WO2009057817A1 - Composition de polysiloxane et procédé de fabrication de celle-ci - Google Patents

Composition de polysiloxane et procédé de fabrication de celle-ci Download PDF

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WO2009057817A1
WO2009057817A1 PCT/JP2008/070242 JP2008070242W WO2009057817A1 WO 2009057817 A1 WO2009057817 A1 WO 2009057817A1 JP 2008070242 W JP2008070242 W JP 2008070242W WO 2009057817 A1 WO2009057817 A1 WO 2009057817A1
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group
formula
substituted
monovalent hydrocarbon
silicon
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Takuya Ogawa
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DuPont Toray Specialty Materials KK
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Dow Corning Toray Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the present invention relates to a polysiloxane composition containing microparticles of a metal or metal oxide having a silicon-containing organic group on the surface thereof.
  • Priority is claimed on Japanese Patent Application No. 2007-283860, filed on October 31, 2007, and Japanese Patent Application No. 2008-190012, filed on July 23 , 2008, the content of which is incorporated herein by reference.
  • Ultramicroparticles generally referred to as nanoparticles have increased surface energy, and for this reason, they exhibit properties different from conventional microparticles, such as changes in optical properties due to quantum size effects, reduction of melting points, increased catalytic properties, increased magnetic properties and the like. Therefore, ultramicroparticles are expected to be applied in various fields of electronic materials , optical materials , catalyst materials, illuminant materials, medicines and the like.
  • various methods for producing nanoparticles are known as described in Japanese Unexamined Patent Application, First Publication No. 2007-51188; Japanese Unexamined Patent Application, First Publication No. 2006-282503; and Japanese Unexamined Patent Application, First Publication No. H10-183207.
  • Japanese Unexamined Patent Application, First Publication No. H09-30.2257 describes complex microparticles in which microparticles are complexed with a polymer by means of a hydrolyzation and condensation reaction.
  • Japanese Unexamined Patent Application, First Publication No. 2002-210356 describes complex microparticles in which microparticles are complexed with a polymer by using carbon dioxide under elevated pressure.
  • composition can be obtained in which nanoparticles are suitably dispersed in a polymer by simultaneously carrying out a reaction of synthesizing a polymer and a reaction of producing nanoparticles. Disclosure of Invention
  • the present invention is performed under the circumstances of the prior art described above, and the present invention has the first objective to provide a composition in which microparticles are suitably dispersed in a polymer.
  • the present invention has the second objective to provide a convenient method for producing the aforementioned composition.
  • the first objective of the present invention can be achieved by a polysiloxane composition
  • a polysiloxane composition comprising: a polysiloxane having average structural formula (A) shown below:
  • each R 1 independently represents a substituted or unsubstituted monovalent hydrocarbon group or a monovalent organic group having a reactive functional group
  • each R 2 independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 4 or less carbon atoms
  • m and n are respectively numbers that satisfy the following conditions: 0 ⁇ m; 0 ⁇ n; and m + n ⁇ 3, and microparticles of a metal or metal oxide on the surface of which a silicon-containing organic group is fixed by means of chemical bonding wherein the silicon-containing organic group is represented by general formula (B) shown below:
  • each R 3 independently represents a substituted or unsubstituted monovalent hydrocarbon group or a monovalent organic group having a reactive functional group
  • L represents a divalent linking group of a formula:
  • Y is -0-, -S-, or a formula: -NR 4 - wherein R 4 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, Z is -NH- or -N(CH 3 )-, x is an integer ranging from 3 to 20, y is an integer ranging from 0 to 5, z is 0 or 1, w is an integer ranging from 0 to 5, t is an integer ranging from 0 to 50, and v is 0 or 1; and p and q are respectively numbers that satisfy the following conditions: 0 ⁇ p ⁇ 2; 0 ⁇ q ⁇ 2; and 0 ⁇ p + q ⁇ 2.
  • the ratio by amount (weight) of the aforementioned polysiloxane and the aforementioned microparticles of a metal or metal oxide preferably ranges from 5:95 to 95:5.
  • the second objective of the present invention can be achieved by reacting a silicon-containing compound and an aqueous solution or aqueous dispersion of a metal salt under conditions at a temperature of not less than 300 0 C under pressure of not less than 10 MPa to simultaneously form the polysiloxane and the microparticles of a metal or metal oxide on the surface of which a silicon-containing organic group is fixed by means of chemical bonding.
  • the aforementioned silicon-containing compound is preferably a reactive silane represented by general formula (C) shown below:
  • R 4 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and R 5 is the same as described above; and a group of a formula: -ONH 2 ; and a and b are respectively numbers that satisfy the following conditions: 0 ⁇ a ⁇ 2; 0 ⁇ b ⁇ 2; and 0 ⁇ a + b ⁇ 2, and/or a linear reactive organosiloxane oligomer represented by general formula (D) shown below:
  • each R 5 independently represents a substituted or unsubstituted monovalent hydrocarbon group
  • the aforementioned reactive functional group in general formulae (C) and (D) is preferably selected from the group consisting of hydroxyl, mercapto, epoxy, amino, amide, ester, carboxyl, and isocyanate groups.
  • the aforementioned metal salt is preferably a sulfate, nitrate, acetate, oxalate, hydrochloride, or oxychloride of a metal ranging from group IV to group XV of the periodic table of the elements.
  • Fig. 1 is a conceptual view showing one example of a batch-type reaction apparatus by which the preparation method of the present invention is carried out.
  • Fig. 2 is an SEM photograph of microparticles of the present invention obtained in Example 1.
  • Fig. 3 is another SEM photograph of microparticles of the present invention obtained in Example 1.
  • Fig. 4 is an SEM photograph of microparticles of the present invention obtained in Example 2.
  • the polysiloxane composition of the present invention contains, as essential components,
  • each R 1 independently represents a substituted or unsubstituted monovalent hydrocarbon group or a monovalent organic group having a reactive functional group
  • each R 2 independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 4 or less carbon atoms
  • m and n are respectively numbers that satisfy the following conditions: 0 ⁇ m; 0 ⁇ n; and m + n ⁇ 3 , and
  • each R 3 independently represents a substituted or unsubstituted monovalent hydrocarbon group or a monovalent organic group having a reactive functional group
  • L represents a divalent linking group of a formula:
  • Y is -0-, -S-, or a formula: -NR 4 - wherein R 4 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, Z is -NH- or -N(CH 3 )-, x is an integer ranging from 3 to 20, y is an integer ranging from 0 to 5, z is 0 or 1, w is an integer ranging from 0 to 5, t is an integer ranging from 0 to 50, and v is 0 or 1; and p and q are respectively numbers that satisfy the following conditions: 0 ⁇ p ⁇ 2; 0 ⁇ q ⁇ 2; and 0 ⁇ p + q ⁇ 2.
  • the monovalent hydrocarbon group of R 1 is typically a substituted or unsubstituted, monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, and more preferably having 1 to 4 carbon atoms; a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms and preferably 6 to 12 carbon atoms; or a monovalent unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms.
  • monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms mention may be made of, for example, straight or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; and cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl groups .
  • aromatic hydrocarbon groups include groups in which aromatic hydrocarbons and saturated aliphatic hydrocarbons are combined, in addition to groups consisting of only aromatic hydrocarbons.
  • groups in which aromatic hydrocarbons and saturated hydrocarbons are combined mention may be made of, for example, aralkyl group such as benzyl and phenethyl groups.
  • monovalent unsaturated aliphatic hydrocarbon groups having 2 to 20 carbon atoms mention may be made of, for example, straight or branched alkenyl groups such as vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl groups, as well as cycloalkenyl groups such as cyclopentenyl, and cyclohexenyl groups, and cycloalkenylalkyl groups such as cyclopentenylethyl, cyclohexenylethyl , and cyclohexenylpropyl groups .
  • a vinyl or cyclohexenylethyl group is preferable.
  • the hydrogen atom on the aforementioned monovalent hydrocarbon group may be substituted by one or more substituent s , and the aforementioned substituents are selected from halogen atoms (fluorine, chlorine, bromine and iodine atoms) .
  • R 1 examples of the aforementioned monovalent organic group having a reactive functional group of R 1 , mention may be made of monovalent saturated or aromatic hydrocarbon groups having a reactive functional group selected from the group consisting of hydroxyl, mercapto, epoxy, amino, amide, ester, carboxyl, and isocyanate groups.
  • the preferable R 1 is a monovalent saturated or aromatic hydrocarbon group having the aforementioned reactive functional group.
  • the substituted or unsubstituted monovalent hydrocarbon groups having 4 or less carbon atoms of R 2 are not particularly limited.
  • R 2 is a hydrogen atom or a methyl group.
  • the aforementioned polysiloxane (a) may be linear, branched, or crosslinked .
  • m and n are respectively numbers that satisfy the following conditions: 0 ⁇ m, 0 ⁇ n, and m + n ⁇ 3.
  • m + n is not less than 2
  • the polysiloxane is linear, and when the value thereof is less than 2, the polysiloxane is branched or crosslinked.
  • the aforementioned polysiloxane (a) has, for example, a hydroxyl group or alkoxy group bonded to a silicon atom.
  • polysiloxanes (a) mention may be made of, for example, linear diorganopolysiloxanes having hydroxyl groups or alkoxy groups bonded to silicon atoms at both terminals of the molecular chain, linear diorganopolysiloxanes having a hydroxyl group or an alkoxy groups bonded to a silicon atom at one terminal of the molecular chain, linear diorganopolysiloxanes having hydroxyl groups or alkoxy groups bonded to silicon atoms at a terminal and at the pendant position of the molecular chain, cyclic diorganopolysiloxanes having a hydroxyl group or groups or an alkoxy group or groups bonded to a silicon atom or atoms at the pendant position or positions, silicone resins having a hydroxyl group or groups or an alkoxy group or groups bonded to a silicon atom or atoms, and the like.
  • microparticles (b) of a metal or metal oxide on the surface of which a silicon-containing organic group is fixed by means of chemical bonding are not particularly limited as long as the silicon-containing organic group represented by general formula (B) shown below:
  • each R 3 independently represents a substituted or unsubstituted monovalent hydrocarbon group or a monovalent organic group having a reactive functional group
  • L represents a divalent linking group of a formula:
  • Y is -0-, -S-, or a formula: -NR 4 - wherein R 4 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, Z is -NH- or -N(CH 3 )-, x is an integer ranging from 3 to 20, y is an integer ranging from 0 to 5, z is 0 or 1, w is an integer ranging from 0 to 5, t is an integer ranging from 0 to 50, and v is 0 or 1; and p and q are respectively numbers that satisfy the following conditions: 0 ⁇ p ⁇ 2; 0 ⁇ q ⁇ 2; and 0 ⁇ p + q ⁇ 2, is fixed on the surface of the microparticles of a metal or metal oxide by means of chemical bonding.
  • the metals forming the aforementioned metal microparticles or metal-oxide microparticles are not particularly limited, and any metal elements can be used. Typically, as examples thereof, mention may be made of elements of group IV of the periodic table of the elements, and those which are positioned at the right side of the elements of group IV on the periodic table of the elements but at the left and lower side of the line of boron (B) of group XIII - silicon (Si) of group XIV - arsenic (As) of group XV, as well as the elements on that line on the periodic table of the elements.
  • Ti, Zr, V, Fe, Ni, Cu, Ag, Au, Zn, Al, Ge and Sn are preferable, and Cu, Ag, Fe and Zn are, in particular, preferable .
  • the aforementioned metal elements may be used alone or as a mixture by combining two or more types thereof.
  • metal oxides examples include, for example, oxides of Fe, Co, Ni, Cu, Ag, Au, Zn, Al, Ga, In, Si, Ge, Sn, Pb, Ti, Zr, Mn and the like, such as SiO 2 , TiO 2 , ZnO, SnO 2 , Al 2 O 3 , AlOOH, MnO 2 , NiO, Fe 2 O 3 , Fe 3 O 4 , Co 3 O 4 , ZrO 2 , BaTiO 3 , LiCoO 2 , LiMn 2 O 4 , CuO, Cu 2 O, as well as mixtures thereof.
  • Al 2 O 3 , AlOOH, Cu 2 O and CuO are preferable.
  • microparticles are not particularly limited, and may be any form such as sphere, spindle, prismatic column, cylinder, plate, needle, or the like.
  • a spherical microparticle is preferable.
  • the aforementioned microparticles preferably have an average particle size of 1 ⁇ m or less, and in particular, nanoparticles are preferable.
  • Nanoparticles means, in general, particles having an average particle size of 200 nm or less, preferably 150 nm or less, more preferably 100 nm or less, and further preferably 50 nm or less .
  • the aforementioned microparticles may ⁇ be a mixture of fine particles having various particle sizes, but microparticles having a uniform particle size are preferable, Measurement of the average particle size can be carried out by means of a common measurement method in the art.
  • particle size can be measured by means of a transmission electron microscope (TEM) , field-emission transmission electron microscope (FE-TEM) , scanning electron microscope (SEM) , field emission scanning electron microscope (FE-SEM) or the like, and an average value therefrom can be obtained.
  • TEM transmission electron microscope
  • FE-TEM field-emission transmission electron microscope
  • SEM scanning electron microscope
  • FE-SEM field emission scanning electron microscope
  • the silicon-containing organic group is fixed on the surface of microparticles of a metal or metal oxide by means of chemical bonding.
  • chemical bonding means a strong binding due to covalent bonding, ion bonding or the like, and does not include a binding due to merely physical adsorption or the like.
  • the substituted or unsubstituted monovalent hydrocarbon group of R 3 is not particularly limited.
  • the substituted or unsubstituted monovalent hydrocarbon group is a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, and more preferably having 1 to 4 carbon atoms; a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms and preferably 6 to 12 carbon atoms; or a monovalent unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms.
  • R 3 mention may be made of substituted or unsubstituted monovalent hydrocarbon groups listed in the aforementioned R 1 .
  • the monovalent organic group having a reactive functional group for R 3 means a monovalent organic group having a hydroxyl group, a mercapto group (-SH) , an epoxy group, an amino group, an amide group, an ester group, a carboxyl group, an isocyanate group, or the like.
  • the aforementioned organic group the aforementioned monovalent hydrocarbon group, or a monovalent hydrocarbon group having at least one oxygen atom, sulfur atom, or nitrogen atom in the main chain is preferable.
  • the monovalent organic group having a reactive functional group for R 3 mention may be made of the same groups as those for the aforementioned R 1 .
  • L represents a divalent linking group of a formula: - (YC x H 2x ) t (C x H 2x -yZ z O w ) v- wherein Y is -0-, -S-, or a formula: -NR 4 - wherein R 4 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, Z is -NH- or -N(CH 3 )-, x is an integer ranging from 3 to 20, y is an integer ranging from 0 to 5, z is 0 or 1, w is an integer ranging from 0 to 5, t is an integer ranging from 0 to 50, and v is 0 or 1.
  • R 4 the substituted or unsubstituted monovalent hydrocarbon groups listed in the aforementioned R 1 may be mentioned.
  • divalent linking groups mention may be made of -(OCH 2 CH 2 ) C OCH 2 CH 2 CH 2 - wherein c is an integer ranging from 0 to 50, -(OCH(CH 3 )CH 2 ) C iOCH 2 CH 2 CH 2 - wherein d is an integer ranging from 1 to 51, -SCH 2 CH 2 CH 2 -, -NHCH 2 CH 2 CH 2 -, -N (CH 3 ) CH 2 CH 2 CH 2 -, -NHCH 2 CH 2 NHCH 2 CH 2 CH 2 -,
  • f 2 or 3
  • p and q are respectively numbers that satisfy the following conditions: 0 ⁇ p ⁇ 2; 0 ⁇ q ⁇ 2; and 0 ⁇ p + q ⁇ 2.
  • silicon-containing organic groups represented by general formula (B) mention may be made of, for example,
  • the silicon-containing organic groups are not limited thereto.
  • the ratio of the amounts (weight) of the polysiloxane and the microparticles of a metal or metal oxide onto which the silicon-containing organic group is fixed by means of chemical bonding in the polysiloxane composition of the present invention is not particularly limited.
  • the ratio preferably ranges from 5:95 to 95:5, and in particular, preferably ranges from 15:85 to 85:15. If the weight ratio of the microparticles is less than the aforementioned range, useful properties obtained by the aforementioned microparticles may not be sufficiently provided. On the other hand, if the weight ratio of the microparticles exceeds the aforementioned range, good properties such as optical transparency, electrical insulation, molding processability and the like which the polysiloxane possesses may not be obtained.
  • the polysiloxane composition of the present invention can be produced by reacting a silicon-containing compound and an aqueous solution or aqueous dispersion of a metal salt under conditions at a temperature of not less than 300°C under pressure of not less than 10 MPa, and thereby, forming at the same time the polysiloxane and the microparticles of the metal or metal oxide, in which the silicon-containing organic group is fixed on the surface of the microparticles by means of chemical bonding .
  • the silicon-containing compounds are not particularly limited as long as the compounds contain silicon, and are preferably organic compounds including a silicon atom or atoms such as organosilane , organosiloxane oligomer and the like.
  • the aforementioned organic compounds containing silicon atom(s) may be used alone or in combination with two or more types thereof.
  • a reactive silane represented by general formula (C) shown below is preferable.
  • R 4 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and R 5 is the same as described above; and a group of a formula: -ONH 2 ; and a and b are respectively numbers that satisfy the following conditions: 0 ⁇ a ⁇ 2; 0 ⁇ b ⁇ 2; and 0 ⁇ a + b ⁇ 2.
  • the aforementioned organosilanes may be used alone or in combination with two or more types thereof.
  • the substituted or unsubstituted monovalent hydrocarbon groups of R 5 are not particularly limited, and are typically, substituted or non-substituted, monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, and more preferably having 1 to 4 carbon atoms; monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and preferably having 6 to 12 carbon atoms; or monovalent unsaturated aliphatic hydrocarbon groups having 2 to 20 carbon atoms.
  • R 5 mention may be made of the substituted or unsubstituted monovalent hydrocarbon groups listed in the aforementioned R 1 .
  • the monovalent organic group having a reactive functional group of R 6 means a monovalent organic group having a hydroxyl group, a mercapto group (-SH) , an epoxy group, an amino group, an amide group, an ester group, a carboxyl group, an isocyanate group or the like.
  • the aforementioned organic group the aforementioned monovalent hydrocarbon groups or monovalent hydrocarbon groups containing at least one oxygen atom, sulfur atom or nitrogen atom in the main chain, having the aforementioned reactive functional group are preferable.
  • monovalent organic groups having a reactive functional group of R 6 mention may be made of, for example, 3-hydroxypropyl , 3- ( 2-hydroxyethoxy ) propyl , 3-mercaptopropyl , 2 , 3-epoxypropyl , 3, 4-epoxybutyl, 4 , 5-epoxypentyl, 2-glycidoxyethyl , 3-glycidoxypropyl , 4-glycidoxybutyl , 2- (3, 4-epoxycyclohexyl) ethyl, 3- ('3, 4-epoxycyclohexyl ) propyl, aminopropyl, N-butylaminopropyl, N-methylaminopropyl , N, N-dibutylaminopropyl, 3- ( 2-aminoethoxy ) propyl, 3- ( 2-aminoethylamino ) propyl , 3-carboxypropyl , 10-carboxydecyl,
  • halogen atoms mention may be made of fluorine, chlorine, bromine, and iodine atoms.
  • monovalent hydrocarbon groups of R 2 , R 4 and R 5 may be the same as described above.
  • a and b are respectively numbers that satisfy the following conditions: 0 ⁇ a ⁇ 2; 0 ⁇ b ⁇ 2; and 0 ⁇ a + b ⁇ 2.
  • preferable reactive silanes mention may be made of, for example, 3-hydroxypropyltrimethoxysilane,
  • organosiloxane oligomers a linear reactive organosiloxane oligomer represented by general formula (D) shown below is preferable,
  • the substituted or unsubstituted monovalent hydrocarbon groups of R 5 are not particularly limited, and are typically, substituted or non-substituted, monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, and more preferably having 1 to 4 carbon atoms; monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and preferably having 6 to 12 carbon atoms; or monovalent unsaturated aliphatic hydrocarbon groups having 2 to 20 carbon atoms.
  • R 5 may include the same substituted or unsubstituted monovalent hydrocarbon groups as listed for the aforementioned R 1 .
  • halogen atoms mention may be made of fluorine, chlorine, bromine, and iodine atoms.
  • monovalent hydrocarbon groups of R 2 , R 4 and R 5 may include the same groups as described above.
  • examples of the aforementioned hydrolyzable group or condensation-reactive group of R 7 may include the same groups as described in the aforementioned X.
  • the substituted or unsubstituted monovalent hydrocarbon group of R 7 is not particularly limited, and is typically a substituted or unsubstituted, monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, and more preferably having 1 to 4 carbon atoms; a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms and preferably 6 to 12 carbon atoms; or a monovalent unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms.
  • R 7 mention may be made of substituted or unsubstituted monovalent hydrocarbon groups listed in the aforementioned R 1 .
  • the monovalent organic group having a reactive functional group for R 7 means a monovalent organic group having a hydroxyl group, a mercapto group (-SH) , an epoxy group, an amino group, an amide group, an ester group, a carboxyl group, an isocyanate group, or the like.
  • the aforementioned organic group the aforementioned monovalent hydrocarbon group, or a monovalent hydrocarbon group having at least one oxygen atom, sulfur atom, or nitrogen atom in the main chain is preferable.
  • the monovalent organic group having a reactive functional group for R 7 mention may be made of the same groups as those for the aforementioned R 6 .
  • At least one R 7 is the aforementioned hydrolyzable group or condensation-reactive group, or the aforementioned monovalent organic group.
  • preferable reactive siloxane oligomers mention may be made of, for example, dimethylsiloxane oligomers having methoxy groups bonded to silicon atoms at both terminals and at a pendant position of the molecular chain, dimethylsiloxane oligomers having hydroxyl groups at both terminals and at a pendant position of the molecular chain, and the like.
  • the types of metal salts contained in the aqueous solution or aqueous dispersion of a metal salt are not limited, and any metal salts can be used.
  • a water-soluble salt is preferable, and, a sulfate, nitrate, acetate, oxalate, hydrochloride, or oxychloride of a metal ranging from group IV to group XV of the periodic table of the elements is preferable.
  • the ratio of the reaction amounts of the silicon-containing compound and the aqueous solution or aqueous dispersion of the metal salt is determined so that the ratio of the amounts (weight) of the polysiloxane and microparticles of a metal or metal oxide onto which the silicon-containing organic group is fixed by means of chemical bonding in the polysiloxane composition of the present invention ranges from 5:95 to 95:5, and in particular, preferably ranges from 15:85 to 85:15. If the weight ratio of the microparticles is less than the aforementioned range, useful properties obtained by the aforementioned microparticles may not be sufficiently provided. On the other hand, if the weight ratio of the microparticles exceeds the aforementioned range, good properties such as optical transparency, electrical insulation, molding processability and the like which the polysiloxane possesses may not be obtained.
  • the present invention is characterized by reacting the silicon-containing compound and the metal salt at a temperature of 300 0 C or greater, and under pressure of 10 MPa or greater.
  • a preferable reaction temperature is 33O 0 C or greater, and a more preferable temperature is not less than 374°C which is the critical temperature of water.
  • a preferable reaction pressure is 15 MPa or greater, and a more preferable pressure is not less than 22 MPa which is the critical pressure of water.
  • supercritical state means a state of the critical temperature or greater, and the critical pressure or greater.
  • Subcritical state means a state of the critical temperature or greater and less than the critical pressure, or alternatively, a state of less than the critical temperature and the critical pressure or greater.
  • an alcohol such as methanol, ethanol or the like; a glycol such as ethylene glycol, propylene glycol or the like; a carboxylic acid such as formic acid, acetic acid or the like; an aldehyde such as formaldehyde, acetaldehyde, or the like; a ketone such as acetone, methyl ethyl ketone or the like; a thiol such as methane thiol or the like; an amine such as methylamine, dimethylamine, or the like; ammonia; or a surfactant may be added, if necessary.
  • an alcohol such as methanol, ethanol or the like
  • a glycol such as ethylene glycol, propylene glycol or the like
  • a carboxylic acid such as formic acid, acetic acid or the like
  • an aldehyde such as formaldehyde, acetaldehyde, or the like
  • a ketone such as ace
  • the blending amount thereof preferably ranges from 0.1 to 20% by weight based on the total weight of the aqueous solution or aqueous dispersion, more preferably ranges from 0.1 to 10% by weight, and further preferably ranges from 0.1 to 5% by weight.
  • An apparatus for carrying out the preparation method of the present invention is not particularly limited, and a common apparatus in the art can be used.
  • Fig. 1 is a conceptual view showing one example of a batch-type reaction apparatus by which a preparation method of the present invention is carried out.
  • a reaction tube formed from a strong material such as SUS 316 or the like
  • an aqueous solution or aqueous dispersion of a metal salt and a silicon-containing compound is charged with an aqueous solution or aqueous dispersion of a metal salt and a silicon-containing compound, and the reaction tube is then heated to temperature not less than the critical temperature of water (for example, 400 0 C) by means of a heating means such as a salt bath or the like, so that water in the reaction system is in a supercritical state or a subcritical state.
  • the metal salt, the silicon-containing compound and water in a supercritical state or a subcritical state are reacted for a specified period, and the reaction tube is then cooled to stop the reaction.
  • the product in the reaction tube is recovered.
  • the aforementioned polysiloxane composition can exhibit characteristics originating from the aforementioned microparticles well.
  • properties of the aforementioned particles can be exhibited.
  • the method for producing the polysiloxane composition does not use a large amount of an organic solvent. For this reason, the method can reduce the burden on the environment, and is safe. In addition, the method can be carried out by means of a simple device. For this reason, production cost can be controlled. In addition, the polysiloxane can be synthesized without using an acid catalyst or a base catalyst.
  • the polysiloxane and the microparticles with the metal or metal oxide having compatibility with the polysiloxane can be produced together.
  • the microparticles can be dispersed well in the polysiloxane .
  • the polysiloxane compositions of the present invention can be used alone or by adding other components thereto, and can be applied in the fields of paints, pigments, cosmetics, catalysts, glass, medicines, and the like.
  • the polysiloxane composition containing microparticles formed from copper of the present invention can be used as electrode materials, wiring materials, or catalyst materials.
  • polysioxane compositions of the present invention and preparation methods thereof are described in detail with reference to Examples and Comparative Examples. Identification of the polysiloxane in a polysiloxane composition was carried out in accordance with the following. In addition, identification of microparticles of a metal or metal oxide having a silicon-containing organic group was carried out in accordance with the following.
  • the size of microparticles of the metal or metal oxide on the surface of which silicon-containing organic groups were fixed in the polysiloxane composition which was a product was calculated on the basis of the particles observed with the use of a scanning electron microscope (hereinafter, simply referred to as SEM) , JSM-5600 manufactured by JEOL Ltd.
  • SEM scanning electron microscope
  • a reaction tube made from SUS 316 having an inner diameter of 10 mm and a capacity of 12.5 cm 3 was loaded with 5.5 ml of a 0.1 mol/1 aqueous solution of copper nitrate and 0.26 ml of mercaptopropyltrimethoxysilane, and then, the reaction tube was sealed.
  • the reaction mixture was placed in a salt bath heated to 385 0 C beforehand, and was heated for 10 minutes. Subsequently, the reaction mixture was rapidly cooled in a water bath, and the reaction tube was opened.
  • the reaction product was a phase separated mixture of black solids and a pale yellow liquid. From the spectral data shown below, it could be confirmed that the polymer component in the aforementioned solid product was a polysiloxane having an average structural formula:
  • the yield of the isolated polysiloxane product calculated on the basis of the weight of the starting materials was 90%.
  • Peak positions (cm -1 ) 3,425; 2,960; 2,881; 1,635; 1,080.
  • the ratio of the weight of the copper microparticles on the surface of which the silicon-containing organic groups were fixed by means of chemical bonding and the weight of the polysiloxane in the- aforementioned polysiloxane composition was 20:80.
  • the yield of the isolated polysiloxane product calculated on the basis of the weight of the starting materials was 88%.
  • Peak positions (cm '1 ) 3,430; 2,929; 2,881; 1,713; 1,124; 929.
  • the ratio of the weight of the copper microparticles on the surface of which the silicon-containing organic groups were fixed by means of chemical bonding and the weight of the polysiloxane in the aforementioned polysiloxane composition was 20:80.
  • Example 3 A reaction was carried out in the same manner as described in Example 1, with the exception that 0.13 ml of phenyl trimethoxysilane and 0.11 ml of 2- ( 3 , 4-epoxycyclohexyl ) ethyl trimethoxysilane was used instead of using 0.26 ml of mercaptopropyltrimethoxysilane . Thereby, a phase separated mixture of brown solids and a brown liquid was obtained. From the spectral data shown below, it was confirmed that the polymer component in the aforementioned solid product was a polysiloxane having an average structural formula:
  • the yield of the isolated polysiloxane product calculated on the basis of the weight of the starting materials was 87%.
  • the product was formed from microparticles with various shapes having a large particle size distribution.
  • the smallest particle size was about 50 nm.
  • Peak positions (cm 1 ) 3,430; 2,932; 2,882; 1,703; 1,105; 943
  • the ratio of the weight of the copper microparticles on the surface of which the silicon-containing organic groups were fixed by means of chemical bonding and the weight of the polysiloxane in the aforementioned polysiloxane composition was 20:80.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention porte sur une composition de polysiloxane contenant des microparticules d'un métal ou oxyde métallique ayant un groupe organique contenant du silicium avec une réactivité sur la surface de celles-ci, et sur un procédé de fabrication de cette composition. La composition de polysiloxane contient un polysiloxane représenté par la formule structurale moyenne (A) et des microparticules d'un métal ou oxyde métallique sur la surface desquelles un groupe organique contenant du silicium représenté par la formule générale spécifiée (B) est fixé au moyen d'une liaison chimique. Dans le procédé de fabrication de la composition de polysiloxane susmentionnée, un composé contenant du silicium et une solution aqueuse ou une dispersion aqueuse d'un sel métallique sont mis à réagir dans les conditions à une température de 300°C ou plus sous une pression de 10 MPa ou plus. De ce fait, le polysiloxane et les microparticules du métal ou de l'oxyde métallique sont obtenus en même temps.
PCT/JP2008/070242 2007-10-31 2008-10-30 Composition de polysiloxane et procédé de fabrication de celle-ci Ceased WO2009057817A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010073970A1 (fr) * 2008-12-24 2010-07-01 Dow Corning Toray Co., Ltd. Composition de polysiloxane et son procédé de fabrication

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849022A (en) * 1986-06-25 1989-07-18 Toray Silicone Co., Ltd. Method for modifying the surface of finely divided silica
JP2006282503A (ja) * 2006-04-10 2006-10-19 Tohoku Techno Arch Co Ltd 有機修飾微粒子
WO2007011057A1 (fr) * 2005-07-19 2007-01-25 Dow Corning Toray Co., Ltd. Polysiloxane et procédé pour produire celui-ci

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849022A (en) * 1986-06-25 1989-07-18 Toray Silicone Co., Ltd. Method for modifying the surface of finely divided silica
WO2007011057A1 (fr) * 2005-07-19 2007-01-25 Dow Corning Toray Co., Ltd. Polysiloxane et procédé pour produire celui-ci
EP1905795A1 (fr) * 2005-07-19 2008-04-02 Dow Corning Toray Co., Ltd. Polysiloxane et procédé pour produire celui-ci
JP2006282503A (ja) * 2006-04-10 2006-10-19 Tohoku Techno Arch Co Ltd 有機修飾微粒子

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DATABASE WPI Week 200678, Derwent World Patents Index; AN 2006-761346, XP002513266 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010073970A1 (fr) * 2008-12-24 2010-07-01 Dow Corning Toray Co., Ltd. Composition de polysiloxane et son procédé de fabrication

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