WO2009139450A1 - Alumina composite material - Google Patents

Abstract

Disclosed is an alumina composite material wherein the hydrogen atom in a surface hydroxy group of alumina is substituted by a silicon atom and a polymer chain is bonded to the oxygen atom in the surface hydroxy group through the silicon atom.  This alumina composite material is characterized in that the polymer chain contains a structure derived from a living radical polymerization initiation group and a structural unit derived from a monomer having a radically polymerizable unsaturated bond.

Description

 Alumina composite technology

 The present invention relates to an alumina composite material.

 Light

Background technology

 J. Mater. C he m., 1 9 9 7, 7_, 1 5 2 7— 1 5 3 2, alumina obtained by reacting alumina with 3- (trimethoxysilyl) propyl metatalylate An alumina composite in which the hydrogen atom of the surface hydroxyl group is substituted with a 3- (methacryloxy) propyl silyl group is disclosed.

 Macromolecules 2 0 0 2, 3 5, 8 9 1 3— 8 9 1 6 are reacted with alumina and 2-bromopropionic acid, and then atom transfer radical polymerization of methyl methacrylate and butyl acrylate. An alumina composite material obtained by polymerizing is disclosed. Disclosure of the invention

 The present invention

<1> Alumina composite material in which hydrogen atoms of surface hydroxyl groups of alumina are substituted with carbon atoms, and polymer chains are bonded to oxygen atoms of surface hydroxyl groups via the silicon atoms, and the polymer chains are bonded to each other. An alumina composite comprising a structure derived from a bing radical polymerization initiating group and a structural unit derived from a monomer having a radical polymerizable unsaturated bond;

<2> The alumina composite material according to 1>, wherein the linking radical polymerization initiating group is an atom transfer radical polymerization initiating group;

<3> The alumina composite according to <2>, wherein the atom transfer radical polymerization initiating group includes an α-haloacyloxy group, an _α -haloacyl group, a halosulfonyl group, or an α-halobenzyl group; 09 059024

> Atom transfer radical polymerization initiating group is represented by formula (2)

The alumina composite material according to <2>, which is a group represented by:

 <5> The structure derived from the linking radical polymerization initiating group is bonded to the silicon atom directly or via an alkylene group having 1 to 20 carbon atoms, or any one of 1> to <4> Alumina composite material;

 <6> Monomers having radically polymerizable unsaturated bonds are styrene monomers, acrylate monomers, methacrylate monomers, acrylamide monomers, methacrylamide monomers, acrylic acid, methacrylic acid, acrylate The alumina composite material according to any one of <1> to <5>, which is at least one selected from the group consisting of nitrile, methacrylonitrile, 4-butylpyridine, and vinyl acetate;

<7> The average particle diameter of the alumina (D _{5 0)} is 6 0 nm~ 5 0 ^ m <1> alumina composite material according to any of ~ rather 6>;

<8> Alumina composite material obtained by surface-treating alumina with a silane coupling agent containing a linking radical polymerization initiating group and then reacting with a monomer having a radical polymerizable unsaturated bond;

 <9> A resin composition comprising a resin obtained by polymerizing at least one monomer having a radical polymerizable unsaturated bond and the alumina composite material according to any one of 1> to <8>. object';

 <1 0> The resin composition according to 9>, wherein the resin is obtained by polymerizing an acrylate or methacrylate.

 <11> The resin composition according to <9>, wherein the resin is polymethyl methacrylate;

<1 2> alumina composition comprising the alumina composite material according to any one of 1> to 8>;

<1 3> Silane power containing alumina and riving radical polymerization initiator A method for producing an alumina composite, characterized by reacting a curing agent and then polymerizing a monomer having a radical polymerizable unsaturated bond by living radical polymerization;

 <14> Alumina in which a hydroxyl group is substituted with a hydrogen atom on the surface hydroxyl group thereof, and a living radical polymerization initiating group is bonded to the silicon atom directly or via a linking group; is there. BEST MODE FOR CARRYING OUT THE INVENTION

 The alumina composite material according to the present invention is an alumina composite material in which a hydrogen atom of a surface hydroxyl group of alumina is substituted with a carbon atom, and a polymer chain is bonded to an oxygen atom of the surface hydroxyl group through the silicon atom, The polymer chain includes a structure derived from a living radical polymerization initiating group and a structural unit derived from a monomer having a radical polymerizable unsaturated bond.

Alumina is not limited, and examples include α-alumina, γ-alumina, Θ-alumina, and δ-alumina. The shape of the alumina is not limited, and may be, for example, particulate alumina or fibrous alumina. In the case of particulate alumina, its average particle size (D ₅₀ ) or primary particle size is not limited, but D ₅ . Is usually 60 nm or more, preferably 60 nm or more and 50 μm or less, or alumina whose primary particle size is usually 1 to 100 nm, preferably 10 to 500 nm. . As such alumina, commercially available ones may be used, and for example, those produced in accordance with a known method such as Japanese Patent Publication No. 2000-08888 may be used. In the alumina composite of the present invention, the hydrogen atom of the surface hydroxyl group of alumina is substituted with a key atom, and an oxygen-ca-bond is formed. 1 to 3 polymer chains are bonded to the silicon atom, and preferably one polymer chain is bonded. In addition, the key atom usually has (3-n) chlorine atom, bromine atom, iodine atom, hydroxyl group, C 1-4 alkoxy group, etc., depending on the number of polymer chains (n) Or oxygen atoms of surface hydroxyl groups of alumina are bonded to each other. As the substituent, a chlorine atom, a hydroxyl group, and an alkoxy group having 1 to 4 carbon atoms are preferable because the production of the alumina composite material is easy. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, and an n-propoxy group.

 The polymer chain includes a structure derived from a living radical polymerization initiating group and a structural unit derived from a monomer having a radical polymerizable unsaturated bond, and may include a linking group bonded to a silicon atom.

 Examples of the linking group include an alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a decamethylene group, and a dodecamethylene group, and has 2 to 10 carbon atoms. An alkylene group is preferred.

 A living radical polymerization initiating group is a functional group that can generate radicals by reacting with light, heat, or other electromagnetic waves, or a functional group that can generate radicals upon reaction with a catalyst. A group having an azo group (one N = N +) such as an azoalkyl group, a group having a peroxide group such as a peroxyalkyl group, C he m. R ev. 2 0 0 6 , 1 0 6, 3 9 3 6— a group having an iodine atom such as an alkyl iodide group described in 3 9 6 2, C he m.

Living radical polymerization initiator group via a nitroxide such as ditoxyl alkynole group described in R e v. 200 1, 1 0 1, 3 6 6 1— 3 6 8 8, Au st. J. C he m., Initiation of reversible addition / elimination chain transfer polymerization reaction having a thiocarbothio group such as phenenoretiocanol benzoylthiomethyl group described in 2 0 0 5, 5 8, 3 7 9— 4 10 R e v. 2 0 0 1, 1 0 1, 2 9 2 1— 2 9 9 0 and C he m. R e. 2 0 0 1, 1 0 1, 3 6 8 9— Examples of the atom transfer radical polymerization initiating group such as α-no-nanoguchi asinoleoxy group, α-no-no-ashinoreoxy group, no- rosolephoninole group, and α-no-ninoguchi benzyl group described in 3 745. Among these, from the viewpoint of controlling the primary structure and chain length of polymer chains in the production of alumina composites, living radical polymerization initiation groups via iodine atoms and ditroxides, reversible addition / elimination chain transfer polymerization initiation groups and An atom transfer radical polymerization initiating group is preferable, an atom transfer radical polymerization initiating group is more preferable, and a haloacyloxy group is particularly preferable.

α —Haloashi 7 reoxy group, one haloacinole group, nosnorehoninole group and ct-ha benzyl group include halogen atom, chlorine atom, bromine atom, iodine atom Four

 Five

Chlorine and bromine atoms are preferred.

 Examples of the α-haloacinole group of the a-haloacinoleoxy group and α-haloacinole group include a chloroacetyl group and a 2-bromopropioel group. Examples of the halosulfol group include a chlorosulfoninole group and a promosulfol group, and examples of the α-noxyl benzyl group include a chloromethylphenyl group and a bromomethylphenyl group.

Examples of the structure derived from the linking radical polymerization initiating group include the following structures.

(Wherein R ¹ and R ² independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group). A monomer having a radical-polymerizable unsaturated bond of a structural unit derived from a monomer having a radical-polymerizable unsaturated bond may be a monomer having an unsaturated bond capable of proceeding with a free radical polymerization reaction in the presence of an organic radical. Methacrylic acid, acrylic acid, methacrylate monomers, acrylate monomers, styrene monomers, a-olefin monomers, vinylenoesterol monomers, vinylenoketone monomers, vinyl substituted complexes Aromatic monomers, acrylic amide monomers, methacrylamide monomers, vinyl halide monomers, acrylonitrile, methacrylates, maleic acid, maleic anhydride, gen monomers, dialyl System monomers and the like.

Examples of methacrylate monomers include methyl methacrylate, ethyl methacrylate, η-propyl methacrylate, isopropylene methacrylate, η-butyl methacrylate, tert-butyl methacrylate, n-noel methacrylate. Benzene / Remethacrylate, Dioxin Hexinoremethacrylate, 2-Methoxychichinolemethacrylate, 2-N-Butchichechinolemethacrylate, 2-Hydroxyethylenomethacrylate, 2-Hydroxypropinoremethacrylate, Diethylenegue Examples include recall monomethacrylate, diethylene glycolate methacrylate, glycidyl methacrylate, 2- (dimethylamino) ethyl methacrylate, and the like.

 Examples of the acrylate monomer include methyl acrylate, ethyl acrylate, n-propinorea acrylate, n-butyl acrylate, tert-butyl acrylate, n-hexino acrylate, n-nonino acrylate, pendino rare acrylate ', Chick mouth hex / reactylate, 2—methoxetinoreactylate, 2—n-butoxetinorearelate, 2—hydroxichetinoleate, 2-hydroxypropinoreata Examples thereof include relate, diethylene glycol monoacrylate, dimethylene glycol diacrylate, glycidyl acrylate, 2_ (dimethylamino) ethyl acrylate, and the like.

 Styrene monomers include styrene, ct-methylol styrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o- tert-butyl styrene, m- tert-butyl styrene, p- tert-Putinolestyrene, o_chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-styrene sulphonic acid, m-styrene Examples include sulphonic acid and p-styrene sulphonic acid.

 Examples of α-olefin monomers include ethylene, propylene, isobutene, 1-hexene, and cyclohexene.

 Examples of the butyl ester monomer include butyl acetate, butyl propionate, and vinyl benzoate. Examples of the vinyl ketone monomer include vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone. Examples of vinyl-substituted heteroaromatic monomers include Ν-Bulylpyrrolidone, Ν-Vinylvinylolole, Ν-Vinylcarbazole, Ν-Vinylindole, Ν-Vinyl polyaromatic monomers, 4 Monovinylpyridine, 2 — And vinyl pyridine monomers such as vinyl pyridine.

Examples of acrylamide monomers include Ν-propyl acrylamide, ,, Ν-dimethyl acrylamide, Ν, Ν-jetyl acrylamide, and the like. , Ν-isopropyl methacrylate,,, 9024

N-dimethylmethacrylamide, N, N-jetylmethacrylamide, and the like can be mentioned.

 Examples of the halogenated butyl monomer include butyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropylene, and vinylol fluoride.

 Examples of the gen-based monomer include butadiene and isoprene, and examples of the diaryl monomer include monomers having two aryl groups such as diaryl phthalate.

 The alumina composite material of the present invention may have a structural unit derived from a monomer having two or more radically polymerizable unsaturated bonds.

The number average molecular weight (M _n ) of the polymer chain is usually from 100 to 40,000. In the present invention, the “number average molecular weight of polymer chain” means the number average molecular weight of a polymer obtained by separating the polymer chain from the alumina composite of the present invention by a predetermined method such as hydrolysis. The alumina composite material of the present invention is obtained by, for example, reacting alumina and a silane coupling agent having a libbing radical polymerization initiating group, and then polymerizing a monomer having a radical polymerizable unsaturated bond by ribbing radical polymerization. Can be manufactured. A silane-powered pulling agent having an atom transfer radical polymerization initiating group is preferred as the riving radical polymerization initiating group in that an alumina composite having a polymer chain with a primary structure controlled is easily obtained.

A silane-powered printing agent having an atom transfer radical polymerization initiating group is represented by the formula (2)

(Wherein R ¹ and R ² independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, m represents an integer of 0 to 20; X represents a chlorine atom, bromine Represents an atom or an iodine atom, and Y Υ ² and Υ ³ independently represent an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a chlorine atom, a bromine atom, or an iodine atom.)

And silane-powered printing agent represented by Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, and n-propoxy group.

 The silane-powered printing agent represented by the formula (2) is, for example, J. Pol ym er S c i nc ce: P a r t A: P o 1 ym e r C h e m i s t r y 2 0 0 1,

It can be produced by the method described in 3 9, 4 2 94.

 Examples of the silane coupling agent represented by the formula (2) include 2-chloro-2-methylpropionic acid {6- (trimethoxysilyl) 1-n-hexyl}, 2-chloro-mouth 1-methylpropionic acid { 6- (triethoxysilyl) 1-n-hexyl}, 2 1-bromo — 2-methylpropionic acid {6- (trimethyoxylinole) 1-n-hexyl}, 2— promote 2-methylpropionic acid {6— (to Riethoxysilinole) 1-n-hexenole}, 2--iodo-one 2-methylpropionic acid {6 -— (trimethyoxysilyl) -1-n-hexyl}, 2--odo-2-methylpropionic acid {6-— (triethoxy Silyl) 1 n 1 hexyl},

 2—Black mouth_ 2—Methylolepropionic acid {4- (trimethyoxysilyl) 1-n-butyl}, 2_Chloro-2-methylpropionic acid {4-1 (triethoxysilyl) 1-n-butyl}, 2— Bromo-2-methylpropionic acid {4 (trimethoxysilinole) 1 η-butyl}, 2-bromo-1-2-methylpropionic acid {4 1 (triethoxysilyl)-η-butyl}, 2-odo-2-methylpropion Acid {4-(trimethyoxysilyl) 1 η-butyl}, 2-iodine 1 -methylpropionic acid {4-(triethoxysilyl) 1 η-butynole),

 2-chloro-2-methylpropionic acid {2- (trimethyoxysilyl) ethyl}, 2-chloro-2-methylpropionic acid {2- (triethoxysilyl) ethyl}, 2 monopromo 2-methylpropionic acid {2- (trimethyl Toxylyl) ethyl: k 2 -promo-2-methylpropionic acid {2- (triethoxysilyl) ethyl}, 2-methyl 2-dimethylpropionic acid {2- (trimethoxysilyl) ethyl}, 2-methyl 1 2-methylpropionic acid {2- (triethoxysilyl) ethyl},

2—Chloro-2-methinorepropionic acid trimethyoxylinole, 2—Black mouth _ 2—Methinorepropionic acid triethoxysilane <re, 2-Promo 2—Methyl ^ / propionic acid Trimethoxysilyl, 2-promo 2-triethoxysilyl 2-methylpropionate, 2-Edo 2-trimethylsilyl trimethyl thiopionate, 2-Edo 2-triethoxysilyl 2-methyl propionate,

 2-chloropropionic acid {6- (trimethyoxysilyl) -1-n-hexyl}, 2-chloro-propionic acid {6- (triethoxysilyl) 1-n-hexyl}, 2-monobromopropionic acid {6- ( Trimethyoxysilyl) 1 n-hexyl}, 2 Monobromopropionic acid {6- (Triethoxysilyl) 1 n — Hexyl}, 2 Rhodopropionic acid {6 — (Trimethyoxysilyl) 1 n — Hexyl}, 2 — Yoodopropion The acid {6- (tritoxisilyl) 1 n -hexynole},

 2-chloropropionic acid {4-1 (trimethyoxysilyl)-n-butyl}, 2-chloropropionic acid {4-1 (triethyoxysilyl)-n-butyl}, 2-promopropionic acid {4-1 (trimethyoxysilyl) 11-Putyl}, 2 Monobromopropionic acid {4- (Triethoxysilyl) 1-n-Butyl}, 2-Odopropionic acid {4- (Trimethoxysilyl) 1-N_butyl}, 2-Oodopropionic acid {4 — (Triethoxysilyl) One n-Ptyl}, '

 2-Chloropropionic acid {2- (trimethyoxysilyl) ethynole}, 2-Chlorobutoxypionic acid {2- (triethoxysilyl) ethyl}, 2-Promopropionic acid {2 (trimethysilyl) ethyl}, 2 —Bromopropionic acid {2— (triethoxysilyl) ethyl}, 2- odopropionic acid {2— (trimethyoxysilyl) ethyl}, 2- odopropionic acid {2— (triethoxysilyl) ethyl},

 2_trimethoxysilinore, 2-propoxypropionate, triethoxysilyl 2-bromopropionate, trimethoxysilylole 2-bromopropionate, 2-ethoxysilylpropoxypropionate, 2-methoxysilyl 2-propidopropionate, 2-triodepropionate trie Toxisilyl,

2—Black mouth _ 2—Methylpropionic acid {6-(trihydroxysilyl) mono n-hexenole}, 2-chloro-2-methinorepropionic acid {6— (trihydroxysilinole) mono n monohexyl}, 2-Promo 1-Methylenopropionic acid {6- (trihydroxysilyl)-n monohexyl}, 2-bromo-2-methylpropionic acid {6-(trihydroxysilyl) mono n monohexyl}, 2 —Dodo 2—Methylpropionic acid {6 (Trihydroxysilyl) 1 n-hexynole}, 2-hydroxy-2-methylpropionic acid {6- (trihydroxysilyl) 1-hexynole},

2-chloro-2-methylpropionic acid {4 (trihydroxysilyl) 1-n-butyl}, 2-chloro-2-methylpropionic acid {4-1 (trihydroxysilanol)-n-butyl}, 2-promo 2-Methylpropionic acid {4 (trihydroxysilyl) -1-n-butyl}, 2-bromo-2-methylpropionic acid {4- (trihydroxysilyl) _n-butyl}, 2-iodo-2-methylpropion acid {4 i (tri arsenate Dorokishiriru) one _n - butyl}, 2- Yodo 2-methylpropionic acid {4- (vii Li arsenate Dorokishiriru) Single n _ butyl},

 2_Chloro-2-methylepropionic acid {2- (trihydroxysilinore) ethinole},

2-chloro-2-methylpropionic acid {2- (trihydroxysilyl) ethyl}, 2-bromo-2-methylpropionic acid {2- (trihydroxysilyl) ethyl}, 2-bromo-2-methylpropionic acid {2- ( Trihydroxyloxy) ethyl}, 2-hydroxyl 2-methylpropionic acid {2- (trihydroxysilyl) ethyl}, 2-hydroxy-2-methylpropionic acid {2- (trihydroxysilyl) ethyl}, 2 —Trihydroxysilyl 2-chloro-2-methylpropionate, 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl-2-methylpropionate, 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropylone 2 — Monod 2-trimethyl droxysilinole, 2-3 Methylpropionic Santo Li human Dorokishishiriru,

2_Black-mouth propionic acid {6- (trihydroxysilyl) 1 1 1 hexyl}, 2 1 bromopropionic acid {6-(trihydroxysilyl) 1 n-hexyl}, 2-chloropropionic acid {6— (Trihydroxysilyl) 1- _n- hexyl}, 2-chloropropionic acid {4 1 (Trihydroxysilyl) 1-n-butyl}, 2 1-bromopropionic acid {4 1 (Trihydroxysilyl) 1 n-butyl }, 2-odopropionic acid {4-(trihydroxysilyl) mono-n-butyl},

2-chloropropionic acid {2- (trihydroxysilyl) ethyl}, 2-bromopropionic acid {2- (trichlorosilyl) ethyl}, 2-iodopropionic acid {2-1 (trihydroxysilyl) ethynole}, 2- Black mouth propionate trihydroxide Lyl, 2-hydroxypropyl 2-bromopropionate, 2-hydroxysilyl 2-iodopropionate,

2-chloro-2-methylpropionic acid {6-(trichlorosilyl) mono _n- hexinole 2-bromomono 2-methylpropionic acid {6-(trichlorosilyl)-n-hexyl}, 2- 2-Methylpropionic acid {6- (trichlorosilinole) -n monohexyl}, 2-chloro-mouth _2-methylpropionic acid {4-1 (trichlorosilinole) mono-n-butyl}, 2-bromo-2-methyl Propionic acid {4 _ (trichlorosilyl)-n-butyl}, 2-iodine 1-2-methylpropionic acid {4 1 (trichlorosilyl)-n-butyl},

 2-chloro-2-methinorepropionic acid {2-(trichlorosilyl) ethynole}, 2

—Bromo-2-methylpropionic acid {2- (trichlorosilyl) ethyl}, 2-3—do-2-methylpropionic acid {2-1 (triethoxysilyl) ethyl}, 2-chloro mouth _ 2-methinolepropion Trichlorosilyl acid, 2-Promo 2-trichlorosilyl 2-methylpropionate, 2-Yodo 2-Tripropoxysilyl 2-methylpropionate, 2-Chloropropionic acid {6- (Trichlorosilino) 1 n-Hexenore}, 2 — Bromopropionic acid {6-(trichlorosilyl) mono-n-hexyl}, 2- odopropionic acid {6-(trichlorosilyl) mono-n-hexyl},

 2-chloropropionic acid {4- (trichlorosilinole) mono-n-butyl}, 2-bromopropionic acid {4-mono (trichlorosilyl) mono-n-butyl}, 2-monopropionic acid {4-1 (trichloro Silyl) 1-n-butyl}, 2_black-propionic acid {2- (trichlorosilyl) ethyl Λ ^}, 2-monobromopropionic acid {2- (trichlorosilyl) ethyl}, 2-iodopropionic acid {2- (Trichlorosilyl) ethyl},

Examples thereof include 2-chlorotripropionate trichlorosilyl, 2-bromopropionate trichlorosilyl, and 2-chloropropionate trichlorosilyl.

 The amount of the silane coupling agent having a living radical polymerization initiating group is not limited, and is usually from 0.001 to 10 moles per mole of alumina.

The reaction between the alumina and the silane force pulling agent having a linking radical polymerization initiating group may be carried out without a solvent, but is preferably carried out in a solvent. Examples of the solvent include water, an organic solvent, and a mixed solvent of water and an organic solvent. As organic solvent Aromatic hydrocarbon solvents such as benzene, toluene, xylene, 1,4-dioxane, tetrahydrofuran, jetyl ether, tert-butyl methyl ether, ethylene glycol solvent such as ethylene glycol solvent, methanol solvent, Alcohol solvents such as ethanol and isopropanol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide solvents, dimethyl sulfoxide and other sulfoxide solvents Etc. The amount of such solvent used is not limited.

 In order to make the reaction proceed smoothly, a catalyst such as a base such as ammonia or an acid such as acetic acid may be used. The amount used is usually from 0.001 to 100 moles per mole of alumina. is there.

 The reaction temperature is usually _78 ° C to 200 ° C.

 After completion of the reaction, for example, by concentrating, filtering or centrifuging the reaction mixture, the hydrogen atom of the hydroxyl group on the surface of alumina is replaced with a key atom, and the radical radical polymerization initiating group is directly or linked to the key atom. Alumina bonded through the group can be removed. The extracted alumina may be washed with water, an organic solvent, or a mixed solvent of water and an organic solvent.

For example, when the silane coupling agent represented by the formula (2) is used, the hydrogen atom of the surface hydroxyl group of alumina is substituted with a key atom, and the key atom is substituted with the following formula:

Alumina bonded with a group represented by By polymerizing the obtained alumina and a monomer having a radical polymerizable unsaturated bond, the living radical polymerization reaction proceeds from the living radical polymerization initiating group, and the alumina composite material of the present invention is obtained. Examples of the monomer having a radical polymerizable unsaturated bond include the same ones as described above. A monomer having two or more types of radically polymerizable unsaturated bonds may be used.

The amount of the monomer having a radically polymerizable unsaturated bond is the amount of the resin in the alumina. The amount is usually from 10 to 100 moles per mole of the bing radical polymerization initiating group. The polymerization reaction may be appropriately performed depending on the type of living radical polymerization initiating group. For example, when the living radical polymerization initiating group is an atom transfer radical polymerization initiating group, the polymerization reaction may be carried out according to the atom transfer radical polymerization method.

 Atom transfer radical polymerization is usually carried out in the presence of a catalyst.

Monovalent or divalent copper complexes, divalent ruthenium complexes, divalent iron complexes, divalent nickel complexes, etc. are preferred, and zero-valent, monovalent or divalent copper complexes are preferred, and monovalent copper Complexes are more preferred. Two or more types of catalysts may be used.

 Copper complexes can usually be prepared by contacting a copper compound with a ligand such as cuprous chloride, cuprous bromide, cupric chloride, cupric bromide, copper powder and the like. The ligands include bipyridyl compounds such as 2,2 monobipyridyl, N, N, NN '—tetramethylethylentriamine, N, N, N', N ,, N "monopentamethylethylentriamine , Tris (dimethylaminoethyl) amine, etc. The amount of the ligand used is usually 0.5 to 5 mol per 1 mol of the copper compound.

 The amount of the catalyst used is usually from 0.001 to 100 mol, preferably from 0.001 to 500 mol in terms of metal per 1 mol of the living radical polymerization initiating group in the alumina. is there.

 The polymerization reaction may be carried out without a solvent or in a solvent. Solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene, 1,4-dioxan, tetrahydrofuran, jetinore tenore, tert-butinoremethinoleenotenole, ethylene glycol Ether solvents such as tenole, anisol and diphenyl ether, alcohol solvents such as methanol, ethanol and isopropanol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone Amide solvents such as dimethyl sulfoxide, sulfoxide solvents such as dimethyl sulfoxide, nitrile solvents such as acetonitrile and benzonitryl, and ester solvents such as ethyl acetate. Two or more solvents may be mixed and used.

 The polymerization temperature is usually from 1 to 20 ° C., preferably from 0 to 150 ° C.

When the linking radical polymerization initiating group is an atom transfer radical polymerization initiating group, the polymerization reaction may be carried out in combination with an atom transfer radical polymerization initiator. By using a polymerization initiator in combination, an alumina composite material having a polymer chain with a low degree of dispersion can be obtained. It is preferable to use an atom transfer radical polymerization initiator having the same atom transfer radical polymerization initiator as the atom transfer radical polymerization initiator. When used together with an atom transfer radical polymerization initiator, the amount used is usually 0.1 to 2 with respect to 1 mol of an atom transfer radical polymerization initiating group in alumina obtained by reaction with a silane coupling agent. 0 mole.

 After the completion of the polymerization reaction, for example, the alumina composite material of the present invention can be taken out by filtering or centrifuging the obtained reaction mixture. The removed alumina composite material may be washed with an organic solvent. Then, the resin composition containing the alumina composite material of this invention and a resin is demonstrated. The resin may be a resin derived from a monomer having an unsaturated bond that can undergo radical polymerization reaction in the presence of an organic radical. Such monomers include methacrylic acid, acrylic acid, methacrylate monomers, acrylate monomers, styrene monomers, α-olefin monomers, buresterol monomers, vinyl ketone monomers, vinyl substituted monomers. Heteroaromatic monomers, acrylic amide monomers, methacrylamide monomers, halogenated butyl monomers, chloronitriles, meta-trityl, maleic acid, maleic anhydride, genic monomers, diallylic monomers, etc. Is mentioned. Examples of these monomers include the same ones as described above. In the resin composition of the present invention, the structural unit derived from the monomer having a radical polymerizable unsaturated bond in the alumina composite material may be the same as or different from the structural unit derived from the monomer in the resin. Also good. The weight ratio of the alumina composite material to the resin in the resin composition (alumina composite material: resin) is usually 0.1: 99.9 to 99.9: 0.1, preferably 1:99. ~ 20: 80.

 The resin composition of the present invention may be prepared by mixing an alumina composite material and a resin. For example, a method of directly mixing the two, a method of kneading the two, mixing the two in a solvent, and then removing the solvent And the like.

The resin composition of the present invention comprises injection molding, blow molding, extrusion molding and inflation. Forming can also be performed using methods such as vacuum forming and compression molding after forming and sheet processing. Example

 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

 The polymer content in the alumina composite was determined by the thermogravimetric differential thermal analyzer (equipment: sii, TG / DTA 6 200 R, manufactured by NanoTechnoguchiji, measurement temperature: 25-600 ° C, heating rate: 10 ° CZ Min). Reference example 1

 In a reaction vessel equipped with a condenser, dropping funnel and stirrer, benzoate containing 2-bromo-2-methylpropionic acid 5-hexenyl 70 g and platinic acid chloride hexahydrate at room temperature under argon atmosphere. -Tolyl solution (0.05 mol / L) 3.3 8 mL was added, and the resulting mixture was stirred at 80 ° C for 30 minutes. After 41.5 g of triethoxysilane was added dropwise to the mixture, the resulting mixture was stirred at 80 ° C. for 27.5 hours to react. After completion of the reaction, the solvent was removed from the obtained reaction mixture at 8'0 ° C under reduced pressure, and then the insoluble matter was removed from the resulting concentrate by filtration to give 2-promo 2-methylpropionic acid { 6- (Triethoxysilyl) hexyl} 8 2 g was obtained. Reference example 2.

To a reaction vessel equipped with a cooling apparatus, 56.5 g of 2-promo-2-methylpropionic acid 5-hexenyl and 700 mL of toluene were added at room temperature. To the obtained solution, 206.9 mL of triethoxysilane was added dropwise. The resulting mixture was mixed with platinum (0) — 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene (Aldrich, 0.1 M) 8 50 μ L was added and stirred at room temperature. The resulting reaction mixture was concentrated at 32 ° C, and further dried under reduced pressure at 55 ° C for 3 hours to give 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl} 89.7 g Got. Area percentage obtained by gas chromatographic analysis The value was 93%. Example 1

(1) In a reaction vessel equipped with a dropping funnel and a stirrer, in an argon atmosphere at room temperature, α-alumina powder (Sumicorundum (Su-04 grade) manufactured by Sumitomo Chemical Co., Ltd.); D ₅ = 0.5 1 μ πι) 1 5 g, was charged ethanol 5 5 m L and 2 8 wt _^0/0 en Monia aqueous 3 O m L. The resulting mixture was stirred at 40 ° C. for 2 hours. To the obtained mixture, 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl} 3.34 g and ethanol 5 mL were added dropwise. The obtained mixture was stirred at 40 ° C. for 18 hours to be reacted. After completion of the reaction, insoluble matter was removed from the reaction mixture by centrifugation. The insoluble matter taken out was washed with ethanol, tetrahydrofuran, and chloroform. The obtained insoluble matter was dried under reduced pressure at room temperature, and the hydrogen atom of the surface hydroxyl group of alumina was replaced with a key atom, and 6- (2-bromo-2-methylpropionyloxy) hexyl group was substituted for the key atom. 14.9 g of alumina bonded with was obtained.

Elemental analysis C: 0.4%, B r: 2 0 0 0 p p m

(2) In a reaction vessel equipped with a stirrer, 7 g of alumina obtained in (1) above, 7 mg of bromide (I) 5.02 mg, copper powder 4.5 9 mg in an argon atmosphere , Carsol 4. 9 2 mL, N, Ν, Ν ', Ν,,, Ν "Anisole solution of monopentamethylgerylenetriamine (0 · 4 0 m ο 1 / L) 0.5 3 mL and methyl methacrylate 1 1. 2 3 mL were added The resulting mixture was stirred at room temperature for 1 minute and then stirred at 90 ° C. for 24 hours to carry out a polymerization reaction. After completion, the insoluble matter was removed from the reaction mixture by centrifugation, and the insoluble matter removed was washed with ethanol, tetrahydrobran, and chloroform, and dried in vacuo at 60 ° C. The hydrogen atom of the surface hydroxyl group is substituted with a key atom, and the key atom is substituted with the following formula (1 0)

And the following formula (1 1) JP2009 / 059024

 17

As a result, 11.2 g of an alumina composite material to which a polymer chain having the structural unit represented by FIG.

Elemental analysis C: 20.9%, Br: 320 p pm

The polymer content in the alumina composite was 3.3.2%. Example 2

(1) In a reaction vessel equipped with a cooling device at room temperature, α-alumina powder (Sumitomo Random (ΑΑ—04 grade) manufactured by Sumitomo Chemical Co., Ltd .; D ₅₀ = 0 · 5 1 μm) 80.0 g, ethano plus one Honoré 222. 2 m L and 28 weight _^0/0 aqueous ammonia 1 33. 3 mL. After the resulting mixture was stirred at 40 ° C for 2 hours, 2-Promo 2 _methyl propionic acid {6- (triethoxysilyl) hexyl} 17.8 g was dissolved in 44.4 mL of ethanol. The solution was added dropwise. The resulting mixture was stirred at 40 ° C. for 18 hours. The insoluble matter was removed from the obtained reaction mixture by centrifugation. The insoluble matter taken out was washed with ethanol, tetrahydrofuran, and black mouth form. The obtained insoluble matter was dried under reduced pressure for 10 hours at room temperature, and the hydrogen atom of the hydroxyl group on the surface of alumina was replaced with a key atom, which was replaced with 6- (2-promo-2-methylpropionyloxy). 79.4 g of alumina bonded with hexyl groups was obtained.

Elemental analysis C: 0.3%, Br: 1 700 p pm

(2) In a reaction vessel equipped with a cooling device at room temperature, 35.0 g of alumina obtained in (1) above, copper bromide (I) 21. 39 mg, copper powder 1 9.54 mg, anisole 20. 3 mL, N, N, N ', N ", N" Anisole solution of one pentamethino retylene triamine (0.40 mol lL) 2. 24 mL and methyl methacrylate 4 7. 8 5 mL was added. The resulting mixture was stirred at room temperature for 1 minute and then stirred at 90 ° C. for 2.5 hours to carry out a polymerization reaction. After completion of the reaction, insoluble matter was removed from the reaction mixture by centrifugation. The insoluble matter taken out was washed with ethanol, tetrahydrofuran, and black mouth form. Insoluble matter was dried under reduced pressure at 60 ° C for 10 hours, 9059024

 18

The hydrogen atom of the surface hydroxyl group of alumina is replaced with a key atom, and a polymer chain having the structure represented by the above formula (1 0) and the structural unit represented by the above formula (1 1) is bonded to the key atom. 54.0 g of an alumina composite material was obtained.

Elemental analysis C: 2 1. 4%, B r: 450 p pm

The polymer content in the alumina composite was 35.9%. Example 3

(1) In a reaction vessel equipped with a cooling device, at room temperature, α-alumina powder (Sumicorundum (A Α—04 grade) manufactured by Sumitomo Chemical Co., Ltd .; D ₅₀ = _0.5 1 m) 1 00. 0 g, ethanol 2 77. 7 mL, 28 weight _^0/0 aqueous ammonia 1 6 6 plus 6 m L. After stirring the resulting mixture at 40 ° C for 2 hours, 26.4 g of 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl} 26.5 mL of ethanol The solution obtained by dissolving was added dropwise. The resulting mixture was stirred at 40 ° C. for 18 hours. The insoluble matter was removed from the obtained reaction mixture by centrifugation. The insoluble matter taken out was washed with ethanol, tetrahydrofuran, and chloroform. The obtained insoluble matter was dried under reduced pressure at room temperature for 10 hours, and the hydrogen atom of the surface hydroxyl group of alumina was replaced with a key atom, and 6- (2-bromo-l-methylpropionyl chloride) was replaced with the key atom. 96.4 g of alumina bonded with (xy) hexyl group was obtained.

Elemental analysis C: 0.2%, Br: 1400 p pm

 (2) In a reaction vessel equipped with a cooling device, at room temperature, 85.0 g of alumina obtained in (1) above, 85.35 mg of copper bromide (I), 350.84 mg of copper powder, 1 6 · 7 5 ml L, N, N, Ν ',, ", ，', a solution of monopentamethylethylenediamine triamine ^" Nore solution (0.40 mo 1 / L) 29. 74mL , 2-Promoysobutyric acid in vinylol solution (0.50 mo 1 / L) 2. 98 mL and styrene 1 02.

2 6 mL was added. The resulting mixture was stirred at room temperature for 1 minute and then stirred at 90 ° C. for 6 hours to carry out a polymerization reaction. After completion of the reaction, the insoluble matter was removed from the reaction mixture by centrifugation. The insoluble matter taken out was washed with ethanol, tetrahydrofuran, and black mouth form. Insoluble matter was dried under reduced pressure at 60 ° C for 10 hours. PT / JP2009 / 059024

 19

The hydrogen atom of the surface hydroxyl group of Na is replaced by a key atom, and the structure represented by the above formula (1 0) is replaced by the following formula (1 2)

Thus, an alumina composite material 1 1 5. 46 g with a polymer chain having a structural unit represented by the following formula was obtained.

Elemental analysis C: 2 7. 4%, B r: 3 0 0 p p m

The polymer content in the alumina composite was 29.5%.

(3) In a reaction vessel at room temperature, the alumina composite material obtained above 1.5 g, tetrahydrofuran 15 mL, methanol 7.5 mL and 50 weight ⁰ /. 2. 1 mL of aqueous sodium hydroxide solution was added. The resulting mixture was stirred at 40 ° C. for 8 hours. The resulting mixture was concentrated, and 1 N hydrochloric acid was added to the concentrated residue. The obtained mixture was centrifuged to remove insoluble matter. The insoluble matter taken out was washed with water and then dried under reduced pressure. A part of the insoluble matter was collected and mixed with tetrahydrofuran to obtain a solution in which the polymer separated from the alumina composite was dissolved. When the solution was subjected to gel permeation chromatography (GPC) analysis (GPC analysis conditions are as follows), the number average molecular weight (M _n ) of the polymer was 1 0.9 X 10 ⁴ (M _n / M _w = 1.5 5).

<GPC analysis conditions>

Equipment: Shimadzu Corporation L C 1 1 0 A T

Column: Polymer Laboratories P L g e l M i x e d-C 5 ιχ m (7.5 mm φ X 30 mm)

Flow rate: 1 mL

Mobile phase: Tetrahy drofuran

Detector: R I

Temperature: 40 ° C

Reference material: A 1 drich standard polystyrene Example 4

(1) In a reaction vessel equipped with a cooling device, 30 ° O α-alumina powder with a primary particle size of 70 nm at room temperature, 100.000 mL of ethanol and 28 wt. / ₀ Aqueous ammonia 40. OmL was added. The obtained mixture was stirred at 40 ° C for 2 hours, and then 2-promo 2-methylpropionic acid {6- (trioxysilyl) hexyl} 2 7.5 g was dissolved in 1 OmL of ethanol. The solution was added dropwise. The resulting mixture was stirred at 40 ° C. for 18 hours. The insoluble matter was removed from the resulting reaction mixture by centrifugation. The insoluble matter taken out was washed with ethanol, terahydrofuran, and chloroform. The insoluble matter was dried under reduced pressure at room temperature for 10 hours, and the hydrogen atom of the hydroxyl group on the surface of alumina was replaced with a key atom, which was replaced by a 6- (2-promo-2-methylpropionyloxy) hexyl group. 30.2 g of alumina bonded with was obtained.

Elemental analysis C: l.0%, Br: 5 500 p pm

 (2) In a reaction vessel equipped with a cooling device, at room temperature, 22.0 g of the alumina obtained in (1) above, copper bromide (I) 43. 43 mg, copper powder 39.6 6 mg, anisole 45 . Five

7 mL, N,, N,, N, ', N', Anisol solution of monopentamethylgerylenetriamine (0.40 mol / L) 4.54 mL and methyl methacrylate 9 7.14 mL were added. It was. The resulting mixture was stirred at room temperature for 1 minute and then stirred at 90 ° C. for 1.5 hours to carry out a polymerization reaction. After completion of the reaction, insoluble matter was removed from the reaction mixture by centrifugation. The removed insoluble matter was washed with ethanol, tetrahydrofuran, and chloroform. The insoluble matter was dried under reduced pressure at 60 ° C. for 10 hours, and the hydrogen atom of the surface hydroxyl group of the alumina was replaced with a key atom, and the structure represented by the above formula (1 0) and the above formula were replaced with the key atom. 6.1.1 g of an alumina composite material to which a polymer chain having the structural unit represented by (1 1) was bonded was obtained.

Elemental analysis C: 38.4%, Br: 6 90 p pm

The polymer content in the alumina composite was 53.1%. Example 5

(1) In a reaction vessel equipped with a cooling device, _α- alloy with a primary particle size of 70 nm at room temperature. Mina powder 80.0 g, ethanol 222. 2 mL and 28 weight _^0/0 aqueous ammonia 1 3 3. 3 mL were added. The resulting mixture was stirred at 40 ° C for 2 hours, and then 2-bromo-2-methylpropionic acid {6- (triethoxysilyl) hexyl} 84.7 g was dissolved in 44.4 mL of ethanol. The resulting solution was added dropwise. The resulting mixture was stirred at 40 ° C. for 18 hours. Insoluble matter was removed from the resulting reaction mixture by centrifugation. The insoluble matter taken out was washed with ethanol, tetrahydrofuran, and black mouth form. The insoluble matter is dried under reduced pressure at room temperature for 10 hours, and the hydrogen atom of the hydroxyl group on the surface of alumina is replaced with a key atom, and a 6- (2-bromo-2-methylpropionyloxy) hexyl group is bound to the key atom. 75.5 g of alumina was obtained.

Elemental analysis C: 1.0%, Br: 6 100 p pm The ²⁹ Si—C PMA S spectrum of the obtained alumina was measured to be _49.5 p pm, −56.4 p It was confirmed that there was a peak at 1pm and 15.4 ppm. From this result, it was found that the hydrogen atom of the hydroxyl group on the surface of alumina was replaced by a silicon atom.

(2) In a reaction vessel equipped with a cooling device, at room temperature, 70.0 g of alumina obtained in (1) above, copper bromide (I) 306. 47 mg, copper powder 1 2 5 9 · 7 1 mg, -Sole 3 0. 1 0 ml, N, N, N ', N ", N,' Anisole solution of pentamethylgerylenetriamine (0.40 mol / L) 1 0 6. 7 7 mL, 2 —Anisole solution of ethyl bromoisobutyrate (0.50 mol ZL) 1 0.6 8 mL and styrene 1 8 3. 60 mL were added, and the resulting mixture was stirred at room temperature for 1 min. The polymerization reaction was carried out for 2.5 hours with stirring at ° C. The insoluble matter was removed from the reaction mixture by centrifugation, and the insoluble matter removed was washed with ethanol, tetrahydrofuran and chloroform. After pressure drying at 60 ° C. for 10 hours, the hydrogen atom of the surface hydroxyl group of alumina is substituted with a key atom, and the structure represented by the above formula (10) and 30.20 g of an alumina composite material 1 in which a polymer chain having a structural unit represented by the formula (12) was bonded was obtained. Elemental analysis C: 44.6%, bromine content: 1400 ppm

The polymer content in the alumina composite was 49.1%. To the reaction vessel, at room temperature, the alumina composite obtained above 1. 5 g, Tetorahi Dorobura down 1 5 mL, methanol 7.5 m L and 50 weight ⁰ /. Aqueous sodium hydroxide solution 9.

2 mL was added. The resulting mixture was stirred at 40 ° C. for 8 hours. The resulting mixture was concentrated, and 1 N hydrochloric acid was added to the concentrated residue. The obtained mixture was centrifuged to remove insoluble matter. The insoluble matter taken out was washed with water and then dried under reduced pressure. A part of the insoluble matter was collected and mixed with tetrahydrofuran to obtain a solution in which the polymer separated from the alumina composite was dissolved. When the solution was subjected to GPC analysis under the analysis conditions described in Example 3 (3), the number average molecular weight (Μ _π ) of the polymer was 6. 40 X 10 ⁴ (M _n / M _w = 1 5 1). Example 6

(1) A reaction vessel equipped with a cooling apparatus, at room temperature, alpha-alumina powder (Sumitomo Chemical Co., Ltd. made Sumicorandom (Arufaarufa- 1 8 _{grade);. D 5 = 1 7.} 4 m) 7 5. 0 g , ethanol 104. 2 mL and 28 weight _^0/0 aqueous ammonia 6 2. 5 m L was pressurized example. The resulting mixture was stirred at 40 ° C for 2 hours and then obtained by dissolving 8-8 g of 2-promo-2-methylpropionic acid {6 _ (triethoxysilyl) hexyl} in 20.8 mL of ethanol. The resulting solution was added dropwise. The resulting mixture was stirred at 40 ° C. for 18 hours. Insoluble matter was removed from the reaction mixture by centrifugation. The insoluble matter removed was washed with ethanol, tetrahydrofuran, and black mouth form. The insoluble matter is dried under reduced pressure at room temperature for 10 hours, and the hydrogen atom of the surface hydroxyl group of alumina is replaced with a key atom, and a 6- (2-bromo-2-methylpropionyloxy) hexyl group is bonded to the key atom. Alumina 73. lg was obtained.

 Elemental analysis C: 0.2%, Br: 1 500 p pm

(2) In a reaction vessel equipped with a cooling device, at room temperature, 70.0 g of alumina obtained in (1) above, copper bromide (I) 75.5 1 mg, powder 3 1 0. 39 mg, Sole 5 6.0 ◦ ml L, N, N, Ν ', Ν ", Ν" One pentamethyldiethylenetriamine Disosol solution (0.40 mol lL) 26.3 3 mL, 2-bromoisobutyric acid ethanol solution (0.50 mol l / L) 2.6 3 ml and styrene 1 80.90xnL added. The resulting mixture was stirred at room temperature for 1 minute and then stirred at 90 ° C. for 5 hours to carry out a polymerization reaction. The insoluble matter was removed from the resulting reaction mixture by centrifugation. The insoluble matter taken out was washed with ethanol, tetrahydrofuran, and black mouth form. The insoluble matter was dried under reduced pressure at 60 ° C. for 10 hours, and the hydrogen atom of the surface hydroxyl group of alumina was replaced with a key atom, and the structure represented by the above formula (10) and the above formula ( 1 66.5 g of an alumina composite with a polymer chain having the structural unit represented by 1 2) bound thereto was obtained.

Elemental analysis C: 33.4%, Br: 360ppm

The polymer content in the alumina composite was 36.2%. When the obtained alumina composite material was observed with an electron microscope (SEM and STEM), it was confirmed that the alumina particles were covered with a substantially uniform polymer layer. Comparative example.1

(1) In a reaction vessel equipped with a cooling device, at room temperature, Hiichi Alumina powder (Sumitomo Random (AA—04 grade) manufactured by Sumitomo Chemical Co., Ltd .; D ₅₀ = _0.5 1 μm) 30 g, ethanol 1 00 . were added OML and 2 8 wt _^0/0 aqueous ammonia 40. OML. 40. After stirring at C for 2 hours, a solution obtained by dissolving 16.5 g of (3-methacrylopropyl) triethoxysilane in 10 mL of ethanol was added dropwise. The resulting mixture was stirred at 40 ° C. for 18 hours. Insoluble matter was removed from the reaction mixture by centrifugation. The insoluble matter taken out was washed with ethanol, tetrahydrofuran, and black mouth-hol. The insoluble matter was dried under reduced pressure for 10 hours at room temperature, the hydrogen atom of the surface hydroxyl group of alumina was replaced with a key atom, and 7_4 g of alumina bonded with 3_methacryloyloxypropyl group was obtained. It was.

 Elementary analysis C: 0.18%, H: <0.0. 1%

(2) In a reaction vessel equipped with a cooling device, the alumina obtained in (1) above at room temperature 22.0 g 2, 2, azobis (isopropylonitrile) 77. 30 mg, toluene 1 8. 50 mL and 5.04 mL methyl methacrylate were added. The resulting mixture was stirred at room temperature for 1 minute, and then stirred at 90 ° C. for 10 hours to carry out a polymerization reaction. Insoluble matter was removed from the reaction mixture by centrifugation. The insoluble matter taken out was washed with tetrahydrodolfuran and black mouth form. The insoluble matter was dried under reduced pressure for 10 hours at 60 ° C, and the hydrogen atom of the surface hydroxyl group of alumina was replaced with the key atom. The key atom was represented by the trimethylene group and the above formula (11). As a result, 2.75 g of an alumina composite material to which polymer chains having structural units were bonded was obtained.

Elemental analysis C: 0.8%, H: 0.1%

The polymer content in the alumina composite was 1.1%. Comparative Example 2

 (1) In a reaction vessel equipped with a cooling device, at room temperature, 50.0 g of alumina powder with a primary particle size of 70 nm, ethanol 1 3 8. 9 mL, and 28 wt% ammonia water 8 3.3 mL Was added. The resulting mixture was stirred at 40 ° C for 2 hours, and then a solution obtained by dissolving 6.69 g of (3-methacryloyloxypropyl) triethoxysilane in 27.8 mL of ethanol was prepared. It was dripped. The resulting mixture was stirred at 40 ° C. for 18 hours. The insoluble matter was removed from the resulting reaction mixture by centrifugation. The insoluble matter removed was washed with ethanol, tetrahydrofuran, and chloroform. The insoluble matter was dried under reduced pressure at room temperature for 10 hours, the hydrogen atom of the surface hydroxyl group of alumina was replaced with a carbon atom, and 48.7 g of alumina bonded with a 3-methacryloyloxypropyl group was substituted on the silicon atom. Obtained.

Elemental analysis C: 1.1%, H: 0.29%

(2) In a reaction vessel equipped with a cooling device, at room temperature, 13.0 g of alumina obtained in (1) above, 2, 2'-azobis (isopropylonitrile) 2 79.4 mg, toluene 6 6. 8 8 mL and methyl methacrylate 18.2 mL were added. The resulting mixture was stirred at room temperature for 1 minute, and then stirred at 90 ° C. for 10 hours to carry out a polymerization reaction. The insoluble matter was removed from the resulting reaction mixture by centrifugation. The removed insoluble matter was washed with tetrahydrofuran and then with black mouth form. The insoluble matter was dried under reduced pressure at 60 ° C. for 10 hours, and the hydrogen atom of the surface hydroxyl group of alumina was replaced with the key atom, An alumina composite material (13.06 g) was obtained in which a trimerene group and a polymer chain having a structural unit represented by the above formula (11) were bonded to the silicon atom.

Elemental analysis C _: 4.0%, H: 0.6% '

The polymer content in the alumina composite material was 6.6%. Comparative Example 3

 (1) In a reaction vessel equipped with a cooling device, at room temperature, the alumina obtained in the above Comparative Example 1 (1) 22.0 g, 2, 2, 1azobis (Isopuchi-tril) 77. 30 mg, Trench 1 8.06 mL and 5.48 mL styrene were added. The resulting mixture was stirred at room temperature for 1 minute and then stirred at 90 ° C. for 10 hours to carry out a polymerization reaction. Insoluble matter was removed from the obtained reaction mixture by centrifugation. The extracted insoluble matter was washed with tetrahydrofuran and then with black mouth form. The insoluble matter was dried under reduced pressure at 60 ° C for 10 hours, and the hydrogen atom of the surface hydroxyl group of alumina was replaced with the key atom. The key atom was represented by the trimethylene group and the above formula (12). Alumina composite material 2 1. 3 5 g to which a polymer chain having a structural unit was bonded was obtained.

Elemental analysis C: 0.6%, H: 0.1%

The polymer content in the alumina composite was 0.4%. Comparative Example 4

 In a reaction vessel equipped with a cooling device, the alumina obtained in Comparative Example 2 (1) at room temperature 1

3.0 g, 2, 2, azobis (isobutyronitrile) 2 79. 4 mg, tosylene 6 5.26 mL and styrene 19.8 2 mL were added. The resulting mixture was stirred at room temperature for 1 minute and then stirred at 90 ° C. for 10 hours to carry out a polymerization reaction. Insoluble matter was removed from the resulting reaction mixture by centrifugation. The insoluble matter removed was washed with tetrahydrofuran and further with mouth-opening form. The insoluble matter was dried under reduced pressure at 60 ° C. for 10 hours, and the hydrogen atom of the surface hydroxyl group of alumina was replaced with the key atom, and the key atom was converted to the trimethylene group according to the above formula (12). 1. 2.86 g of an alumina composite material with a polymer chain bonded having the structural unit shown was obtained.

Elemental analysis C: 3.2%, H: 0.4% TJP2009 / 059024

 26

The polymer content in the alumina composite was 4.1%.

[Measurement of glass transition temperature]

 Alumina composite material obtained in Examples 1 to 6, Alumina composite material obtained in Comparative Examples 1 to 4, polymethylmethacrylate (A 1 drich, weight average molecular weight (Mw) = 96, 700, number Average molecular weight (Mn) = 44, 700) and polystyrene (A

1 Use a differential scanning calorimeter (TA Instruments DSCQ 2000 or SII Nanotech DSC 6 200 R) with a glass transition temperature of drich Mw = 230,000, Mn = l 40,000) (The heating rate was 20 ° CZ min). The results are shown in Table 1.

Example 7

3.9 g of the alumina composite material obtained in Example 1 and polymethyl methacrylate (A 2009/059024

 27

1 Weight average molecular weight (Mw) = 9 6, 7 0 0, number average molecular weight (M n) = 44, 7 0 0) 2. 6 g, a small kneader minilab (manufactured by Hermo Haake) In addition, the mixture was melt-kneaded at 20 ° C. for 10 minutes (rotation speed: 50 rpm), and then granulated by an extruder to obtain a resin composition. Using a press molding machine (manufactured by Shinfuji Metal Industry Co., Ltd .; compression molding machine NF-3 7), the resulting resin composition was heated at 20 ° C (preheating 3 minutes, 15 minutes after pressurizing to 15 MPa) After pressing, the sheet was cooled at 30 ° C. for 5 minutes to obtain a sheet of lO OmmX lOOmm having a thickness of about 2 μmππι. A tensile test was performed on the obtained sheet. The results are shown in Table 2. Example 8

 Alumina composite material obtained in Example 2 4.0 6 g and methacrylic resin (Sumitex MHF manufactured by Sumitomo Chemical Co., Ltd.) 2.4 4 g are added to a small kneader minilab (manufactured by Thermo Hake) The mixture was melt-kneaded at 20 ° C. for 20 minutes (rotation speed: 50 rpm), and then granulated by an extruder to obtain a resin composition. Using a press molding machine (Shinfuji Metal Industrial Co., Ltd .; compression molding machine NF-3 7), the resulting resin composition was heated to 20 ° C (preheating 5 minutes, 15 minutes after pressurizing to 15 MPa) ) And then cooled at 30 ° C. for 5 minutes to obtain a sheet of 150 mm × 150 mm with a thickness of about 100 / im. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. Example 9

Alumina composite material obtained in Example 2 5.0 7 g and metathalyl resin (Sumitex MHF manufactured by Sumitomo Chemical Co., Ltd.) 1. 4 3 g were added to a mini-kneader minilab (manufactured by Thermo Haake) 2 The mixture was melt-kneaded at 00 ° C. for 20 minutes (rotation speed: 50 rpm), and then granulated by an extruder to obtain a resin composition. Using a press molding machine (Shinfuji Metal Industrial Co., Ltd .; compression molding machine NF-3 7), the resulting resin composition was heated to 20 ° C (preheating 5 minutes, 15 minutes after pressurizing to 15 MPa) ), And then cooled at 30 ° C. for 5 minutes to obtain a 150 mm × 15 Omm sheet having a thickness of about 100 ° ^ ιη. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. Example 1 0

 Alumina composite material obtained in Example 2 6.0 g and methacrylic resin (Sumitex MHF manufactured by Sumitomo Chemical Co., Ltd.) 0.4 2 g were added to a small kneader minilab (manufactured by Hermo Haake) 2 The mixture was melt-kneaded at 00 ° C. for 20 minutes (rotation speed: 50 rpm), and then granulated by an extruder to obtain a resin composition. Using a press molding machine (manufactured by Shinfuji Metal Industry Co., Ltd .; compression molding machine NF-3 7), the resulting resin composition was heated to a temperature of 200. C (preheat 5 minutes, pressurize to 15 MPa for 3 minutes), then cool at 30 ° C for 5 minutes, and approximately 150 mm thick 150 mm x 15 500 mm sheet Got. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. Example 1 1

 Alumina composite material obtained in Example 4 (5.54 g) and methacrylic resin (Sumipex MHF manufactured by Sumitomo Chemical Co., Ltd.) 0.96 g were placed in a small kneader minilab (made by Thermo Haake), The mixture was melt-kneaded at 20 ° C. for 20 minutes (rotation speed: 50 rpm), and then granulated by an extruder to obtain a resin composition. Using a press molding machine (Shinfuji Metal Industrial Co., Ltd .; compression molding machine NF-3 7), the resulting resin composition was heated to 20 ° C (preheating 5 minutes, 15 minutes after pressurizing to 15 MPa) ) And then cooled at 30 ° C. for 5 minutes to obtain a 150 mm × 1550 mm sheet having a thickness of about 100 μm. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. Example 1 2

Alumina composite material obtained in Example 3 3.69 g and polystyrene (A 1 drich Mw = 2 3 0, 0 0 0, Mn = 1 4 0, 0 0 0) 2. 8 1 g In addition to a kneader minilab (manufactured by Thermo Hake), melt kneaded at 20 ° C. for 20 minutes (rotation speed: 50 rpm), and then granulated by an extruder to obtain a resin composition . Press molding machine; (manufactured by Shinto Metal Industries compression molding machine NF-? 3 7), the resulting resin composition, temperature 2 0 0. ° C (5 min preheat, boosted ³ to 1 5 MP a And then cooled at 30 ° C. for 5 minutes to obtain a 150 mm × 150 mm sheet having a thickness of about 100 / m. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. Example 1 3

 Alumina composite material obtained in Example 5 5.1 lg and polystyrene (manufactured by Aldrich, Mw = 2 3 0, 0 0 0, Mn = 1 4 0, 0 0 0) In addition to a kneader minilab (made by Thermo Haake), it was melt-kneaded at 20 ° C. for 20 minutes (rotation speed: 50 rpm), and then granulated by an extruder to obtain a resin composition. Using a press molding machine (manufactured by Shinfuji Metal Industry Co., Ltd .; compression molding machine NF-3 7), the resulting resin composition was heated to a temperature of 200 ° C (preheating 5 minutes, 15 minutes after pressurizing to 15 MPa) ) And then cooled at 30 ° C. for 5 minutes to obtain a 150 mm × 1500 mm sheet having a thickness of approximately 100 / m. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. Example 1 4

 1. 8 2 g of alumina composite material obtained in Example 6 and polystyrene (Mw = 2 3 0, 0 0 0, Mn = 1 4 0, 0 0 0, manufactured by Aldrich) 1. 6 2 g In addition to a kneader minilab (made by Thermo Haake), it was melt-kneaded at 20 ° C. for 20 minutes (rotation speed: 50 rpm), and then granulated by an extruder to obtain a resin composition. Using a press molding machine (manufactured by Shinfuji Metal Industry Co., Ltd .; compression molding machine NF-3 7), the resulting resin composition was heated to a temperature of 200 ° C (preheating 5 minutes, 15 minutes after pressurizing to 15 MPa) ) And then cooled at 30 ° C. for 5 minutes to obtain a 150 mm × 1500 mm sheet having a thickness of about 100 m. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. Example 1 5

Alumina composite material obtained in Example 6 4.0 8 g and methacrylic resin (Sumitex MH F manufactured by Sumitomo Chemical Co., Ltd.) 2.4 2 g were placed in a small kneader minilab (manufactured by Hermo Haake). In addition, the mixture was melt-kneaded at 20 ° C. for 20 minutes (rotation speed: 50 rpm), and then granulated by an extruder to obtain a resin composition. Using a press molding machine (manufactured by Shinfuji Metal Industry Co., Ltd .; compression molding machine NF-3 7), the resulting resin composition was heated to a temperature of 200. After pressing at C (preheating 5 minutes, 15 minutes after pressurization to 15 MPa), cooling at 30 ° C for 5 minutes, approx. I got the sheet. The obtained shi A tensile test was conducted. The results are shown in Table 2. Example 1 6

 Alumina composite material obtained in Example 6 5.9 g and methacrylic resin (Sumitex MH F manufactured by Sumitomo Chemical Co., Ltd.) 1. 4 1 g were placed in a small kneader minilab (made by Thermo Haake). The mixture was melt-kneaded at 20 ° C. for 20 minutes (rotation speed: 50 rpm) and then granulated by an extruder to obtain a resin composition. Using a press molding machine (Shindo Metal Industry Co., Ltd .; compression molding machine NF-3 7), the resulting resin composition was heated to 20 ° C (preheating 5 minutes, 15 minutes after pressurizing to 15 MPa) ) And then cooled at 30 ° C. for 5 minutes to obtain a 150 mm × 1500 mm sheet having a thickness of about 100 μm. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. Comparative Example 5

In Example 7, in place of 3.9 g of the alumina composite material obtained in Example 1, e—End Lumina powder (Sumitomo Random (AA—04 grade) manufactured by Sumitomo Chemical Co., Ltd.); D ₅ 0 = 0.5 1 μm) A sheet was obtained in the same manner as in Example 7, except that 2.6 g was used and the amount of polymethyl methacrylate used was 3.9 g. A tensile test was performed on the obtained sheet. The results are shown in Table 2. Comparative Example 6

In Example 8, instead of 4.0 6 g of the alumina composite material obtained in Example 2, α-alumina powder (Sumitomo Random Co., Ltd. (ΑΑ—04 grade) manufactured by Sumitomo Chemical Co., Ltd.); D ₅ ο = 0.5 1 m) A sheet was obtained in the same manner as in Example 8 except that 2.6 g was used and the amount of methacrylic resin used was 3.9 g. The resulting sheet was subjected to a tensile test. The results are shown in Table 2. Comparative Example 7

In Example 8, instead of the alumina composite 4 · 0 6 _g obtained in Example 2, _α -alumina powder (Sumitorundum manufactured by Sumitomo Chemical Co., Ltd. (ΑΑ-0-4 grade)); D ₅ o = 0.5 1 μm) A sheet was obtained in the same manner as in Example 8 except that 3.25 g was used and the amount of methallyl resin used was 3.25 g. A tensile test was performed on the obtained sheet. The results are shown in Table 2. Comparative Example 8

 In Example 8, instead of 4.06 g of the alumina composite material obtained in Example 2, 2.6 g of α-alumina powder having a primary particle size of 70 nm was used, and the amount of methacrylic resin used was 3 A sheet was obtained in the same manner as in Example 8, except that 90 g was used. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. Comparative Example 9 '

In Example 1 2, instead of 3.69 g of the alumina composite material obtained in Example 3, α-alumina powder (Sumicorundum (Α Α—18 grade) manufactured by Sumitomo Chemical Co., Ltd.); D ₅ ο = 1 7.4 μm) A sheet was obtained in the same manner as in Example 12 except that 3.25 g was used and the amount of polystyrene used was 3 · 25 g. A tensile test of the obtained sheet was performed. The results are shown in Table 2. Comparative Example 1 0

 In Example 8, 2.63 g of the alumina composite material obtained in Comparative Example 1 was used instead of 4.06 g of the alumina composite material obtained in Example 2, and the amount of methacrylic resin used was 3.8 7 A sheet was obtained in the same manner as in Example 8, except that g was used. A tensile test was performed on the obtained sheet. The results are shown in Table 2. Comparative Example 1 1

In Example 8, instead of 4.06 g of the alumina composite material obtained in Example 2, 3.29 g of the alumina composite material obtained in Comparative Example 1 was used, and the amount of methacrylic resin used was 3.2 1 A sheet was obtained in the same manner as in Example 8, except that g was used. A tensile test of the obtained tote was performed. The results are shown in Table 2. Comparative Example 1 2

 In Example 8, instead of the alumina composite material 4.0 6 g obtained in Example 2, the alumina composite material 2.78 g obtained in Comparative Example 2 was used, and the amount of methacrylic resin used was 3.7 2 A sheet was obtained in the same manner as in Example 8, except that g was used. A tensile test was performed on the obtained sheet. The results are shown in Table 2. Comparative Example 1 3

 In Example 1 2, instead of 3.69 g of the alumina composite material obtained in Example 3, 16.1 g of the alumina composite material obtained in Comparative Example 3 was used, and the amount of polystyrene used was 3.8. A sheet was obtained in the same manner as in Example 12 except that the amount was 9 g. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. Comparative Example 1 4

 In Example 13, instead of the alumina composite material 5.1 1 g obtained in Example 5, the alumina composite material 2.7 1 g obtained in Comparative Example 4 was used, and the amount of polystyrene used was 3.7. A sheet was obtained in the same manner as in Example 13 except that the amount was 9 g. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. Comparative Example 1 5

 In Example 7, a sheet was obtained in the same manner as in Example 7 except that the alumina composite material obtained in Example 1 was not used and the amount of polymethyl methacrylate was changed to 6.5 g. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. Comparative Example 1 6

A sheet was obtained in the same manner as in Example 8 except that the alumina composite material obtained in Example 2 was not used and the amount of methacrylic resin used was 6.5 g. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. Comparative Example 1 7 A sheet was obtained in the same manner as in Example 12 except that the alumina composite material obtained in Example 3 was not used and the amount of polystyrene used was 6.5 g. The obtained sheet was subjected to a tensile test. The results are shown in Table 2. '' I Zhang test]

 A tensile test was carried out under the conditions below using UNI VER SAL TE S TIG MACH I NE S TA — 1 2 25 manufactured by Orientec.

<Conditions> Full scale load: 20 K gf, test speed: 5. mm mmmin, initial sample length: 40 mm, ambient temperature: 23 ° C, ambient humidity: 50% RH

9059024

 34

[Table 2]

Industrial applicability

By adding the novel alumina composite material of the present invention to the resin, the heat resistance of the resin In addition, since the mechanical strength is improved, a resin sheet having excellent heat resistance and mechanical strength can be produced.

Claims

The scope of the claims

1. Alumina composite material in which a hydrogen atom of a surface hydroxyl group of alumina is substituted with a key atom, and a polymer chain is bonded to an oxygen atom of the surface hydroxyl group through the key atom, and the polymer chain is a living radical An alumina composite comprising a structure derived from a polymerization initiating group and a structural unit derived from a monomer having a radically polymerizable unsaturated bond.

 2. The alumina composite material according to claim 1, wherein the living radical polymerization initiating group is an atom transfer radical polymerization initiating group.

 3. The alumina composite material according to claim 2, wherein the atom transfer radical polymerization initiating group includes an α-haloacyloxy group, an α_haloacyl group, a halosulfonyl group, or an α-habenbenzole group.

4. The atom transfer radical polymerization initiating group has the formula (2)

The alumina composite material according to claim 2, which is a group represented by the formula:

 5. The alumina composite material according to claim 1, wherein the structure derived from the living radical polymerization initiating group is bonded directly to a silicon atom or via an alkylene group having 1 to 20 carbon atoms.

 6. A monomer having a radical polymerizable unsaturated bond is selected from the group consisting of a styrene monomer, an acrylate monomer, a methacrylate monomer, an acrylamide monomer, a methallyl monomer, atalic acid, methacrylic acid, acrylonitrile. 2. The alumina composite material according to claim 1, wherein the alumina composite material is at least one selected from the group consisting of methacrylonitrile, 4-butylpyridine, and vinyl acetate.

7. Alumina has an average particle size (D ₅ Q) of 60 η η! 2. The alumina composite material according to claim 1, wherein the alumina composite material is alumina having a particle diameter of ˜50 μm or alumina having a primary particle diameter of 1 to 100 nm.

8. Alumina composite material obtained by surface-treating alumina with a silane coupling agent containing a living radical polymerization initiating group and then recurring a monomer having a radical polymerizable unsaturated bond.

 9. A resin composition comprising: a resin obtained by polymerizing at least one monomer having a radical polymerizable unsaturated bond; and the alumina composite material according to any one of claims 1 to 8.

 10. The resin composition according to claim 9, wherein the resin is obtained by polymerizing atalyl acid ester or methacrylic acid ester.

 1 1. The resin composition according to claim 9, wherein the resin is methyl polymetatalate.

 12. An alumina composition comprising alumina and the alumina composite material according to any one of claims 1 to 8.

 1 3. An alumina composite material characterized by reacting alumina with a silane-powered printing agent containing a living radical polymerization initiating group and then polymerizing a monomer having a radical polymerizable unsaturated bond by living radical polymerization. Production method.

 14. Alumina in which the hydrogen atom of the hydroxyl group on the surface of alumina is substituted with a key atom, and the living radical polymerization initiating group is bonded to the key atom directly or through a linking group.