CN109096766A - A kind of preparation method of gold nanoparticle Composite silicone resin - Google Patents
A kind of preparation method of gold nanoparticle Composite silicone resin Download PDFInfo
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- CN109096766A CN109096766A CN201810886458.XA CN201810886458A CN109096766A CN 109096766 A CN109096766 A CN 109096766A CN 201810886458 A CN201810886458 A CN 201810886458A CN 109096766 A CN109096766 A CN 109096766A
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- gold
- gold nanoparticle
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 128
- 239000010931 gold Substances 0.000 title claims abstract description 127
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 32
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 73
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 35
- 239000002077 nanosphere Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- 230000001376 precipitating effect Effects 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- -1 alkylalkoxy silane Chemical compound 0.000 claims description 11
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 238000005253 cladding Methods 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 230000004224 protection Effects 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- XQQSWXUDAPLMKD-UHFFFAOYSA-N N,N-dimethylheptadecan-1-amine hydrobromide Chemical compound Br.CCCCCCCCCCCCCCCCCN(C)C XQQSWXUDAPLMKD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000013557 residual solvent Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000006798 recombination Effects 0.000 claims description 2
- 238000005215 recombination Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 claims 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 230000018109 developmental process Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 208000016261 weight loss Diseases 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004042 HAuCl4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- OGFYGJDCQZJOFN-UHFFFAOYSA-N [O].[Si].[Si] Chemical compound [O].[Si].[Si] OGFYGJDCQZJOFN-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000003711 photoprotective effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical class CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- PRNFIXKHXAAWKZ-UHFFFAOYSA-N C(C)O.CO[SiH3] Chemical compound C(C)O.CO[SiH3] PRNFIXKHXAAWKZ-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- XEIPQVVAVOUIOP-UHFFFAOYSA-N [Au]=S Chemical compound [Au]=S XEIPQVVAVOUIOP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005055 alkyl alkoxy group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- UUYKGYZJARXSGB-UHFFFAOYSA-N ethanol;ethoxy(trihydroxy)silane Chemical compound CCO.CCO[Si](O)(O)O UUYKGYZJARXSGB-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0831—Gold
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The present invention relates to metal nanometer composite material technical fields, and in particular to a kind of preparation method of gold nanoparticle Composite silicone resin.The method comprises the steps of firstly, preparing the gold nanoparticles of coated with silica, then it is mixed by solvent peptizaiton with organic-silicone prepolymer, it is thoroughly mixed uniform, obtain the uniform dispersion of gold nanoparticle and organic-silicone prepolymer, then curing agent is added and evaporates solvent, room temperature or is prepared for gold nanoparticle Composite silicone resin solid-state sol material after being heating and curing.Gold nanoparticle Composite silicone resin material prepared by the present invention has the characteristics such as excellent resistance to oxidation, chemicals-resistant, and there is very high temperature tolerance and ageing resistance, long-time stability are able to maintain, are had broad application prospects as colour development material and nonlinear optical material, laser protective material etc..
Description
Technical field
The present invention relates to metal nanometer composite material technical fields, and in particular to a kind of gold nanoparticle composite organic tree
The preparation method of rouge.
Background technique
Gold nanoparticle belongs to metal nano material, the differences such as spherical, rodlike for the nanoscale being made of gold atom
The crystal particles of size and shape.Interaction between gold nanoparticle and external electromagnetic field (such as light) generates local surface
Plasma resonance has strong RESONANCE ABSORPTION from visible light near infrared region.Wherein, the table of spherical gold nanoparticle
Surface plasma resonance absorption peak from 515 nm can increase to 600 nm according to the difference of size, show red, pink,
The different colours such as purple；There are radial and axial two absorption peaks for the surface plasma body resonant vibration of gold nanorods, wherein radial inhale
Peak is received near 510 nm, axial absorption peak is stepped up from 550 nm near infrared region with the increase of gold nanorods draw ratio
Domain, the color of dispersion show red, purple, blue, soil Red and khaki etc. with the increase of draw ratio respectively.
Gold nanoparticle because ultraviolet light irradiates due to not decomposing, the color of gold nanoparticle compared with organic dye molecule
Will not be faded variation at any time, be had close to permanent optical stability.The surface plasma body resonant vibration of gold nanoparticle causes
Absorption, surface enhanced scattering, surface-enhanced fluorescence, photothermal conversion and shine etc. characteristics make its optical sensing, biology at
There is potential applications in the fields such as picture, biological detection, disease detection and treatment of cancer.
Organic siliconresin is the highly cross-linked polysiloxanes reticular structure of the ingredient based on silicon oxygen silicon key, and part silicon is former
Son connection organic group, therefore the characteristics of have organic material and inorganic material concurrently, there is excellent thermo oxidative stability, resist cold
Many unique performances such as property, weatherability, electrically-insulating linearly, hydrophobicity and anti-stick release property, have been widely used for resistance to height
Warm insulated paint, sapecial coating, moulding compound etc., and aerospace, electronic apparatus, building, in terms of be used widely.
In the prior art, people pass through Jenner's grain of rice of plasma enhanced chemical vapor deposition silica and cosputtering
Laminated film in the mixed deposit technology preparation insertion silica matrix of son, but requirement of this technology to appointed condition
Very high, technical difficulty and cost are all high, are not suitable for actual production.
Summary of the invention
The purpose of the present invention is search out a kind of uniform point realized in gold nanoparticle and organic siliconresin matrix material
Scattered technology and methods, and meet that at low cost, equipment is simple, environmental-friendly etc. requires.
The present invention prevents nanoparticle in preparation composite material to reunite using silica protection gold nanoparticle
The nano composition homogeneity of problem, preparation is good；The gold nanoparticle that the present invention uses has size, pattern uniform
Advantage；The organic siliconresin that the present invention uses not only has high transparency, also has high temperature tolerance, therefore as host material
It has a clear superiority as optical material especially laser, strong photoprotection material.
To achieve the above object, the method comprises the steps of firstly, preparing the gold nanoparticle of coated with silica, then pass through solvent
Peptizaiton is mixed with organic-silicone prepolymer, is thoroughly mixed uniform, and it is pre- with organic siliconresin to obtain gold nanoparticle
Then the uniform dispersion of aggressiveness is added curing agent and evaporates solvent, room temperature or be prepared for gold nano after being heating and curing
Particle Composite silicone resin solid-state sol material.
In addition, the gold nanoparticle Composite silicone resin being prepared using method of the invention, and institute of the present invention
Scope of protection.
The specific technical solution of the present invention is as follows:
A kind of preparation method of gold nanoparticle Composite silicone resin, comprising the following steps:
(1) gold nanoparticle is prepared using the seed mediating growth method under surfactant protection；
(2) using gold nanoparticle obtained in step (1), using the Jenner of Stoeber Hydrolyze method preparation coated with silica
Rice corpuscles；
(3) organic-silicone prepolymer is prepared；
(4) the organosilicon tree prepared in the gold nanoparticle and step (3) of the silica shell cladding prepared in step (2) is taken
Rouge performed polymer prepares gold nanoparticle Composite silicone resin material by the recombination process that solvent assists.
Preferably, the step (1) are as follows:
Using gold chloride as raw material, under the protection of surfactant cetyl trimethyl ammonia bromide, with sodium borohydride reduction system
Standby gold nano seed solution；
Gold nano seed solution is added in growth-promoting media, is stirred to react；
After reaction, reaction product centrifugation, washing are precipitated, obtains gold nanoparticle, gold nanoparticle is dispersed in water
It saves backup.
Preferably, the step (2) are as follows:
Mercaptopropyl trimethoxysilane solution is added into gold nanoparticle obtained in step (1), makes gold nanoparticle surface
One layer of mercaptopropyl trimethoxysilane molecule is connected by gold-sulfide linkage；
Ethyl orthosilicate is added into system, ammonium hydroxide is added after mixing and forms alkaline environment, is hydrolyzed to silicon-alkoxy key
Silicon-oxygen-silicon bound forms the protective layer of silica on gold nanoparticle surface；The thickness of silicon dioxide layer is by ethyl orthosilicate
Dosage and hydrolysis time, sodium hydroxide the conditions control such as concentration.The thickness of silicon dioxide layer is generally adjusted between 2-50 nm
Section.
After reaction, it is scattered in tetrahydrofuran after the gold nanoparticle of coated with silica being centrifuged, washed.
Preferably, the step (3) are as follows:
The pH of water is adjusted to faintly acid, ethyl orthosilicate is then added, [molecular formula is (RO) to alkylalkoxy silane4-nSiR’n ]
It with mercaptopropyl trimethoxysilane as organic siliconresin predecessor, is stirred to react, hydrolysis, contracting occur for organic siliconresin predecessor
Poly- reaction；
After reaction, revolving removing solvent and water arrive the organic-silicone prepolymer that organic group is R ' to thick,
Contain a certain amount of Si-OH structure in this performed polymer, tetrahydrofuran dilution is added into organic-silicone prepolymer and saves.
Preferably, the step (4) are as follows:
It takes the gold nanoparticle of the silica shell prepared in step (2) cladding to be scattered in tetrahydrofuran solvent, step is added
Suddenly the organic-silicone prepolymer prepared in (3), being sufficiently stirred mixes gold nanoparticle with organic-silicone prepolymer, is formed
Uniform dispersion system；
Then solvent is removed to thick, and aminopropyl triethoxysilane is added as crosslinking agent, after mixing evenly by dispersion
System pours into mold, and vacuum removal gas and residual solvent, solidification obtain gold nanoparticle Composite silicone resin material.
In the step (1) of the present invention, pass through the adjustable gold nanoparticle of concentration of each reactant in change growth-promoting media
Size and shape.The concentration of cetyl trimethyl ammonia bromide is 0.02-0.05 in growth-promoting media when wherein preparing gold nanosphere
Mol/L is free of silver nitrate, and the size of gained gold nanosphere is more uniform, can adjust in 10 nm between 200 nm；Preparation gold
Cetyl trimethyl bromination ammonia density is 0.08-0.15 mol/L, silver nitrate concentration 0.3-1.5 in growth-promoting media when nanometer rods
Mmol/L, control of the draw ratio of gained gold nanorods by silver nitrate concentration, draw ratio range are 1.5-10.
Alkylalkoxy silane [(RO) used in step (3) of the present invention4-nSiR’n], wherein R group includes
Methyl, ethyl etc., R ' include methyl, ethyl, phenyl etc., n 1-2.Alkylalkoxy silane and positive silicic acid are used in this step
The volume ratio of ethyl ester can be adjusted between 3-0.3, and the volume ratio of mercaptopropyl trimethoxysilane and ethyl orthosilicate can be
It is adjusted between 0.01-0.2.
Preferably, gold nanoparticle as described in step (1) is gold nanosphere or gold nanorods；
Wherein gold nanosphere specific the preparation method comprises the following steps:
The preparation of seed solution: taking cetyl trimethylammonium bromide solution and aqueous solution of chloraurate, after mixing, boron is added
Sodium hydride solution, 25-28oUniform stirring 1-2 h obtains brown color gold nano seed solution under C；
The concentration of cetyl trimethylammonium bromide, gold chloride and sodium borohydride is respectively 0.08-0.15 in entire reaction solution
Mol/L, 0.2-0.3 mmol/L and 0.5-0.8 mmol/L；
The preparation of gold nanosphere: gold nano seed solution is taken to be added in growth-promoting media, in 25-28oReaction 6-12 is slowly stirred under C
Hour, by solution centrifugation, the washing after reaction, gold nanosphere precipitating is collected, gold nanosphere precipitating is dispersed in water spare；
In the growth-promoting media, the concentration of cetyl trimethylammonium bromide, gold chloride and ascorbic acid in growth-promoting media is respectively
0.02-0.05 mol/L, 0.05-0.10 mmol/L and 2.0-2.5 mmol/L；
It is 1-10% that the volume that seed solution is added into growth-promoting media, which accounts for the percentage of growth-promoting media volume,；
Gold nanorods specific the preparation method comprises the following steps:
The preparation of seed solution: after mixing by cetyl trimethylammonium bromide solution and chlorauric acid solution, in 25-28oC
Lower addition sodium borohydride solution, high-speed stirred 2-6 h obtain the gold nano seed solution of brown color；
The concentration of cetyl trimethylammonium bromide, gold chloride and sodium borohydride is respectively 0.08-0.15 in entire reaction solution
Mol/L, 0.2-0.3 mmol/L and 0.5-0.8 mmol/L；
The preparation of gold nanorods: in 25-28oUnder C, above-mentioned seed solution is taken to be added in growth-promoting media, stood after mixing evenly anti-
It answers 6-12 hours, by reaction product centrifugation, washing, collects gold nanorods precipitating, gold nanorods precipitating is dispersed in water spare；
In the growth-promoting media, the concentration of cetyl trimethylammonium bromide, gold chloride, silver nitrate and ascorbic acid in growth-promoting media
Respectively 0.08-0.15 mol/L, 0.4-0.7 mmol/L, 0.3-1.5 mmol/L and 0.5-0.8 mmol/L；
It is 0.1-0.5% that the volume that seed solution is added into growth-promoting media, which accounts for the percentage of growth-promoting media volume,；
Preferably, the step (2) specifically:
The dispersion solution of gold nanoparticle made from step (1) is taken, mercaptopropyl trimethoxysilane is added dropwise under stirring condition
Ethanol solution, with ammonium hydroxide adjust solution pH to 10-11, be then added dropwise volume ratio be 10% ethyl orthosilicate second
Alcoholic solution, in 25-28o5-12h is stirred to react under C；Then, it is centrifuged, washs precipitating, obtain the gold nano of coated with silica
Ball, and be scattered in tetrahydrofuran；
The gold nanoparticle of addition is 0.1-2 mg, the amount of the substance of the mercaptopropyl trimethoxysilane and ethyl orthosilicate of addition
Respectively 1-5 mmol and 20-100 mmol.
Preferably, the step (3) specifically:
Dilute hydrochloric acid is added in Xiang Shuizhong, adjusts the pH to 3-4 of water, and ethyl orthosilicate, alkyl alkoxy silicon [molecular formula is then added
For (RO)4-nSiR’n, wherein R is methyl, ethyl etc., and R ' is methyl, ethyl, phenyl etc.] and mercaptopropyl trimethoxysilane,
It is heated to 40-70o4-6 h is stirred to react under the conditions of C；Solution after reaction removes solvent and water to remnants by revolving
Substrate be it is thick, the liquid for obtaining clear viscous is organic-silicone prepolymer, be added tetrahydrofuran solvent (THF) dilution
After save；
Water, ethyl orthosilicate, alkylalkoxy silane and mercaptopropyl trimethoxysilane volume ratio be 1:0.1-0.5:0.1-
0.5:0.003-0.05.
Preferably, in the step (4), Nano silver grain, the organic-silicone prepolymer of silica shell cladding
Quality with aminopropyl triethoxysilane is respectively than being 0.02-2 mg, 0.3-1.0 g and 2-20 mg.
The solid-state colloidal sol that gold nanoparticle prepared by the present invention and organic siliconresin are formed is a kind of optically active material, tool
There is applications well value.
Beneficial effect
The invention discloses it is a kind of it is at low cost, equipment is simple, the preparation of environmental-friendly gold nanoparticle Composite silicone resin
Method, the method comprises the steps of firstly, preparing the gold nanoparticles of coated with silica, then pass through solvent peptizaiton and organosilicon tree
The mixing of rouge performed polymer, is thoroughly mixed uniform, obtains the uniform dispersion of gold nanoparticle and organic-silicone prepolymer
Then system is added curing agent and evaporates solvent, room temperature or be prepared for gold nanoparticle Composite silicone resin after being heating and curing
Solid-state sol material.
The present invention during the preparation process, is first prepared for the gold nanoparticle of coated with silica, on the one hand, gold nanoparticle
The silica shell on surface prevents the reunion of the gold nanoparticle in preparation composite material；On the other hand, the shell with
The general chemical structure (Si-O-Si key) of organic siliconresin is identical, can reduce metal nanoparticle and organic siliconresin matrix it
Between interface can, have better compatibility when preparing compound dispersing agent.
The present invention combines organic siliconresin and gold nanoparticle, prepare metal nanoparticle formed in silicone resin it is uniform
Solid-state sol material, realize gold nanoparticle characteristic and silicone resin temperature tolerance, can the excellent performances such as coating combination, obtain
Obtained a kind of finely dispersed, transparency it is high and it is unique can gold nanoparticle Composite silicone resin material, and can
Using as coating material.Gold nanoparticle Composite silicone resin material prepared by the present invention has excellent resistance to oxidation, resistance toization
The characteristics such as product, and there is very high temperature tolerance and ageing resistance, it is able to maintain long-time stability.
The main Jenner by using of the optical characteristics of gold nanoparticle Composite silicone resin material prepared by the present invention
The optical characteristics of rice corpuscles determines that the absorbance and light transmittance of absorption spectrum are by added gold nanoparticle property and use
Amount control.
Gold nanoparticle Composite silicone resin high temperature resistance prepared by the present invention is good, and thermogravimetic analysis (TGA) proves, and 700oC
When weight-loss ratio be only 5%.The present invention prepares the high weatherability and gold of gold nanoparticle Composite silicone resin combination organic siliconresin
Belong to the high stability of nanoparticle, color has long-time stability in usual environment.Gold nanoparticle prepared by the present invention
Composite silicone resin has broad application prospects as colour development material and nonlinear optical material, strong photoprotection material etc.,
Such as high stable red material, laser protective material.
Detailed description of the invention
Transmission electron microscope (TEM) figure of Fig. 1 gold nanosphere；
Transmission electron microscope (TEM) figure of the gold nanosphere of Fig. 2 coated with silica；
Transmission electron microscope (TEM) figure of Fig. 3 gold nanorods；
Transmission electron microscope (TEM) figure of the gold nanorods of Fig. 4 coated with silica；
The Fourier transform infrared spectroscopy figure (FT-IR) of Fig. 5 organic-silicone prepolymer；
The photo of Fig. 6 gold nanosphere Composite silicone resin material；
The UV-vis spectrogram of Fig. 7 gold nanosphere Composite silicone resin material；
The photo of Fig. 8 gold nanorods Composite silicone resin material；
The UV-vis spectrogram of Fig. 9 gold nanorods Composite silicone resin material；
The thermal weight loss spectrogram of Figure 10 gold nanorods Composite silicone resin material.
Specific embodiment
For a better understanding of the present invention, below with specific example come the technical solution that the present invention will be described in detail, but this
Invention is not limited thereto.
Embodiment 1
The present embodiment prepares gold nanosphere Composite silicone resin material, the specific steps of preparation process are as follows:
(1) gold nanosphere is prepared using the seed mediated growth method of surfactant auxiliary.Take 2 mL cetyl trimethylammonium bromides
After mixing, 0.48 mL sodium borohydride solution (5 is added in (0.2 mol/L) and 2 mL aqueous solution of chloraurate (0.5 mmol/L)
Mmol/L), 27oObtain gold nano seed solution within uniform stirring 2 hours under C.Then, the nanometer seed solution of 0.7 mL is taken to be added
To the cetyl trimethyl ammonia bromide (0.04 mol/L), 10 mL chlorauric acid solutions (1.0 mmol/L) and 0.2 mL of 10 mL
In the mixture (growth-promoting media) of ascorbic acid solution (0.2 mol/L), 27oReaction 6 hours is slowly stirred under C.It will react
The red solution centrifugation arrived, collects gold nanosphere precipitating, is dispersed in water spare.
(2) preparation of coated with silica gold nanosphere.The dispersion solution for taking the above-mentioned gold nanosphere of 10 mL, under stirring by
It is added dropwise to the ethanol solution (10.8 mmol/L) of 0.2 mL mercaptopropyl trimethoxysilane, the pH that solution is adjusted with ammonium hydroxide is 10-
11, the ethanol solution (volume ratio 10%) of 3.2 mL ethyl orthosilicates is then added dropwise, in 27oIt is small that 12 are stirred to react under C
When.Then, it is centrifuged, washs precipitating, the gold nanosphere of obtained coated with silica, and be scattered in tetrahydrofuran (THF).
(3) preparation of organic-silicone prepolymer.0.040 mL dilute hydrochloric acid (0.10 mol/L) is added to 33.75 mL water,
Then 5ml ethyl orthosilicate (4.65g, 0.022mol), 10 mL methyltriethoxysilane (8.96g, 0.050 mol) is added,
0.9 mL mercaptopropyl trimethoxysilane (0.95 g, 0.005mol) is added, mixed solution is 60oIt is stirred at reflux under C 5 hours.
Solution after reaction removes ethyl alcohol and most of water by revolving, and the liquid for obtaining clear viscous is that organic siliconresin is pre-
Aggressiveness saves after the dilution of THF solvent is added.
(4) prepared by gold nanosphere Composite silicone resin material.It takes to be scattered in respectively and takes containing in above-mentioned steps (3)
The Jenner of coated with silica in the step of 1.0 three parts of g organic-silicone prepolymer THF solutions, addition different volumes (2)
Rice ball THF dispersion liquid (be respectively 0.3 mg, 0.8 mg, 1.4 mg containing gold nanosphere, counter sample a, b, c), at room temperature
It is thoroughly mixed uniformly, forms uniform transparent dispersion.Then, solvent evaporated under vacuum to system occurs sticky
Shape is added 20 mg aminopropyl triethoxysilanes and stirs evenly, 0.3 g is taken to pour into mold, removes gas and residual solvent,
45 are put into after saving 5h at room temperatureoC baking oven saves 3 hours to get cured gold nanosphere Composite silicone resin material is arrived.
The present embodiment gold nanosphere TEM photo obtained in step (1) is as shown in Figure 1, it can be seen that the ruler of gold nanosphere
It is very little between 10-20 nm, average-size be 15 nm；The transmission of the gold nanosphere of coated with silica obtained in step (2)
Electron micrograph is as shown in Figure 2, it can be seen that 10 nm of thickness average out to of the silicon dioxide layer of cladding；
The Fourier transform infrared spectroscopy (FT-IR) such as Fig. 5 institute of organic-silicone prepolymer are obtained in the present embodiment step (3)
Show, it can be seen from the figure that 3443 cm-1Place corresponds to the absorption of hydroxyl, 2970,2934 and 1273 cm-1Place corresponds to methyl
Absorption, 1000-1124 cm-1Between broad peak correspond to the absorption of this Si-O-Si key.
The gold nanosphere Composite silicone resin materials optical photo of different content obtained in the present embodiment step (4) and
UV-vis spectrum is as shown in Figure 6,7.In Fig. 6, sample is placed on the bottom plate with letter, it can be seen that the transparency of sample
Preferably, sample a, b, c is red, transparent solid, is increased with the amount that gold nanosphere is added, color burn, plasma resonance absorption
Peak position is set to 540 nm.
Embodiment 2
The present embodiment is prepared for gold nanorods Composite silicone resin material, preparation process specific steps are as follows:
(1) preparation of gold nanorods.By 2 mL cetyl trimethyl bromination ammonia solutions (0.20 mol/L) and 2 mL
HAuCl4Solution (0.5 mmol/L) after mixing, 27o0.48 mL NaBH is added under C4Solution (5 mmol/L), high speed
Stirring obtains the seed solution of brown color in 2 hours.Then, 27oUnder C, the above-mentioned seed solution of 0.024 mL is taken to be added to 10
ML cetyl trimethyl bromination ammonia solution (0.20 mol/L), 10 mL HAuCl4Solution (1.0 mmol/L), 0.12 mL
Ascorbic acid solution (0.1 mol/L) and 0.6 mL AgNO3In the mixture of solution (4 mmol/L), stand after mixing evenly
React 12 h.It is saved being re-dispersed into water after reaction product centrifuge washing.
(2) coated with silica of gold nanorods.It takes 20 mL gold nanorods to disperse solution, 0.2 mL mercapto propyl three is added
Methoxy silane ethanol solution (10.8 mmol/L), 27oThen 0.04 mL ammonium hydroxide (0.4 is added in high-speed stirred 5h under C
Mol/L), be slowly added to 0.08 ml ethyl orthosilicate ethanol solution (0.9 mol/L), stir terminate after 12 h of lower reaction centrifugation,
It is distributed in THF after precipitating is washed with water.
(3) preparation of organic-silicone prepolymer.Take 33.75 mL water that 0.040 mL dilute hydrochloric acid (0.1 mol/L) is added,
Sequentially add 7 mL ethyl orthosilicates, 8 mL methyltriethoxysilane and 0.15 mL mercaptopropyl trimethoxysilane, 60oUnder C
It is stirred to react 5 h.Then revolving removes most of water and ethyl alcohol, obtains organic-silicone prepolymer, protects after THF dilution is added
It deposits.
(4) take three parts of the THF dispersion liquid obtained in step (2) containing different amounts of gold nanorods (containing gold nano respectively
Stick is respectively 0.032 mg, 0.16 mg and 0.32 mg, counter sample number d, e, f), is separately added into and step (3) is taken to prepare
THF solution containing 1.0 g organic-silicone prepolymers, is sufficiently stirred after forming uniform dispersion, and removed in vacuo is most of
Solvent is thick to occurring, and 20 mg aminopropyl trimethoxysilanes are added, 0.3 g is taken to be transferred to mold after being uniformly mixed
In, vacuum removal gas and residual solvent are placed at room temperature for solidification, obtain gold nanorods Composite silicone resin material.
The present embodiment gold nanorods TEM photo obtained in step (1) is as shown in figure 3, titanium dioxide obtained in step (2)
The TEM photo of the gold nanorods of silicon cladding is as shown in Figure 4.It can be seen from the figure that the average length of gold nanorods is 50 nm,
Diameter be 20 nm, wrap up silica shell with a thickness of 10 nm.
The optical photograph of gold nanorods Composite silicone resin material obtained in the present embodiment step (4) as shown in figure 8,
UV-vis spectrogram is as shown in Figure 9.In Fig. 8, by sample be placed on letter bottom plate on, it can be seen that sample the transparency compared with
Good, sample d, e, f are blue-tinted transparent solid, and as gold nanorods concentration increases color burn, long axis plasma resonance is inhaled
It receives peak position and is set to 670 nm, it is 525 nm that short axle, which absorbs peak position,.
The thermal weight loss of gold nanorods Composite silicone resin material in a nitrogen environment obtained in the present embodiment step (4)
Variation is as shown in Figure 10, it can be seen from the figure that 700oThermal weight loss rate when C is about 5%.
Claims (10)
1. a kind of preparation method of gold nanoparticle Composite silicone resin, which comprises the following steps:
(1) gold nanoparticle is prepared using the seed mediating growth method under surfactant protection；
(2) using gold nanoparticle prepared in step (1), using the gold of Stoeber Hydrolyze method preparation coated with silica
Nanoparticle；
(3) organic-silicone prepolymer is prepared；
(4) take the organic siliconresin prepared in the gold nanoparticle and step (3) of the coated with silica prepared in step (2) pre-
Aggressiveness prepares gold nanoparticle Composite silicone resin material by the recombination process that solvent assists.
2. the preparation method of gold nanoparticle Composite silicone resin according to claim 1, which is characterized in that the step
Suddenly (1) are as follows:
Using gold chloride as raw material, under the protection of surfactant cetyl trimethyl ammonia bromide, with sodium borohydride reduction system
Standby gold nano seed solution；
Gold nano seed solution is added in growth-promoting media, is stirred to react；
After reaction, reaction product centrifugation, washing are precipitated, obtains gold nanoparticle, gold nanoparticle is dispersed in water
It saves backup.
3. the preparation method of gold nanoparticle Composite silicone resin according to claim 1, which is characterized in that the step
Suddenly (2) are as follows:
Mercaptopropyl trimethoxysilane solution is added into gold nanoparticle obtained in step (1), is then added into system
Ammonium hydroxide is added after mixing and forms alkaline environment, is stirred to react for ethyl orthosilicate；
After reaction, after product is centrifuged, is washed, the gold nanoparticle of coated with silica is obtained, tetrahydrofuran is scattered in
In save backup.
4. the preparation method of gold nanoparticle Composite silicone resin according to claim 1, which is characterized in that the step
Suddenly (3) are as follows:
The pH of water is adjusted to faintly acid, ethyl orthosilicate, alkylalkoxy silane and mercaptopropyl trimethoxysilane is then added
It as organic siliconresin predecessor, is stirred to react, hydrolysis, polycondensation reaction occur for organic siliconresin predecessor；
After reaction, revolving removing solvent and water arrive organic-silicone prepolymer to thick, pre- to organic siliconresin
Tetrahydrofuran dilution is added in aggressiveness to save.
5. the preparation method of gold nanoparticle Composite silicone resin according to claim 1, which is characterized in that the step
Suddenly (4) are as follows:
It takes the gold nanoparticle of the silica shell prepared in step (2) cladding to be scattered in tetrahydrofuran solvent, step is added
Suddenly the organic-silicone prepolymer prepared in (3), being sufficiently stirred mixes gold nanoparticle with organic-silicone prepolymer, is formed
Uniform dispersion system；
Then revolving removes solvent to thick, and aminopropyl triethoxysilane is added, after mixing evenly pours into dispersion
In mold, vacuum removal gas and residual solvent, solidification obtain gold nanoparticle Composite silicone resin material.
6. the preparation method of gold nanoparticle Composite silicone resin according to claim 1, which is characterized in that step
(1) gold nanoparticle described in is gold nanosphere or gold nanorods；
Wherein gold nanosphere specific the preparation method comprises the following steps:
The preparation of seed solution: taking cetyl trimethylammonium bromide solution and aqueous solution of chloraurate, after mixing, boron is added
Sodium hydride solution, 25-28oUniform stirring 1-2 h obtains brown color gold nano seed solution under C；
The concentration of cetyl trimethylammonium bromide, gold chloride and sodium borohydride is respectively 0.08-0.15 in entire reaction solution
Mol/L, 0.2-0.3 mmol/L and 0.5-0.8 mmol/L；
The preparation of gold nanosphere: gold nano seed solution is taken to be added in growth-promoting media, in 25-28oReaction 6-12 is slowly stirred under C
Hour, by solution centrifugation, the washing after reaction, gold nanosphere precipitating is collected, gold nanosphere precipitating is dispersed in water spare；
In the growth-promoting media, the concentration of cetyl trimethylammonium bromide, gold chloride and ascorbic acid in growth-promoting media is respectively
0.02-0.05 mol/L, 0.05-0.10 mmol/L and 2.0-2.5 mmol/L；
It is 1-10% that the volume that seed solution is added into growth-promoting media, which accounts for the percentage of growth-promoting media volume,；
Gold nanorods specific the preparation method comprises the following steps:
The preparation of seed solution: after mixing by cetyl trimethylammonium bromide solution and chlorauric acid solution, in 25-28oC
Lower addition sodium borohydride solution, high-speed stirred 2-6 h obtain the gold nano seed solution of brown color；
The concentration of cetyl trimethylammonium bromide, gold chloride and sodium borohydride is respectively 0.08-0.15 in entire reaction solution
Mol/L, 0.2-0.3 mmol/L and 0.5-0.8 mmol/L；
The preparation of gold nanorods: in 25-28oUnder C, above-mentioned seed solution is taken to be added in growth-promoting media, stands reaction after mixing evenly
6-12 hours, by reaction product centrifugation, washing, gold nanorods precipitating is collected, gold nanorods precipitating is dispersed in water spare；
In the growth-promoting media, the concentration of cetyl trimethylammonium bromide, gold chloride, silver nitrate and ascorbic acid in growth-promoting media
Respectively 0.08-0.15 mol/L, 0.4-0.7 mmol/L, 0.3-1.5 mmol/L and 0.5-0.8 mmol/L；
It is 0.1-0.5% that the volume that seed solution is added into growth-promoting media, which accounts for the percentage of growth-promoting media volume,.
7. the preparation method of gold nanoparticle Composite silicone resin according to claim 1, which is characterized in that the step
Suddenly (2) specifically:
The dispersion solution of gold nanoparticle made from step (1) is taken, mercaptopropyl trimethoxysilane is added dropwise under stirring condition
Ethanol solution, with ammonium hydroxide adjust solution pH to 10-11, the ethanol solution of ethyl orthosilicate is then added dropwise, in 25-
28o5-12 h is stirred to react under C；Then, it is centrifuged, washs precipitating, obtain the gold nanosphere of coated with silica, and be scattered in four
In hydrogen furans；
The gold nanoparticle of addition is 0.1-2 mg, the amount of the substance of the mercaptopropyl trimethoxysilane and ethyl orthosilicate of addition
Respectively 1-5 mmol and 20-100 mmol.
8. the preparation method of gold nanoparticle Composite silicone resin according to claim 1, which is characterized in that the step
Suddenly (3) specifically:
Dilute hydrochloric acid is added in Xiang Shuizhong, adjusts the pH to 3-4 of water, and ethyl orthosilicate, alkyl alkoxy silicon and mercapto propyl is then added
Trimethoxy silane is heated to 40-70o4-6 h is stirred to react under the conditions of C；Solution after reaction removes molten by revolving
Agent and water to residual substrate be it is thick, the liquid for obtaining clear viscous is organic-silicone prepolymer, and tetrahydrofuran is added
It is saved after solvent dilution；
Water, ethyl orthosilicate, alkylalkoxy silane and mercaptopropyl trimethoxysilane volume ratio be 1:0.1-0.5:0.1-
0.5:0.003-0.05.
9. the preparation method of gold nanoparticle Composite silicone resin according to claim 1, which is characterized in that the step
Suddenly in (4), the matter of Nano silver grain, organic-silicone prepolymer and aminopropyl triethoxysilane that silica shell coats
Amount is respectively than being 0.02-2 mg, 0.3-1.0 g and 2-20 mg.
10. a kind of gold nanoparticle Composite silicone resin, which is characterized in that by any method system of claim 1-9
It is standby to obtain.
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| CN112987340A (en) * | 2021-03-31 | 2021-06-18 | 华中科技大学 | Color blindness and color weakness correcting glasses and preparation method thereof |
| CN112987340B (en) * | 2021-03-31 | 2022-05-17 | 华中科技大学 | Color blindness and color weakness correcting glasses and preparation method thereof |
| CN115815611A (en) * | 2022-07-08 | 2023-03-21 | 天津师范大学 | Super-hydrophobic nano porous silver-based material and preparation method and application thereof |
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