US20140135446A1 - Methods for preparing polyheterosiloxanes - Google Patents
Methods for preparing polyheterosiloxanes Download PDFInfo
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- US20140135446A1 US20140135446A1 US14/160,635 US201414160635A US2014135446A1 US 20140135446 A1 US20140135446 A1 US 20140135446A1 US 201414160635 A US201414160635 A US 201414160635A US 2014135446 A1 US2014135446 A1 US 2014135446A1
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- 0 *[Si](C)(C)OC.*[Si](C)(OC)OC.*[Si](OC)(OC)OC.CO[Si](OC)(OC)OC Chemical compound *[Si](C)(C)OC.*[Si](C)(OC)OC.*[Si](OC)(OC)OC.CO[Si](OC)(OC)OC 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N Cc1cc(C)cc(O)c1 Chemical compound Cc1cc(C)cc(O)c1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/58—Metal-containing linkages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
Definitions
- This invention relates to methods for preparing polyheterosiloxanes with chemically bonded non-Si metal elements using both metal salts and metal alkoxides.
- the metal salts and metal alkoxides can contain the same or different metal elements.
- the polyheterosiloxanes prepared by these methods are solid materials which can be easily dispersed in a solvent of choice.
- the other method is based on sol-gel hydrolysis and condensation chemistries involving a two-component system of metal alkoxides and alkoxysilanes.
- the type of metal elements incorporated into the polysiloxane resins by this method is limited by the availability of the metal alkoxide precursors since metal elements other than Ti, Zr, Al, Ge, and Sn are either not available or difficult to synthesize.
- the present invention relates to methods of making polyheterosiloxanes having at least two non-Si metal elements which utilize both metal salts and metal alkoxides.
- the present invention relates to a method for preparing a polyheterosiloxane having at least two non-Si metal elements comprising the step of: (1) adding an amount of water to a dispersion comprising (A) at least one metal (M1) alkoxide, (B) at least one silicon-containing material, and (C) at least one hydrolyzable metal (M2) salt so a polyheterosiloxane having at least two non-Si metal elements is formed.
- a dispersion comprising (A) at least one metal (M1) alkoxide, (B) at least one silicon-containing material, and (C) at least one hydrolyzable metal (M2) salt so a polyheterosiloxane having at least two non-Si metal elements is formed.
- the present invention provides a method for preparing a polyheterosiloxane having at least two non-Si metal elements comprising reacting:
- (M1) and (M2) are non-Si metal elements and different from each other.
- the expression “at least one” means one or more and this includes individual components as well as mixtures/combinations.
- Component (A) is a metal (M1) alkoxide.
- the metal (M1) alkoxide (A) is selected from metal alkoxides having a general formula (I) R 1 m M1O n X p (OR 2 ) v1-m-p-2n , where M1 is selected from Ti, Al, Ge, Zr, Sn, Cr, Ca, Ba, Sb, Cu, Ga, Hf, In, Fe, Mg, Mo, Nb, Ce, Er, La, Nd, Pr, Sm, Y, Sr, Ta, Te, W, and V, each X is independently selected from carboxylate ligands, organosulfonate ligands, organophosphate ligands, ⁇ -diketonate ligands, and chloride ligands, v1 is the oxidation state of M1, m is a value from 0 to 3, n is a value from 0 to 2, p is a value from
- Component (B) is a silicon-containing material having hydrolyzable groups selected from (B1) an organosiloxane, or (B2) a silane.
- component (B) is at least one silicon-containing material selected from (B1) an organosiloxane having an average formula (II) R 5 b (R 6 O) a SiO (4 ⁇ (a+b))/2 or (B2) a silane having a general formula (III) R 5 c SiY d , where Y is Cl or OR 6 , each R 5 is an independently selected hydrogen atom, alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 18 carbon atoms, aryl group having from 6 to 12 carbon atoms, epoxy group, amino group, or carbinol group, R 6 is an independently selected hydrogen atom or alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI)
- Component (C) is a hydrolyzable metal (M2) salt.
- the hydrolyzable metal (M2) salt is selected from (C1) a non-hydrated metal salt having a general formula (IV) R 7 e M2(Z) (v2 ⁇ e)/w or (C2) a hydrated metal salt having a general formula (V) M2(Z) v2/w .xH 2 O, where M2 is selected from any of the metal elements in the periodic table, v2 is the oxidation state of M2, w is the oxidation state of ligand Z where Z is independently chosen from carboxylates, ⁇ -diketonates, fluoride, chloride, bromide, iodide, organic sulfonate, nitrate, nitrite, sulphate, sulfite, cyanide, phosphites, phosphates, organic phosphites, organic phosphates, and oxalate, each R 7 is an independently selected alky
- Component (A) may comprise at least one metal alkoxide selected from metal alkoxides having a general formula (I) R 1 m M1O n X p (OR 2 ) v1-m-p-2n , where M1 is selected from Ti, Al, Ge, Zr, Sn, Cr, Ca, Ba, Sb, Cu, Ga, Hf, In, Fe, Mg, Mo, Nb, Ce, Er, La, Nd, Pr, Sm, Y, Sr, Ta, Te, W, and V, each X is independently selected from carboxylate ligands, organosulfonate ligands, organophosphate ligands, 3-diketonate ligands, and chloride ligands, subscript v1 is the oxidation state of M1, m is a value from 0 to 3, n is a value from 0 to 2, p is a value from 0 to 3, each R 1 is a monovalent alkyl group having from 1 to 18
- R 1 is a monovalent alkyl group having from 1 to 18 carbon atoms.
- the alkyl group of R 1 include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl.
- the alkyl group comprises 1 to 8 carbon atoms.
- the alkyl group is methyl, ethyl, propyl, butyl, hexyl, and octyl.
- each R 2 is an independently selected monovalent alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R 3 O) q R 4 , where q is a value from 1 to 4, each R 3 is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R 4 is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms.
- Examples of the alkyl groups of R 2 include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and hexyl.
- Examples of the aryl groups of R 2 include phenyl and benzyl.
- Examples of the divalent alkylene group having from 2 to 6 carbon atoms of R 3 include —CH 2 CH 2 — and —CH 2 CH(CH 3 )—.
- Examples of the alkyl groups having from 1 to 6 carbon atoms of R 4 are as described above for R 2 .
- Subscript q in Formula (VI) is a value from 1 to 4, alternatively 1 to 2.
- Examples of the polyether group of Formula (VI) include methoxyethyl, methoxypropyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, methoxyethoxyethyl, and ethoxyethoxyethyl.
- R 2 is R 2 is alkyl group having from 1 to 6 carbon atoms, alternatively ethyl, propyl, and butyl, alternatively propyl and butyl.
- X is selected from carboxylate ligands, organosulfonate ligands, organophosphate ligands, ⁇ -diketonate ligands, and chloride ligands, alternatively carboxylate ligands and ⁇ -diketonate ligands.
- the carboxylate ligands useful for X have a formula R 15 COO ⁇ where R 15 is selected from hydrogen, alkyl groups, alkenyl groups, and aryl groups. Examples of useful alkyl groups for R 15 include alkyl groups having from 1 to 18 carbon atoms, alternatively 1 to 8 carbon atoms as described above for R 1 .
- Examples of useful alkenyl groups for R 15 include alkenyl groups having from 2 to 18 carbon atoms, alternatively 2 to 8 carbon atoms such as vinyl, 2-propenyl, allyl, hexenyl, and octenyl.
- Examples of useful aryl groups for R 15 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and benzyl.
- R 15 is methyl, 2-propenyl, allyl, and phenyl.
- the ⁇ -diketonate ligands useful for X can have the following structures:
- R 16 , R 18 , and R 21 are selected from monovalent alkyl and aryl groups.
- useful alkyl groups for R 16 , R 18 , and R 21 include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 4 carbon atoms such as methyl, ethyl, trifluoromethyl, and t-butyl.
- useful aryl groups for R 16 , R 18 , and R 21 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl.
- R 19 is selected from alkyl groups, alkenyl groups and aryl groups.
- Examples of useful alkyl groups for R 19 include C1 to C18 alkyl groups, alternatively C1 to C8 alkyl groups such as methyl, ethyl, propyl, hexyl and octyl.
- Examples of useful alkenyl groups for R 19 include alkenyl groups having from 2 to 18 carbon atoms, alternatively C2 to C8 carbon atoms such as allyl, hexenyl, and octenyl.
- Examples of useful aryl groups for R 19 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl.
- R 17 and R 20 are hydrogen or alkyl, alkenyl, and aryl groups.
- Examples of useful alkyl groups for R 17 and R 20 include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 8 carbon atoms such as methyl and ethyl.
- Examples of useful alkenyl groups for R 17 and R 20 include alkenyl groups having from 2 to 18 carbon atoms, alternatively 2 to 8 carbon atoms such as vinyl, allyl, hexenyl, and octenyl.
- Examples of useful aryl groups for R 17 and R 20 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl.
- R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 are each independently selected and can be the same or different.
- Each metal alkoxide group described by Formula (I) contains a metal (M1) element selected from Ti, Al, Ge, Zr, Sn, Cr, Ca, Ba, Sb, Cu, Ga, Hf, In, Fe, Mg, Mo, Nb, Ce, Er, La, Nd, Pr, Sm, Y, Sr, Ta, Te, W, and V.
- M1 is Ti, Zr, Al, Ge, Ta, Nb, and Sn.
- M1 is Ti, Zr, Al, and Sn.
- subscript v1 is the oxidation state of M1, ranging from 1 to 7. Alternatively, v1 ranges from 1 to 5.
- subscript m is a value from 0 to 3, alternatively 0 to 2, alternatively 0.
- n is a value from 0 to 2, alternatively 0 to 1, alternatively 0.
- subscript p is a value from 0 to 3, alternatively 0 to 2, alternatively 0.
- Examples of the metal alkoxides described by Formula (I) useful in the present method include titanium tetrapropoxides, titanium tetrabutoxides, zirconium tetrapropoxides, and zirconium tetrabutoxides from DuPont, aluminum tripropoxides, aluminum tributoxides, aluminum phenoxide, antimony (III) ethoxide, barium isopropoxide, cadmium ethoxide, cadmium methoxide, cadmium methoxyethoxide, chromium (III) isopropoxide, copper (II) ethoxide, copper (II) methoxyethoxyethoxide, gallium ethoxide, gallium isopropoxide, diethyldiethoxygermane, ethyltriethoxygermane, methyltriethoxygermane, tetra-n-butoxygermane, hafnium ethoxid
- the metal alkoxides described by Formula (I) are generally available from Gelest (Morrisville, Pa. USA).
- Component (B) is a silicon-containing material having hydrolyzable groups selected from (B1) an organosiloxane, or (B2) a silane.
- component (B) is at least one silicon-containing material selected from (B1) an organosiloxane having an average formula (II) R 5 b (R 6 O) a SiO (4 ⁇ (a+b))/2 or (B2) a silane having a general formula (III) R 5 c SiY d , where Y is Cl or OR 6 , each R 5 is an independently selected hydrogen atom, alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 18 carbon atoms, aryl group having from 6 to 12 carbon atoms, epoxy group, amino group, or carbinol group, R 6 is an independently selected hydrogen atom or alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI)
- Formula (II) are composed of M, D, T, and Q building blocks.
- M building block refers to a siloxy unit that contains one silicon atom bonded to one oxygen atom, with the remaining three substituents on the silicon atom being other than oxygen.
- D building block refers to a siloxy unit that contains one silicon atom bonded to two oxygen atoms, with the remaining two substituents on the silicon atom being other than oxygen.
- T building block refers to a siloxy unit that contains one silicon atom bonded to three oxygen atoms, with the remaining one substituent on the silicon atom being other than oxygen.
- Q building block refers to a siloxy unit that contains one silicon atom bonded to four oxygen atoms. Their molecular structures are listed below:
- alkyl groups having 1 to 18 carbon atoms of R 5 in Formulas (II) and (III) are as described above for R 1 .
- the alkyl group comprises 1 to 6 carbon atoms; alternatively, the alkyl group is methyl, ethyl, propyl, butyl, and hexyl.
- alkenyl groups having from 2 to 18 carbon atoms of R 5 in Formulas (II) and (III) are illustrated by vinyl, propenyl, butenyl, pentenyl, hexenyl, or octenyl.
- the alkenyl group comprises 2 to 8 carbon atoms.
- the alkenyl group is vinyl, allyl, and hexenyl.
- aryl groups having 6 to 12 carbon atoms of R 5 in Formulas (II) and (III) are illustrated by phenyl, naphthyl, benzyl, tolyl, xylyl, methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl.
- the aryl group comprises 6 to 8 carbon atoms.
- the aryl group is phenyl.
- the epoxy groups of R 5 in Formulas (II) and (III) are selected from glycidyl ether groups, alkyl epoxy groups and cycloaliphatic epoxy groups.
- the glycidyl ether group is illustrated by alkyl glycidyl ether groups such as 2-glycidoxyethyl, 3-glycidoxypropyl, 4-glycidoxybutyl, and 2-(3,4-epoxycyclohexyl)ethyl.
- alkyl epoxy groups are 2,3-epoxypropyl, 3,4-epoxybutyl, and 4,5-epoxypentyl
- the cycloaliphatic epoxy group is illustrated by monovalent epoxycycloalkyl groups such as 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexylethyl, 3,4-epoxycyclohexylpropyl, 3,4-epoxycyclohexylbutyl, and alkyl cyclohexene oxide groups.
- the epoxy group is 3-glycidoxypropyl.
- R 5 in Formulas (II) and (III) typically have the formula —R 9 NHR 10 or —R 9 NHR 9 NHR 10 wherein each R 9 is independently a divalent hydrocarbon radical having at least 2 carbon atoms and R 10 is hydrogen or an alkyl group having from 1 to 18 carbon atoms.
- R 9 group examples include an alkylene radical having from 2 to 20 carbon atoms and are illustrated by —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CHCH 3 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH(CH 3 )CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —, and —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —.
- the alkyl groups of R 10 are methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl.
- R 10 is an alkyl group it is methyl.
- Typical aminofunctional hydrocarbon groups are —CH 2 CH 2 NH 2 , —CH 2 CH 2 CH 2 NH 2 , —CH 2 CHCH 3 NH, —CH 2 CH 2 CH 2 CH 2 NH 2 , —CH 2 CH 2 CH 2 CH 2 CH 2 NH 2 , —CH 2 CH 2 CH 2 CH 2 CH 2 NH 2 , —CH 2 CH 2 NHCH 3 , —CH 2 CH 2 CH 2 NHCH 3 , —CH 2 (CH 3 )CHCH 2 NHCH 3 , —CH 2 CH 2 CH 2 CH 2 NHCH 3 , —CH 2 CH 2 NHCH 2 CH 2 NH 2 , —CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 NH 2 , —CH 2 CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 CH 2 NH 2 , —CH 2 CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 CH 2 NH 2 , —CH 2 CH 2 NHCH 2 CH 2 CH 2 CH
- the carbinol groups of R 5 in Formulas (II) and (III) are selected from carbinol groups free of aryl groups having at least 3 carbon atoms and aryl-containing carbinol groups having at least 6 carbon atoms.
- a “carbinol” group is any group containing at least one carbon-bonded hydroxyl (COH) group.
- the carbinol groups may contain more than one COH group such as for example
- Carbinol groups free of aryl groups having at least 3 carbon atoms are illustrated by groups having the formula R 11 OH wherein R 11 is a divalent hydrocarbon group having at least 3 carbon atoms or a divalent hydrocarbonoxy group having at least 3 carbon atoms.
- the group R 11 is illustrated by alkylene groups selected from —(CH 2 ) s — where s has a value of 3 to 10 and —CH 2 CH(CH 3 )—, —CH 2 CH(CH 3 )CH 2 —, —CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH 2 —, and —OCH(CH 3 )(CH 2 ) t — wherein t has a value of 1 to 10.
- the carbinol group free of aryl groups having at least 3 carbon atoms is also illustrated by groups having the formula R 12 (OH) CH 2 OH where R 12 is a group having the formula —CH 2 CH 2 (CH 2 ) t OCH 2 CH— wherein t has a value of 1 to 10.
- the aryl-containing carbinol group having at least 6 carbon atoms is illustrated by groups having the formula R 13 OH wherein R 13 is an arylene group selected from —(CH 2 ) u C 6 H 4 —, —CH 2 CH(CH 3 )(CH 2 ) u C 6 H 4 — wherein u has a value of 0 to 10, and —(CH 2 ) t C 6 H 4 (CH 2 ) u — wherein u and t are as described above.
- the aryl-containing carbinol groups have from 6 to 14 carbon atoms, alternatively 6 to 10 carbon atoms.
- Amino and/or carbinol containing silanes or siloxanes are applicable for some metal-containing resins, such as tin, germanium, and aluminium, however, gelation problems may occur during the synthetic process with certain metal elements (such as Zn and Cu) because of the amino and carbinol silanes or siloxanes ability to chelate to certain metals.
- each R 5 in Formulas (II) and (III) is an independently selected hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkenyl group having from 2 to 8 carbon atoms, or an aryl group having from 6 to 12 carbons atoms.
- each R 5 in Formulas (II) and (III) is an independently selected alkyl group having from 1 to 6 carbon atoms, an alkenyl group having from 2 to 6 carbon atoms, or an aryl group having from 6 to 8 carbons atoms.
- each R 5 is methyl, vinyl, or phenyl.
- the R 6 group of Formula (II) is an independently selected hydrogen atom, alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R 3 O) q R 4 , where q is a value from 1 to 4, each R 3 is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R 4 is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms or alkyl group. Examples of the alkyl group, aryl group and polyether group of R 6 are as described above for R 2 . Alternatively, R 6 is a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms. Alternatively, R 6 is hydrogen, methyl, or ethyl.
- subscript a is a value from 0.1 to 3, alternatively 1 to 3.
- subscript b is a value from 0.5 to 3, alternatively 1.5 to 2.5.
- subscripts (a+b) have a value from 0.6 to 3.9, alternatively 1.5 to 3.
- organosiloxanes (B1) described by Formula (II) and useful in the present method include oligomeric and polymeric organosiloxanes, such as silanol-terminated polydimethylsiloxane, polymethylmethoxysiloxane, polysilsesquioxane, alkoxy and/or silanol containing MQ resin, and combinations thereof. They are made by hydrolysis of the corresponding organomethoxysilanes, organoethoxysilanes, organoisopropoxysilanes, and organochlorosilanes.
- each Y is a chloro atom (CI) or OR 6 , where R 6 is as described above.
- R 6 is as described above.
- Y is OR 6 .
- subscript c is a value from 0 to 3, alternatively, c is a value from 1 to 3, alternatively, from 2 to 3.
- subscript d is a value from 1 to 4, alternatively d is a value from 1 to 3, alternatively, from 1 to 2.
- Examples of the silanes (B2) described by Formula (III) include methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, phenylmethyldichlorosilane, methyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, phenylsilanetriol, diphenylsilanediol, phenylmethylsilanediol, dimethylsilanediol, trimethylsilanol, triphenylsilanol, phenyldimethoxysilanol, phenylmethoxysilanediol, methyldimethoxysilanol, methylmethoxysilanediol, phenyldiethoxysilanol, phenylethoxysilanediol, methyldieth
- Component (C) may comprise at least one metal (M2) salt selected from (C1) a non-hydrated metal salt having a general formula (IV) R 7 e M2(Z) (v2 ⁇ e)/w or (C2) a hydrated metal salt having a general formula (V) M2(Z) v2/w .xH 2 O, where M2 is selected from any of the metal elements in the Periodic Table, v2 is the oxidation state of M2, w is the oxidation state of ligand Z where Z is independently chosen from carboxylates, ⁇ -diketonates, fluoride, chloride, bromide, iodide, organic sulfonate, nitrate, nitrite, sulphate, sulfite, cyanide, phosphites, phosphates, organic phosphites, organic phosphates, and oxalate, each R 7 is an independently selected alkyl group having 1 to 18 carbon atoms, alkenyl group
- the metal element described by M2 is selected from all of the metals in the Periodic Table.
- M2 is selected from Li, Na, Ca, Mg, Ba, Ti, Zr, Ce, Eu, Nd, Er, Yb, Y, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn, Cd, Al, Ge, and Pb.
- subscript v2 is the oxidation state of M2 and can range from 1 to 7, alternatively 1 to 4.
- subscript w is the oxidation state of ligand Z and can range from 1 to 3, alternatively 1 to 2.
- each Z is independently selected from carboxylate ligands, ⁇ -diketonate ligands, fluoride ligand, chloride ligand, bromide ligand, iodide ligand, organic sulfonate ligands, nitrate ligand, nitrite ligand, sulphate ligand, sulfite ligand, cyanide ligand, phosphate ligand, phosphite ligand, organic phosphite ligands, organic phosphate ligands, and oxalate ligand.
- the carboxylate ligands and ⁇ -diketonate ligands useful for Z are as described above for X.
- the organic sulfonate ligands useful for Z have a formula R 22 SO 3 ⁇ , where R 22 is selected from monovalent alkyl groups, alkenyl groups and aryl groups. Examples of useful alkyl groups, alkenyl groups and aryl groups are as described above for R 15 . Alternatively R 22 is tolyl, phenyl, and methyl.
- the organic phosphate ligands useful for Z have a formula (R 23 O) 2 PO 2 ⁇ or R 23 O—PO 3 2 ⁇ , where R 23 is selected from monovalent alkyl groups, alkenyl groups and aryl groups. Examples of useful alkyl groups, alkenyl groups and aryl groups are as described above for R 15 . Alternatively R 23 is phenyl, butyl, and octyl.
- the organic phosphite ligands useful for Z have a formula (R 24 O) 2 PO ⁇ or R 24 O—PO 2 2 ⁇ , where R 24 is selected from monovalent alkyl groups, alkenyl groups and aryl groups. Examples of useful alkyl groups, alkenyl groups and aryl groups are as described above for R 15 . Alternatively R 24 is phenyl, butyl, and octyl.
- Z in Formulas (IV) and (V) is independently selected from carboxylate ligands, ⁇ -diketonate ligands, nitrate ligand, sulphate ligand, and chloride ligand.
- Z includes carboxylate ligands and ⁇ -diketonate ligands.
- subscript e is a value from 0 to 3, alternatively 0 to 2, alternatively 0.
- R 7 is an independently selected alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 8 carbon atoms, or aryl group having from 6 to 8 carbon atoms. Examples of R 7 are as described above for R 5 .
- x is a value from 0.5 to 12, alternatively 1 to 9.
- non-hydrated metal salts (C1) described by Formula (IV) useful in the present method include but are not limited to lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, scandium acetate, yttrium acetate, luterium acetate, hafnium acetate, vanadium acetate, niobium acetate, tantalum acetate, chromium acetate, molybdenum acetate, tungsten acetate, manganese acetate, technetium acetate, rhenium acetate, iron acetate, ruthenium acetate, osmium acetate, cobalt acetate, rhodium acetate, iridium acetate, nickel acetate, palladium acetate, platinum acetate, copper acetate, silver acetate, zinc acetate
- Examples of hydrated metal salts (C2) described by Formula (VI) useful in the present method include but are not limited to zinc acetate dihydrate, nickel acetate tetrahydrate, magnesium acetate tetrahydrate, zinc nitrate hexahydrate, and copper sulphate pentahydrate.
- non-hydrated metal salts and the hydrated metal salts described above are commercially available through the major chemical vendors, such as Sigma-Aldrich, Fisher Scientific, Alfa-Aesar, Gelest, etc.
- the present invention relates to methods for preparing polyheterosiloxanes having at least two non-Si metal elements.
- Components (A), (B), and (C) are dispersed or dissolved, water is added and a reaction proceeds forming a polyheterosiloxane having at least two non-Si metal elements.
- Another embodiment for preparing a polyheterosiloxane having at least two non-Si metal elements comprises: (1) adding an amount of water to a dispersion comprising at least one Component (A) and at least one Component (B1) or (B2) to form a heterosiloxane containing M1-O—Si linkages; and (2) adding at least one Component (C1) or (C2) and if necessary an additional amount of water to the heterosiloxane containing M1-O—Si linkages such that polyheterosiloxanes having at least two non-Si metal elements are formed, where the total amount of water added is between 50 and 200% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups on Components (A), (B), and (C).
- Another embodiment for preparing a polyheterosiloxane having at least two non-Si metal elements comprises: (1) adding an amount of water to a dispersion comprising at least one Component (A) and at least one Component (C1) or (C2) to form a mixed metal oxides solution containing M1-O-M2 oxo-linkages, and (2) adding at least one Component (B1) or (B2) to the mixed metal oxides solution containing M1-O-M2 oxo-linkages and if necessary adding an additional amount of water such that polyheterosiloxanes having at least two non-Si metal elements are formed, where the total amount of water added is between 50 and 200% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups on Components (A), (B), and (C).
- Another embodiment for preparing a polyheterosiloxane having at least two non-Si metal elements comprises: (1) adding an amount of water to a dispersion comprising at least one Component (C1) or (C2) and at least one Component (B1) or (B2) to form a heterosiloxane containing M2-O—Si linkages; and (2) adding at least one Component (A) to the heterosiloxane containing M2-O—Si linkages and if necessary an additional amount of water such that polyheterosiloxanes having at least two non-Si metal elements are formed, where the total amount of water added is between 50 and 200% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups on Components (A), (B), and (C).
- the term “dispersion” in each of the methods means that the molecules of the various components are homogenously distributed.
- Each of the components may be liquid or solids and so it is preferred that they are pre-mixed or dispersed. Stirring one or more of the components in a solvent is an excellent way to get a homogenous dispersion; or a solvent may not be needed if one or more components can be dispersed in another component.
- any kind of solvent is useful including polar solvents, non-polar solvent, hydrocarbon solvents including aromatic and saturated hydrocarbons, alcohols, etc.
- solvents useful for dispersing Components (A), (B), and (C) includes hydrocarbonethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, methoxyethanol, methoxyethoxyethanol, butyl acetate, and toluene, alternatively isopropanol, 1-butanol, 2-butanol, and butyl acetate.
- One type of solvent could be used or a mixture of different solvents would also be useful.
- the dispersing or mixing may be done by any conventional means such as stirring.
- the reaction between Components (A), (B), and (C) in each of the methods proceeds at room temperature (20° C.) but if desired, elevated temperatures up to about 140° C. may be used. Alternatively, the temperature can range from 20° C. to 120° C. Generally, the reaction can take between 30 minutes to 24 hours, alternatively 10 minutes to 4 hours.
- An optional step in all the methods comprises removing the solvent to produce a solid polyheterosiloxane having at least two non-Si metal elements.
- the solvents can be removed by any conventional manner such as heating to elevated temperatures or using reduced pressure.
- This solid material can then be redispersed in a solvent of choice such as toluene, THF, butyl acetate, chloroform, dioxane, 1-butanol, and pyridine. Since the Si—O-M linkages made by the present method can be susceptible to hydrolytic cleavage in the presence of H 2 O, to ensure longer shelf life it is preferred to minimize the polyheterosiloxane having at least two non-Si metal elements' exposure to moisture.
- the polyheterosiloxanes having at least two non-Si metal elements formed by each of the methods have molecular weights (weight average) ranging from 1000 to 1000000, alternatively from 2000 to 100000.
- the non-Si metal elements are uniformly distributed in the materials and have a domain size smaller than 10 nanometers.
- the polyheterosiloxane resins produced by the present method may be characterized by UV transmission spectroscopy.
- the present polyheterosiloxane resins exhibit excellent absorption capability in the UV range (280-400 nm). In many instances, the present resins absorb visible light which should enable their use as colorants in coatings.
- the polyheterosiloxanes having at least two non-Si metal elements formed by the present methods preferably contain from 1% to 25% by weight alkoxy groups, alternatively, from 5% to 15% by weight alkoxy groups.
- the molar percentage of the non-Si metal element (M1 and M2) content in the polyheterosiloxane materials can also be from 0.5 to 90 mole percent, alternatively from 5 to 60 mole percent, alternatively from 20 to 50 mole percent. No fatty acid is needed in the present methods.
- the molar ratio of M2 to M1 useful in each embodiment ranges from 0.001 to 2, alternatively from 0.05 to 1.
- the molar ratio of Si units to M1 useful in the present methods range from 0.1 to 200, alternatively from 0.6 to 20.
- an amount of water must be added in each embodiment so that polyheterosiloxanes having at least two non-Si metal elements are formed. Since water can also be incorporated via the hydrated metal salts (C2), a person skilled in the art would understand that when hydrated metal salts are utilized either smaller amounts or no additional amounts of water may need to be added in order for the needed amount of water to be present. Generally, the amount of water needed for making polyheterosiloxanes having at least two non-Si metal elements ranges from 50% to 200% of the theoretical amount of water necessary for complete hydrolysis and condensation of all the alkoxy and other hydrolyzable groups present on each of the components.
- the amount of water needed to make polyheterosiloxanes having at least two non-Si metal elements ranges from 70% to 150% of the theoretical amount of H 2 O necessary for complete hydrolysis and condensation of all the alkoxy and other hydrolyzable groups present on each of the components, alternatively, 80% to 120% on the same basis. It is preferred in each of the embodiments that the water is added slowly to ensure the metal alkoxide doesn't react so quickly with the water that it precipitates from the solution. A preferred method of accomplishing this is by diluting the water with solvents.
- the solvents useful for diluting the water are the same as used for dispersing the components. Depending on the components used and when they are added the needed water may also be added at one time or during one or more of the steps.
- Other hydrolyzable groups that may be present and need to be hydrolyzed and condensed are any found on the components used including but not limited to chloro.
- the polyheterosiloxanes having at least two non-Si metal elements are soluble in many solvents and are compatible with many polymers, such as epoxy and polyurethane. These advantages, along with the low cost of the metal precursors will facilitate the practical use of the polyheterosiloxanes having at least two non-Si metal elements.
- the material properties and applications depend on the properties of the metal elements incorporated into the polyheterosiloxane. Potential applications include, but not limited to, UV protective coatings, thermal conductive materials, conductive/antistatic materials, self-cleaning coating, photocatalytic materials, colorants for coatings or paints, gloss/mechanical property enhancement, reinforcement components, adhesive components, scratch/impact resistant coating, and catalysts.
- Solubility of the products were tested by mixing 1 gram of the solid product in 9 grams of solvent, such as THF, toluene, butyl acetate, and chloroform. Soluble means that the solid product dissolves sufficiently in the solvent (without noticeable insoluble solid).
- solvent such as THF, toluene, butyl acetate, and chloroform. Soluble means that the solid product dissolves sufficiently in the solvent (without noticeable insoluble solid).
- Me means methyl
- Ac means acetate
- acac means acetylacetonate
- Ph means phenyl.
- a silanol-containing organosiloxane was prepared by mixing 5.47 g phenylmethyldimethoxysilane (PhMeSi(OMe) 2 ), 5.95 g phenyltrimethoxysilane (PhSi(OMe) 3 ), and 2.54 g 0.04M HCl and sonicating the mixture for 40 minutes (Sonicator: Fisher Scientific Instrument (Pittsburgh, Pa.), Model FS60). The silanol-containing organosiloxane solution was added to the 250 ml flask and the solution turned clear after 10 minutes. Stirring was continued at RT for 2 hours.
- the total amount of H 2 O in the reaction mixture was 100% of the amount of water theoretically necessary for complete hydrolysis and condensation of all alkoxy groups. Solvents were removed using a rotary evaporator. No signs of unreacted precursors appear in the GPC analysis of the product.
- the product was a white solid with a theoretic composition of Ti 0.33 Zn 0.17 DPhMe 0.25 T Ph 0.25 (6.8 w % alkoxy based on 13 C NMR) which was soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform.
- polyheterosiloxane materials were synthesized using the same synthetic procedures described above.
- the metal elements included Li, Na, Mg, Ca, Ba, Y, Ce, Eu, Er, Yb, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn, Cd, Al, and Pb—at least one metal element in each column from column 1 to column 14 in the Periodic Table.
- the polyheterosiloxane materials were solid materials dissolvable in various organic solvents. See Table 1.
- Metal oxides have intrinsic absorption bands, thus exhibit different colors when incorporated into the resins.
- the UV transmission spectra of various polyheterosiloxane resins of the above examples exhibited excellent absorption capability in the UV range (280-400 nm).
- Polyurethane coatings were formulated using Bayer Desmophen A870 and Desmodur N3390.
- a typical formulation was composed of 0.60 g polyheterosiloxane resin, 2.58 g butyl acetate, 8.00 g Desmophen A870, and 2.96 g Desmodur N3390.
- the gel time greatly changed from more than 8 hours (uncatalyzed) to less than 2 minutes (catalyzed with Si+Ti+V resins).
Abstract
This invention relates to methods for preparing polyheterosiloxane materials having at least two different non-Si metal elements. The polyheterosiloxane materials prepared by these methods are solid materials which can be easily dispersed in a solvent of choice.
Description
- This application is a divisional of U.S. patent application Ser. No. 13/379,370, currently pending, filed on 20 Dec. 2011 and claims priority thereto under 35 U.S.C. §120 and 35 U.S.C. §365(c); which application is a U.S. national stage filing under 35 U.S.C. §371 of PCT Application No. PCT/US10/40510 filed on 30 Jun. 2010, which claims the benefit of U.S. Provisional Patent Application No. 61/222,693 filed 2 Jul. 2009 under 35 U.S.C. §119 (e). U.S. patent application Ser. No. 13/379,370, PCT Application No. PCT/US10/40510, and U.S. Provisional Patent Application No. 61/222,693 are hereby incorporated by reference.
- This invention relates to methods for preparing polyheterosiloxanes with chemically bonded non-Si metal elements using both metal salts and metal alkoxides. The metal salts and metal alkoxides can contain the same or different metal elements. The polyheterosiloxanes prepared by these methods are solid materials which can be easily dispersed in a solvent of choice.
- Incorporation of metal elements into polysiloxanes has been of great interest for a wide range of applications due to their ability to impart high refractive index, impact resistance, scratch resistance, fire retardance, anti-corrosion, anti-stain, etc. Generally, two synthetic methods have previously been used to prepare the hybrid materials containing metal elements and polysiloxanes. One method involves modification of prefabricated metal oxide particles with organosilanes or polysiloxanes. This particle modification method often confronts challenges on particle aggregation, dispersion, and opacity issues. Further, the inhomogeneity of the metal oxides severely limits their use for optical and electronic applications. The other method is based on sol-gel hydrolysis and condensation chemistries involving a two-component system of metal alkoxides and alkoxysilanes. The type of metal elements incorporated into the polysiloxane resins by this method is limited by the availability of the metal alkoxide precursors since metal elements other than Ti, Zr, Al, Ge, and Sn are either not available or difficult to synthesize.
- The inventors have unexpectedly discovered that adding both a metal alkoxide and a hydrolyzable metal salt in a siloxane polymerization reaction provides a convenient method of incorporating various metal elements into an organosiloxane via Metal-O—Si and Metal-O-Metal oxo-linkages. Thus, the present invention relates to methods of making polyheterosiloxanes having at least two non-Si metal elements which utilize both metal salts and metal alkoxides.
- The present invention relates to a method for preparing a polyheterosiloxane having at least two non-Si metal elements comprising the step of: (1) adding an amount of water to a dispersion comprising (A) at least one metal (M1) alkoxide, (B) at least one silicon-containing material, and (C) at least one hydrolyzable metal (M2) salt so a polyheterosiloxane having at least two non-Si metal elements is formed.
- The present invention provides a method for preparing a polyheterosiloxane having at least two non-Si metal elements comprising reacting:
- (A) a metal (M1) alkoxide,
- (B) a silicon-containing material having hydrolyzable groups selected from
-
- (B1) an organosiloxane, or
- (B2) a silane, and
- (C) a hydrolyzable metal (M2) salt,
- with an amount of water that provides between 50 and 200% necessary to hydrolyze and condense the alkoxy groups and other hydrolyzable groups on Components (A), (B), and (C), to form the polyheterosiloxane, with the proviso that at least two non-Si metal elements are provided by Component (A) and/or (C). In one embodiment, (M1) and (M2) are non-Si metal elements and different from each other.
- As used herein, the expression “at least one” means one or more and this includes individual components as well as mixtures/combinations.
- Component (A) is a metal (M1) alkoxide. In one embodiment of the present invention the metal (M1) alkoxide (A) is selected from metal alkoxides having a general formula (I) R1 mM1On Xp(OR2)v1-m-p-2n, where M1 is selected from Ti, Al, Ge, Zr, Sn, Cr, Ca, Ba, Sb, Cu, Ga, Hf, In, Fe, Mg, Mo, Nb, Ce, Er, La, Nd, Pr, Sm, Y, Sr, Ta, Te, W, and V, each X is independently selected from carboxylate ligands, organosulfonate ligands, organophosphate ligands, β-diketonate ligands, and chloride ligands, v1 is the oxidation state of M1, m is a value from 0 to 3, n is a value from 0 to 2, p is a value from 0 to 3, each R1 is an alkyl group having from 1 to 18 carbon atoms, each R2 is an independently selected monovalent alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R3O)qR4, where q is a value from 1 to 4, each R3 is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R4 is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms,
- Component (B) is a silicon-containing material having hydrolyzable groups selected from (B1) an organosiloxane, or (B2) a silane. In one embodiment, component (B) is at least one silicon-containing material selected from (B1) an organosiloxane having an average formula (II) R5 b(R6O)aSiO(4−(a+b))/2 or (B2) a silane having a general formula (III) R5 cSiYd, where Y is Cl or OR6, each R5 is an independently selected hydrogen atom, alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 18 carbon atoms, aryl group having from 6 to 12 carbon atoms, epoxy group, amino group, or carbinol group, R6 is an independently selected hydrogen atom or alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R3O)qR4, where q is a value from 1 to 4, each R3 is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R4 is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms, a is a value from 0.1 to 3, b is a value from 0.5 to 3, and (a+b) is a value from 0.6 to 3.9, c is a value from 0 to 3, d is a value from 1 to 4 and (c+d) equals 4, and
- Component (C) is a hydrolyzable metal (M2) salt. In one embodiment, the hydrolyzable metal (M2) salt is selected from (C1) a non-hydrated metal salt having a general formula (IV) R7 eM2(Z)(v2−e)/w or (C2) a hydrated metal salt having a general formula (V) M2(Z)v2/w.xH2O, where M2 is selected from any of the metal elements in the periodic table, v2 is the oxidation state of M2, w is the oxidation state of ligand Z where Z is independently chosen from carboxylates, β-diketonates, fluoride, chloride, bromide, iodide, organic sulfonate, nitrate, nitrite, sulphate, sulfite, cyanide, phosphites, phosphates, organic phosphites, organic phosphates, and oxalate, each R7 is an independently selected alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 8 carbon atoms, or aryl group having from 6 to 8 carbon atoms, e is a value from 0 to 3 and x is a value from 0.5-12, so a polyheterosiloxane having at least two non-Si metal elements is formed, where the total amount of water added is between 50 and 200% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups on Components (A), (B), and (C).
- Component (A) may comprise at least one metal alkoxide selected from metal alkoxides having a general formula (I) R1 mM1On Xp(OR2)v1-m-p-2n, where M1 is selected from Ti, Al, Ge, Zr, Sn, Cr, Ca, Ba, Sb, Cu, Ga, Hf, In, Fe, Mg, Mo, Nb, Ce, Er, La, Nd, Pr, Sm, Y, Sr, Ta, Te, W, and V, each X is independently selected from carboxylate ligands, organosulfonate ligands, organophosphate ligands, 3-diketonate ligands, and chloride ligands, subscript v1 is the oxidation state of M1, m is a value from 0 to 3, n is a value from 0 to 2, p is a value from 0 to 3, each R1 is a monovalent alkyl group having from 1 to 18 carbon atoms, each R2 is an independently selected monovalent alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R3O)qR4, where q is a value from 1 to 4, each R3 is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R4 is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms.
- In Formula (I), R1 is a monovalent alkyl group having from 1 to 18 carbon atoms. Examples of the alkyl group of R1 include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl. Alternatively, the alkyl group comprises 1 to 8 carbon atoms. Alternatively, the alkyl group is methyl, ethyl, propyl, butyl, hexyl, and octyl.
- In Formula (I), each R2 is an independently selected monovalent alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R3O)qR4, where q is a value from 1 to 4, each R3 is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R4 is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms.
- Examples of the alkyl groups of R2 include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and hexyl. Examples of the aryl groups of R2 include phenyl and benzyl.
- Examples of the divalent alkylene group having from 2 to 6 carbon atoms of R3 include —CH2CH2— and —CH2CH(CH3)—. Examples of the alkyl groups having from 1 to 6 carbon atoms of R4 are as described above for R2. Subscript q in Formula (VI) is a value from 1 to 4, alternatively 1 to 2. Examples of the polyether group of Formula (VI) include methoxyethyl, methoxypropyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, methoxyethoxyethyl, and ethoxyethoxyethyl.
- Alternatively, R2 is R2 is alkyl group having from 1 to 6 carbon atoms, alternatively ethyl, propyl, and butyl, alternatively propyl and butyl.
- In Formula (I), X is selected from carboxylate ligands, organosulfonate ligands, organophosphate ligands, β-diketonate ligands, and chloride ligands, alternatively carboxylate ligands and β-diketonate ligands. The carboxylate ligands useful for X have a formula R15COO− where R15 is selected from hydrogen, alkyl groups, alkenyl groups, and aryl groups. Examples of useful alkyl groups for R15 include alkyl groups having from 1 to 18 carbon atoms, alternatively 1 to 8 carbon atoms as described above for R1. Examples of useful alkenyl groups for R15 include alkenyl groups having from 2 to 18 carbon atoms, alternatively 2 to 8 carbon atoms such as vinyl, 2-propenyl, allyl, hexenyl, and octenyl. Examples of useful aryl groups for R15 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and benzyl. Alternatively R15 is methyl, 2-propenyl, allyl, and phenyl.
- The β-diketonate ligands useful for X can have the following structures:
- where R16, R18, and R21 are selected from monovalent alkyl and aryl groups. Examples of useful alkyl groups for R16, R18, and R21 include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 4 carbon atoms such as methyl, ethyl, trifluoromethyl, and t-butyl. Examples of useful aryl groups for R16, R18, and R21 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl. R19 is selected from alkyl groups, alkenyl groups and aryl groups. Examples of useful alkyl groups for R19 include C1 to C18 alkyl groups, alternatively C1 to C8 alkyl groups such as methyl, ethyl, propyl, hexyl and octyl. Examples of useful alkenyl groups for R19 include alkenyl groups having from 2 to 18 carbon atoms, alternatively C2 to C8 carbon atoms such as allyl, hexenyl, and octenyl. Examples of useful aryl groups for R19 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl. R17 and R20 are hydrogen or alkyl, alkenyl, and aryl groups. Examples of useful alkyl groups for R17 and R20 include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 8 carbon atoms such as methyl and ethyl. Examples of useful alkenyl groups for R17 and R20 include alkenyl groups having from 2 to 18 carbon atoms, alternatively 2 to 8 carbon atoms such as vinyl, allyl, hexenyl, and octenyl. Examples of useful aryl groups for R17 and R20 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl. R16, R17, R18, R19, R20, and R21 are each independently selected and can be the same or different.
- Each metal alkoxide group described by Formula (I) contains a metal (M1) element selected from Ti, Al, Ge, Zr, Sn, Cr, Ca, Ba, Sb, Cu, Ga, Hf, In, Fe, Mg, Mo, Nb, Ce, Er, La, Nd, Pr, Sm, Y, Sr, Ta, Te, W, and V. Alternatively, M1 is Ti, Zr, Al, Ge, Ta, Nb, and Sn. Alternatively, M1 is Ti, Zr, Al, and Sn.
- In Formula (I), subscript v1 is the oxidation state of M1, ranging from 1 to 7. Alternatively, v1 ranges from 1 to 5.
- In Formula (I), subscript m is a value from 0 to 3, alternatively 0 to 2, alternatively 0.
- In Formula (I), subscript n is a value from 0 to 2, alternatively 0 to 1, alternatively 0.
- In Formula (I), subscript p is a value from 0 to 3, alternatively 0 to 2, alternatively 0.
- Examples of the metal alkoxides described by Formula (I) useful in the present method include titanium tetrapropoxides, titanium tetrabutoxides, zirconium tetrapropoxides, and zirconium tetrabutoxides from DuPont, aluminum tripropoxides, aluminum tributoxides, aluminum phenoxide, antimony (III) ethoxide, barium isopropoxide, cadmium ethoxide, cadmium methoxide, cadmium methoxyethoxide, chromium (III) isopropoxide, copper (II) ethoxide, copper (II) methoxyethoxyethoxide, gallium ethoxide, gallium isopropoxide, diethyldiethoxygermane, ethyltriethoxygermane, methyltriethoxygermane, tetra-n-butoxygermane, hafnium ethoxide, hafnium 2-ethylhexoxide, hafnium 2-methoxymethyl-2-propoxide, indium methoxyethoxide, iron (III) ethoxide, magnesium ethoxide, magnesium methoxyethoxide, magnesium n-propoxide, molybdenum (V) ethoxide, niobium (V) n-butoxide, niobium (V) ethoxide, cerium (IV) t-butoxide, cerium (IV) isopropoxide, cerium (IV) ethylthioethoxide, cerium (IV) methoxyethoxide, erbium methoxyethoxide, lanthanum isopropoxide, lanthanum methoxyethoxide, neodymium methoxyethoxide, praseodymium methoethoxide, samarium (III) isopropoxide, yttrium isopropoxide, yttrium methoxyethoxide, strontium isopropoxide, strontium methoxypropoxide, tantalum (V) ethoxide, tantalum (V) methoxide, tantalum (V) isopropoxide, tantalum tetraethoxide dimethylaminoethoxide, di-n-butyldi-n-butoxytin, di-n-butyldimethoxytin, tetra-t-butoxytin, tri-n-butylethoxytin, titanium ethoxide, titanium 2-ethylhexoxide, titanium methoxide, titanium methoxypropoxide, titanium n-nonyloxide, tungsten (V) ethoxide, tungsten (VI) ethoxide, vanadium triisobutoxide oxide, vanadium triisopropoxide oxide, vanadium tri-n-propoxide oxide, vanadium oxide tris(methoxyethoxide), zinc methoxyethoxide, zirconium ethoxide, zirconium 2-ethylhexoxide, zirconium 2-methyl-2-butoxide, and zirconium 2-methoxymethyl-2-propoxide, aluminum s-butoxide bis(ethylacetoacetate), aluminum di-s-butoxide ethylacetoacetate, aluminum diisopropoxide ethylacetoacetate, aluminum 9-octdecenylacetoacetate diisopropoxide, tantalum (V) tetraethoxide pentanedionate, titanium allylacetoacetate triisopropoxide, titanium bis(triethanolamine) diisopropoxide, titanium chloride triisopropoxide, titanium dichloride diethoxide, titanium diisopropoxy bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate),
- titanium diisopropoxide bis(ethylacetoacetate), titanium methacrylate triisopropoxide, titanium methacryloxyethylacetoacetate triisopropoxide, titanium trimethacrylate methoxyethoxyethoxide, titanium tris(dioctylphosphato)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, zirconium (bis-2,2′-(alloxymethyl)-butoxide)tris(dioctylphosphate), zirconium diisopropoxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate), zirconium dimethacrylate dibutoxide, zirconium methacryloxyethylacetoacetate tri-n-propoxide.
- The metal alkoxides described by Formula (I) are generally available from Gelest (Morrisville, Pa. USA).
- Component (B) is a silicon-containing material having hydrolyzable groups selected from (B1) an organosiloxane, or (B2) a silane. In one embodiment, component (B) is at least one silicon-containing material selected from (B1) an organosiloxane having an average formula (II) R5 b(R6O)aSiO(4−(a+b))/2 or (B2) a silane having a general formula (III) R5 cSiYd, where Y is Cl or OR6, each R5 is an independently selected hydrogen atom, alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 18 carbon atoms, aryl group having from 6 to 12 carbon atoms, epoxy group, amino group, or carbinol group, R6 is an independently selected hydrogen atom or alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R3O)qR4, where q is a value from 1 to 4, each R3 is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R4 is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms, a is a value from 0.1 to 3, b is a value from 0.5 to 3, and (a+b) is a value from 0.6 to 3.9, c is a value from 0 to 3, d is a value from 1 to 4 and (c+d) equals 4.
- Formula (II) are composed of M, D, T, and Q building blocks. By definition, M building block refers to a siloxy unit that contains one silicon atom bonded to one oxygen atom, with the remaining three substituents on the silicon atom being other than oxygen. D building block refers to a siloxy unit that contains one silicon atom bonded to two oxygen atoms, with the remaining two substituents on the silicon atom being other than oxygen. T building block refers to a siloxy unit that contains one silicon atom bonded to three oxygen atoms, with the remaining one substituent on the silicon atom being other than oxygen. Q building block refers to a siloxy unit that contains one silicon atom bonded to four oxygen atoms. Their molecular structures are listed below:
- The alkyl groups having 1 to 18 carbon atoms of R5 in Formulas (II) and (III) are as described above for R1. Alternatively, the alkyl group comprises 1 to 6 carbon atoms; alternatively, the alkyl group is methyl, ethyl, propyl, butyl, and hexyl.
- The alkenyl groups having from 2 to 18 carbon atoms of R5 in Formulas (II) and (III) are illustrated by vinyl, propenyl, butenyl, pentenyl, hexenyl, or octenyl. Alternatively, the alkenyl group comprises 2 to 8 carbon atoms. Alternatively, the alkenyl group is vinyl, allyl, and hexenyl.
- The aryl groups having 6 to 12 carbon atoms of R5 in Formulas (II) and (III) are illustrated by phenyl, naphthyl, benzyl, tolyl, xylyl, methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl. Alternatively, the aryl group comprises 6 to 8 carbon atoms. Alternatively, the aryl group is phenyl.
- The epoxy groups of R5 in Formulas (II) and (III) are selected from glycidyl ether groups, alkyl epoxy groups and cycloaliphatic epoxy groups. The glycidyl ether group is illustrated by alkyl glycidyl ether groups such as 2-glycidoxyethyl, 3-glycidoxypropyl, 4-glycidoxybutyl, and 2-(3,4-epoxycyclohexyl)ethyl. Examples of the alkyl epoxy groups are 2,3-epoxypropyl, 3,4-epoxybutyl, and 4,5-epoxypentyl, and the cycloaliphatic epoxy group is illustrated by monovalent epoxycycloalkyl groups such as 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexylethyl, 3,4-epoxycyclohexylpropyl, 3,4-epoxycyclohexylbutyl, and alkyl cyclohexene oxide groups. Alternatively, the epoxy group is 3-glycidoxypropyl.
- The amino groups of R5 in Formulas (II) and (III) typically have the formula —R9NHR10 or —R9NHR9NHR10 wherein each R9 is independently a divalent hydrocarbon radical having at least 2 carbon atoms and R10 is hydrogen or an alkyl group having from 1 to 18 carbon atoms. Examples of the R9 group include an alkylene radical having from 2 to 20 carbon atoms and are illustrated by —CH2CH2—, —CH2CH2CH2—, —CH2CHCH3—, —CH2CH2CH2CH2—, —CH2CH(CH3)CH2—, —CH2CH2CH2CH2CH2—, —CH2CH2CH2CH2CH2CH2—, —CH2CH2CH(CH2CH3)CH2CH2CH2—, —CH2CH2CH2CH2CH2CH2CH2CH2—, and —CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2—. Alternatively, the alkyl groups of R10 are methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl. Alternatively, when R10 is an alkyl group it is methyl.
- Typical aminofunctional hydrocarbon groups are —CH2CH2NH2, —CH2CH2CH2NH2, —CH2CHCH3NH, —CH2CH2CH2CH2NH2, —CH2CH2CH2CH2CH2NH2, —CH2CH2CH2CH2CH2CH2NH2, —CH2CH2NHCH3, —CH2CH2CH2NHCH3, —CH2(CH3)CHCH2NHCH3, —CH2CH2CH2CH2NHCH3, —CH2CH2NHCH2CH2NH2, —CH2CH2CH2NHCH2CH2CH2NH2, —CH2CH2CH2CH2NHCH2CH2CH2CH2NH2, —CH2CH2NHCH2CH2NHCH3, —CH2CH2CH2NHCH2CH2CH2NHCH3, —CH2CH2CH2CH2NHCH2CH2CH2CH2NHCH3, and —CH2CH2NHCH2CH2NHCH2CH2CH2CH3.
- The carbinol groups of R5 in Formulas (II) and (III) are selected from carbinol groups free of aryl groups having at least 3 carbon atoms and aryl-containing carbinol groups having at least 6 carbon atoms. Generally a “carbinol” group is any group containing at least one carbon-bonded hydroxyl (COH) group. Thus the carbinol groups may contain more than one COH group such as for example
- Carbinol groups free of aryl groups having at least 3 carbon atoms are illustrated by groups having the formula R11OH wherein R11 is a divalent hydrocarbon group having at least 3 carbon atoms or a divalent hydrocarbonoxy group having at least 3 carbon atoms. The group R11 is illustrated by alkylene groups selected from —(CH2)s— where s has a value of 3 to 10 and —CH2CH(CH3)—, —CH2CH(CH3)CH2—, —CH2CH2CH(CH2CH3)CH2CH2CH2—, and —OCH(CH3)(CH2)t— wherein t has a value of 1 to 10. The carbinol group free of aryl groups having at least 3 carbon atoms is also illustrated by groups having the formula R12(OH) CH2OH where R12 is a group having the formula —CH2CH2(CH2)tOCH2CH— wherein t has a value of 1 to 10.
- The aryl-containing carbinol group having at least 6 carbon atoms is illustrated by groups having the formula R13OH wherein R13 is an arylene group selected from —(CH2)uC6H4—, —CH2CH(CH3)(CH2)uC6H4— wherein u has a value of 0 to 10, and —(CH2)tC6H4(CH2)u— wherein u and t are as described above. Alternatively, the aryl-containing carbinol groups have from 6 to 14 carbon atoms, alternatively 6 to 10 carbon atoms.
- Amino and/or carbinol containing silanes or siloxanes are applicable for some metal-containing resins, such as tin, germanium, and aluminium, however, gelation problems may occur during the synthetic process with certain metal elements (such as Zn and Cu) because of the amino and carbinol silanes or siloxanes ability to chelate to certain metals.
- Alternatively, each R5 in Formulas (II) and (III) is an independently selected hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkenyl group having from 2 to 8 carbon atoms, or an aryl group having from 6 to 12 carbons atoms. Alternatively, each R5 in Formulas (II) and (III) is an independently selected alkyl group having from 1 to 6 carbon atoms, an alkenyl group having from 2 to 6 carbon atoms, or an aryl group having from 6 to 8 carbons atoms. Alternatively, each R5 is methyl, vinyl, or phenyl.
- The R6 group of Formula (II) is an independently selected hydrogen atom, alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R3O)qR4, where q is a value from 1 to 4, each R3 is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R4 is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms or alkyl group. Examples of the alkyl group, aryl group and polyether group of R6 are as described above for R2. Alternatively, R6 is a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms. Alternatively, R6 is hydrogen, methyl, or ethyl.
- In Formula (II), subscript a is a value from 0.1 to 3, alternatively 1 to 3.
- In Formula (II), subscript b is a value from 0.5 to 3, alternatively 1.5 to 2.5.
- In Formula (II), subscripts (a+b) have a value from 0.6 to 3.9, alternatively 1.5 to 3.
- Examples of the organosiloxanes (B1) described by Formula (II) and useful in the present method include oligomeric and polymeric organosiloxanes, such as silanol-terminated polydimethylsiloxane, polymethylmethoxysiloxane, polysilsesquioxane, alkoxy and/or silanol containing MQ resin, and combinations thereof. They are made by hydrolysis of the corresponding organomethoxysilanes, organoethoxysilanes, organoisopropoxysilanes, and organochlorosilanes.
- In Formula (III), each Y is a chloro atom (CI) or OR6, where R6 is as described above. Alternatively, Y is OR6.
- In Formula (III), subscript c is a value from 0 to 3, alternatively, c is a value from 1 to 3, alternatively, from 2 to 3.
- In Formula (III), subscript d is a value from 1 to 4, alternatively d is a value from 1 to 3, alternatively, from 1 to 2.
- In Formula (III), subscripts (c+d) equal 4.
- Examples of the silanes (B2) described by Formula (III) include methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, phenylmethyldichlorosilane, methyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, phenylsilanetriol, diphenylsilanediol, phenylmethylsilanediol, dimethylsilanediol, trimethylsilanol, triphenylsilanol, phenyldimethoxysilanol, phenylmethoxysilanediol, methyldimethoxysilanol, methylmethoxysilanediol, phenyldiethoxysilanol, phenylethoxysilanediol, methyldiethoxysilanol, methylethoxysilanediol, etc.
- Component (C) may comprise at least one metal (M2) salt selected from (C1) a non-hydrated metal salt having a general formula (IV) R7 eM2(Z)(v2−e)/w or (C2) a hydrated metal salt having a general formula (V) M2(Z)v2/w.xH2O, where M2 is selected from any of the metal elements in the Periodic Table, v2 is the oxidation state of M2, w is the oxidation state of ligand Z where Z is independently chosen from carboxylates, β-diketonates, fluoride, chloride, bromide, iodide, organic sulfonate, nitrate, nitrite, sulphate, sulfite, cyanide, phosphites, phosphates, organic phosphites, organic phosphates, and oxalate, each R7 is an independently selected alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 8 carbon atoms, or aryl group having from 6 to 8 carbon atoms, e is a value from 0 to 3 and x is a value from 0.5 to 12 and describes the average number of H2O molecules associated with each metal salt molecule.
- In Formulas (IV) and (V), the metal element described by M2 is selected from all of the metals in the Periodic Table. Alternatively, M2 is selected from Li, Na, Ca, Mg, Ba, Ti, Zr, Ce, Eu, Nd, Er, Yb, Y, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn, Cd, Al, Ge, and Pb.
- In Formulas (IV) and (V), subscript v2 is the oxidation state of M2 and can range from 1 to 7, alternatively 1 to 4.
- In Formulas (IV) and (V), subscript w is the oxidation state of ligand Z and can range from 1 to 3, alternatively 1 to 2.
- The Z group in Formulas (IV) and (V) describes the various counter ligands attached to the metal element (M2). Generally, each Z is independently selected from carboxylate ligands, β-diketonate ligands, fluoride ligand, chloride ligand, bromide ligand, iodide ligand, organic sulfonate ligands, nitrate ligand, nitrite ligand, sulphate ligand, sulfite ligand, cyanide ligand, phosphate ligand, phosphite ligand, organic phosphite ligands, organic phosphate ligands, and oxalate ligand.
- The carboxylate ligands and β-diketonate ligands useful for Z are as described above for X.
- The organic sulfonate ligands useful for Z have a formula R22SO3 −, where R22 is selected from monovalent alkyl groups, alkenyl groups and aryl groups. Examples of useful alkyl groups, alkenyl groups and aryl groups are as described above for R15. Alternatively R22 is tolyl, phenyl, and methyl.
- The organic phosphate ligands useful for Z have a formula (R23O)2 PO2 − or R23O—PO3 2−, where R23 is selected from monovalent alkyl groups, alkenyl groups and aryl groups. Examples of useful alkyl groups, alkenyl groups and aryl groups are as described above for R15. Alternatively R23 is phenyl, butyl, and octyl.
- The organic phosphite ligands useful for Z have a formula (R24O)2 PO− or R24O—PO2 2−, where R24 is selected from monovalent alkyl groups, alkenyl groups and aryl groups. Examples of useful alkyl groups, alkenyl groups and aryl groups are as described above for R15. Alternatively R24 is phenyl, butyl, and octyl.
- Alternatively, Z in Formulas (IV) and (V) is independently selected from carboxylate ligands, β-diketonate ligands, nitrate ligand, sulphate ligand, and chloride ligand. Alternatively, Z includes carboxylate ligands and β-diketonate ligands.
- In Formulas (IV) and (V), subscript e is a value from 0 to 3, alternatively 0 to 2, alternatively 0.
- In Formula (IV), R7 is an independently selected alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 8 carbon atoms, or aryl group having from 6 to 8 carbon atoms. Examples of R7 are as described above for R5.
- In Formula (V), x is a value from 0.5 to 12, alternatively 1 to 9.
- Examples of non-hydrated metal salts (C1) described by Formula (IV) useful in the present method include but are not limited to lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, scandium acetate, yttrium acetate, luterium acetate, hafnium acetate, vanadium acetate, niobium acetate, tantalum acetate, chromium acetate, molybdenum acetate, tungsten acetate, manganese acetate, technetium acetate, rhenium acetate, iron acetate, ruthenium acetate, osmium acetate, cobalt acetate, rhodium acetate, iridium acetate, nickel acetate, palladium acetate, platinum acetate, copper acetate, silver acetate, zinc acetate, cadmium acetate, mercury acetate, aluminum acetate, gallium acetate, indium acetate, thallium acetate, tin, lead acetate, antimony acetate, bismuth acetate, lanthanum acetate, cerium acetate, praseodymium acetate, neodymium acetate, promethium acetate, samarium acetate, europium acetate, gadolinium acetate, terbium acetate, dysprosium acetate, holmium acetate, erbium acetate, thulium acetate, ytterbium acetate, lithium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, rubidium acetylacetonate, cesium acetylacetonate, beryllium acetylacetonate, magnesium acetylacetonate, calcium acetylacetonate, strontium acetylacetonate, barium acetylacetonate, scandium acetylacetonate, yttrium acetylacetonate, luterium acetylacetonate, titanium acetylacetonate, zirconium acetylacetonate, hafnium acetylacetonate, vanadium acetylacetonate, niobium acetylacetonate, tantalum acetylacetonate, chromium acetylacetonate, molybdenum acetylacetonate, tungsten acetylacetonate, manganese acetylacetonate, technetium acetylacetonate, rhenium acetylacetonate, iron acetylacetonate, ruthenium acetylacetonate, osmium acetylacetonate, cobalt acetylacetonate, rhodium acetylacetonate, iridium acetylacetonate, nickel acetylacetonate, palladium acetylacetonate, platinum acetylacetonate, copper acetylacetonate, silver acetylacetonate, zinc acetylacetonate, cadmium acetylacetonate, mercury acetylacetonate, aluminum acetylacetonate, gallium acetylacetonate, indium acetylacetonate, thallium acetylacetonate, tin, lead acetylacetonate, antimony acetylacetonate, lanthanum acetylacetonate, cerium acetylacetonate, praseodymium acetylacetonate, neodymium acetylacetonate, promethium acetylacetonate, samarium acetylacetonate, europium acetylacetonate, gadolinium acetylacetonate, terbium acetylacetonate, dysprosium acetylacetonate, holmium acetylacetonate, erbium acetylacetonate, thulium acetylacetonate, ytterbium acetylacetonate, aluminum acrylate, aluminum methacrylate, aluminum stearate, barium methacrylate, barium acrylate, bismuth 2-ethylhexanoate, calcium methacrylate, calcium acrylate, calcium undecylenate, copper (II) methacrylate, copper (II) 2-ethylhexanoate, hafnium2-ethylhexanoate, iron metacrylate, iron acrylate, lead metacrylate, lead acrylate, lead 2-ethylhexanoate, lithium metacrylate, lithium acrylate, magnesium metacrylate, magnesium acrylate, potassium metacrylate, potassium acrylate, potassium sulfopropylmethacrylate, potassium sulfopropylacrylate, cerium (III) 2-ethylhexanoate, europium (III) acrylate, europium (III) metacrylate, neodymium methacrylate, neodymium neodecanoate, yttrium metacrylate, silver acrylate, silver methacrylate, silver neodecanoate, sodium acrylate, sodium methacrylate, sodium allylsulfonate, strontium acrylate, strontium methacrylate, bis(2-ethylhexanoate)tin, bis(neodecanoate)tin, n-butyltris(2-ethylhexanoate)tin, di-n-butylbis(2-ethylhexanoate)tin, zinc acrylate, zinc methacrylate, zinc neodecanoate, zinc undecanoate, zinc 2-ethylhexanoate, zirconium methacrylate, copper sulphate, zinc chloride, silver nitrate, iron nitrate, nickel nitrate, zinc nitrate, acryloxytri-n-butyltin, acryloxytriphenyltin, di-n-butylbis(2,4-pentanedionate)tin, di-n-butyldiacetoxytin, di-n-butyldiacrylatetin, di-n-butyldilauryltin, di-n-butyldimethacrylatetin, di-n-butyldineodecanoatetin, dimethylbis(2,4-pentanedionate)tin, dimethyldineodecanoatetin, dioctyldilauryltin, methacryloxytri-n-butyltin, tri-n-butylacetoxytin, and tri-n-butylbenzoyloxytin.
- Examples of hydrated metal salts (C2) described by Formula (VI) useful in the present method include but are not limited to zinc acetate dihydrate, nickel acetate tetrahydrate, magnesium acetate tetrahydrate, zinc nitrate hexahydrate, and copper sulphate pentahydrate.
- Both the non-hydrated metal salts and the hydrated metal salts described above are commercially available through the major chemical vendors, such as Sigma-Aldrich, Fisher Scientific, Alfa-Aesar, Gelest, etc.
- The present invention relates to methods for preparing polyheterosiloxanes having at least two non-Si metal elements. In one embodiment, Components (A), (B), and (C) are dispersed or dissolved, water is added and a reaction proceeds forming a polyheterosiloxane having at least two non-Si metal elements.
- Another embodiment for preparing a polyheterosiloxane having at least two non-Si metal elements comprises: (1) adding an amount of water to a dispersion comprising at least one Component (A) and at least one Component (B1) or (B2) to form a heterosiloxane containing M1-O—Si linkages; and (2) adding at least one Component (C1) or (C2) and if necessary an additional amount of water to the heterosiloxane containing M1-O—Si linkages such that polyheterosiloxanes having at least two non-Si metal elements are formed, where the total amount of water added is between 50 and 200% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups on Components (A), (B), and (C).
- Another embodiment for preparing a polyheterosiloxane having at least two non-Si metal elements comprises: (1) adding an amount of water to a dispersion comprising at least one Component (A) and at least one Component (C1) or (C2) to form a mixed metal oxides solution containing M1-O-M2 oxo-linkages, and (2) adding at least one Component (B1) or (B2) to the mixed metal oxides solution containing M1-O-M2 oxo-linkages and if necessary adding an additional amount of water such that polyheterosiloxanes having at least two non-Si metal elements are formed, where the total amount of water added is between 50 and 200% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups on Components (A), (B), and (C).
- Another embodiment for preparing a polyheterosiloxane having at least two non-Si metal elements comprises: (1) adding an amount of water to a dispersion comprising at least one Component (C1) or (C2) and at least one Component (B1) or (B2) to form a heterosiloxane containing M2-O—Si linkages; and (2) adding at least one Component (A) to the heterosiloxane containing M2-O—Si linkages and if necessary an additional amount of water such that polyheterosiloxanes having at least two non-Si metal elements are formed, where the total amount of water added is between 50 and 200% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups on Components (A), (B), and (C).
- As used herein, the term “dispersion” in each of the methods means that the molecules of the various components are homogenously distributed. Each of the components may be liquid or solids and so it is preferred that they are pre-mixed or dispersed. Stirring one or more of the components in a solvent is an excellent way to get a homogenous dispersion; or a solvent may not be needed if one or more components can be dispersed in another component. When solvents are used, any kind of solvent is useful including polar solvents, non-polar solvent, hydrocarbon solvents including aromatic and saturated hydrocarbons, alcohols, etc. Examples of solvents useful for dispersing Components (A), (B), and (C) includes hydrocarbonethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, methoxyethanol, methoxyethoxyethanol, butyl acetate, and toluene, alternatively isopropanol, 1-butanol, 2-butanol, and butyl acetate. One type of solvent could be used or a mixture of different solvents would also be useful. The dispersing or mixing may be done by any conventional means such as stirring.
- Generally, the reaction between Components (A), (B), and (C) in each of the methods proceeds at room temperature (20° C.) but if desired, elevated temperatures up to about 140° C. may be used. Alternatively, the temperature can range from 20° C. to 120° C. Generally, the reaction can take between 30 minutes to 24 hours, alternatively 10 minutes to 4 hours.
- An optional step in all the methods comprises removing the solvent to produce a solid polyheterosiloxane having at least two non-Si metal elements. The solvents can be removed by any conventional manner such as heating to elevated temperatures or using reduced pressure. This solid material can then be redispersed in a solvent of choice such as toluene, THF, butyl acetate, chloroform, dioxane, 1-butanol, and pyridine. Since the Si—O-M linkages made by the present method can be susceptible to hydrolytic cleavage in the presence of H2O, to ensure longer shelf life it is preferred to minimize the polyheterosiloxane having at least two non-Si metal elements' exposure to moisture.
- The polyheterosiloxanes having at least two non-Si metal elements formed by each of the methods have molecular weights (weight average) ranging from 1000 to 1000000, alternatively from 2000 to 100000. In preferred embodiments, the non-Si metal elements are uniformly distributed in the materials and have a domain size smaller than 10 nanometers.
- Metal oxides have intrinsic spectral absorption bands, thus exhibit different colors when incorporated into the resins. The polyheterosiloxane resins produced by the present method may be characterized by UV transmission spectroscopy. The present polyheterosiloxane resins exhibit excellent absorption capability in the UV range (280-400 nm). In many instances, the present resins absorb visible light which should enable their use as colorants in coatings.
- The polyheterosiloxanes having at least two non-Si metal elements formed by the present methods preferably contain from 1% to 25% by weight alkoxy groups, alternatively, from 5% to 15% by weight alkoxy groups. Although there must be at least 2 non-Si metal elements in each polyheterosiloxane molecule, the molar percentage of the non-Si metal element (M1 and M2) content in the polyheterosiloxane materials can also be from 0.5 to 90 mole percent, alternatively from 5 to 60 mole percent, alternatively from 20 to 50 mole percent. No fatty acid is needed in the present methods.
- The molar ratio of M2 to M1 useful in each embodiment ranges from 0.001 to 2, alternatively from 0.05 to 1. The molar ratio of Si units to M1 useful in the present methods range from 0.1 to 200, alternatively from 0.6 to 20.
- An amount of water must be added in each embodiment so that polyheterosiloxanes having at least two non-Si metal elements are formed. Since water can also be incorporated via the hydrated metal salts (C2), a person skilled in the art would understand that when hydrated metal salts are utilized either smaller amounts or no additional amounts of water may need to be added in order for the needed amount of water to be present. Generally, the amount of water needed for making polyheterosiloxanes having at least two non-Si metal elements ranges from 50% to 200% of the theoretical amount of water necessary for complete hydrolysis and condensation of all the alkoxy and other hydrolyzable groups present on each of the components. A person skilled in the art would understand that 0.5 mole of water is necessary for hydrolysis and condensation of 1 mole of alkoxy and other hydrolyzable groups. Alternatively, the amount of water needed to make polyheterosiloxanes having at least two non-Si metal elements ranges from 70% to 150% of the theoretical amount of H2O necessary for complete hydrolysis and condensation of all the alkoxy and other hydrolyzable groups present on each of the components, alternatively, 80% to 120% on the same basis. It is preferred in each of the embodiments that the water is added slowly to ensure the metal alkoxide doesn't react so quickly with the water that it precipitates from the solution. A preferred method of accomplishing this is by diluting the water with solvents. The solvents useful for diluting the water are the same as used for dispersing the components. Depending on the components used and when they are added the needed water may also be added at one time or during one or more of the steps. Other hydrolyzable groups that may be present and need to be hydrolyzed and condensed are any found on the components used including but not limited to chloro.
- As described above, the polyheterosiloxanes having at least two non-Si metal elements are soluble in many solvents and are compatible with many polymers, such as epoxy and polyurethane. These advantages, along with the low cost of the metal precursors will facilitate the practical use of the polyheterosiloxanes having at least two non-Si metal elements. The material properties and applications depend on the properties of the metal elements incorporated into the polyheterosiloxane. Potential applications include, but not limited to, UV protective coatings, thermal conductive materials, conductive/antistatic materials, self-cleaning coating, photocatalytic materials, colorants for coatings or paints, gloss/mechanical property enhancement, reinforcement components, adhesive components, scratch/impact resistant coating, and catalysts.
- The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention. Room temperature (RT) in the present examples is 20° C.
- Solubility of the products were tested by mixing 1 gram of the solid product in 9 grams of solvent, such as THF, toluene, butyl acetate, and chloroform. Soluble means that the solid product dissolves sufficiently in the solvent (without noticeable insoluble solid). As used herein, Me means methyl, Ac means acetate, acac means acetylacetonate, Ph means phenyl.
- 4.40 g ZnAc2.2H2O, 11.37 g titanium tetraisopropoxide (TPT), 20 g isopropanol (IPA), and 10 g toluene were charged to a 250 ml flask. A slightly cloudy solution was obtained after the mixture was stirred at RT for 1 hour. A silanol-containing organosiloxane was prepared by mixing 5.47 g phenylmethyldimethoxysilane (PhMeSi(OMe)2), 5.95 g phenyltrimethoxysilane (PhSi(OMe)3), and 2.54 g 0.04M HCl and sonicating the mixture for 40 minutes (Sonicator: Fisher Scientific Instrument (Pittsburgh, Pa.), Model FS60). The silanol-containing organosiloxane solution was added to the 250 ml flask and the solution turned clear after 10 minutes. Stirring was continued at RT for 2 hours. The total amount of H2O in the reaction mixture was 100% of the amount of water theoretically necessary for complete hydrolysis and condensation of all alkoxy groups. Solvents were removed using a rotary evaporator. No signs of unreacted precursors appear in the GPC analysis of the product. The product was a white solid with a theoretic composition of Ti0.33Zn0.17DPhMe0.25TPh 0.25 (6.8 w % alkoxy based on 13C NMR) which was soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform.
- 0.88 g AgNO3 was dissolved in 1.00 g H2O and 25 g IPA and the solution was added into a TPT solution containing 13.18 g TPT and 6 g IPA. After stirring at RT for 18 minutes, 30 g toluene was added into the flask. A silanol-containing organosiloxane solution was prepared by mixing 3.65 g phenylmethyldimethoxysilane, 1.99 g phenyltrimethoxysilane, 10 g toluene, and 1.36 g 0.1M HNO3 and sonicating the mixture for 30 minutes. The silanol-containing organosiloxane solution was added into the 250 ml flask and the solution turned dark brown color. Stirring was continued at RT for 3.5 hours. 0.50 g H2O in 5.0 g IPA was added to the solution. The total amount of H2O used was 120%. of the amount of water theoretically necessary for complete hydrolysis and condensation of all alkoxy groups. After stirring at RT for 2 hours the solvents were removed using a rotary evaporator. No signs of unreacted precursors appear in the GPC analysis of the product. The product was a yellow solid with a theoretic composition of Ti0.57Ag0.06DPhMe0.25TPh 0.12 (5.8w % alkoxy based on 13C NMR) which was soluble in many organic solvents, such as butyl acetate, acetone, THF, and chloroform.
- A wide variety of polyheterosiloxane materials were synthesized using the same synthetic procedures described above. The metal elements included Li, Na, Mg, Ca, Ba, Y, Ce, Eu, Er, Yb, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn, Cd, Al, and Pb—at least one metal element in each column from column 1 to column 14 in the Periodic Table. The polyheterosiloxane materials were solid materials dissolvable in various organic solvents. See Table 1.
-
TABLE 1 Examples 3-33 Metal EX Alkoxide Metal Salt Theoretic Composition H2O amount 3 TPT CeAc3•1.5H2O Ti0.48Ce0.024DPhMe 0.265TPh 0.237 81% 4 TPT ZnAc2•2H2O Ti0.450Zn0.050DPhMe 0.250TPh 0.250 102% 5 NPZ ZnAc2•2H2O Zr0.275Zn0.275DPhMe 0.228TPh 0.223 110% 6 TPT ZnAc2•2H2O Ti0.341Zn0.171DMe2 0.171TMe 0.171M0.147 88% 7 TPT NiAc2•4H2O Ti0.484Ni0.121DPhMe 0.254TPh 0.140 93% 8 TPT MgAc2•4H2O Ti0.484Mg0.121DPhMe 0.254TPh 0.140 93% 9 TPT CuAc2•2H2O Ti0.500Cu10.125DPhMe 0.250TPh 0.125 106% 10 TPT CaAc2•H2O Ti0.500Ca0.125DPhMe 0.250TPh 0.125 129% 11 TPT FeAc2 Ti0.470FeII 0.116DPhMe 0.250TPh 0.125 115% 12 TPT BaAc2 Ti0.500Ba0.125DPhMe 0.250TPh 0.125 100% 13 TPT Mn(acac)3 Ti0.500Mn0.125DPhMe 0.250TPh 0.125 100% 14 TPT Mn(acac)2 Ti0.500Mn0.125DPhMe 0.250TPh 0.125 100% 15 TPT CdAc2•2H2O Ti0.500Cd0.125DPhMe 0.250TPh 0.125 120% 16 TPT V(acac)3 Ti0.500V0.125DPhMe 0.250TPh 0.125 130% 17 Al(OsBu)3 Zn(acac)2 Al0.400Zn0.200DPhMe 0.300TPh 0.100 104% 18 NPZ Ag(NO3) Zr0.450Ag0.050DPhMe 0.333TPh 0.167 110% 19 TPT CoAc2•4H2O Ti0.500Co0.125DPhMe 0.250TPh 0.125 120% 20 TPT Cr(acac)3 Ti0.444Cr0.111DPhMe 0.333TPh 0.111 104% 21 TPT Fe(NO3)3•9H2O Ti0.500Fe0.125DPhMe 0.250TPh 0.125 110% 22 TPT Zn(NO3)2•6H2O Ti0.500Zn0.125DPhMe 0.250TPh 0.125 110% 23 TPT Ni(NO3)2•6H2O Ti0.500Ni0.125DPhMe 0.250TPh 0.125 110% 24 TPT CUSO4•5H2O Ti0.458Ni0.114DPhMe 0.352TPh 0.076 100% 25 TPT NaAc Ti0.414Na0.103DPhMe 0.345TPh 0.138 100% 26 TPT Li(acac) Ti0.400Li0.100DPhMe 0.400TPh 0.100 120% 27 TPT ZnCl2 Ti0.400Zn0.200DPhMe 0.300TPh 0.100 100% 28 TPT EuAc3•xH2O, x~4 Ti0.600Eu0.030DPhMe 0.270TPh 0.100 110% 29 TPT ErAc3•xH2O, x~4 Ti0.600Er0.030DPhMe 0.270TPh 0.100 110% 30 TPT YbAc3•4H2O Ti0.600Yb0.030DPhMe 0.270TPh 0.100 110% 31 NBZ EuAc3•xH2O, x~4 Zr0.520Eu0.028DPhMe 0.339TPh 0.113 110% 32 NBZ Y(acac)3 Zr0.500Y0.100DPhMe 0.300TPh 0.100 110% 33 TPT PbAc2•3H2O Ti0.500Pb0.100DPhMe 0.300TPh 0.100 110% - 5.32 g Sn(Ac)4, 5.1 g Ti(OnBu)4, 15 g 1-BuOH was charged to a 250 ml flask. Under stirring, a solution containing 0.86 g H2O and 20 g 1-BuOH was slowly added. The solution was clear after 30 minutes. A silanol-containing organosiloxane solution was prepared by mixing 3.12 g Si(OEt)4, 19 g 1-BuOH, and 0.60 g 0.1M HCl and sonicating the mixture for 30 minutes. The silanol-containing organosiloxane solution was added to the 250 ml flask and the solution was still clear after stirring at RT for 4 hours. The amount of H2O used was 90%. of the amount of water theoretically necessary for complete hydrolysis and condensation of all alkoxy groups. Solvents were removed using a rotary evaporator. No signs of unreacted precursors appear in the GPC analysis of the product. The product was a white solid with a theoretic composition of Ti0.333Sn0.333Q0.333 which was soluble in butyl acetate, toluene, THF, and 1-BuOH.
- 4.39 g Zn(Ac)20.2H2O, 9.60 g zirconium tetra(n-butoxide) (NBZ, 80% in 1-BuOH), 15 g 1-BuOH was charged to a 250 ml flask. The solution was clear after 20 minutes. 3.22 g phenyl trimethoxysilane and 3.03 g phenylmethyldimethoxysilane was added and stirred for 10 minutes. Then 1.12 g 0.1 N HCl (6% in 1-BuOH) was added slowly and then 20 g toluene. The solution was still clear after stirring at RT for 4 hours. The amount of H2O used was 100% of the amount of water theoretically necessary for complete hydrolysis and condensation of all alkoxy groups. Solvents were removed using a rotary evaporator. No signs of unreacted precursors appear in the GPC analysis of the product. The product was a white solid with a theoretic composition of Zr0.275Zn0.275DPhMe 0.228TPh 0.223 (8.4 w % alkoxy based on 13C NMR) which was soluble in butyl acetate, toluene, and THF.
- 9.1 g TPT, 10 g IPA was charged to a 250 ml flask. Under stirring, a silanol-containing organosiloxane solution which was prepared by mixing 1.98 g PhSi(OMe)3, 3.65 g PhMeSi(OMe)2, 4.5 g toluene, 1.1 g IPA, and 1.26 g 0.1 N HCl and sonicating the mixture for 30 minutes was slowly added. Solution turned milky after 10 minutes. 20 g toluene was then added and the solution turned clear. Then added 1.72 g Mg(Ac)20.4H2O and 0.10 g H2O in 10 g IPA. The amount of H2O used was 100%. of the amount of water theoretically necessary for complete hydrolysis and condensation of all alkoxy groups. The solution was clear after stirring at RT for 4 hours. Solvents were removed using a rotary evaporator. No signs of unreacted precursors appear in the GPC analysis of the product. The product was a white solid with a composition of Ti0.457Mg0.114DPhMe 0.286TPh 0.143 which was soluble in butyl acetate, toluene, and THF.
- 3.24 g Al(acac)2 was dispersed in a silanol-containing organosiloxane solution which was prepared by mixing 1.98 g PhSi(OMe)3, 3.65 g PhMeSi(OMe)2, 4.5 g toluene, 1.1 g IPA, and 1.26 g 0.1 N HCl and sonicating the mixture for 30 minutes. The dispersion was stirred at RT for 30 minutes. Then 8.53 g TPT and 10 g IPA was added to the dispersion. Under stirring, 1.01 g H2O (6% in IPA) was slowly added. The amount of H2O used was 100%. of the amount of water theoretically necessary for complete hydrolysis and condensation of all alkoxy groups. The solution was clear after stirring at RT for 4 hours. Solvents were removed using a rotary evaporator. No signs of unreacted precursors appear in the GPC analysis of the product. The product was a white solid with a theoretic composition of Ti0.469Al0.156DPhMe 0.250TPh 0.125 (7.4w % alkoxy based on 13C NMR) which was soluble in butyl acetate, toluene, and THF.
- 2.64 g Zn(Ac)20.2H2O, 13.65 g TPT, 5.47 g PhMeSi(OMe)2, 1.99 g PhSi(OMe)3, 10 g IPA, and 30 g toluene were charged to a 250 ml flask. The dispersion was stirred at RT for 40 minutes. Then 2.12 g 0.1N HCl (4% in IPA) was slowly added to the flask. The total amount of H2O was 100% of the amount of water theoretically necessary for complete hydrolysis and condensation of all alkoxy groups. The solution was clear after stirring at RT for 3 hours. Solvents were removed using a rotary evaporator. The product was a white solid with a theoretic composition of Ti0.48Zn0.12DPhMe 0.30TPh 0.10 which was soluble in butyl acetate, toluene, and THF.
- 6.17 g Sn(OtBu)4, 5.10 g Ti(OnBu)4, and 3.12 g Si(OEt)4 was mixed in a 250-ml flask. 3w % H2O/1-BuOH solution was added slowly into the flask under stirring. At 60% stoichiometric amount of H2O, the solution was still clear after refluxing for 30 min. At 80% stoichiometric amount of H2O it gelled and the solid was not soluble in Toluene, IPA, 1-BuOH, and butyl acetate. Calculation of the theoretic alkoxy content in the product at 60% stoichiometric amount of H2O was 55 wt %.
- Metal oxides have intrinsic absorption bands, thus exhibit different colors when incorporated into the resins. The UV transmission spectra of various polyheterosiloxane resins of the above examples exhibited excellent absorption capability in the UV range (280-400 nm).
- Polyurethane coatings were formulated using Bayer Desmophen A870 and Desmodur N3390. A typical formulation was composed of 0.60 g polyheterosiloxane resin, 2.58 g butyl acetate, 8.00 g Desmophen A870, and 2.96 g Desmodur N3390. The gel time greatly changed from more than 8 hours (uncatalyzed) to less than 2 minutes (catalyzed with Si+Ti+V resins).
Claims (18)
1. A method for preparing a polyheterosiloxane having at least two non-Si metal elements comprising:
(1) reacting
(C) a hydrolyzable metal (M2) salt, where (M1) and (M2) are non-Si metal elements and different from each other, and
(B) a silicon-containing material having hydrolyzable groups selected from
(B1) an organosiloxane, or
(B2) a silane, and
with an amount of water to form a reaction product; and
(2) further reacting the reaction product of step (1) and (A) a metal (M1) alkoxide, and
if necessary adding an additional amount of water to form the polyheterosiloxane, such that total amount of the water added is between 50 and 200% of that necessary to hydrolyze and condense the alkoxy groups and other hydrolyzable groups on Components (A), (B), and (C), to form the polyheterosiloxane, and with the proviso that at least two non-Si metal elements are provided by Component (A) and/or (C).
2. The method according to claim 1 wherein;
(A) the metal (M1) alkoxide is selected from metal alkoxides having a general formula (I) R1 mM1OnXp(OR2)v1-m-p-2n, where M1 is selected from Ti, Al, Ge, Zr, Sn, Cr, Ca, Ba, Sb, Cu, Ga, Hf, In, Fe, Mg, Mo, Nb, Ce, Er, La, Nd, Pr, Sm, Y, Sr, Ta, Te, W, and V, each X is independently selected from carboxylate ligands, organosulfonate ligands, organophosphate ligands, β-diketonate ligands, and chloride ligands, v1 is the oxidation state of M1, m is a value from 0 to 3, n is a value from 0 to 2, p is a value from 0 to 3, each R1 is an alkyl group having from 1 to 18 carbon atoms, each R2 is an independently selected monovalent alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R3O)qR4, where q is a value from 1 to 4, each R3 is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R4 is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms,
(B) the silicon-containing material is selected from (B1) an organosiloxane having an average formula (II) R5 b(R6O)aSiO(4−(a+b))/2 or (B2) a silane having a general formula (III) R5 cSiYd, where Y is Cl or OR6, each R5 is an independently selected hydrogen atom, alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 18 carbon atoms, aryl group having from 6 to 12 carbon atoms, epoxy group, amino group, or carbinol group, R6 is an independently selected hydrogen atom or alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R3O)qR4, where q is a value from 1 to 4, each R3 is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R4 is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms, a is a value from 0.1 to 3, b is a value from 0.5 to 3, and (a+b) is a value from 0.6 to 3.9, c is a value from 0 to 3, d is a value from 1 to 4 and (c+d) equals 4, and
(C) the hydrolyzable metal (M2) salt is selected from (C1) a non-hydrated metal salt having a general formula (IV) R7 eM2(Z)(v2−e)/w or (C2) a hydrated metal salt having a general formula (V) M2(Z)v2/w.xH2O, where M2 is selected from any of the metal elements in the periodic table, v2 is the oxidation state of M2, w is the oxidation state of ligand Z where Z is independently chosen from carboxylates, β-diketonates, fluoride, chloride, bromide, iodide, organic sulfonate, nitrate, nitrite, sulphate, sulfite, cyanide, phosphites, phosphates, organic phosphites, organic phosphates, and oxalate, each R7 is an independently selected alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 8 carbon atoms, or aryl group having from 6 to 8 carbon atoms, e is a value from 0 to 3 and x is a value from 0.5-12.
3. The method according to claim 1 , wherein M2 is selected from Li, Na, Ca, Mg, Ba, Ti, Zr, Ce, Eu, Nd, Er, Yb, Y, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn, Cd, Al, Ge, and Pb.
4. The method according to claim 3 , where M2 is Al.
5. The method according to claim 1 where M1 is Ti.
6. The method according to claim 1 , where the total amount of water added is between 70 and 150% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups.
7. The method according to claim 6 , where the total amount of water added is between 80 and 120% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups.
8. A polyheterosiloxane prepared by any of the method of claim 1 .
9. A coating composition comprising the polyheterosiloxane of claim 8 .
10. A method for preparing a polyheterosiloxane having at least two non-Si metal elements comprising:
(1) reacting
(A) a metal (M1) alkoxide, and
(B) a silicon-containing material having hydrolyzable groups selected from
(B1) an organosiloxane, or
(B2) a silane, and
with an amount of water to form a reaction product; and
(2) further reacting the reaction product of step (1) and (C) a hydrolyzable metal (M2) salt, where (M1) and (M2) are non-Si metal elements and different from each other, and
if necessary adding an additional amount of water to form the polyheterosiloxane, such that total amount of the water added is between 50 and 200% of that necessary to hydrolyze and condense the alkoxy groups and other hydrolyzable groups on Components (A), (B), and (C), to form the polyheterosiloxane, and with the proviso that at least two non-Si metal elements are provided by Component (A) and/or (C).
11. The method according to claim 10 wherein;
(A) the metal (M1) alkoxide is selected from metal alkoxides having a general formula (I) R1 mM1On Xp(OR2)v1-m-p-2n, where M1 is selected from Ti, Al, Ge, Zr, Sn, Cr, Ca, Ba, Sb, Cu, Ga, Hf, In, Fe, Mg, Mo, Nb, Ce, Er, La, Nd, Pr, Sm, Y, Sr, Ta, Te, W, and V, each X is independently selected from carboxylate ligands, organosulfonate ligands, organophosphate ligands, 3-diketonate ligands, and chloride ligands, v1 is the oxidation state of M1, m is a value from 0 to 3, n is a value from 0 to 2, p is a value from 0 to 3, each R1 is an alkyl group having from 1 to 18 carbon atoms, each R2 is an independently selected monovalent alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R3O)qR4, where q is a value from 1 to 4, each R3 is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R4 is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms,
(B) the silicon-containing material is selected from (B1) an organosiloxane having an average formula (II) R5 b(R6O)aSiO(4−(a+b))/2 or (B2) a silane having a general formula (III) R5 cSiYd, where Y is Cl or OR6, each R5 is an independently selected hydrogen atom, alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 18 carbon atoms, aryl group having from 6 to 12 carbon atoms, epoxy group, amino group, or carbinol group, R6 is an independently selected hydrogen atom or alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R3O)qR4, where q is a value from 1 to 4, each R3 is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R4 is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms, a is a value from 0.1 to 3, b is a value from 0.5 to 3, and (a+b) is a value from 0.6 to 3.9, c is a value from 0 to 3, d is a value from 1 to 4 and (c+d) equals 4, and
(C) the hydrolyzable metal (M2) salt is selected from (C1) a non-hydrated metal salt having a general formula (IV) R7 eM2(Z)(v2−e)/w or (C2) a hydrated metal salt having a general formula (V) M2(Z)v2/w.xH2O, where M2 is selected from any of the metal elements in the periodic table, v2 is the oxidation state of M2, w is the oxidation state of ligand Z where Z is independently chosen from carboxylates, β-diketonates, fluoride, chloride, bromide, iodide, organic sulfonate, nitrate, nitrite, sulphate, sulfite, cyanide, phosphites, phosphates, organic phosphites, organic phosphates, and oxalate, each R7 is an independently selected alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 8 carbon atoms, or aryl group having from 6 to 8 carbon atoms, e is a value from 0 to 3 and x is a value from 0.5-12.
12. The method according to claim 10 , wherein M2 is selected from Li, Na, Ca, Mg, Ba, Ti, Zr, Ce, Eu, Nd, Er, Yb, Y, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn, Cd, Al, Ge, and Pb.
13. The method according to claim 12 , wherein M2 is Mg.
14. The method according to claim 10 , wherein M1 is Ti.
15. The method according to claim 10 , wherein the total amount of water added is between 70 and 150% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups.
16. The method according to claim 15 , wherein the total amount of water added is between 80 and 120% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups.
17. A polyheterosiloxane prepared by any of the method of claim 10 .
18. A coating composition comprising the polyheterosiloxane of claim 17 .
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WO2000071553A1 (en) | 1999-05-21 | 2000-11-30 | Yang Jae Kun | Novel aluminosiloxane compound and process for preparing the same |
JP3846545B2 (en) | 2000-06-08 | 2006-11-15 | 信越化学工業株式会社 | Coating agent composition, coating method and coated article |
JP4499907B2 (en) | 2000-12-07 | 2010-07-14 | 富士化学株式会社 | Method for producing inorganic polymer compound, inorganic polymer compound, and inorganic polymer compound film |
JP4041966B2 (en) | 2002-06-18 | 2008-02-06 | 信越化学工業株式会社 | Article with hard coat agent and hard coat film formed |
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JP5137503B2 (en) | 2006-09-15 | 2013-02-06 | 株式会社日本触媒 | UV-cutting agent for cosmetics and cosmetics using the same |
US7652157B2 (en) | 2007-06-22 | 2010-01-26 | General Electric Company | Metal oxide coatings |
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2010
- 2010-06-30 EP EP10729042A patent/EP2448999A1/en not_active Withdrawn
- 2010-06-30 KR KR1020127002876A patent/KR20120098588A/en not_active Application Discontinuation
- 2010-06-30 CN CN2010800300129A patent/CN102471492A/en active Pending
- 2010-06-30 WO PCT/US2010/040510 patent/WO2011002826A1/en active Application Filing
- 2010-06-30 US US13/379,370 patent/US8674048B2/en not_active Expired - Fee Related
- 2010-06-30 JP JP2012517876A patent/JP2012532213A/en not_active Ceased
-
2014
- 2014-01-22 US US14/160,635 patent/US20140135446A1/en not_active Abandoned
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US4746366A (en) * | 1984-02-27 | 1988-05-24 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Process and lacquer for the production of scratch-resistant coatings |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140273447A1 (en) * | 2013-03-15 | 2014-09-18 | Shin-Etsu Chemical Co., Ltd. | Composition for forming titanium-containing resist underlayer film and patterning process |
US9188866B2 (en) * | 2013-03-15 | 2015-11-17 | Shin-Etsu Chemical Co., Ltd. | Composition for forming titanium-containing resist underlayer film and patterning process |
Also Published As
Publication number | Publication date |
---|---|
US8674048B2 (en) | 2014-03-18 |
US20120101222A1 (en) | 2012-04-26 |
WO2011002826A1 (en) | 2011-01-06 |
KR20120098588A (en) | 2012-09-05 |
JP2012532213A (en) | 2012-12-13 |
EP2448999A1 (en) | 2012-05-09 |
CN102471492A (en) | 2012-05-23 |
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