JP2010090272A - Titanate compound chemically modified with polymer chain - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a titanate compound chemically modified with a polymer chain. <P>SOLUTION: The titanate compound (A) chemically modified with a polymer chain is obtained by polymerizing a monomer having a radically polymerizable unsaturated bond using a radical polymerization initiating group introduced onto the surface of a titanate (1) through a chemical bond as the starting point. A living radical polymerization initiating group or an atom transfer radical polymerization initiating group is used as the radical polymerization initiating group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a titanate compound chemically modified with a polymer chain, wherein a polymer compound is chemically bonded to titanate.

In recent years, various electronic devices have been reduced in size and performance. Along with this, miniaturization of capacitors in integrated circuits is also demanded, and studies are being made to increase the capacitance density. For increasing the density of the capacitance, a resin to which inorganic high dielectric constant particles such as titanate are added is used.
For example, regarding a printed wiring board in which a thermoplastic resin is used as an inner layer, Patent Documents 1 and 2 have been studied to increase the dielectric constant by filling inorganic high dielectric constant particles into the thermoplastic resin. If the particle filling amount is large, the moldability is lowered.
Non-Patent Document 1 describes a dielectric polymer thin film added with barium titanate. However, when the amount of barium titanate added increases, particle aggregates are formed, resulting in poor film formability. .
Therefore, various methods for coating the surface have been studied in order to suppress the aggregation of inorganic high dielectric constant particles, but most of them are surface treatments with low molecules and have low affinity with the base resin. There is a case. In addition, surface treatment by reacting a pre-synthesized polymer with inorganic particles is also known, but its efficiency tends to be low due to the polymer reaction. Therefore, it cannot be said that the effects obtained by these methods are necessarily sufficient.
JP-A-5-57851 JP-A-5-57852 Yoshio Kobayashi, Mikio Konno, B.I. 5 Creation of Barium Titanate Nanoparticle-added Dielectric Polymer Thin Films, New Phases of Organic / Inorganic Nanocomposites, NTS, 2004

  An object of the present invention is to provide a titanate compound chemically modified with a polymer chain that retains good moldability even when highly filled into a resin and is excellent in mechanical strength.

  The inventors of the present invention can introduce titanate compound particles chemically modified with polymer chains by introducing radical polymerization initiating groups into the titanate particles in advance through chemical bonds and reacting the particles with monomers. I found out.

That is, the present invention
[1]: Chemistry with a polymer chain obtained by polymerizing a monomer having a radical polymerizable unsaturated bond starting from a radical polymerization initiating group introduced through a chemical bond to the surface of titanate (1) Modified titanate compound (A);
[2]: Titanate compound (A) in which the radical polymerization initiating group is a living radical polymerization initiating group or an atom transfer radical polymerization initiating group.
[3]: Titanate (1) and (a) phosphoric acid group, carboxylic acid group, acid halide group, acid anhydride group, isocyanate group, glycidyl group, chlorosilane group, alkoxysilyl group, silanol A titanate compound (A) formed by reacting at least one functional group selected from the group consisting of groups.
[4] Group consisting of titanate (1) and (a) phosphoric acid group, carboxylic acid group, acid halide group, acid anhydride group, isocyanate group, glycidyl group, chlorosilane group, alkoxysilyl group, silanol group At least one functional group selected from
And (b) reacting with a compound having a radical polymerization initiating group to obtain a compound (2) having a radical polymerization initiating group introduced into the surface of titanate (1) via a chemical bond. A method for producing a titanate compound (A), which comprises polymerizing a compound having a radical polymerizable unsaturated bond with the above compound;
[5]: A resin composition comprising a titanate compound (A) chemically modified with a polymer chain and a resin is provided.

  According to the present invention, it is possible to provide a titanate compound chemically modified with a polymer chain, which retains good moldability even when highly filled into a resin and is excellent in mechanical strength.

Hereinafter, the present invention will be described in detail.
First, the titanate compound (A) will be described.

If titanate (1) is at least one kind of titanate selected from the group consisting of magnesium titanate, calcium titanate, strontium titanate and barium titanate, its crystal structure and size The shape and the like are not particularly limited.

（式中、Ｍは、Ｍｇ、Ｃａ、Ｓｒ又はＢａであり、Ｘは、０．１〜１．１の数を表す。）
で示されるチタン酸塩が挙げられ、その結晶構造や大きさ、形状等は特に限定されない。 Usually, the titanate (1) has the formula (1)

(In the formula, M represents Mg, Ca, Sr or Ba, and X represents a number of 0.1 to 1.1.)
The crystal structure, size, shape, etc. are not particularly limited.

  A “radical polymerization initiating group” is a functional group that generates radicals by reacting with a functional group or a catalyst that generates radicals under light, heat, or other electromagnetic irradiation conditions, and serves as a starting point for radical polymerization. The functional group is not particularly limited as long as it is a functional group. For example, an azo group, a peroxide group, an iodine group as described in Non-Patent Document 2, and a starting group of Nitroxide-Mediated Polymerization (NMP) as described in Non-Patent Document 3 A thioester group as an initiation group of Reversible Addition-Fragmentation Polymerization (RAFT), as described in Non-Patent Document 4, and Atom Transfer Radical Polymerization as described in Non-Patent Documents 5 and 6 An α-haloester group, an α-haloketone group, a halogenated sulfonyl group, a benzyl halide group, or the like, which serves as an initiation group for ATRP (atom transfer radical polymerization), is generated. From the viewpoint that the primary structure and chain length of the polymer chain can be controlled, the “living radical polymerization initiating group” is preferable, for example, the functional groups described in Non-Patent Documents 2 and 3, 4, 5, and 6, A functional group that is an “atom transfer radical polymerization initiating group” as described in Non-Patent Documents 5 and 6 is more preferable.

[Non-Patent Document 2]
Chem. Rev. 2006, 106, 3936.
[Non-Patent Document 3]
Chem. Rev. 2001, 101, 3661.
[Non-Patent Document 4]
Aust. J. et al. Chem. 2005, 58, 379.
[Non-Patent Document 5]
Chem. Rev. 2001, 101, 2921.
[Non-Patent Document 6]
Chem. Rev. 2001, 101, 3689.

  The “living radical polymerization initiating group” is not particularly limited. For example, iodine group, nitroxide group, thioester group, α-haloester group, α-haloketone group, sulfonyl halide group, benzyl halide group, etc. Is mentioned.

  The “atom transfer radical polymerization initiating group” is not particularly limited, and examples thereof include an α-haloester group, an α-haloketone group, a halogenated sulfonyl group, and a benzyl halide group.

“Chemical bond” in “radical polymerization initiating group introduced via chemical bond” is not particularly limited, and for example, titanate (1) and (a) phosphate group, carboxylic acid group, acid Examples include a bond formed by reacting at least one functional group selected from the group consisting of a halide group, an acid anhydride group, an isocyanate group, a glycidyl group, a chlorosilane group, an alkoxysilyl group, and a silanol group, Preferably, a bond formed by reacting titanate (1) with a chlorosilane group, alkoxysilane group, or silanol group is mentioned, and more preferably, titanate (1) and alkoxysilane group are reacted. Can be formed. The functional group to be reacted with the titanate (1) may be one type or two or more types.

（Ｙは、ラジカル重合開始基を有する置換基、Ｚ^１は、ヒドロキシル基又は置換されていてもよいリン酸エステル基を表わす。）

ｉｉ）カルボン酸基、酸ハライド基、酸無水物基の場合；

（Ｙは、ラジカル重合開始基を有する置換基を表わす。）

ｉｉｉ）イソシアナート基の場合；

（Ｙは、ラジカル重合開始基を有する置換基を表わす。）

ｉｖ）クロロシラン基、アルコキシシリル基、シラノール基の場合；

（Ｙは、ラジカル重合開始基を有する置換基を表し、Ｚ^２及びＺ^３は、同一又は相異なり、クロロ原子、アルコキシ基、ヒドロキシル基、アルキル基又は置換されていてもよいシロキシ基を表わす。） Below, from the group consisting of titanate (1) and (a) phosphoric acid group, carboxylic acid group, acid halide group, acid anhydride group, isocyanate group, glycidyl group, chlorosilane group, alkoxysilyl group, silanol group Although the example of the coupling | bonding formed by making it react with the at least 1 sort (s) of functional group chosen is represented using a conceptual diagram, it is not necessarily limited to these.
i) in the case of a phosphate group;

(Y represents a substituent having a radical polymerization initiating group, and Z ¹ represents a hydroxyl group or an optionally substituted phosphate group.)

ii) In the case of a carboxylic acid group, an acid halide group, or an acid anhydride group;

(Y represents a substituent having a radical polymerization initiating group.)

iii) in the case of an isocyanate group;

(Y represents a substituent having a radical polymerization initiating group.)

iv) In the case of chlorosilane group, alkoxysilyl group, silanol group;

(Y represents a substituent having a radical polymerization initiating group, and Z ² and Z ³ are the same or different and represent a chloro atom, an alkoxy group, a hydroxyl group, an alkyl group or an optionally substituted siloxy group. )

The “monomer having a radically polymerizable unsaturated bond” is not particularly limited as long as it is a monomer that is polymerized by radical polymerization. For example, carbon-carbon double such as ethylene, propylene, isobutene, hexene, butadiene, styrene, and the like. Hydrocarbons having bonds, (meth) acrylic esters such as methyl methacrylate and butyl acrylate, (meth) acrylamides such as N, N-dimethylmethacrylamide, N, N-diethylmethacrylate and N, N-dimethylacrylamide , Acrylonitrile, vinyl acetate, 4-vinylpyridine and the like. These monomers may be one kind, or two or more kinds may be polymerized.

The “polymer chain” is not particularly limited as long as 10 or more monomers are polymerized starting from a polymerization initiating group.

Next, from the group consisting of titanate (1) and (a) phosphoric acid group, carboxylic acid group, acid halide group, acid anhydride group, isocyanate group, glycidyl group, chlorosilane group, alkoxysilyl group, silanol group At least one functional group selected,
And (b) a compound in which a radical polymerization initiating group is introduced via a chemical bond to the surface of titanate (1) by reacting with a compound having a radical polymerization initiating group (2)
To state.

(A) at least one functional group selected from the group consisting of phosphoric acid group, carboxylic acid group, acid halide group, acid anhydride group, isocyanate group, glycidyl group, chlorosilane group, alkoxysilyl group, silanol group, and (B) The compound having a radical polymerization initiating group is not particularly limited.

4-chloromethylphenylphosphonic acid, 4-bromomethylphenylphosphonic acid,
2-chloropropionic acid, 2-bromopropionic acid, 2-iodopropionic acid,
2-chloro-2-methylpropionic acid, 2-bromo-2-methylpropionic acid, 2-iodo-2-methylpropionic acid,

2-chloropropionyl chloride, 2-chloropropionyl bromide, 2-bromopropionyl chloride, 2-bromopropionyl bromide,
2-chloro-2-methyl-propionyl chloride, 2-chloro-2-methyl-propionyl bromide, 2-bromo-2-methyl-propionyl chloride, 2-bromo-2-methyl-propionyl bromide,

Trichloroacetyl isocyanate,

2-chloro-2-methylpropionic acid {6- (trichlorosilyl) pentyl}, 2-bromo-2-methylpropionic acid {6- (trichlorosilyl) hexyl}, 2-iodo-2-methylpropionic acid {6 -(Trichlorosilyl) butyl},

2-chloro-2-methylpropionic acid {6- (trimethoxysilyl) hexyl}, 2-chloro-2-methylpropionic acid {6- (triethoxysilyl) hexyl}, 2-chloro-2-methylpropion Acid {6- (triethoxysilyl) butyl}, 2-bromo-2-methylpropionic acid {6- (trimethoxysilyl) hexyl}, 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) Hexyl}, 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) pentyl}, 2-bromo-2-methylpropionic acid {6- (methyldiethoxysilyl) hexyl}, 2-bromo- 2-methylpropionic acid {6- (dimethylethoxysilyl) hexyl}, 2-iodo-2-methylpropionic acid {6- (trimethoxysilyl) hexyl }, Hexyl} to 2-iodo-2-methylpropionic acid {6- (triethoxysilyl)
4- {2- (trimethoxysilyl) ethyl} benzenesulfonyl chloride, 4- {2- (triethoxysilyl) ethyl} benzenesulfonyl chloride, 4- {2- (methyldiethoxysilyl) ethyl} benzenesulfonyl chloride, 4 -{2- (dimethylethoxysilyl) ethyl} benzenesulfonyl chloride,
1- (chloromethyl) -4- (trimethoxysilyl) benzene, 1- (chloromethyl) -4- (triethoxysilyl) benzene, 1- (bromomethyl) -4- (trimethoxysilyl) benzene, 1- ( Bromomethyl) -4- (triethoxysilyl) benzene,

2-chloro-2-methylpropionic acid {6- (trihydroxysilyl) pentyl}, 2-bromo-2-methylpropionic acid {6- (trihydroxysilyl) hexyl}, 2-iodo-2-methylpropionic acid {6- (trihydroxysilyl) butyl}, 2-bromopropionic acid {6- (trihydroxysilyl) hexyl}
Etc.

2-chloro-2-methylpropionic acid {6- (trimethoxysilyl) hexyl}, 2-chloro-2-methylpropionic acid {6- (triethoxysilyl) hexyl}, 2-chloro-2-methylpropion Acid {6- (triethoxysilyl) butyl}, 2-bromo-2-methylpropionic acid {6- (trimethoxysilyl) hexyl}, 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) Hexyl}, 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) pentyl}, 2-bromo-2-methylpropionic acid {6- (methyldiethoxysilyl) hexyl}, 2-bromo- 2-methylpropionic acid {6- (dimethylethoxysilyl) hexyl}, 2-iodo-2-methylpropionic acid {6- (trimethoxysilyl) hexyl }, Hexyl} to 2-iodo-2-methylpropionic acid {6- (triethoxysilyl)
4- {2- (trimethoxysilyl) ethyl} benzenesulfonyl chloride, 4- {2- (triethoxysilyl) ethyl} benzenesulfonyl chloride, 4- {2- (methyldiethoxysilyl) ethyl} benzenesulfonyl chloride, 4 -{2- (dimethylethoxysilyl) ethyl} benzenesulfonyl chloride,
1- (chloromethyl) -4- (trimethoxysilyl) benzene, 1- (chloromethyl) -4- (triethoxysilyl) benzene, 1- (bromomethyl) -4- (trimethoxysilyl) benzene, 1- ( Compounds having an alkoxysilyl group and a radical polymerization initiating group such as bromomethyl) -4- (triethoxysilyl) benzene are preferred.

  Group consisting of titanate (1) and (a) phosphoric acid group, carboxylic acid group, acid halide group, acid anhydride group, isocyanate group, glycidyl group, chlorosilane group, alkoxysilyl group, silanol group shown above The reaction with the compound having at least one kind of functional group selected from (b) and a radical polymerization initiating group is carried out by bringing them into contact with each other.

When contacting, a solvent-free may be used, but it is usually carried out by mixing both in a solvent. Examples of the solvent include water, an organic solvent, and a mixed solvent of water and an organic solvent. Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; ether solvents such as 1,4-dioxane, tetrahydrofuran, diethyl ether, tert-butyl methyl ether, and ethylene glycol dimethyl ether; methanol, ethanol, isopropanol, and the like Examples include alcohol solvents; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide.

The contact temperature is usually −78 to 200 ° C.
If necessary, the contact may be performed in the presence of an appropriate additive (for example, an acid such as acetic acid or a base such as aqueous ammonia).
In addition, at least one selected from the group consisting of (a) phosphoric acid group, carboxylic acid group, acid halide group, acid anhydride group, isocyanate group, glycidyl group, chlorosilane group, alkoxysilyl group and silanol group shown above. There are no particular restrictions on the amount of the functional group of the type and the amount of the compound (b) having a radical polymerization initiating group.

  The obtained compound can be taken out, for example, by concentration, filtration, or centrifugation. The extracted compound may be further purified by washing with water, an organic solvent, a mixed solvent of water and an organic solvent, or the like.

Subsequently, titanate (1) is selected from the group consisting of (a) phosphoric acid group, carboxylic acid group, acid halide group, acid anhydride group, isocyanate group, glycidyl group, chlorosilane group, alkoxysilyl group, silanol group. At least one functional group selected,
And (b) reacting with a compound having a radical polymerization initiating group to obtain a compound (2) having a radical polymerization initiating group introduced into the surface of titanate (1) via a chemical bond. The step of radical polymerization of the compound and a monomer having a radical polymerizable unsaturated bond will be described.

  As the radical polymerization, any polymerization method may be used, but since the molecular weight of the polymer chain bonded to the titanate surface is preferably uniform, living radical polymerization is preferable. And atom transfer radical polymerization as described in 1 and 6. Therefore, there is no particular limitation as long as it is a monomer that can be reacted by atom transfer radical polymerization. For example, styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, butyl acrylate, acrylic Examples thereof include t-butyl acid, N, N-dimethylmethacrylamide, methacrylonitrile, methyl acrylate, ethyl polyacrylate, N, N-dimethylacrylamide, acrylonitrile, 4-vinylpyridine, vinyl acetate and the like. These monomers may be one kind or two or more kinds. The amount of the monomer to be used is not particularly limited, but is usually 10 to 10,000 moles with respect to the polymerization initiating group contained in the compound (2).

  Although it does not specifically limit as a catalyst used for atom transfer radical polymerization, For example, the complex of bivalent copper, monovalent copper, zerovalent copper, bivalent ruthenium, bivalent iron, or bivalent nickel And a copper complex is preferable. These complexes may be one kind or two or more kinds.

A copper complex can be obtained by adding a ligand using a copper compound such as cupric chloride, cupric bromide, cuprous chloride, cuprous bromide, or copper powder.
The ligand is not particularly limited. For example, 2,2-bipyridyl, bipyridyl compounds such as derivatives thereof, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ′ ', N ″ -pentamethyldiethylenetriamine, tris (dimethylaminoethyl) amine and the like. Although the quantity of the ligand to be used is not specifically limited, Preferably, it is 0.3 mol times-5 mol times with respect to the total amount of a copper compound.

The total amount of the copper compound to be used is usually 0.0001 to 100 mol times, preferably 0.001 to 50 mol times based on the polymerization initiating group contained in the compound (2).

Atom transfer radical polymerization may be carried out without a solvent, or a solvent may be used. Solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene; ether solvents such as 1,4-dioxane, tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, anisole, diphenyl ether; methanol, ethanol, Alcohol solvents such as isopropanol; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and benzonitrile; ethyl acetate Ester solvent etc. are mentioned. These solvents may be one kind or two or more kinds.

  The temperature at which atom transfer radical polymerization of the compound (2) and the monomer is usually −20 ° C. to 200 ° C., and preferably 0 ° C. to 150 ° C.

  After completion of the polymerization, the unreacted monomer and solvent are distilled off, the suspension of the polymerization reaction is filtered, or the suspension is centrifuged, and the titanate compound (A) chemically modified with the polymer chain is unreacted. Monomers and solvents can be separated. The obtained titanate compound (A) may be further purified by washing with an appropriate solvent or the like.

Furthermore, the resin composition characterized by including a titanate compound (A) and resin is described.

  Although the kind of resin is not specifically limited, What is compatible with the polymer chain in a titanate compound (A) is preferable, for example, polymethyl methacrylate and polystyrene are mentioned.

  The ratio of the titanate compound (A) and the resin is not particularly limited, but usually the titanate weight in the titanate compound (A) (that is, the weight excluding the weight of the chemically modified polymer chain) The resin weight ratio ranges from 1:99 to 99: 1.

  The mixing method of the titanate compound (A) and the resin is not particularly limited, but for example, a method of directly mixing or kneading, and further, once mixing using a solvent, Examples include a method of distilling off the solvent.

In addition, the resin composition characterized by including the titanate compound (A) and a resin uses methods such as injection molding, blow molding, extrusion molding, inflation molding, vacuum molding after sheet processing, and compression molding. It is also possible to perform molding.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to the following Example.

[Example 1]
[Synthesis of 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl}]
The synthesis was performed with reference to Non-Patent Document 7.
2-bromo-2-methylpropionic acid-5-hexene 50.0 g and toluene 625 mL were added to a reaction vessel equipped with a cooling device at room temperature. 184 mL of triethoxysilane was added dropwise to the resulting solution. To the obtained mixture was added 740 μL of a platinum complex (manufactured by Aldrich; platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution, 0.10 M in xylene), and then overnight at room temperature. Stir. Thereafter, the reaction solution was concentrated at 32 ° C. and further dried under reduced pressure at 55 ° C. for 3 hours to obtain 73.96 g of 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl}. It was. The area percentage value obtained by gas chromatography analysis was 91%.
[Non-Patent Document 7]
Macromolecules, 2005, 38, 2137.

[Example 2]
[Synthesis of Compound (2) in which Radical Polymerization Initiating Group is Introduced through a Chemical Bond on the Titanate Surface; Barium Titanate and 2-Bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl} Reaction of]
10.00 g of barium titanate (BET specific surface area 6 m ² / g (BET specific surface area was measured by a BET one-point method using Flowsorb II model 2300 manufactured by Shimadzu Corporation)) at room temperature in a reaction vessel equipped with a cooling device, ethanol 35.2 mL and 21.1 mL of 28% aqueous ammonia were added. After the resulting mixture was stirred at 40 ° C. for 2 hours, a solution obtained by dissolving 3.52 g of 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl} in 7.0 mL of ethanol Was dripped. After dropping, the mixture was further stirred at 40 ° C. for 20 hours. Thereafter, the insoluble portion was collected by centrifugation, and washed twice with 100 mL of ethanol, twice with 100 mL of tetrahydrofuran, and twice with 100 mL of chloroform. The obtained solid was dried under reduced pressure at 60 ° C. for 4 hours, and a compound in which a radical polymerization initiating group was introduced to the surface of barium titanate via a chemical bond (barium titanate and 2-bromo-2-methylpropion). 8.93 g of a compound obtained by reacting the acid {6- (triethoxysilyl) hexyl} was obtained.
Elemental analysis: C: 0.3%, Br: 0.12%

[Example 3]
[Reaction of compound (2) (barium titanate and 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl} in which radical polymerization initiating group is introduced through a chemical bond on the surface of titanate) Atom transfer radical polymerization of methyl methacrylate
In a reaction vessel equipped with a cooling device, the compound synthesized in Example 2 at room temperature was “a compound in which a radical polymerization initiating group was introduced to the surface of titanate via a chemical bond; barium titanate and 2-bromo-2- Compound obtained by reacting methylpropionic acid {6- (triethoxysilyl) hexyl} "4.50 g, 1.94 mg of copper (I) bromide, 1.77 mg of copper powder, 2.20 mL of anisole, N, N, N ' , N ″, N ″ -pentamethyldiethylenetriamine in 0.202 mL (0.40 mol / L) and methyl methacrylate 4.33 mL are added, and the mixture is stirred at room temperature for 1 minute and further stirred at 90 ° C. for 8 hours. did. Thereafter, the insoluble part was recovered by centrifugation, and washed twice with 100 mL of tetrahydrofuran and twice with 100 mL of chloroform. The obtained solid was dried under reduced pressure at 60 ° C. for 4 hours to obtain 4.57 g of barium titanate modified with polymethyl methacrylate.
Elemental analysis: C: 3.4%, Br: 550 ppm

[Example 4]
[Reaction of compound (2) (barium titanate and 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl} in which radical polymerization initiating group is introduced through a chemical bond on the surface of titanate) Atom transfer radical polymerization of methyl methacrylate
In a reaction vessel equipped with a cooling device, the compound synthesized in Example 2 at room temperature was “a compound in which a radical polymerization initiating group was introduced to the surface of titanate via a chemical bond; barium titanate and 2-bromo-2- Compound obtained by reacting methyl propionic acid {6- (triethoxysilyl) hexyl} "4.00 g, copper (I) bromide 3.44 mg, copper powder 3.14 mg, anisole 1.79 mL, N, N, N ' , N ″, N ″ -pentamethyldiethylenetriamine in anisole solution (0.360 mL, 0.40 mol / L) and methyl methacrylate (3.85 mL) were added, and the mixture was stirred at room temperature for 1 minute, and further stirred at 90 ° C. for 8 hours. did. Thereafter, the insoluble part was recovered by centrifugation, and washed twice with 100 mL of tetrahydrofuran and twice with 100 mL of chloroform. The obtained solid was dried under reduced pressure at 60 ° C. for 4 hours to obtain 4.38 g of barium titanate modified with polymethyl methacrylate.
Elemental analysis: C: 8.9%, Br: 340 ppm

[Example 5]
[Reaction of compound (2) (barium titanate and 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl} in which radical polymerization initiating group is introduced through a chemical bond on the surface of titanate) Atom transfer radical polymerization of styrene from the compound)
In a reaction vessel equipped with a cooling device, at room temperature, “a compound in which a radical polymerization initiating group was introduced via a chemical bond on the surface of titanate; barium titanate and 2-bromo-2-methylpropionic acid {6- (Triethoxysilyl) hexyl} reacted compound (elemental analysis: C: 0.4%, Br: 1300 ppm) "10.00 g, copper (I) 9.35 mg, copper powder 38.44 mg, anisole 1 .84 mL, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine anisole solution 3.258 mL (0.40 mol / L) and styrene 11.21 mL were added, and the mixture was stirred at room temperature for 1 minute. Furthermore, it stirred at 90 degreeC for 4 hours and 30 minutes. Thereafter, the insoluble part was recovered by centrifugation, and washed with 100 mL of tetrahydrofuran three times and with 100 mL of chloroform three times. The obtained solid was dried under reduced pressure at 60 ° C. for 4 hours to obtain 14.01 g of barium titanate modified with polystyrene.
Elemental analysis: C: 27.7%, Br: 490 ppm

[Measurement of glass transition temperature]

With respect to Examples 3 and 4 and polymethylmethacrylate (Aldrich; Mw˜120,000), the glass transition temperature was measured using DSC. (Measuring condition: Temperature rising rate 20 ° C / min)

ポリメチルメタクリレートで修飾されたチタン酸バリウムが、ポリメチルメタクリレート単独樹脂よりガラス転移温度が高くなり、耐熱性が向上していることが明らかである。

It is clear that barium titanate modified with polymethyl methacrylate has a higher glass transition temperature and improved heat resistance than polymethyl methacrylate single resin.

[Example 6]
It was added to 4.79 g of polystyrene modified with barium titanate obtained in Example 5 and 1.71 g of polystyrene (manufactured by Aldrich; Mw-230,000), and 200 using a mini-kneader minilab (manufactured by ThermoHaake). Melt kneading was carried out at 20 ° C. for 20 minutes (rotation speed: 50 rpm). After kneading, the mixture was granulated with an extruder to obtain a resin composition. The obtained resin composition was pressed at a temperature of 200 ° C. (preheating 5 minutes, 3 minutes after pressurization (15 MPa)) using a press molding machine, and then cooled at 30 ° C. for 5 minutes to be about 100 μm × 150 mm × A 150 mm press sheet was obtained.
A tensile test was performed using the obtained press sheet. The results are shown in Table 2.

[Comparative Example 1]
In Example 6, instead of barium titanate modified with polystyrene, barium titanate (BET specific surface area of 6 m ² / g (BET specific surface area was measured by a BET one-point method using Flowsorb II2300 manufactured by Shimadzu Corporation)) The same operation as in Example 6 was carried out except that 3.25 g and 3.25 g of polystyrene (manufactured by Aldrich; Mw-230,000) were used.
A tensile test was performed using the obtained press sheet. The results are shown in Table 2.

[Implementation of tensile test]
[Tensile test conditions]
Tensile test conditions; load full scale: 20 kgf, test speed: 5.0 mm / min, initial sample length: 40 mm, environmental temperature: 23 ° C., environmental humidity: 50% RH

[Tensile test results]

ポリスチレンで修飾されたチタン酸バリウムが、破断点応力、破断点伸度ともに高いことがわかる。

It can be seen that the barium titanate modified with polystyrene has high stress at break and elongation at break.

Claims (8)

A chemical bond is formed on the surface of at least one titanate selected from the group consisting of magnesium titanate, calcium titanate, strontium titanate, and barium titanate (hereinafter sometimes abbreviated as titanate (1)). The titanate compound (A) (hereinafter referred to as titanate) chemically modified with a polymer chain, obtained by polymerizing a monomer having a radical polymerizable unsaturated bond, starting from a radical polymerization initiating group introduced via (It may be abbreviated as compound (A)). The titanate compound (A) according to claim 1, wherein the radical polymerization initiating group according to claim 1 is a living radical polymerization initiating group. The titanate compound (A) according to claim 1, wherein the radical polymerization initiating group according to claim 1 is an atom transfer radical polymerization initiating group. The chemical bond according to claim 1 is composed of titanate (1) and (a) phosphoric acid group, carboxylic acid group, acid halide group, acid anhydride group, isocyanate group, glycidyl group, chlorosilane group, alkoxysilyl group. The titanate compound (A) according to any one of claims 1 to 3, which is formed by reacting at least one functional group selected from the group consisting of silanol groups. The titanate compound (A) according to any one of claims 1 to 3, wherein the chemical bond according to claim 1 is formed by reacting a titanate (1) with an alkoxysilyl group. Titanate (1) and (a) at least selected from the group consisting of phosphoric acid group, carboxylic acid group, acid halide group, acid anhydride group, isocyanate group, glycidyl group, chlorosilane group, alkoxysilyl group, silanol group One kind of functional group,
And (b) a compound (2) in which a radical polymerization initiating group is introduced to the surface of titanate (1) through a chemical bond by reacting with a compound having a radical polymerization initiating group (hereinafter referred to as compound (2) ) May be abbreviated.). Titanate (1) and (a) at least selected from the group consisting of phosphoric acid group, carboxylic acid group, acid halide group, acid anhydride group, isocyanate group, glycidyl group, chlorosilane group, alkoxysilyl group, silanol group One kind of functional group,
And (b) reacting with a compound having a radical polymerization initiating group to obtain a compound (2) having a radical polymerization initiating group introduced into the surface of titanate (1) via a chemical bond. The method for producing a titanate compound (A) according to claim 1, wherein the compound (2) and a monomer having a radical polymerizable unsaturated bond are polymerized. A resin composition comprising the titanate compound (A) according to claim 1 and a resin.