JP2003119225A - Syndiotactic hydroxystyrene copolymer and method for producing the same - Google Patents

Abstract

(57) [Problem] To provide a syndiotactic hydroxystyrene-based copolymer comprising a hydroxystyrene-based structural unit and a styrene-based structural unit and a method for producing the same. SOLUTION: This is a copolymer containing a structural unit derived from a hydroxystyrene-based monomer and a styrene-based monomer, wherein the phenyl group has a C1 carbon tacticity of ¹³ CN
A syndiotactic hydroxystyrene-based copolymer having a racemic pentad content of at least 30% by MR and a reaction product of a transition metal compound and a cocatalyst as main catalyst components and a dielectric constant of 2.0 to 10.0 A method for producing a syndiotactic-substituted hydroxystyrene-based copolymer which is copolymerized in the presence of a solvent, and a hydroxystyrene-based copolymer in which this is contacted with an acid or a base in the presence of an organic solvent to carry out a deprotection grouping reaction A method for producing a syndiotactic hydroxystyrene-based copolymer containing a structural unit and a styrene-based structural unit.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a copolymer of a substituted hydroxystyrene-based structural unit and a styrene-based structural unit, wherein the structural units constituting the copolymer each have a high syndiotactic structure. A substituted hydroxystyrene-based copolymer having the same, a method for producing the same, and a syndiotactic copolymer having a hydroxystyrene-based structural unit and a styrene-based structural unit, each of which has a high structural unit. TECHNICAL FIELD The present invention relates to a hydroxystyrene-based copolymer having a tic structure and a method for producing them.

[0002]

2. Description of the Related Art Styrene-based polymers conventionally produced by radical polymerization or the like are molded into various shapes by various molding methods, and household electric appliances, office equipment, household products, packaging containers, toys, It is widely used as furniture, synthetic paper, and other industrial materials, but its three-dimensional structure has an atactic structure, which has the drawback of poor heat resistance and chemical resistance. As a solution to the drawback of the styrene-based polymer having such an atactic structure, a styrene-based polymer having a highly syndiotactic structure, and a styrene-based copolymer obtained by copolymerizing this styrene-based structure with other components Considered (JP-B-3-7685, JP-B1-37403, JP-A-63-241)
No. 009). These polymers are excellent in heat resistance, chemical resistance and electrical characteristics, and are expected to be applied in various fields.

However, the syndiotactic polystyrene type polymers according to the techniques disclosed in these patent publications are homopolymers having a styrene type structure consisting of only hydrocarbons having no polar group necessary for imparting a function, or a small amount thereof. Since it is a random copolymer in which the polar vinyl structure is introduced, it has a drawback that the range of properties that can be modified is narrow and the applicable applications are limited. Especially, coating, adhesive, resin modification The resin material was not suitable for application as a functional material such as an agent, a compatibilizer, a pigment dispersant, and a heat-resistant sealing agent. As a technique for compensating for the above-mentioned drawbacks of syndiotactic polystyrene, it is conceivable to copolymerize a substituted hydroxystyrene monomer with a syndiotactic polystyrene polymer.

Conventionally, a syndiotactic substituted hydroxystyrene copolymer obtained by copolymerizing 4-t-butyldimethylsilyloxystyrene as a substituted hydroxystyrene monomer has been disclosed in Macromolecular Rapid Communication, 199.
9 years, 20th volume, pages 175-178, Macromolecules, 1999,
Vol. 32, pp. 8703-8710, etc., discloses a copolymer composed of a styrene unit having a syndiotactic structure and a 4-t-butyldimethylsilyloxystyrene unit having an atactic structure. However, the copolymers of 4-t-butyldimethylsilyloxystyrene and styrene disclosed in these documents are due to the structural unit derived from 4-t-butyldimethylsilyloxystyrene being an atactic structure. However, it had a defect that the adhesiveness and the coating film strength were weak.

Further, in the above-mentioned document, deprotection of a copolymer composed of a styrene unit having a syndiotactic structure and a 4-t-butyldimethylsilyloxystyrene unit having an atactic structure was not deprotected. Therefore, nothing has been known about the characteristics of the copolymer composed of a styrene unit having a syndiotactic structure and a hydroxystyrene unit having an atactic structure.

[0006]

An object of the present invention is to provide a highly syndiotactic structure which is excellent in heat resistance, adhesiveness, coating film strength, and moldability and which is useful as a raw material for high-performance resins and functional resins. PROBLEM TO BE SOLVED: To provide a copolymer having a highly syndiotactic structure in which each structural unit consisting of a substituted hydroxystyrene-based monomer and a styrene-based monomer, which is a precursor of the hydroxystyrene-based copolymer, and a method for producing the same Furthermore, it is to provide a hydroxystyrene-based copolymer having a high syndiotactic structure derived from this substituted hydroxystyrene-based copolymer, and a method for producing the same. In particular, the hydroxystyrene-based copolymer having a high syndiotactic structure obtained by the present invention has a high heat resistance by imparting crystallization ability by copolymerization, which cannot be expressed by a hydroxystyrene-based homopolymer. The purpose is to exhibit the properties, adhesiveness, and moldability at the same time.

[0007]

As a result of intensive studies to solve the above problems, the present inventors have found that (1) a specific substituted hydroxystyrene-based monomer having a highly syndiotactic structure Copolymer with styrene monomer,
Further, (2) a copolymer having a specific composition range consisting of a hydroxystyrene-based structural unit and a styrene-based structural unit obtained by deprotecting the protective group in this copolymer, and these The structural unit derived from each of the monomer components constituting the copolymer of the above solves the problem of the present invention by a substituted hydroxystyrene-based copolymer and a hydroxystyrene-based copolymer each having a high syndiotactic structure. I found that I could do it.

Furthermore, the present inventors have (3) added a specific transition metal component and a co-catalyst component in the presence of an aromatic hydrocarbon and / or halogenated aromatic hydrocarbon solvent having a dielectric constant in a specific range. Producing a copolymer having a high syndiotactic structure by copolymerizing a specific substituted hydroxystyrene-based monomer and a styrene-based monomer at a temperature within a specific range, and (4) obtaining The resulting syndiotactic substituted hydroxystyrene-based copolymer is brought into contact with an acid or a base in the presence of an organic solvent to carry out a deprotection group-forming reaction, thereby containing the target hydroxystyrene-based structural unit and styrene-based structural unit. Moreover, it has been found that all these structural units can produce a hydroxystyrene copolymer having a high syndiotactic structure.

Furthermore, the hydroxystyrene copolymer, in which each structural unit derived from each monomer has a high degree of syndiotactic structure, exhibits a high degree of crystallinity in a specific composition range, so that a syndyne having a low crystallinity is obtained. It has been found that an unexpected effect that the heat resistance of the hydroxystyrene polymer having an tactic structure can be further enhanced can be obtained. Then, they have found that these problems can solve the problems of the present invention, and have completed the present invention.

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

[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. ) Substituted hydroxystyrene structural unit (I)
55 mol%

General formula (2)

[Chemical 8] (Wherein, R ² represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 30 carbon atoms, n is an integer of 0 to 5. However, when n is plural, each R ² is Which may be the same or different.) A copolymer comprising 45 to 99 mol% of a styrenic structural unit (II) represented by the general formula (1) in the copolymer. C ₁ of the phenyl group in the copolymer of the substituted hydroxystyrene structural unit (I) and the styrene structural unit (II) represented by the general formula (2)
It is a syndiotactic substituted hydroxystyrene copolymer characterized by having a carbon tacticity of 30% or more in terms of racemic pentads by ¹³ C-NMR.

The present invention also provides a compound of the general formula (3) in the presence of a solvent and a catalyst component.

[Chemical 9] (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. ) A substituted hydroxystyrene-based monomer represented by

General formula (4)

[Chemical 10] (Wherein, R ² represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 30 carbon atoms, n is an integer of 0 to 5. However, when n is plural, each R ² is May be the same or different.) In the method of copolymerizing a styrenic monomer represented by

The catalyst component is (A) the following general formula (5) and / or general formula (6) MR ³ R ⁴ _a X _3-a (5) MR ³ R ⁴ _b X _2-b (6) R ³ represents a π ligand, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group,
It shows an acyloxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, and a thioaryloxy group having 6 to 20 carbon atoms. M represents a transition metal element of Group 4 of the periodic table, and X represents a halogen atom. R ⁴
May be the same or different.
Further, each a is an integer of 0 to 3, and each b is an integer of 0 to 2. ) A transition metal compound represented by

(B) (a) to (d) (a) Modified methyl obtained by reacting tetraalkyldialuminoxane and / or polyalkylaluminoxane having an alkyl group having 2 or more carbon atoms with trimethylaluminum. Aluminoxane, (b) an ionic compound capable of reacting with the transition metal compound to form a cationic transition metal compound, (c) a Lewis acid compound capable of reacting with the transition metal compound to form a cationic transition metal compound, (d) ) It contains as a main catalyst component a reaction product with at least one co-catalyst selected from organometallic compounds of metals of Groups 1, 2 and 13 of the Periodic Table, and as the above-mentioned solvent, the dielectric constant is Is 2.0-1
The present invention also relates to a method for producing a syndiotactic substituted hydroxystyrene-based copolymer characterized by using an aromatic hydrocarbon and / or a halogenated aromatic hydrocarbon in the range of 0.0.

Further, the present invention provides the following general formula (7)

[Chemical 11] (M is an integer of 1 to 3) and 1 to 55 mol% of a hydroxystyrene structural unit (III) represented by the following general formula (2).

[Chemical 12] (Wherein, R ² represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 30 carbon atoms, n is an integer of 0 to 5. However, when n is plural, each R ² is Which may be the same or different) and a styrene-based structural unit (II) represented by 45 to 99 mol%.
The hydroxystyrene-based structural unit (III) represented by the general formula (7) and the styrene-based structural unit (II) represented by the general formula (2) each have a C ₁ carbon tacticity of ¹³ C-. It also relates to a syndiotactic hydroxystyrene copolymer characterized by having a racemic pentad by NMR of 30% or more.

In addition, the present invention is characterized in that the syndiotactic substituted hydroxystyrene-based copolymer is brought into contact with an acid or a base in the presence of an organic solvent to carry out a deprotecting group-forming reaction. It is also a method for producing a syndiotactic hydroxystyrene-based copolymer containing the structural unit (III) and the styrene structural unit (II) in a specific composition range.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The syndiotactic substituted hydroxystyrene-based copolymer of the present invention has 1 to 55 mol% of the substituted hydroxystyrene-based structural unit (hereinafter abbreviated as structural unit (I)) represented by the general formula (1) and the general formula (2)
Styrene-based structural unit represented by (hereinafter structural unit (II)
Abbreviated as 45) to 99 mol% and the tacticity of the C ₁ carbons of the phenyl groups of the structural unit (I) and the structural unit (II) is ¹³ C-NM, respectively.
It is a syndiotactic substituted hydroxystyrene-based copolymer (hereinafter abbreviated as copolymer P), characterized in that it is 30% or more in racemic pentad by R.

In the copolymer P of the present invention, the ratio of the structural unit (II) varies depending on the use of the polymer of the present invention and is not uniquely determined, but is 45 to 9 in all structural units.
It is 9 mol%. Preferably 46 mol% or more and 98 mol%
It is the following. More preferably 47 mol% or more and 97 mol% or more
It is the following. Most preferably 50 mol% or more and 94 mol%
It is the following.

When the structural unit (II) is 45 mol% or less, the moldability of the syndiotactic hydroxystyrene copolymer (hereinafter abbreviated as copolymer Q) obtained by deprotecting the copolymer P is obtained. In addition, the effect of improving heat resistance becomes small, which is not preferable. On the other hand, the structural unit (II) is 9
When it exceeds 9 mol%, the adhesiveness of the copolymer Q and the coating film strength are lowered, which is not preferable. The structural unit (II)
In the range of 50 mol% or more and 94 mol% or less, although different structures having different structures are often used in composition, excellent crystallinity is exhibited, resulting in excellent heat resistance. In addition, since it exhibits unexpectedly excellent properties such as excellent adhesiveness and coating film strength, it is the most preferable composition range of the present invention. The structural units (I) and (II) in the copolymer P of the present invention also include those composed of an arbitrary combination of two or more kinds. That is, the copolymer P of the present invention
In addition to the binary copolymer, includes ternary copolymers and multicomponent copolymers such as quaternary copolymers.

In the present invention, the structural units (I) and (II) and other structural units which can give a copolymer in the copolymer P, if necessary, within a range not impairing the effects of the present invention. Can be included. Other monomers in this case include ethylene, propylene, structural units derived from olefins such as 1-butene, cyclopentene, structural units derived from cyclic olefins such as 2-norbornene, 1,
3-butadiene, 2-methyl-1,3-butadiene,
2,3-dimethyl-1,3-butadiene, 2-chloro-
1,3-butadiene, 1,3-pentadiene, 1,3-
Structural units derived from conjugated dienes such as hexadiene,
1,5-hexadiene, 1,6-heptadiene, 1,7
-Structural units derived from non-conjugated dienes such as -octadiene, dicyclopentadiene and 5-ethylidene-2-norbornene, structural units derived from (meth) acrylic acid esters such as methyl methacrylate and methyl acrylate, and the like.

Here, the syndiotactic substituted hydroxystyrene-based copolymer of the present invention contains the above-mentioned monomers as repeating units, and further comprises structural units (I) and (II). Have a stereoregularity of predominantly a syndiotactic structure, ie a stereostructure in which phenyl groups with or without substitutions that are side chains with respect to the main chain formed from carbon-carbon bonds are located in opposite directions. The tacticity is quantified by a nuclear magnetic resonance method (NMR method). Specifically, ¹³ C-NM
By analysis of the C1 carbon signal of the aromatic ring, the methine / methylene carbon signal, or the proton signal of ¹³ H-NMR by the R method (nuclear magnetic resonance spectrum with isotope carbon).

Tacticity quantified by NMR is the abundance ratio of a plurality of continuous constitutional units (that is, the abundance ratio of relative conformational relations of continuous constitutional units). In the case of, the number can be represented by triad, and in the case of 5, the number can be represented by pentad, but the term "having mainly a syndiotactic structure" in the present invention means that the degree of syndiotacticity depends on the kind of substituents and the content of each repeating unit. Varies slightly, but is usually 30% or more in racemic pentad. The racemic diad is preferably 75% or more, more preferably 85% or more, or the racemic pentad is 5% or more.
Those having a syndiotacticity of 0% or more, more preferably 70% or more, and further preferably 85% or more are shown.

In the syndiotactic substituted hydroxystyrene-based copolymer of the present invention, the repeating units bonded to each other have a syndiotactic structure (co-syndiotactic structure) between two or more structural units. Has become. Further, the copolymer composed of these structural units has various aspects such as block copolymerization, random copolymerization and alternating copolymerization. The substituted hydroxystyrene-based copolymer mainly having a syndiotactic structure in the present invention does not necessarily have to be a copolymer having a single stereoregularity. As long as the syndiotacticity of the structural unit derived from each monomer component is in the above range, a mixture with a styrene-based polymer having an isotactic or atactic structure or a substituted hydroxystyrene-based copolymer having an atactic structure has a polymer chain. It may be built in.

In the syndiotactic substituted hydroxystyrene copolymer of the present invention, its number average molecular weight (M
n) is preferably 1,000 to 10,000,000, more preferably
2,500-5,000,000, more preferably 5,000-2,000,0
00. 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. Weight average molecular weight (Mw) and number average molecular weight (Mn) of the syndiotactic substituted hydroxystyrene-based copolymer of the present invention
The preferable range of the molecular weight distribution (Mw / Mn), which is the ratio of the above, is 15 or less, more preferably 10 or less, and most preferably 3.0 or less. If the molecular weight distribution is too wide,
This is not preferable because it causes a problem of deterioration of physical properties such as abrasion resistance.

In the production of the copolymer P of the present invention, the substituted hydroxystyrene-based monomer represented by the general formula (3) and the styrene-based monomer represented by the general formula (4) are used. R ¹ in the general formula (3) has 3 to 30 carbon atoms.
Is a trialkylsilyloxy group 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 s} may be the same or different. Good. Specific examples of such a substituted hydroxystyrene-based monomer include 4-triethylsilyloxystyrene, m-triethylsilyloxystyrene, 4-triisopropylsilyloxystyrene, m-
Triisopropylsilyloxystyrene, 4-tri-n
-Propylsilyloxystyrene, m-tri-n-propylsilyloxystyrene,

4-t-butyldimethylsilyloxystyrene, m-t-butyldimethylsilyloxystyrene,
4-isopropyldimethylsilyloxystyrene, m-
Isopropyldimethylsilyloxystyrene, 4-triisopropylgermanium oxystyrene, m-triisopropylgermanium oxystyrene, 4-tri-n
-Propyl germanium oxystyrene, m-tri-n
-Propyl germanium oxystyrene, 4-t-butyldimethyl germanium oxystyrene, m-t-butyl dimethyl germanium oxystyrene, 4-isopropyl dimethyl germanium oxystyrene, m-isopropyl dimethyl germanium oxystyrene, 3,5-
Bis (triethylsilyloxy) styrene, 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 (triethylgermaniumoxy) styrene, 3,5-bis (tri) Isopropylgermaniumoxy) styrene, 3,5-bis (tri-n-propylgermaniumoxy) styrene, 3,5-bis (t-butyldimethylgermaniumoxy) styrene, 3,5-bis (isopropyldimethylgermaniumoxy) styrene, And so on. These may use only 1 type and may use 2 or more types together. Of these, 4-t-butyldimethylsilyloxystyrene, 4
-T-Butyldimethylgermanium oxystyrene is preferably used.

R ² in the general formula (4) is
A hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 30 carbon atoms, n is an integer of 0 to 5, and when n is plural, each R ² may be the same or different. Specific examples of such a styrene-based monomer include styrene; 4-
Alkyl such as methyl styrene, 3-methyl styrene, 2-methyl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, 3,4-dimethyl styrene, 3,5-dimethyl styrene, 4-tert-butyl styrene Styrene; 4-chlorostyrene, 3-chlorostyrene, 2-chlorostyrene, 4-bromostyrene, 3-
Halogenated styrenes such as bromostyrene, 2-bromostyrene, 4-fluorostyrene, 3-fluorostyrene, 2-fluorostyrene, and 2-methyl-4-fluorostyrene; These styrene-based monomers may be used alone or in combination of two or more. Of these, styrene is preferably used from the viewpoint of cost and polymerization activity.

The ratio of the styrenic monomer represented by the above general formula (4) to be used varies depending on the use of the polymer of the present invention and cannot be uniquely determined, but is preferably 45 in all monomers. ~ 99 mol%, more preferably 47 mol% or more 9
It is 8 mol% or less. Particularly preferably 50 mol% or more 9
It is 8 mol% or less. Particularly preferably, it is 46 mol% or more and 97 mol% or less. Most preferably, it is 50 mol% or more and 94 mol% or less. Outside of this range, the composition of the copolymer P obtained is not preferable. Further, in the present invention, a syndiotactic substituted hydroxystyrene-based copolymer can be optionally copolymerized with a substituted hydroxystyrene-based monomer and a styrene-based monomer within a range that does not impair the effects of the present invention. Other monomers can be copolymerized.

In this case, the substituted hydroxystyrene monomer and the other monomer copolymerizable with the styrene monomer are ethylene, propylene, olefin such as 1-butene, cyclopentene, 2-norbornene and the like. Cyclic olefin, 1,3-butadiene, 2-methyl-1,
Conjugated dienes such as 3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene, 1,
5-hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-
Non-conjugated dienes such as 2-norbornene and (meth) acrylic acid esters such as methyl methacrylate and methyl acrylate are included. The amount of the substituted hydroxystyrene-based monomer represented by the general formula (3) and the other monomer that can be used together with the styrene-based monomer represented by the general formula (4) is the polymer of the present invention. The amount is preferably 45 mol% or less, and particularly preferably 0.1 to 30 mol% in all the monomers, although it varies depending on the use and is not uniquely determined. Most preferably, it is 0.5 to 10 mol%.

In the method for producing the syndiotactic substituted hydroxystyrene copolymer according to the present invention, the compounds represented by the general formula (5) and the general formula (6) of the above-mentioned component (A) as the catalyst component. And at least one transition metal compound selected from the group (a)
What contains the reaction product with at least 1 type of cocatalyst selected from (d) as a main catalyst component is used. (A) a transition metal compound of the component, the above general formula (5)
And / or at least one compound selected from the group consisting of transition metal compounds represented by the general formula (6) MR ² R ³ _a X _3-a (5) MR ² R ³ _b X _2-b (6) Is.

R ^{2 in the} above general formula (5) or (6)
Represents a π ligand. Specifically, cyclopentadienyl group, substituted cyclopentadienyl group (specifically, methylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, etc.), indenyl Group, substituted indenyl group, fluorenyl group, or substituted fluorenyl group. R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (specifically, methyl group, ethyl group, propyl group, butyl group, amyl group, isoamyl group, isobutyl group, octyl group, 2-ethylhexyl group, etc.) An aryl group having 6 to 20 carbon atoms,
Alkylaryl group, arylalkyl group (specifically, phenyl group, tolyl group, xylyl group, benzyl group, etc.), acyloxy group having 1 to 20 carbon atoms (specifically, heptadecylcarbonyloxy group, etc.), carbon number 1 ~ 20
Alkoxy group (specifically, methoxy group, ethoxy group,
Propoxy group, butoxy group, amyloxy group, hexyloxy group, 2-ethylhexyloxy group, etc.), thioalkoxy group having 1 to 20 carbon atoms (specifically, thiomethoxy group, etc.), thioaryloxy group having 6 to 20 carbon atoms (Specifically, a thiophenoxy group etc.) is shown.

M represents a transition metal element belonging to Group 4 of the periodic table, specifically a transition metal selected from the group consisting of titanium (Ti), zirconium (Zr) or hafnium (Hf). X represents a halogen atom (specifically chlorine, bromine, iodine, fluorine). R ^{3 s} in the general formulas (5) and (6) may be the same or different. Further, a is an integer of 0 to 3, and b is 0 to 2
Indicates an integer. 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 (8).

TiR ³ R ⁴ _a X _3-a (8) (In the formula, R ³ represents a π ligand. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon atom having 6 to 20 carbon atoms, respectively. Aryl group, alkylaryl group, arylalkyl group,
It shows an acyloxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, and a thioaryloxy group having 6 to 20 carbon atoms. M represents a transition metal element of Group 4 of the periodic table, and X represents a halogen atom. R ⁴
May be the same or different.
Further, each a is an integer of 0 to 3, and each b is an integer of 0 to 2. )

Specific examples of the titanium compound represented by the general formula (8) include cyclopentadienyltrimethyl 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
-Tetramethylcyclopentadienyl trimethyl titanium; pentamethyl cyclopentadienyl trimethyl titanium; pentamethyl cyclopentadienyl triethyl titanium;

Pentamethylcyclopentadienyltripropyltitanium; pentamethylcyclopentadienyltributyltitanium; cyclopentadienylmethyltitanium dichloride; cyclopentadienylethyltitanium dichloride; pentamethylcyclopentadienylmethyltitanium dichloride; pentamethyl Cyclopentadienylethyl titanium dichloride; Cyclopentadienyl dimethyl titanium monochloride; Cyclopentadienyl diethyl titanium monochloride; Cyclopentadienyl titanium trimethoxide; Cyclopentadienyl titanium triethoxide; Cyclopentadienyl titanium trichloride Propoxide; cyclopentadienyl titanium triphenoxide; pentamethyl cyclopentadienyl titanium trimethoxide; pentamethyl cyclopentadienyl Titanium triethoxide; pentamethylcyclopentadienyltitanium tripropoxide; pentamethylcyclopentadienyltitanium tributoxide; pentamethylcyclopentadienyltitanium tri phenoxide;

Cyclopentadienyl titanium trichloride; Pentamethyl cyclopentadienyl titanium trichloride; Cyclopentadienyl methoxy titanium dichloride; Cyclopentadienyl dimethoxy titanium chloride;
Pentamethylcyclopentadienylmethoxytitanium dichloride; Cyclopentadienyltribenzyl titanium; Pentamethylcyclopentadienylmethyldiethoxytitanium; Indenyl titanium trichloride; Indenyl titanium trimethoxide; Indenyl titanium triethoxide; Nyltrimethyl titanium; indenyl tribenzyl titanium; pentamethylcyclopentadienyl titanium trithiomethoxide; pentamethylcyclopentadienyl titanium trithiophenoxide and the like.

Among these transition metal compounds, cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride and indenyl titanium trichloride are particularly preferable in view of availability, cost and polymerization activity. It is suitable. Further, pentamethylcyclopentadienyl titanium trichloride and indenyl titanium trichloride are most preferable in terms of stereoregularity of the obtained polymer. On the other hand, the above titanium compounds and the like,
You may use what formed the complex with ester, ether, etc. In the polymerization catalyst used in the present invention,
The transition metal compound of the component (A) may be used alone or in combination of two or more.

The catalyst component in the present invention is the transition metal compound which is the above-mentioned component (A) and the co-catalyst (B).
The reaction product with the components is contained as a main catalyst component, but the component (B) which is a promoter uses at least one promoter selected from the following (a) to (d). (A) modified methylaluminoxane obtained by reacting tetraalkyldialuminoxane and / or polyalkylaluminoxane having an alkyl group having 2 or more carbon atoms with trimethylaluminum, (b) a cation by reacting with the transition metal compound Compounds capable of forming a polar transition metal compound (c) Lewis acid compounds capable of forming a cationic transition metal compound by reacting with the above transition metal compound (d) Organometallic compounds of metals of group 1, 2 and 13 of the periodic table

First, the modified methylaluminoxane (a) is preferably a modified methylaluminoxane obtained by reacting tetraalkyldialuminoxane and / or polyalkylaluminoxane having an alkyl group having 2 or more carbon atoms with trimethylaluminum. is there. Here, 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 (9).

[0042]

[Chemical 13] (Here, R ⁶ represents an alkyl group having 2 or more carbon atoms.) Here, as the tetraalkyldialuminoxane which is the precursor of the modified methylaluminoxane used in the present invention, R ⁶ in the general formula (9) is An alkyl group having 2 or more carbon atoms is used. Preferably, a linear, branched, or cyclic alkyl group having 2 to 20 carbon atoms can be used. Examples of suitable alkyl groups include n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, cyclohexyl and the like.

On the other hand, the polyalkylaluminoxane having an alkyl group having 2 or more carbon atoms, which is another raw material of the modified methylaluminoxane used in the present invention, has the general formula (1)
It is represented by 0).

[Chemical 14] (Here, R ⁷ represents an alkyl group having 2 or more carbon atoms. N
Is an integer of 1 to 50. Here, as the tetraalkyldialuminoxane which is the precursor of the modified methylaluminoxane used in the present invention, an alkyl group in which R ⁷ in the general formula (10) has 2 or more carbon atoms is used. Preferably, a linear, branched, or cyclic alkyl group having 2 to 20 carbon atoms can be used. Examples of suitable alkyl groups include n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, cyclohexyl and the like.

Tetraalkyldialuminoxane and / or polyalkylaluminoxane having an alkyl group having 2 or more carbon atoms represented by the above general formulas (9) and / or (10) was added at any time with trimethylaluminum. By reacting in the presence of water, the modified methylaluminoxane used in the present invention can be obtained. The content of the alkane having 2 or more carbon atoms, which represents the modified amount of the modified methylaluminoxane obtained by analyzing methane produced by hydrolyzing the modified methylaluminoxane and the alkane having 2 or more carbon atoms, is in the range of 5 to 80 mol%. It is preferable to be within. 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. More preferably 10-6
It is 5 mol%. Most preferably, it is 15 to 50 mol%.

The ionic compound capable of forming a cationic transition metal compound by reacting with the transition metal compound represented by the general formula (5) and / or the general formula (6) in (b) is a non-coordinating property. Examples include anions and cations. Examples of the non-coordinating anion include tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra (xyyl) borate, triphenylpentafluorophenylborate, tris (pentafluorophenyl) phenylborate and the like can be mentioned.

Among these non-coordinating anions, tetrakis (pentafluorophenyl) borate is particularly preferable. Specific examples include, for example, triphenylcarbenium tetrakis (pentafluorophenyl) borate; 4,4 ′, 4 ″ -tri (methoxyphenyl) carbenium tetrakis (pentafluorophenyl) borate; tri (toluyl) carbenium tetrakis (penta). Fluorophenyl) borate; 4,4 ', 4 "-tri (chlorophenyl) carbenium tetrakis (pentafluorophenyl) borate; Triphenylsilyltetrakis (pentafluorophenyl) borate; Trimethoxysilyltetrakis (pentafluorophenyl) borate; Tri (Thioisopropyl) silyltetrakis (pentafluorophenyl) borate; Trimethylsilyltetrakis (pentafluorophenyl) borate; 4,
4 ', 4 "-tri (methoxyphenyl) silyltetrakis (pentafluorophenyl) borate; tri (toluyl) silyltetrakis (pentafluorophenyl) borate; 4,4', 4" -tri (chlorophenyl) silyltetrakis (pentafluoro Phenyl) borate and the like.

Examples of cations include a) carbonium cations, b) oxonium cations, c) ammonium cations, d) phosphonium cations, and e) transition metal-containing ferrocenium cations. Specific examples of the a) carbonium cation include tri-substituted carbonium cations such as triphenyl carbonium cation and tri-substituted phenyl carbonium cation. Specific examples of the tri-substituted phenyl carbonium cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation.

B) Specific examples of oxonium cations
Is a hydroxonium cation OH ⁵⁺, Methyl oxoni
Um cation CH₃OH⁴⁺Such as alkyloxonium
Cation, dimethyloxonium cation (CH₃)₂O
H⁺Dialkyloxonium cations, such as trimethyl
Ruoxonium cation (CH₃)₃O⁺, Triethyl
Xonium cation (C₂H_Five)₃O⁺Such as trialkyl
Examples include oxonium cations.

C) Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation and tributylammonium cation, N, N-diethylanilinium cation, N, N-2. N, N-dialkylanilinium cations such as 4,4,6-pentamethylanilinium cation, diamine
Examples thereof include dialkylammonium cations such as (i-propyl) ammonium cation and dicyclohexylammonium cation. Specific examples of d) phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

As the ionic compound (b), any of the non-coordinating anions and cations exemplified above may be arbitrarily selected and combined. Among the above, particularly triphenylcarbonium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetra (pentafluorophenyl) borate, etc. Ionic compounds can be more preferably used.

Specific examples of the Lewis acid compound capable of forming a cationic transition metal compound by reacting with the transition metal compound represented by the above general formula (5) and / or general formula (6) of (c) are tris. Examples thereof include (pentafluorophenyl) boron, tris (monofluorophenyl) boron, tris (difluorophenyl) boron and triphenylboron.

The organometallic compounds of the metals of the groups 1, 2 and 13 of the periodic table in (d) include not only the organometallic compounds in a narrow sense but also the organometallic halogen compounds of the metals of the elements of the groups 1, 2 and 13 of the periodic table. Also included are hydrogenated organometallic compounds. Here, the elemental metals of the periodic table 1 include: Li and Na, the elemental metals of the periodic table 2 include: Mg, Be, and the elemental metals of the periodic table 13 include: Al and B. Among these, preferable elemental metals include Li, Mg,
Al, particularly preferably Al.

Examples of the organometallic compound (d) include methyllithium, butyllithium, phenyllithium, dibutylmagnesium, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, etc., and trialkylaluminum. Is preferred.
Examples of the organometallic halogen compound (d) include ethyl magnesium chloride, butyl magnesium chloride, dimethyl aluminum chloride, diethyl aluminum chloride, sesquiethyl aluminum chloride, ethyl aluminum dichloride and the like.

Examples of the hydrogenated organometallic compound (d) include diethylaluminum hydride and sesquiethylaluminum hydride. In the present invention, the promoters (a) to (d) may be used alone or in combination. Preferred cocatalysts are (a) alone, (c) alone, (a) and (d), (b) and (d), and (c) and (d) in combination. Particularly preferred is (a) alone.

The catalyst for producing the syndiotactic substituted hydroxystyrene copolymer used in the present invention contains the above-mentioned components (A) and (B) as the main components of the catalyst. Other catalyst components may be added within a range that does not impair the effect of. The blending ratio of the component (A) and the component (B) in the catalyst of the present invention varies depending on the type of compound and various polymerization conditions and is not uniquely determined, but is usually determined independently of the component (B). The molar ratio of each compound (a), (b), (c), (d) to the transition metal compound of the component (A) is preferably within the following range.

The molar ratio of aluminum / (A) transition metal compound in the organoaluminum oxy compound (a) is usually 1
~ 1,000,000, preferably 10-5, 000, more preferably
30 to 5,000. The molar ratio of (b) ionic compound / (A) transition metal compound is usually 0.01 to 100, preferably 0.1 to 10. The molar ratio of (c) Lewis acidic compound / (A) transition metal compound is usually 0.01 to 100, preferably 0.1 to 10.
When a Lewis acid compound is used as the cocatalyst component, it is preferable to use an organometallic compound of a metal of group 1, 2 and 13 of the periodic table together. When the (d) organometallic compound is used, the molar ratio of (d) organometallic compound / (A) transition metal compound is usually 0.1.
It is from about 10,000, preferably from 1 to 1,000. If it is out of the above range, the polymerization activity is lowered, which is not preferable.

The mixing ratio of the component (A) to the substituted hydroxystyrene monomer and the styrene monomer in the catalyst of the present invention varies depending on the kind of the compound and various polymerization conditions and is not uniquely determined. However, it is desirable that the molar ratio of the transition metal compound of the component (A) to the substituted hydroxystyrene-based monomer and the styrene-based monomer is usually within the following range. That is, usually 0.1 to 10,000,000, preferably 1 to 5,
It is, 000,000, more preferably 10 to 500,000. (A)
If the blending ratio of the component to the substituted hydroxystyrene-based monomer and the styrene-based monomer is less than 0.1, the polymerization rate becomes slow and the productivity of the polymer becomes low, which is not preferable. Further, the compounding ratio of the component (A) to the substituted hydroxystyrene monomer and the styrene monomer is 10,00.
When it is larger than 000, the molecular weight of the produced polymer is small, and the strength of the syndiotactic substituted hydroxystyrene-based copolymer is lowered, which is not preferable.

In the present invention, the metal hydride compound is further used in combination with the above-mentioned organometallic compounds of the metals of the groups 1, 2, and 13 of the periodic table, organometallic halogen compounds, hydrogenated organometallic compounds, and the like to prepare styrene. The system monomer may be polymerized. Here, as the metal hydride compound, for example, N
Examples thereof include aH, LiH, CaH ₂ , LiAlH ₄ , NaBH ₄ . Examples of the organometallic compounds, organometallic halogen compounds and hydrogenated organometallic compounds of the main element metals of the metals of the groups 1, 2 and 13 of the periodic table include those mentioned above.

In the present invention, the transition metal compound may be used alone, or at least one cocatalyst selected from the above (a) to (d) may be supported 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, and 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 ⁴ / g.
The above porous fine particles are preferable, and they can be used after heat treatment at 100 to 800 ° C., for example.

The organic polymer compound is preferably one having 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.
Examples include olefin homopolymers, α-olefin copolymers, polymers having units such as acrylic acid, methacrylic acid, vinyl chloride, vinyl alcohol, styrene and divinylbenzene, and chemical modifications thereof.

As these organic polymer compounds, spherical fine particles having an average particle diameter of 5 to 250 μm are used. By supporting the transition metal compound and the cocatalyst on a simple substance, it is possible to prevent the catalyst from being contaminated due to adhesion to the polymerization reactor. In the method for producing a syndiotactic substituted hydroxystyrene-based copolymer of the present invention, by using the above-mentioned monomer, transition metal compound, co-catalyst and the like, polymerization is performed by the following production method to obtain a high syndiotactic A syndiotactic substituted hydroxystyrene-based copolymer having a tic structure can be obtained.

<Production Method of Syndiotactic Substituted Hydroxystyrene Copolymer> In the production method of the present invention, the transition metal compound of the above component (A) and the above (a) to
Existence of component (B), which is at least one cocatalyst selected from component (d), and aromatic hydrocarbon and / or halogenated aromatic hydrocarbon having a dielectric constant in the range of 2.0 to 10.0. Below, the substituted hydroxystyrene-based monomer represented by the general formula (3) and the styrene-based monomer represented by the general formula (4) are polymerized. In the present invention, the substituted hydroxystyrene-based monomer represented by the general formula (3) and the general formula (4)
The method of adding the styrene-based monomer represented by and the respective catalyst components and the monomer in the case of copolymerizing the monomer copolymerizable therewith are not particularly limited. The following methods (I) to (VI) using a metal compound and at least one type of cocatalyst selected from the above (a) to (d) are applicable.

In the following description, the component (A) represents a transition metal compound and the component (B) represents at least one cocatalyst selected from the above (a) to (d). After the components (I) and (B), the substituted hydroxystyrene-based monomer represented by the general formula (1) and the monomer component such as the styrene-based monomer represented by the general formula (2) are contacted with each other in advance. Further, polymerization is carried out by contacting with the component (A). (II) After the components (A) and (B) are contacted in advance, the substituted hydroxystyrene-based monomer represented by the general formula (3) and the styrene-based monomer represented by the general formula (4) are further added. Polymerization is carried out by contact with a monomer component such as.

The component (III) (A), the substituted hydroxystyrene monomer represented by the general formula (3) and the monomer component such as the styrene monomer represented by the general formula (4) are previously prepared. After the contact, the component (B) is further contacted for polymerization. (IV) The component (A) and the component (B) are mixed, brought into contact with a carrier, and the generated supported catalyst is separated to obtain a supported catalyst and a substituted hydroxystyrene-based monomer represented by the general formula (3). Polymerization is carried out by contacting with a monomer component such as a styrene-based monomer represented by the general formula (4).

After bringing the components (V) and (A) into contact with the carrier,
Further, it is brought into contact with the component (B), the produced supported catalyst is separated, and the supported catalyst, the substituted hydroxystyrene-based monomer represented by the general formula (3) and the styrene-based monomer represented by the general formula (4) are separated. Polymerization is carried out by contacting the monomer components such as the body. After bringing the components (VI) and (B) into contact with the carrier,
The produced supported catalyst is separated from the components, and the supported catalyst, the substituted hydroxystyrene-based monomer represented by the general formula (3) and the styrene-based monomer represented by the general formula (4) are mixed. Polymerization is carried out by contacting the monomer components.

Here, in the catalytic reaction product, the above-mentioned transition metal compound and co-catalyst may be combined in any order. These catalyst components are suitably mixed in an inert atmosphere such as nitrogen or argon. The components are mixed at a suitable temperature, preferably -50 to 150 ° C, more preferably -40 to 100 ° C. Particularly preferably, the catalyst reaction product can be easily obtained only by mixing at -30 to 80 ° C. Among the above methods (I) to (VI),
From the viewpoint of improving the initiator efficiency and the polymerization activity, and further narrowing the molecular weight distribution of the obtained polymer, (I),
The methods (II) and (IV) to (VI) are preferable. More preferred are the methods (I) and (II). According to this method, a syndiotactic substituted hydroxystyrene polymer having a molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn), of 15 or less can be obtained with high efficiency.

The component (A) and the component (B) can be used either in the form of a solution or a slurry, but the form of a solution is preferable in order to obtain higher polymerization activity. The solvent used to prepare the solution or slurry is butane, pentane, hexane, heptane, octane, cyclohexane, an aliphatic hydrocarbon solvent such as mineral oil, an aromatic hydrocarbon solvent such as benzene, toluene, xylene, or chloroform. , Methylene chloride, dichloroethane, etc., halogenated aliphatic hydrocarbon solvent, 2-fluorotoluene, 2-chlorotoluene, fluorobenzene, 2,6-dichlorotoluene, 1,2,4-trichlorobenzene, chlorobenzene, etc. It is a hydrogen solvent. Preferred are aromatic hydrocarbon solvents and halogenated aromatic hydrocarbons.

Particularly preferred are aromatic hydrocarbons and / or halogenated aromatic hydrocarbons having a dielectric constant in the range of 2.0 to 10.0 used as a polymerization solvent in the production method of the present invention. Specific examples include toluene, xylene,
1,2,4-trichlorobenzene, 2-fluorotoluene, 2-chlorotoluene, fluorobenzene, chlorobenzene, 2,6-dichlorotoluene and the like can be mentioned.
Further, two or more kinds of solvents may be mixed and used.

From the viewpoint of producing a substituted hydroxystyrene copolymer having a high syndiotactic structure, which is a feature of the present invention, the polymerization temperature condition is usually in the range of -50 to 150 ° C. . Preferably -40 to 1
It is carried out at a temperature of 00 ° C, more preferably -30 to 80 ° C. When the polymerization temperature is lower than -50 ° C, syndiotacticity is lowered, which is not preferable, and when the polymerization temperature is higher than 150 ° C, the molecular weight is lowered, which is not preferable.

Typical polymerization time is 30 seconds to 36 hours, preferably 1 minute to 20 hours, more preferably 5 minutes to 10 hours.
It's time. The optimum time required to produce the desired polymer will vary depending on the temperature used, the solvent and other polymerization conditions. The polymerization can be carried out 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.

In the production method of the present invention, the solvent used for the polymerization has a dielectric constant of 2 from the viewpoint of producing the substituted hydroxystyrene-type polycopolymer having a high syndiotactic structure, which is a feature of the present invention. It is essential to use aromatic hydrocarbons and / or halogenated aromatic hydrocarbons and mixtures thereof which are in the range from 0 to 10.0.
Specific examples thereof include toluene, xylene, tetralin, ethylbenzene, 2-fluorotoluene, 2-chlorotoluene, fluorobenzene, chlorobenzene, 2,6-dichlorotoluene and 1,2,4-trichlorobenzene. Among these aromatic hydrocarbons and / or halogenated aromatic hydrocarbons, methylstyrene-based monomers can be introduced with high efficiency, and from the viewpoint that production can be performed under a wide range of polymerization temperature conditions, toluene, ethylbenzene, 2- They are fluorotoluene, 2-chlorotoluene, fluorobenzene and chlorobenzene. Particularly preferably, toluene, 2-fluorotoluene, 2-chlorotoluene and chlorobenzene can be mentioned.

When the dielectric constant of the solvent is smaller than 2.0,
It is not preferable because the polymerization activity of the monomer component is lowered during the polymerization. Further, when the dielectric constant of the solvent is larger than 10, the polymerization activity is remarkably lowered, and it becomes difficult to efficiently obtain the copolymer P, which is not preferable. The polymerization solvent is used in an amount suitable to give a structural concentration of 0.1 to 98% by weight. Particularly preferred is the use of a suitable amount of solvent to give a structural concentration of 0.3 to 70% by weight. When the structural concentration is lower than 0.1% by weight, the polymerization rate becomes slow, the productivity of the polymer becomes low, and the recovery cost of the polymer from the polymerization reaction product becomes high, which is not preferable. Also, 9
When the structural concentration is higher than 9% by weight, the viscosity of the polymerization reaction product becomes remarkably high as the polymerization conversion rate becomes high, and thus there is a drawback that the construction cost of the manufacturing facility becomes high.

Further, anisole, diphenyl ether,
The polymerization reaction may be carried out by adding a small amount of polar compounds such as ethers such as ethyl ether, diglyme, tetrahydrofuran, dioxane, amines such as triethylamine, tetramethylethylenediamine, etc. within a range that does not impair the effects of the present invention. The termination of the polymerization reaction is usually performed by adding a polymerization terminator to the polymerization system at the time when a predetermined conversion rate is reached. As the polymerization terminator, for example,
Methanol, ethanol, propanol, butanol,
Alcohols such as isobutanol are used, which may contain acids such as hydrochloric acid. The method of recovering the polymer after the termination of the polymerization reaction is not particularly limited, and for example, a steam stripping method, precipitation with a poor solvent, or the like may be used. 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, allenes such as 1,2-butadiene, cyclic dienes such as cyclooctadiene, and hydrogen are preferably used.

The present invention is also represented by the general formula (7).
Hydroxystyrene-based structural unit (hereinafter structural unit (II
Abbreviated as I)) 1 to 55 mol% represented by the general formula (2)
Styrene-based structural unit (II) 45-99 mol%
Of the structural unit (III) and the structural unit (I
C of the phenyl group of I)₁Each tacticity of carbon
¹³30% or more by racemic pentad by C-NMR
A syndiotactic hydroxysty characterized by
A ren-based copolymer (hereinafter abbreviated as copolymer Q)
It The copolymer Q referred to in the present invention means the structural unit (III)
C of the phenyl group of the structural unit (II)₁Carbon Tactite
Each is 30% or more of racemic pentad
Is. It is preferably 75% or more in racemic diad
More preferably 85% or more, or racemic penta
50% or more, more preferably 70% or more,
It preferably has a syndiotacticity of 85% or more.
To do.

In the copolymer Q having a high syndiotactic structure having the structural unit (III) and the structural unit (II) produced by the production method of the present invention, the repeating units bonded are of one type. 2 not only between structural units
The syndiotactic structure (co-syndiotactic structure) is present between the two or more types of structural units. Further, the copolymer composed of these structural units,
There are various embodiments such as block copolymerization, random copolymerization and alternating copolymerization. The hydroxystyrene-based copolymer having a highly syndiotactic structure composed of the structural unit (III) and the structural unit (II) in the present invention does not necessarily have to be a polymer having a single steric structure. .

As long as the syndiotacticity is within the above range, a mixture with a structural unit having an isotactic or atactic structure or a structural unit having an atactic structure may be incorporated in the polymer chain. The composition of the structural unit (III) and the structural unit (II) varies depending on the use of the polymer of the present invention and is not uniquely determined, but the ratio of the structural unit (II) to the total structural units is 45 to 45%. It is 99 mol%. It is preferably 46 mol% or more and 98 mol% or less. It is more preferably 47 mol% or more and 97 mol% or less. Most preferably, it is 50 mol% or more and 94 mol% or less.

When the proportion of the structural unit (II) is 45 mol% or less, the effect of improving the moldability and heat resistance of the copolymer Q becomes small, which is not preferable. On the other hand, structural unit (II)
If the ratio exceeds 99 mol%, the adhesiveness and coating strength of the syndiotactic hydroxystyrene-based copolymer will decrease, which is not preferable. Therefore, in the case where the ratio of the structural unit (II) is in the range of more than 45 mol% and 99 mol% or less, heterogeneous structures differing in composition from each other are often used, but a high specific ratio is obtained. By exhibiting crystallinity, it has excellent heat resistance, and also has excellent adhesiveness and coating film strength.
This is the most preferable composition range of the present invention.

Further, the molecular weight of the copolymer Q of the present invention is
The number average molecular weight is 600 or more, preferably 1000 to 20.
It is preferably in the range of 0,000, more preferably 2,000 to 1,500,000, and particularly preferably 5,000 to 1,000,000. 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 weight average molecular weight (Mw)
Molecular weight distribution (Mw / which is the ratio of the number average molecular weight (Mn) to
The preferred range of Mn) is 15 or less, preferably 10 or less, more preferably 3 or less, particularly preferably 2 or less, and most preferably 1.5 or less. If the molecular weight distribution is too wide, there is a problem of deterioration of physical properties, which is not preferable.

The copolymer Q of the present invention as described above is prepared by bringing the copolymer P described in the preceding section into contact with an acid or a base in the presence of an organic solvent to carry out a deprotecting group reaction to remove a hydroxyl group. It is obtained by forming. Examples of the acid used in the present invention include hydrogen halides such as hydrogen chloride, hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, or mineral acids such as phosphoric acid, trichloroacetic acid, trifluoroacetic acid, oxalic acid,
Carboxylic acids such as acetic acid or malonic acid, or 4-
Examples thereof include acids such as toluenesulfonic acid and organic sulfonic acids such as trifluoromethylsulfuric acid. Of these, tetrabutylammonium fluoride, hydrogen chloride,
Hydrochloric acid, sulfuric acid, trifluoroacetic acid, 4-toluenesulfonic acid, or trifluoromethyl sulfuric acid are preferred.

Further, as the base used in the present invention,
For example, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium 4-toluenesulphonate, tetrapropylammonium fluoride, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropyl Examples thereof include ammonium salts such as ammonium iodide and tetrapropylammonium 4-toluenesulfonate, and alkali hydroxides such as sodium hydroxide and potassium hydroxide. The amount of the acid or base used is usually 0.0000 with respect to the number of moles of repeating units of the copolymer derived from the substituted styrenic monomer represented by the general formula (2).
It is used in an amount of 1 time mol or more, but preferably 0.00
It is in the range of 001 to 1000 times by mole, and more preferably in the range of 0.0001 to 100 times by mole.

As the organic solvent, any solvent can be used so long as at least one of the syndiotactic substituted hydroxystyrene copolymer and the syndiotactic hydroxystyrene copolymer produced by deprotection is dissolved. But usually n-hexane,
Aliphatic or alicyclic hydrocarbons such as n-pentane, n-heptane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, ethylbenzene and cumene; aliphatic such as dichloromethane, chloroform, chlorobenzene and dichlorobenzene, or Aromatic halogen compounds; alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, t-butanol, amyl alcohol, cyclohexanol, ethylene glycol; diethyl ether, diphenyl ether,
Ethers such as tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether; ketones such as acetone, ethyl methyl ketone, 2-pentanone, 2-heptanone, acetophenone; nitriles such as acetonitrile and propionitrile And esters such as ethyl acetate, ethyl propionate and ethyl lactate.

Alternatively, carboxylic acids such as acetic acid used as a protic acid may be used. These organic solvents may be used alone or in combination of two or more. The amount of these solvents to be used is not uniform depending on the type of solvent used, but is usually in the range of 0.005% by weight to 50% by weight as the concentration of the syndiotactic substituted hydroxystyrene copolymer, and preferably , 0.01% to 30% by weight. Particularly preferably, it is 0.1% by weight to 25% by weight.

The method for carrying out the deprotection group reaction in the method of the present invention is not particularly limited, and the syndiotactic substituted hydroxystyrene copolymer is effectively mixed with an acid or base and an organic solvent. Any method may be used as long as they are brought into contact with each other, and any of a batch type, a semi-batch type and a continuous flow type may be used. The temperature and time during the deprotection reaction vary depending on the concentration and molecular weight of the syndiotactic substituted hydroxystyrene-based copolymer, the type and amount of acid or base, the type of organic solvent and the like, and are not uniform.

However, the temperature of the deprotection reaction is usually in the range of -20 ° C to 200 ° C, and preferably,
It is in the range of 0 ° C to 150 ° C. Particularly preferably 15
It is in the range of ℃ to 100 ℃. More preferably 50
It is in the range of ℃ to 100 ℃. The reaction time of the deprotection reaction is usually 72 hours or less, preferably 0.01
To 48 hours. Particularly preferably 0.05
To 24 hours is also in range. Further, depending on the case, it can be carried out under reduced pressure, normal pressure or increased pressure. Further, this deprotection group reaction can be carried out in an inert gas atmosphere or in the presence of molecular oxygen such as air.

The obtained syndiotactic hydroxystyrene copolymer is precipitated as a solid during the deprotection reaction when an organic solvent having low solubility such as hydrocarbon is used in the deprotection reaction. Therefore, it can be isolated by a normal separation operation such as filtration or decantation, or, when an organic solvent having a high solubility such as alcohol is used, it is uniformly dissolved, and therefore extraction,
After performing ordinary purification operations such as stripping and ion exchange, or without performing any purification operation, a method of precipitating and separating using a suitable poor solvent, or a method of using a drying operation such as a desolvation method It can be isolated by a conventional method such as.

[0086]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. Each evaluation and measurement method used in the examples of the present invention will be described.

1) Catalytic activity 1 mmol of catalytic metal The amount of polymer produced (gram) per hour was expressed. 2) Polymer molecular weight and molecular weight distribution The molecular weight and molecular weight distribution of the syndiotactic hydroxystyrene copolymer are measured by GPC (manufactured by Tosoh Corporation, HLC-
8120 GPC), solvent: tetrahydrofuran (THF), flow rate: 1.0 ml / min, column temperature:
It was carried out at 40 ° C. The molecular weight of the copolymer was measured as a polystyrene-equivalent molecular weight using a calibration curve based on monodisperse polystyrene.

3)% Syndiotacticity It was determined by measuring pentad (racemic pentad) by ¹³ C-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL Ltd. Tetrachloroethane-d ₂ and methanol-d ₄ were used as the solvent. Resonance lines of NMR measurement solvents tetrachloroethane-d ₂ and methanol-d ₄ were used as internal standards.

4) Composition of polymer Determined by ³ H-NMR analysis using JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL Ltd. Tetrachloroethane-d ₂ and methanol-d ₄ were used as the solvent. N
The resonance lines of tetrachloroethane-d ₂ and methanol-d ₄ which are MR measurement solvents were used as internal standards. 5) Glass transition temperature (Tg), melting temperature (Tm) and crystallization temperature (Tc) SSC / 5200 type DSC manufactured by Seiko Instruments Inc. was used to measure the thermal characteristics of the polymer, and nitrogen was used. The measurement was performed at a temperature rising rate of 10 ° C./min under an air flow.

6) The transparent polymer solution was cast on a glass substrate and evaporated to form a film. The transparency of the cast film at that time was visually confirmed. 7) Coating strength and adhesiveness The polymer cast film on the glass substrate was cross-cut with a new cutter blade at 1 mm intervals, and the cut cast film was visually observed for cracks and peeling.

Reference Example 1 (modified methylaluminoxane-1
Preparation) Triisobutylaluminum (TIBAL) as a 25% toluene solution was charged into a 300 ml flask under a nitrogen atmosphere. With vigorous stirring at a temperature of 0 to 15 ° C, water was added dropwise over 3 hours to prepare an isobutylaluminoxane (IBAO) solution. After the addition of water is completed, I
The clear colorless solution of BAO was heated to 70-80 ° C to complete the reaction and remove the dissolved isobutane. Trimethylaluminum (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 give modified methylaluminoxane-1.
Of toluene solution was obtained. Modified methylaluminoxane-1
As a result of analyzing the toluene solution, its aluminum content is
5.7 wt%, hydrolyzed gas composition is isobutane 29%,
It was 70% 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. A toluene solution of 26.2 ml of toluene and the modified methylaluminoxane-1 obtained in Reference Example 1 (aluminum concentration:
5.7 wt%) 10.8 ml was charged into a glass three-necked flask and aged at 0 ° C for 10 minutes. Indenyl titanium trichloride 0.02 mmol was charged here, and then a toluene solution of styrene 0.02 mmol was charged to prepare 1
It was aged for 0 minutes. Finally, 4-t-butyldimethylsilyloxystyrene 1.0 mmol, styrene 19.0
A toluene solution containing 0.1 mmol of triisobutylaluminum and 0.1 mmol of triisobutylaluminum was charged, and a polymerization reaction was performed at 0 ° C. for 5 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 is redissolved in toluene and filtered,
The solution was poured again into a large amount of methanol to precipitate a polymer. After washing, filtering, drying, and weighing, copolymer P-1
0.457 g (yield: 20.6 wt%) was obtained. Polymerization activity is 275 (g
Polymer / mmolTi · hr).

Weight average molecular weight (Mw) of the obtained polymer.
Was 65,400, the number average molecular weight (Mn) was 30,600, and the molecular weight distribution (Mw / Mn) was 2.14. The composition of the copolymer-1 obtained by ¹ H-NMR measurement was 4-t-butyldimethylsilyloxystyrene: 4.2 mol% and styrene: 95.8%. The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. As a result of DSC measurement, Tg: 97 ° C, Tc: 188 ° C and T
m: 234 ° C. The obtained polymer cast film was a transparent film without clouding, and even when a cross cut test was performed, no large cracks or peeling of the film were observed, but slight peeling occurred along the cut line. Was observed.

Comparative Example 1 A three-necked glass 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. Toluene 30.0 ml and normal unmodified methylaluminoxane (PMAO- manufactured by Tosoh Finechem Co., Ltd.)
Toluene solution of S) (aluminum concentration: 8.9 wt%)
Add 6.9 ml to a glass three-necked flask and keep it for 10 minutes.
Aged at ℃. Charge 0.02 mmol of indenyl titanium trichloride, and then add styrene.
A 0.02 mmol toluene solution was charged and the mixture was aged for 10 minutes. Finally, a toluene solution of 1.0 mmol of 4-t-butyldimethylsilyloxystyrene, 19.0 mmol of styrene and 0.1 mmol of triisobutylaluminum was charged and a polymerization reaction was carried out at 0 ° C for 5 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, filtered, and then the solution was poured into a large amount of methanol again to precipitate the polymer. After washing, filtering, drying and weighing, 0.127 g of copolymer-R1 (yield:
5.7 wt%) was obtained. Polymerization activity is 76.5 (g polymer /
mmol Ti · hr).

Weight average molecular weight (Mw) of the obtained polymer.
Was 53,200, the number average molecular weight (Mn) was 23,000, and the molecular weight distribution (Mw / Mn) was 2.31. The composition of the copolymer-R1 determined by ¹ H-NMR measurement was 4-t-butyldimethylsilyloxystyrene: 7.6 mol% and styrene: 92.4 mol%. The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentads for styrene units, but was atactic structure for 4-t-butyldimethylsilyloxystyrene units. As a result of DSC measurement, Tg: 96 ° C. and Tm: 263 ° C. The resulting polymer cast film was a hazy, semi-transparent film. Further, when a cross cut test was performed, cracking and peeling of the film were observed over the entire cut.

Example 2 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. 26.2 ml of toluene and 10.8 ml of a toluene solution of the 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 0.02 mmol was charged, and then a toluene solution of styrene 0.02 mmol was charged, and aging was performed for 10 minutes. Polymerization activity is 368
(G polymer / mmol Ti · hr). Finally, 4-t
-Butyldimethylsilyloxystyrene 4.0 mmol, styrene 16.0 mmol and triisobutylaluminum 0.1 m
A mol toluene solution was charged and the polymerization reaction was carried out at 0 ° C for 5 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. Redissolving the obtained polymer in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. It was washed, filtered, dried and weighed to obtain 0.611 g (yield: 23.5 wt%) of copolymer P-2.

Weight average molecular weight (Mw) of the obtained polymer.
Was 70,500, the number average molecular weight (Mn) was 38,900, and the molecular weight distribution (Mw / Mn) was 1.81. The composition of copolymer-2 determined by ¹ H-NMR measurement was 4-t-butyldimethylsilyloxystyrene: 20.2 mol% and styrene: 79.8 mol%. The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. As a result of DSC measurement, it was Tg: 99 ° C. The cast film of the obtained polymer was a transparent film without clouding, and cracking or peeling of the film was not observed even when a cross cut test was performed.

Example 3 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. 26.2 ml of toluene and 10.8 ml of a toluene solution of the 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 indenyl titanium trichloride was charged therein, and then a toluene solution of 0.02 mmol of styrene was charged therein, followed by aging for 10 minutes. Finally, 4-
t-butyldimethylsilyloxystyrene 8.0 mmol,
Styrene 12.0 mmol and triisobutylaluminum 0.
A 1 mmol toluene solution was charged and a polymerization reaction was carried out at 0 ° C. for 5 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, filtered, and then the solution was poured into a large amount of methanol again to precipitate the polymer. After washing, filtering, drying and weighing, 0.695 g (yield: 22.2 wt%) of copolymer P-3 was obtained.
The polymerization activity was 418 (g polymer / mmolTi · hr).

Weight average molecular weight (Mw) of the obtained polymer.
Was 81,700, the number average molecular weight (Mn) was 48,800, and the molecular weight distribution (Mw / Mn) was 1.67. The composition of copolymer-3 determined by ¹ H-NMR measurement was 4-t-butyldimethylsilyloxystyrene: 44.3 mol% and styrene: 55.7 mol%. The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. As a result of DSC measurement, it was Tg: 102 ° C. The cast film of the obtained polymer was a transparent film without clouding, and cracking or peeling of the film was not observed even when a cross cut test was performed.

Comparative Example 2 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. 26.2 ml of toluene and 10.8 ml of a toluene solution of the modified methylaluminoxane-1 obtained in Reference Example 1 (aluminum concentration: 5.7 wt%) were charged into a three-neck glass flask and aged at 0 ° C. for 10 minutes. To this, 0.02 mmol of indenyl titanium trichloride was charged, and then, a toluene solution of 0.02 mmol of styrene was charged.
Aged for minutes. Finally, 4-t-butyldimethylsilyloxystyrene 14.0 mmol, styrene 6.0 mmo
A toluene solution of 0.1 mmol of triisobutylaluminum and 0.1 mmol of triisobutylaluminum was charged and a polymerization reaction was carried out at 0 ° C for 5 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, filtered, and then the solution was poured into a large amount of methanol again to precipitate the polymer. After washing, filtering, drying, and weighing, 1.000 g of copolymer-R2
(Yield: 25.6 wt%) was obtained. The polymerization activity was 602 (g polymer / mmolTi · hr).

Weight average molecular weight (Mw) of the obtained polymer.
Was 104,000, the number average molecular weight (Mn) was 64,500, and the molecular weight distribution (Mw / Mn) was 1.62. The composition of the copolymer-4 obtained by ¹ H-NMR measurement was 4-t-butyldimethylsilyloxystyrene: 73.3 mol% and styrene: 26.7 mol%. The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. As a result of DSC measurement, it was Tg: 105 ° C. The cast film of the obtained polymer was a partly cloudy film, and a large peeling of the film was not observed even when a cross cut test was performed, but the cast film slightly peeled at the intersection of the cut lines. It was observed that it was doing.

Example 4 Using a glass eggplant-shaped flask having an internal volume of 100 ml which had been dried and purged with nitrogen, the reaction was carried out under a nitrogen atmosphere. 0.324 g of the copolymer P-1 obtained in Example 1 was charged into a glass three-necked flask, and then 50 ml of tetrahydrofuran was charged to dissolve the polymer. After that, add 37% hydrochloric acid
2.0 ml was charged and heated, and the mixture was stirred at a temperature at which tetrahydrofuran refluxed for 240 minutes. After stopping the heating,
The polymer solution was poured into methanol to precipitate a polymer. The obtained polymer was thoroughly washed with methanol,
By filtering, drying and weighing, 0.296 g (yield: 95.6 wt%) of polymer Q-1 was obtained.

As a result of ¹ H-NMR measurement, it was found that the resonance line derived from the protective group was completely disappeared, and the desired hydroxystyrene-styrene copolymer was obtained. ^The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. Further, when thermal analysis was performed, Tm was observed at 268.5 ° C and Tg was observed at 99.4 ° C. The cast film of the obtained polymer was a transparent film without clouding, and cracking or peeling of the film was not observed even when a cross cut test was performed.

Example 5 Using a glass eggplant-shaped flask having an internal volume of 100 ml which had been dried and purged with nitrogen, the reaction was carried out under a nitrogen atmosphere. 0.484 g of the copolymer P-2 obtained in Example 2 was charged into a glass three-necked flask, and then 50 ml of tetrahydrofuran was charged to dissolve the polymer. After that, add 37% hydrochloric acid
2.0 ml was charged and heated, and the mixture was stirred at a temperature at which tetrahydrofuran refluxed for 240 minutes. After stopping the heating,
The polymer solution was poured into methanol to precipitate a polymer. The obtained polymer was thoroughly washed with methanol,
After separation by filtration, re-dissolving in THF and reprecipitation in water, separation by filtration, drying and weighing, 0.391 g of polymer Q-2 (yield:
98.1 wt%) was obtained.

As a result of ¹ H-NMR measurement, it was found that the resonance line derived from the protective group was completely disappeared, and the desired hydroxystyrene-styrene copolymer was obtained. ^The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. Moreover, when thermal analysis was performed, Tm was observed at 265.1 ° C and Tg was observed at 117.2 ° C. The cast film of the obtained polymer was a transparent film without clouding, and cracking or peeling of the film was not observed even when a cross cut test was performed.

Example 6 A glass eggplant-shaped flask having an internal volume of 30 ml which had been dried and purged with nitrogen was used to carry out the reaction under a nitrogen atmosphere. Example 3
0.586 g of the copolymer P-3 obtained in 1. was charged into a three-neck glass flask, and then 50 ml of tetrahydrofuran was charged to dissolve the polymer. Then, add 37% hydrochloric acid to 2.0
The mixture was charged in ml and heated, and the mixture was stirred at a temperature at which tetrahydrofuran refluxed for 240 minutes. After stopping the heating, the polymer solution was poured into water to precipitate a polymer. The obtained polymer was thoroughly washed with water, redissolved in THF and poured into hexane to precipitate the polymer. Furthermore, THF
Redissolved in water and reprecipitated in water. After washing, filtering, drying and weighing, 0.367 g of polymer Q-3 (yield: 91.2w
t%) was obtained.

As a result of ¹ H-NMR measurement, it was found that the resonance line derived from the protective group was completely disappeared, and the desired hydroxystyrene-styrene copolymer was obtained. ^The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. Further, when thermal analysis was performed, Tm was observed at 267.5 ° C., Tc was observed at 197.4 ° C., and Tg was observed at 132.6 ° C. The cast film of the obtained polymer was a transparent film without clouding, and cracking or peeling of the film was not observed even when a cross cut test was performed.

Comparative Example 3 A glass eggplant-shaped flask having an inner volume of 30 ml which had been dried and purged with nitrogen was used to carry out the reaction under a nitrogen atmosphere. Comparative example 2
0.904 g of the copolymer-R2 obtained in 1. was charged into a three-neck glass flask, and then 50 ml of tetrahydrofuran was charged to dissolve the polymer. Then, add 37% hydrochloric acid to 2.0
The mixture was charged in ml and heated, and the mixture was stirred at a temperature at which tetrahydrofuran refluxed for 240 minutes. After stopping the heating, the polymer solution was poured into water to precipitate a polymer. The obtained polymer was thoroughly washed with water, redissolved in THF and poured into hexane to precipitate the polymer. Furthermore, THF
Redissolved in water and reprecipitated in water. After washing, filtering, drying and weighing, 0.489 g of polymer (yield: 93.2 wt%)
Got

As a result of ¹ H-NMR measurement, it was found that the resonance line derived from the protective group was completely disappeared, and the desired hydroxystyrene-styrene copolymer was obtained. ^The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. Further, when thermal analysis was performed, Tg was observed at 168.6 ° C. No Tm was observed. The cast film of the obtained polymer was a transparent film without clouding. Even when a cross-cut test was performed, no large peeling of the film was observed,
Small cracks were observed along the cut line.

Example 7 A polymerization reaction was carried out in a nitrogen atmosphere using a glass three-necked flask having an inner volume of 500 ml which was dried and purged with nitrogen. 21.56 ml of a toluene solution of 62.2 ml of toluene and the modified methylaluminoxane-1 obtained in Reference Example 1 (aluminum concentration: 5.7 wt%) were placed in a three-neck glass flask and aged at 0 ° C. for 10 minutes. To this, 0.04 mmol of indenyl titanium trichloride was added, and then a toluene solution of 0.04 mmol of styrene was added to
Aged for minutes. Finally, 4-t-butyldimethylsilyloxystyrene 37.0 mmol, styrene 333.
A toluene solution of 0 mmol and 0.2 mmol of triisobutylaluminum was charged, and a polymerization reaction was performed at 0 ° C for 5 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, filtered, and then the solution was poured into a large amount of methanol again to precipitate the polymer.
After washing, filtering, drying, and weighing, 2.35 g of copolymer P-4
(Yield: 5.4 wt%) was obtained. The polymerization activity was 118 (g polymer / mmol Ti · hr).

Weight average molecular weight (Mw) of the obtained polymer.
Was 166,000, the number average molecular weight (Mn) was 88,200, and the molecular weight distribution (Mw / Mn) was 1.88. The composition of the copolymer-1 obtained by ¹ H-NMR measurement was 4-t-butyldimethylsilyloxystyrene: 8.8 mol%, styrene: 91.2 mol%. The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. As a result of DSC measurement, Tg was 96 ° C. The cast film of the obtained polymer was a transparent film without clouding, and cracking or peeling of the film was not observed even when a cross cut test was performed.

Example 8 Using a glass eggplant-shaped flask having an internal volume of 200 ml which had been dried and purged with nitrogen, the reaction was carried out under a nitrogen atmosphere. 2.015 g of the copolymer P-4 obtained in Example 7 was charged in a three-neck glass flask, and then 80 ml of tetrahydrofuran was charged to dissolve the polymer. After that, add 37% hydrochloric acid
2.0 ml was charged and heated, and the mixture was stirred at a temperature at which tetrahydrofuran refluxed for 240 minutes. After stopping the heating,
The polymer solution was poured into water to precipitate a polymer. The obtained polymer was thoroughly washed with water, redissolved in THF and poured into hexane to precipitate the polymer. Further, it was redissolved in THF and reprecipitated in water. Washing,
It was filtered, dried and weighed to obtain 1.794 g of polymer Q-4 (yield: 97.5 wt%).

As a result of ¹ H-NMR measurement, it was found that the resonance line derived from the protective group was completely disappeared, and the desired hydroxystyrene-styrene copolymer was obtained. ^The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. Further, when thermal analysis was performed, Tm was observed at 265.7 ° C and Tg was observed at 107.1 ° C. The cast film of the obtained polymer was a transparent film without clouding, and cracking or peeling of the film was not observed even when a cross cut test was performed.

Example 9 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. Toluene 33.3 ml and triisobutylaluminum 0.05 mmol
Charge the toluene solution of to a glass three-necked flask and
Aging was performed at 0 ° C for minutes. Where trimethyl (pentamethylcyclopentadienyl titanium) 0.05
Then, a solution of 0.05 mmol of styrene in toluene was charged and the mixture was aged for 10 minutes. Finally, 4-t-butyldimethylsilyloxystyrene 9.1
A toluene solution containing 1 mmol of styrene, 72.0 mmol of styrene and 0.05 mmol of triisobutylaluminum was charged, and a polymerization reaction was carried out at 0 ° C. for 5 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, filtered, and then the solution was poured into a large amount of methanol again to precipitate the polymer. Wash, filter, dry, weigh,
0.984 g (yield: 10.2 wt%) of copolymer P-5 was obtained. The polymerization activity was 240 (g polymer / mmolTi · hr).

Weight average molecular weight (Mw) of the obtained polymer.
Was 325,000, the number average molecular weight (Mn) was 151,000, and the molecular weight distribution (Mw / Mn) was 2.15. The composition of the copolymer-1 obtained by ¹ H-NMR measurement was 4-t-butyldimethylsilyloxystyrene: 7.5 mol% and styrene: 92.5 mol%. The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. As a result of DSC measurement, it was Tg: 97 ° C. The cast film of the obtained polymer was a transparent film without clouding, and cracking or peeling of the film was not observed even when a cross cut test was performed.

Example 10 A glass eggplant-shaped flask having an internal volume of 200 ml which had been dried and purged with nitrogen was used to carry out the reaction under a nitrogen atmosphere. 0.750 g of the copolymer P-5 obtained in Example 11 was charged in a glass three-necked flask, followed by 50 ml of tetrahydrofuran.
Is charged to dissolve the polymer. Then, 2.0 ml of 37% hydrochloric acid was charged and heated, and the mixture was stirred at a temperature at which tetrahydrofuran refluxed for 240 minutes. After stopping the heating, the polymer solution was poured into water to precipitate a polymer. The obtained polymer was thoroughly washed with water, redissolved in THF and poured into hexane to precipitate the polymer. Further, it was redissolved in THF and reprecipitated in water. Washing,
The polymer Q-5 was separated by filtration, dried and weighed to obtain 0.647 g of polymer Q-5 (yield: 93.3 wt%).

As a result of ¹ H-NMR measurement, it was found that the resonance line derived from the protective group was completely disappeared, and the desired hydroxystyrene-styrene copolymer was obtained. ^The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. Moreover, when thermal analysis was performed, Tm was observed at 266.0 ° C. and Tg was observed at 106.8 ° C. The cast film of the obtained polymer was a transparent film without clouding, and cracking or peeling of the film was not observed even when a cross cut test was performed.

Example 11 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. 26.2 ml of toluene and 10.8 ml of a toluene solution of the modified methylaluminoxane-1 obtained in Reference Example 1 (aluminum concentration: 5.7 wt%) were charged into a three-neck glass flask and aged at 0 ° C. for 10 minutes. To this, 0.02 mmol of indenyl titanium trichloride was charged, and then, a toluene solution of 0.02 mmol of styrene was charged.
Aged for minutes. Finally, 4-t-butyldimethylgermanium oxystyrene 14.0 mmol, styrene
A toluene solution of 6.0 mmol and 0.1 mmol of triisobutylaluminum was charged, and a polymerization reaction was carried out at 0 ° C for 5 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 is redissolved in toluene and filtered,
The solution was poured again into a large amount of methanol to precipitate a polymer. The copolymer P-6 was washed, filtered, dried, and weighed.
0.733 g (yield: 16.2 wt%) was obtained. Polymerization activity is 44
It was 1 (g polymer / mmol Ti · hr).

Weight average molecular weight (Mw) of the obtained polymer.
Was 121,000, the number average molecular weight (Mn) was 56,000, and the molecular weight distribution (Mw / Mn) was 2.16. The composition of the copolymer-4 obtained by ¹ H-NMR measurement is 4-t-butyldimethylgermanium oxystyrene: 71.3 mol%,
Styrene: It was 29.7 mol%. The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. As a result of DSC measurement, it was Tg: 103 ° C.
The cast film of the obtained polymer was a transparent film without clouding, and cracking or peeling of the film was not observed even when a cross cut test was performed.

Example 12 A glass eggplant-shaped flask having an inner volume of 200 ml which had been dried and purged with nitrogen was used to carry out the reaction under a nitrogen atmosphere. Copolymer P-6 obtained in Example 13: 0.650 g was charged into a glass three-necked flask, followed by tetrahydrofuran (50 ml).
Is charged to dissolve the polymer. Then, 2.0 ml of 37% hydrochloric acid was charged and heated, and the mixture was stirred at a temperature at which tetrahydrofuran refluxed for 240 minutes. After stopping the heating, the polymer solution was poured into water to precipitate a polymer. The obtained polymer was thoroughly washed with water, redissolved in THF and poured into hexane to precipitate the polymer. Further, it was redissolved in THF and reprecipitated in water. Washing,
After filtering, drying and weighing, 0.314 g (yield: 95.2 wt%) of polymer Q-6 was obtained.

As a result of ¹ H-NMR measurement, it was found that the resonance line derived from the protective group was completely disappeared, and the desired hydroxystyrene-styrene copolymer was obtained. ^The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. Further, when thermal analysis was performed, Tg was observed at 165.3 ° C. The cast film of the obtained polymer was a transparent film without clouding, and cracking or peeling of the film was not observed even when a cross cut test was performed.

Example 13 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. Toluene 33.3 ml and triisobutylaluminum 0.05 mmol
Charge the toluene solution of to a glass three-necked flask and
Aging was performed at 0 ° C for minutes. Where trimethyl (pentamethylcyclopentadienyl titanium) 0.05
Then, a solution of 0.05 mmol of styrene in toluene was charged and the mixture was aged for 10 minutes. Finally, 4-t-butyldimethylsilyloxystyrene 9.1
Toluene solution of mmol, 72.0 mmol of 3-methylstyrene and 0.05 mmol of triisobutylaluminum was charged at 0 ° C.
Polymerization reaction was carried out for 5 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, filtered, and then the solution was poured into a large amount of methanol again to precipitate the polymer. Washing, filtering, drying,
Weighed to obtain 1.212 g of Copolymer P-7 (yield: 11.4 w
t%) was obtained. Polymerization activity is 730 (g polymer / mmolTi · h
r).

Weight average molecular weight (Mw) of the obtained polymer.
Was 215,000, the number average molecular weight (Mn) was 103,000, and the molecular weight distribution (Mw / Mn) was 2.09. The composition of the copolymer-1 obtained by ¹ H-NMR measurement was 4-t-butyldimethylsilyloxystyrene: 9.3 mol%, 3-methylstyrene: 90.7 mol%. Also, ¹³ C-NM
The syndiotacticity calculated by R measurement is
95% with racemic pentad for all structural units
That was all. As a result of DSC measurement, it was Tg: 93 ° C. The cast film of the obtained polymer was a transparent film without clouding, and cracking or peeling of the film was not observed even when a cross cut test was performed.

Example 14 A glass eggplant-shaped flask having an internal volume of 200 ml which had been dried and purged with nitrogen was used to carry out the reaction under a nitrogen atmosphere. 1.150 g of the copolymer P-7 obtained in Example 13 was charged into a glass three-necked flask, followed by 50 ml of tetrahydrofuran.
Is charged to dissolve the polymer. Then, 2.0 ml of 37% hydrochloric acid was charged and heated, and the mixture was stirred at a temperature at which tetrahydrofuran refluxed for 240 minutes. After stopping the heating, the polymer solution was poured into water to precipitate a polymer. The obtained polymer was thoroughly washed with water, redissolved in THF and poured into hexane to precipitate the polymer. Further, it was redissolved in THF and reprecipitated in water. Washing,
The polymer Q-7 was separated by filtration, dried and weighed to obtain 0.956 g of polymer Q-7 (yield: 90.6 wt%).

As a result of ¹ H-NMR measurement, it was found that the resonance line derived from the protective group was completely disappeared, and the desired hydroxystyrene-styrene copolymer was obtained. ^The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for all structural units. Further, when thermal analysis was performed, Tm was observed at 234.0 ° C and Tg was observed at 98.6 ° C. The cast film of the obtained polymer was a transparent film without clouding, and cracking or peeling of the film was not observed even when a cross cut test was performed.

[0126]

INDUSTRIAL APPLICABILITY According to the present invention, each structural unit comprising a substituted hydroxystyrene-based monomer and a styrene-based monomer which are precursors of a hydroxystyrene-based copolymer having a high syndiotactic structure. It is possible to obtain a substituted hydroxystyrene-based copolymer having a high syndiotactic structure. Furthermore, the hydroxystyrene-based copolymer having a syndiotactic structure obtained by deprotecting the copolymer is excellent in practical heat resistance and excellent in various physical properties such as chemical resistance. And
It is not only extremely useful as a plastic material used in a wide range of home appliances, office automation equipment, etc., but also printed wiring boards, offset PS printing plates, photoresists, color filters, sliding materials, brake materials,
Ion exchange resin raw materials, adsorbents, synthetic carriers, chromatogram fillers, separation membranes, and other materials, as well as flame retardant raw materials, sealing materials, coating materials, flocculants, CB-containing film resistors, magnetic tape binders. It is useful as a functional resin such as an adhesive or a metal surface treatment agent or a functional resin raw material.

Continued front page    F-term (reference) 4J028 AA01A AB01A AC09A AC27A                       AC38A BA01B BB01B BC01B                       BC05B BC06B BC12B BC14B                       BC15B BC19B BC25B EB21                       EC02 FA02 GA01 GA06 GA12                       GB02                 4J100 AB02P AB04P AB07P AB07Q                       BA03Q BA75Q BA93Q BB01P                       BB03P BB07P CA04 CA12                       DA01 DA04 FA09 FA19 JA03                       JA16 JA38

Claims (5)

[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. ) Substituted hydroxystyrene structural unit (I)
55 mol% and the following general formula (2): (Wherein, R ² represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 30 carbon atoms, n is an integer of 0 to 5. However, when n is plural, each R ² is Which may be the same or different) and which is a copolymer comprising 45 to 99 mol% of a styrene structural unit (II) represented by the general formula (1) in the copolymer. The tacticity of the C ₁ carbon of the phenyl group of the substituted hydroxystyrene structural unit (I) and the styrene structural unit (II) represented by the general formula (2) is 30% or more in racemic pentad by ¹³ C-NMR. Is a syndiotactic substituted hydroxystyrene copolymer. 2. In the presence of a solvent and a catalyst component, the following general formula (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. ) And a substituted hydroxystyrene-based monomer represented by the following general formula (4): (Wherein, R ² represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 30 carbon atoms, n is an integer of 0 to 5. However, when n is plural, each R ² is May be the same or different.) In the method of copolymerizing a styrene-based monomer represented by the formula (A), the catalyst component is (A) the following general formula (5) and / or general formula (6) MR ³ R ⁴ _a X _3-a (5) MR ³ R ⁴ _b X _2-b (6) (In the formula, R ³ represents a π ligand. R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, respectively. Group, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group,
It shows an acyloxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, and a thioaryloxy group having 6 to 20 carbon atoms. M represents a transition metal element of Group 4 of the periodic table, and X represents a halogen atom. R ⁴
May be the same or different.
Further, each a is an integer of 0 to 3, and each b is an integer of 0 to 2. ), And (B) the following (a) to (d) (a) tetraalkyldialuminoxane and / or polyalkylaluminoxane having an alkyl group having 2 or more carbon atoms are reacted with trimethylaluminum. Thus obtained modified methylaluminoxane, (b) an ionic compound capable of reacting with the transition metal compound to form a cationic transition metal compound, (c) reacting with the transition metal compound to form a cationic transition metal compound A Lewis acid compound which is capable of reacting with at least one cocatalyst selected from the group consisting of (d) organometallic compounds of Group 1, 2, and 13 element metals of the periodic table, as a main catalyst component, Aromatic hydrocarbons and / or halogenated aromatic hydrocarbons whose dielectric constant is within the range of 2.0 to 10.0 The method for producing a syndiotactic substituted hydroxystyrene-based copolymer according to claim 1, which is used. 3. The general formula (5) and / or the general formula (6)
In Claim 2, M is titanium.
The method for producing the syndiotactic substituted hydroxystyrene-based copolymer according to 1. 4. The following general formula (7): (M is an integer of 1 to 3) 1 to 55 mol% of a hydroxystyrene structural unit (III) represented by the following general formula (2): (Wherein, R ² represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 30 carbon atoms, n is an integer of 0 to 5. However, when n is plural, each R ² is Which may be the same or different) and a styrene-based structural unit (II) represented by 45 to 99 mol%.
The tacticity of the C ₁ carbons of the phenyl groups of the hydroxystyrene structural unit (III) represented by the general formula (7) and the styrene structural unit (II) represented by the general formula (2) are respectively determined by ¹³ C-NMR. A syndiotactic hydroxystyrene-based copolymer, characterized by being 30% or more in terms of racemic pentad. 5. The deprotection group-forming reaction is carried out by contacting the syndiotactic substituted hydroxystyrene-based copolymer according to claim 1 with an acid or a base in the presence of an organic solvent. 4. The method for producing the syndiotactic hydroxystyrene-based copolymer as described in 4.