JP2010222520A - Magnesium oxide compound chemically modified with polymer chain - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a magnesium oxide compound chemically modified with a polymer chain, which is obtained by polymerizing a monomer having a radical polymerizable unsaturated bond. <P>SOLUTION: The magnesium oxide compound chemically modified with a polymer chain is obtained by polymerizing the monomer having the radical polymerizable unsaturated bond starting from a radical polymerization initiation group of the compound having the radical polymerization initiation group introduced into a surface of a magnesium oxide through a chemical bond. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

It is known that a polymer composite composed of a polymer-inorganic filler can remarkably improve characteristics such as rigidity and heat resistance as compared with a polymer alone. The characteristics of these polymer composites are greatly affected by the dispersion state of the filler in the matrix resin and its structure.

Conventionally, a method of compounding by kneading a resin and an inorganic filler is known, but it has been difficult to uniformly disperse the inorganic filler in the matrix resin. Thus, attempts have been made to improve the dispersibility of the resin by modifying the surface of the inorganic filler.
One of the methods for modifying the surface of the inorganic filler is a method of coating with a resin by bonding a polymer to the surface of the inorganic filler. For example, surface modification is performed by radical polymerization of a filler into which a radically polymerizable unsaturated bond such as a vinyl group, an acrylate group, or a methacrylate group is introduced in the presence of a monomer such as ethylene, styrene, or methyl methacrylate. However, although this method can modify the surface, a free polymer that is not bonded to the filler is generated, so that the surface cannot be modified with the polymer at a high density. The effect was not always sufficient.

Chem. Rev. 2006, 106, 3936. Chem. Rev. 2001, 101, 3661. Aust. J. et al. Chem. 2005, 58, 379. Chem. Rev. 2001, 101, 2921. Chem. Rev. 2001, 101, 3689.

  An object of the present invention is to provide a magnesium oxide 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 have previously introduced a radical polymerization initiating group into a magnesium oxide particle through a chemical bond, and reacting the particle with a monomer to obtain magnesium oxide compound particles chemically modified with a polymer chain. I found it.

That is, the present invention
[1]:
Radical polymerizable unsaturated starting from the radical polymerization initiating group of a compound having a radical polymerization initiating group introduced through a chemical bond to the surface of magnesium oxide (hereinafter sometimes abbreviated as magnesium oxide (1)). A magnesium oxide compound (A) chemically modified with a polymer chain obtained by polymerizing a monomer having a bond (hereinafter sometimes abbreviated as magnesium oxide compound (A)).
[2]:
The magnesium oxide compound (A) whose radical polymerization initiating group is a living radical polymerization initiating group or an atom transfer radical polymerization initiating group.
[3]:
The chemical bond is selected from the group consisting of magnesium oxide (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. A magnesium oxide compound (A) formed by reacting at least one selected functional group.
[4]:
(A) At least one functional group and radical 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 and silanol group A compound having a polymerization initiating group;
A compound in which a radical polymerization initiating group is introduced through a chemical bond to the surface of magnesium oxide obtained by reacting with magnesium oxide (hereinafter sometimes abbreviated as compound (2)).
[5]:
At least selected from the group consisting of magnesium oxide (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, One kind of functional group,
And (b) obtaining a compound (2) obtained by reacting a compound having a radical polymerization initiating group with a radical polymerization initiating group introduced through a chemical bond on the surface of magnesium oxide (1). A method for producing a magnesium oxide compound (A) comprising polymerizing a monomer having a radically polymerizable unsaturated bond with the obtained compound;
[6]:
A resin composition comprising a magnesium oxide compound (A) chemically modified with a polymer chain and a resin is provided.

  According to the present invention, it is possible to provide a magnesium oxide 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 magnesium oxide compound (A) will be described.

Magnesium oxide (1) is not particularly limited in its crystal structure, size, shape and the like.

  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 or a peroxide group, iodine as described in Non-Patent Document 1, or the like, or a starting group of Nitroxide-Mediated Polymerization (NMP) as described in Non-Patent Document 2. A nitroxide group, a thiocarbonylthio group as an initiation group of Reversible Addition-Fragmentation Polymerization (RAFT) as described in Non-Patent Document 3, and an Atom Transfer Radical Polymerization as described in Non-Patent Documents 4 and 5. An α-halocarbonyloxy group, an α-halocarbonyl group, a halosulfonyl group, a halomethylaryl group, and the like, which are initiation groups for (ATRP: atom transfer radical polymerization) From the viewpoint that the primary structure and chain length of the generated polymer chain can be controlled, the “living radical polymerization initiating group” is, for example, functional groups described in Non-Patent Documents 1 and 2, 3, 4, and 5. A functional group that is an “atom transfer radical polymerization initiating group” as described in Non-Patent Documents 4 and 5 is more preferable.

  The “living radical polymerization initiating group” is not particularly limited. For example, iodine, nitroxide group, thiocarbonylthio group, α-halocarbonyloxy group, α-halocarbonyl group, halosulfonyl group, halomethyl An aryl group etc. are mentioned.

  The “atom transfer radical polymerization initiating group” is not particularly limited, and examples thereof include an α-halocarbonyloxy group, an α-halocarbonyl group, a halosulfonyl group, and a halomethylaryl group.

The “chemical bond” in the “radical polymerization initiating group introduced via a chemical bond” is not particularly limited. For example, magnesium oxide (1) and (a) phosphate group, carboxylic acid group, acid halide And a bond formed by reacting at least one functional group selected from the group consisting of a group, an acid anhydride group, an isocyanate group, a glycidyl group, a chlorosilane group, an alkoxysilyl group, and a silanol group. Includes a bond formed by reacting magnesium oxide (1) with a chlorosilane group, alkoxysilane group, or silanol group, and more preferably by reacting magnesium oxide (1) with an alkoxysilane group. The bond formed is mentioned.
The functional group to be reacted with magnesium oxide (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, selected from the group consisting of magnesium oxide (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 Examples of bonds formed by reacting with at least one kind of functional group are represented using conceptual diagrams, but are not limited thereto.
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 usually polymerized starting from a polymerization initiating group.

Next, (a) at least one function selected from the group consisting of a phosphoric acid group, a carboxylic acid group, an acid halide group, an acid anhydride group, an isocyanate group, a glycidyl group, a chlorosilane group, an alkoxysilyl group, and a silanol group. Group,
And (b) compound (2) in which a radical polymerization initiating group is introduced via a chemical bond to the surface of magnesium oxide (1) by reacting the compound having a radical polymerization initiating group with magnesium oxide (1). State.

(A) at least one functional group selected from the group consisting of a phosphoric acid group, a carboxylic acid group, an acid halide group, an acid anhydride group, an isocyanate group, a glycidyl group, a chlorosilane group, an alkoxysilyl group, and a silanol group; b) The compound having a radical polymerization initiating group is not particularly limited, and specific examples thereof include the following compounds, and preferred examples include compounds having an alkoxysilyl group and a radical polymerization initiating group. .

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.

  From the group consisting of magnesium oxide (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 functional group selected and (b) 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.

  After the reaction, the compound (2) in which a radical polymerization initiating group is introduced through a chemical bond to the surface of the produced magnesium oxide (1) 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.

Next, (a) at least one functional group selected from the group consisting of a phosphoric acid group, a carboxylic acid group, an acid halide group, an acid anhydride group, an isocyanate group, a glycidyl group, a chlorosilane group, an alkoxysilyl group, and a silanol group And (b) a compound obtained by reacting a compound having a radical polymerization initiating group with magnesium oxide (1), wherein the surface of magnesium oxide (1) is introduced with a radical polymerization initiating group via a chemical bond (2 )
And a step of radical polymerization of a monomer having a radical polymerizable unsaturated bond.

As the radical polymerization, any polymerization method may be used, but since the molecular weight of the polymer chain bonded to the surface of magnesium oxide is preferably uniform, living radical polymerization is preferable. Atom transfer radical polymerization as described in 5 is more preferred.
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).

  A catalyst is usually used for atom transfer radical polymerization, and the catalyst is not particularly limited. For example, divalent copper, monovalent copper, zero-valent copper, divalent ruthenium, divalent iron, or Examples include divalent nickel complexes, and copper complexes are preferred. 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 from -20 ° C to 200 ° C, and preferably from 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 magnesium oxide compound (A) chemically modified with the polymer chain and the unreacted monomer. And the solvent can be separated. The obtained magnesium oxide compound (A) may be further purified by washing with an appropriate solvent or the like.

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

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

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

  The mixing method of the magnesium oxide compound (A) and the resin is not particularly limited. For example, the mixing method or the kneading method may be used. Furthermore, the solvent may be mixed once using a solvent. The method of distilling off is mentioned.

  The resin composition containing the magnesium oxide compound (A) and the resin may be molded using methods such as injection molding, blow molding, extrusion molding, inflation molding, vacuum molding after sheet processing, and compression molding. Is possible.

  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}]
(Synthesized with reference to Macromolecules, 2005, 38, 2137.)
To a reaction vessel equipped with a cooling apparatus, 56.5 g of 2-bromo-2-methylpropionic acid-5-hexene and 700 mL of toluene were added at room temperature. To the resulting solution, 207 mL of triethoxysilane was added dropwise. The obtained mixture was heated to 30 ° C., and 850 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) was added. Thereafter, the mixture was stirred for 3 hours, and further stirred overnight at room temperature. Thereafter, the reaction solution was concentrated at 32 ° C. and further dried under reduced pressure at 55 ° C. for 4 hours to obtain 89.7 g of 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl}. It was. The area percentage value obtained by gas chromatography analysis was 89%.

[Example 2]
[Synthesis of Compound (2) Introduced with Radical Polymerization Initiating Group via Chemical Bond on the Surface of Magnesium Oxide; Magnesium Oxide and 2-Bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl} reaction]
In a reaction vessel equipped with a cooling device, at room temperature, magnesium oxide (manufactured by Aldrich; specific surface area 46.5 m ^{2 /} g) 25.00 g, 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl } 13.79 g and 230 mL of toluene were added. The resulting mixture was stirred for 8 hours under reflux. Thereafter, the insoluble part was recovered by centrifugation and washed four times with 280 mL of tetrahydrofuran. The obtained solid was dried under reduced pressure at room temperature for 8 hours, and a compound in which a radical polymerization initiating group was introduced onto the surface of magnesium oxide via a chemical bond (magnesium oxide and 2-bromo-2-methylpropionic acid {6 Compound obtained by reacting with-(triethoxysilyl) hexyl} was obtained.
Elemental analysis: C: 1.5%, Br: 0.8%

[Example 3]
[Compound (2) in which radical polymerization initiating group is introduced via chemical bond on the surface of magnesium oxide (reacting magnesium oxide with 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl}) Transfer Radical Polymerization of Compound) with 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 through a chemical bond on the surface of magnesium oxide; magnesium oxide and 2-bromo-2-methylpropion. Compound reacted with acid {6- (triethoxysilyl) hexyl} "10.00 g, copper (I) bromide 28.73 mg, copper powder 26.24 mg, anisole 32.86 mL, N, N, N ', An anisole solution of N ″, N ″ -pentamethyldiethylenetriamine (3.002 mL (0.40 mol / L)) and methyl methacrylate (64.26 mL) were added, and the mixture was stirred at room temperature for 5 minutes, and further stirred at 90 ° C. for 8 hours. . Thereafter, the insoluble part was recovered by centrifugation and washed 6 times with 280 mL of tetrahydrofuran. The obtained solid was dried under reduced pressure at room temperature for 8 hours to obtain 20.80 g of magnesium oxide modified with polymethyl methacrylate.
Elemental analysis: C: 35.7%, Br: 0.2%

[Measurement of glass transition temperature]

For the compound obtained in Example 3 and polymethylmethacrylate (Aldrich; Mw to 120,000), the glass transition temperature was measured using DSC (TA Instruments; DSC Q2000). (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酸化マグネシウムが、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 magnesium oxide modified with polymethyl methacrylate has a higher glass transition temperature and improved heat resistance than polymethyl methacrylate alone resin.

[Example 4]
4.85 g of magnesium oxide modified with polymethylmethacrylate obtained in Example 3 and 1.65 g of polymethylmethacrylate (manufactured by Aldrich; Mw˜120,000) are added to a small kneader minilab (manufactured by ThermoHake) Was used for melt kneading at 200 ° C. for 20 minutes (rotation speed: 50 rpm). After kneading, the mixture was granulated with an extruder to obtain a resin composition. About the obtained resin composition, after pressing at a temperature of 200 ° C. (preheating 5 minutes, 3 minutes after pressurization (15 MPa)) using a press molding machine (manufactured by Shinfuji Metal Industry Co., Ltd .; compression molding machine NF-37), A press sheet having a size of about 100 μm × 150 mm × 150 mm was obtained by cooling at 30 ° C. for 5 minutes.
Using the obtained press sheet, a tensile test (manufactured by Orientec; UNIVERSAL TESTING MACHINE STA-1225) was performed. The results are shown in Table 2.

[Comparative Example 1]
In Example 3, instead of magnesium oxide modified with polymethyl methacrylate, magnesium oxide (Aldrich; specific surface area 46.5 m ^{2 /} g) 1.95 g, polymethylmethacrylate (Aldrich; Mw˜120, 000) Except for using 4.55 g, it was carried out in the same manner as in Example 4, but it was very brittle and a press sheet was not obtained.

[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]

Claims (8)

Chemistry with a polymer chain obtained by polymerizing a monomer having a radical polymerizable unsaturated bond starting from the radical polymerization initiating group of a compound having a radical polymerization initiating group introduced to the surface of magnesium oxide via a chemical bond Modified magnesium oxide compound. The magnesium oxide compound according to claim 1, wherein the radical polymerization initiating group according to claim 1 is a living radical polymerization initiating group. The magnesium oxide compound 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 magnesium oxide and (a) a phosphoric acid group, a carboxylic acid group, an acid halide group, an acid anhydride group, an isocyanate group, a glycidyl group, a chlorosilane group, an alkoxysilyl group, and a silanol group. The magnesium oxide compound according to any one of claims 1 to 3, wherein the magnesium oxide compound is formed by reacting at least one functional group selected from the group consisting of: The magnesium oxide compound according to any one of claims 1 to 3, wherein the chemical bond according to claim 1 is formed by reacting magnesium oxide (1) with an alkoxysilyl group. (A) At least one functional group and radical 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 and silanol group A compound having a polymerization initiating group;
A compound in which a radical polymerization initiating group is introduced through a chemical bond to the surface of magnesium oxide obtained by reacting with magnesium oxide. (A) At least one functional group and radical 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 and silanol group A compound having a polymerization initiating group is reacted with magnesium oxide to obtain a compound having a radical polymerization initiating group introduced on the surface of magnesium oxide via a chemical bond, and the resulting compound and a radical polymerizable unsaturated bond are obtained. The method for producing a magnesium oxide compound according to claim 1, wherein a monomer having an acid is polymerized. A resin composition comprising the magnesium oxide compound according to claim 1 and a resin.