a color filter, a sliding material, a brake material, an ion exchange resin raw material, Materials for adsorbents, carriers for synthesis, packing materials for chromatograms, separation membranes, etc., as well as raw materials for flame retardants, sealing materials,
Efficiently use syndiotactic substituted hydroxystyrene polymer as a precursor of syndiotactic hydroxystyrene polymer useful as a coating material, a flocculant, a CB-containing film resistor, a magnetic tape binder, an adhesive or a metal surface treatment agent. It can be manufactured.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J028 AA01A AB01A AC01A AC10A                       AC28A BA00A BA01B BB00A                       BB01B BC25B CA16A CA25A                       CA27A CA28A CA29A CB09A                       EB21 FA01 FA02 FA04 GA01                       GA06 GA15                 4J100 AB04Q AB07P AB08Q AB10Q                       BA76P BA93P CA01 CA04                       CA12 DA01 DA04 FA10 FA18                       FA19 FA21 FA22

Claims (2)

[Claims] 1. The following general formula (1): (In the formula, R ¹ is a trialkylsilyloxy group having 3 to 30 carbon atoms or a trialkylgermaniumoxy group having 3 to 30 carbon atoms, m is an integer of 1 to 3, and when m is plural, R 1
¹ may be the same or different. From a substituted hydroxystyrene-based monomer represented by the following general formula (2) (In the formula, R ¹ is a trialkylsilyloxy group having 3 to 30 carbon atoms or a trialkylgermaniumoxy group having 3 to 30 carbon atoms, m is an integer of 1 to 3, and when m is plural, R 1
¹ may be the same or different) and has a tacticity of ¹³
In the method for producing a substituted hydroxystyrene polymer having a syndiotactic structure, which is 30% or more in racemic pentad by C-NMR, a catalyst component is
(A) General formula (3) and / or general formula (4) MR ² R ³ _a X _3-a (3) MR ² R ³ _b X _2-b (4) (wherein M is a periodic table A transition metal element of Group 4 is shown, and R
² represents a π ligand. R ³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms.
20 alkylaryl group, C7-20 arylalkyl group, C1-20 acyloxy group, C1-20 alkoxy group, C1-20 thioalkoxy group, C6-20 Represents a thioaryloxy group,
They may be the same or different. X
Represents a halogen atom. a shows the integer of 0-3, b shows the integer of 0-2. ) A transition metal compound represented by
(B) Tetraalkyldialuminoxane having an alkyl group having 2 or more carbon atoms and / or a reaction product with a modified methylaluminoxane obtained by reacting trimethylaluminum with a polyalkylaluminoxane having an alkyl group having 2 or more carbon atoms A method for producing a syndiotactic substituted hydroxystyrene-based polymer, which comprises polymerizing the above-mentioned substituted hydroxystyrene-based monomer in the presence thereof. 2. The transition metal compound (A) has the general formula (5):
The method for producing a syndiotactic substituted hydroxystyrene polymer according to claim 1, which is a titanium compound represented by: TiR ² R ³ _a X _3-a (5) (In the formula, R ² represents a π ligand. R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
Alkylaryl group having 7 to 20 carbon atoms, 7 to 20 carbon atoms
Of the arylalkyl group, the C1-C20 acyloxy group, the C1-C20 alkoxy group, the C1-C20 thioalkoxy group, and the C6-C20 thioaryloxy group. It may be different or different. X represents a halogen atom. a shows the integer of 0-3. )