US9617396B2
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Method for in-situ synthesis of silicon nanoparticles
Assignee: Commissariat à l'Énergie Atomique et Aux Énergies Alternatives
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Filing: 2013-02-20
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Granted: 2017-04-11
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Expires: 2033-02-20
Abstract
Abstract The invention relates to a method for in-situ synthesis of silicon nanoparticles in a thermosetting polymeric matrix, the thermosetting and thermoset matrices obtained in this way and a material including same. The method includes the following steps: a) forming an aqueous-phase/organic-phase inverse emulsion, wherein the aqueous phase includes at least a basic catalyst and the organic phase includes at least a non-cross-linked (co)polymer precursor chosen from an aliphatic, cycloaliphatic or aromatic epoxy resin precursor, a polyester-imide precursor, an unsaturated/epoxy polyester (co)polymer precursor, a polyether/epoxy (co)polymer precursor and a polyurethane precursor; b) introducing, into the inverse emulsion formed in step a), at least one silicon precursor forming a complete network whereof the rate of hydrolysis is greater than the cross-linking speed of the (co)polymer and c) stirring the mixture obtained in step b) and heating to a temperature between 20° C. and 70° C.
Inventors
- 👤 Chloé Schubert
- 👤 Olivier Poncelet
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 01:45
CPC Classifications
C; C08; C08J; C08J3/00; C08J3/20; C08J3/205; C08J3/21; C08J3/215; C08K; C08K7/00; C08K7/22; C08K7/24; C08K7/26; H; H01; H01B; H01B3/00; H01B3/18; H01B3/30; H01B3/302; H01B3/303; H01B3/305; H01B3/306; H01B3/40; H01B3/42; H01B3/421; H01B3/422; C08J2300/00; C08J2300/24; C08J2367/00; C08J2367/02; C08J2379/00; C08J2379/04; C08J2379/08; C08K3/00; C08K3/34; C08K3/36
Claims Analysis
Total Claims: 22
Claim 1
Independent Claim
153 words
A method for in-situ synthesis of silica nanoparticles in a thermosetting polymer matrix, wherein the method comprises the following steps: a) forming an aqueous phase-organic phase inverted emulsion, in which the aqueous phase comprises at least one basic catalyst and the organic phase comprises at least one noncrosslinked (co)polymer precursor selected from a precursor of aliphatic, cycloaliphatic or aromatic epoxy resin, a polyester-imide precursor, a precursor of unsaturated polyester/epoxy (co)polymer, a precursor of polyether/epoxy (co)polymer and a polyurethane precursor; b) introducing at least one silica precursor into the inverted emulsion formed in step a) forming a complete network whose rate of hydrolysis is greater than the rate of crosslinking of the (co)polymer and c) stirring the mixture obtained in step b) and heating to a temperature between 20° C. and 70° C., and wherein no step of functionalization of the polymer precursor is carried out and no solvent or coupling agent is added.
Claim 2
Independent Claim
153 words
A method for in-situ synthesis of silica nanoparticles in a thermosetting polymer matrix, wherein the method comprises the following steps: a) forming an aqueous phase-organic phase inverted emulsion, in which the aqueous phase comprises at least one basic catalyst and the organic phase comprises at least one noncrosslinked (co)polymer precursor selected from a precursor of aliphatic, cycloaliphatic or aromatic epoxy resin, a polyester-imide precursor, a precursor of unsaturated polyester/epoxy (co)polymer, a precursor of polyether/epoxy (co)polymer and a polyurethane precursor; b) introducing at least one silica precursor into the inverted emulsion formed in step a) forming a complete network whose rate of hydrolysis is greater than the rate of crosslinking of the (co)polymer and c) stirring the mixture obtained in step b) and heating to a temperature between 20° C. and 70° C., and wherein no step of functionalization of the polymer precursor is carried out and no solvent or coupling agent is added.
Claim 3
Dependent Claim
18 words
The method as claimed in claim 1 , wherein the basic catalyst is selected from ammonia or urea.
Claim 4
Dependent Claim
30 words
The method as claimed in claim 1 , wherein the silica precursor forming a complete network is selected from the group consisting of tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetrakis(2,2,2-trifluoroethoxy)silane and tetrakis(1,1,1,3,3,3-hexafluoropropoxy)silane.
Claim 5
Dependent Claim
54 words
The method as claimed in claim 1 , characterized in that the precursor is a precursor of polyether/epoxy (co)polymer or a precursor of polyester-imide polymer and in that steps a) and b) are carried out in a double-wall reactor with temperature controlled at 20° C. and step c) is carried out at 70° C.
Claim 6
Dependent Claim
28 words
The method as claimed in claim 1 , wherein the ratio of the weight of silica precursor to the weight of (co)polymer precursor is between 1/100 and 35/100.
Claim 7
Dependent Claim
37 words
The method as claimed in claim 1 , wherein in step a) the noncrosslinked (co)polymer precursor does not contain hardener and in that it comprises a step of adding hardener to the mixture obtained after step c).
Claim 8
Dependent Claim
18 words
The method as claimed in claim 6 , wherein the hardener is a hardener based on acid anhydride.
Claim 9
Dependent Claim
34 words
The method as claimed in claim 6 , wherein the hardener is selected from the group consisting of methylhexahydrophthalic anhydride (MHHPA), methyltetrahydrophthalic anhydride (MTHPA), phthalic anhydride (PA), tetrahydrophthalic anhydride (THPA), and hexahydrophthalic anhydride (HHPA).
Claim 10
Dependent Claim
23 words
The method as claimed in claim 1 wherein the ratio of the weight of silica precursor to the weight of (co)polymer precursor 9/100.
Claim 11
Dependent Claim
50 words
A method for synthesis of a thermoset polymer matrix doped with silica nanoparticles comprising the following steps: a1) carrying out the method as claimed in claim 1 , b1) heating the thermosetting matrix doped with silica nanoparticles obtained in step a1) to the temperature of hardening of the polymer matrix.
Claim 12
Independent Claim
163 words
A method for in-situ synthesis of silica nanoparticles in a thermosetting polymer matrix, wherein the method comprises the following steps: a) forming an aqueous phase-organic phase inverted emulsion, in which the aqueous phase comprises at least one basic catalyst and the organic phase comprises at least one noncrosslinked (co)polymer precursor selected from a precursor of aliphatic, cycloaliphatic or aromatic epoxy resin, a polyester-imide precursor, a precursor of unsaturated polyester/epoxy (co)polymer, a precursor of polyether/epoxy (co)polymer and a polyurethane precursor; b) introducing at least one silica precursor into the inverted emulsion formed in step a) forming a complete network whose rate of hydrolysis is greater than the rate of crosslinking of the (co)polymer and c) stirring the mixture obtained in step b) and heating to a temperature between 20° C. and 70° C., and wherein in step a) the noncrosslinked (co)polymer precursor does not contain hardener, and wherein the method comprises a step of adding a hardener to the mixture obtained after step c).
Claim 13
Independent Claim
163 words
A method for in-situ synthesis of silica nanoparticles in a thermosetting polymer matrix, wherein the method comprises the following steps: a) forming an aqueous phase-organic phase inverted emulsion, in which the aqueous phase comprises at least one basic catalyst and the organic phase comprises at least one noncrosslinked (co)polymer precursor selected from a precursor of aliphatic, cycloaliphatic or aromatic epoxy resin, a polyester-imide precursor, a precursor of unsaturated polyester/epoxy (co)polymer, a precursor of polyether/epoxy (co)polymer and a polyurethane precursor; b) introducing at least one silica precursor into the inverted emulsion formed in step a) forming a complete network whose rate of hydrolysis is greater than the rate of crosslinking of the (co)polymer and c) stirring the mixture obtained in step b) and heating to a temperature between 20° C. and 70° C., and wherein in step a) the noncrosslinked (co)polymer precursor does not contain hardener, and wherein the method comprises a step of adding a hardener to the mixture obtained after step c).
Claim 14
Dependent Claim
28 words
The method as claimed in claim 11 , wherein no step of functionalization of the polymer precursor is carried out and no solvent or coupling agent is added.
Claim 15
Dependent Claim
18 words
The method as claimed in claim 11 , wherein the basic catalyst is selected from ammonia or urea.
Claim 16
Dependent Claim
30 words
The method as claimed in claim 11 , wherein the silica precursor forming a complete network is selected from the group consisting of tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetrakis(2,2,2-trifluoroethoxy)silane and tetrakis(1,1,1,3,3,3-hexafluoropropoxy)silane.
Claim 17
Dependent Claim
54 words
The method as claimed in claim 11 , characterized in that the precursor is a precursor of polyether/epoxy (co)polymer or a precursor of polyester-imide polymer and in that steps a) and b) are carried out in a double-wall reactor with temperature controlled at 20° C. and step c) is carried out at 70° C.
Claim 18
Dependent Claim
28 words
The method as claimed in claim 11 , wherein the ratio of the weight of silica precursor to the weight of (co)polymer precursor is between 1/100 and 35/100.
Claim 19
Dependent Claim
18 words
The method as claimed in claim 11 , wherein the hardener is a hardener based on acid anhydride.
Claim 20
Dependent Claim
50 words
A method for synthesis of a thermoset polymer matrix doped with silica nanoparticles comprising the following steps: a1) carrying out the method as claimed in claim 11 , b1) heating the thermosetting matrix doped with silica nanoparticles obtained in step a1) to the temperature of hardening of the polymer matrix.
Claim 21
Dependent Claim
34 words
The method as claimed in claim 11 , wherein the hardener is selected from the group consisting of methylhexahydrophthalic anhydride (MHHPA), methyltetrahydrophthalic anhydride (MTHPA), phthalic anhydride (PA), tetrahydrophthalic anhydride (THPA), and hexahydrophthalic anhydride (HHPA).
Claim 22
Dependent Claim
24 words
The method as claimed in claim 11 , wherein the ratio of the weight of silica precursor to the weight of (co)polymer precursor 9/100.
References Cited (Backward Citations)
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