CN109280389A - A kind of preparation method of Nano silver grain Composite silicone resin - Google Patents
A kind of preparation method of Nano silver grain Composite silicone resin Download PDFInfo
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- CN109280389A CN109280389A CN201810885622.5A CN201810885622A CN109280389A CN 109280389 A CN109280389 A CN 109280389A CN 201810885622 A CN201810885622 A CN 201810885622A CN 109280389 A CN109280389 A CN 109280389A
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- nano silver
- added
- silver grain
- preparation
- silicone resin
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 32
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 28
- 238000005253 cladding Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 70
- 229910052709 silver Inorganic materials 0.000 claims description 65
- 239000004332 silver Substances 0.000 claims description 65
- 239000002105 nanoparticle Substances 0.000 claims description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 21
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 18
- 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 16
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000012279 sodium borohydride Substances 0.000 claims description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 12
- 239000001509 sodium citrate Substances 0.000 claims description 12
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- -1 alkylalkoxy silane Chemical compound 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- UUYKGYZJARXSGB-UHFFFAOYSA-N ethanol;ethoxy(trihydroxy)silane Chemical compound CCO.CCO[Si](O)(O)O UUYKGYZJARXSGB-UHFFFAOYSA-N 0.000 claims description 4
- 230000001404 mediated effect Effects 0.000 claims description 4
- 239000013557 residual solvent Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 230000006798 recombination Effects 0.000 claims description 3
- 238000005215 recombination Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 238000007711 solidification Methods 0.000 abstract description 4
- 230000008023 solidification Effects 0.000 abstract description 4
- 238000002834 transmittance Methods 0.000 abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 235000013339 cereals Nutrition 0.000 description 57
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000008236 heating water Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical class CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [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
- 150000001875 compounds Chemical class 0.000 description 2
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052710 silicon Inorganic materials 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
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- OGFYGJDCQZJOFN-UHFFFAOYSA-N [O].[Si].[Si] Chemical compound [O].[Si].[Si] OGFYGJDCQZJOFN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005055 alkyl alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- C08K9/10—Encapsulated ingredients
-
- 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
-
- 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
- C08K2003/0806—Silver
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention relates to metal nanometer composite material technical fields, and in particular to a kind of preparation method of Nano silver grain Composite silicone resin.The method comprises the steps of firstly, preparing the Nano silver grains and organic-silicone prepolymer of silica shell cladding, then it is prepared for dispersion of finely dispersed, the stable Nano silver grain in organic-silicone prepolymer, finally obtains the solid-state sol material of Nano silver grain Composite silicone resin by solidification.Nano silver grain Composite silicone resin material prepared by the present invention has many advantages, such as high light transmittance, high-weatherability and high temperature tolerance, and there is antistatic effect, antibacterial ability and special optical property, it has broad application prospects as nonlinear optical material or optical coating material etc..
Description
Technical field
The present invention relates to metal nanometer composite material technical fields, and in particular to a kind of Nano silver grain composite organic tree
The preparation method of rouge.
Background technique
Nano silver grain is a kind of nanocrystal of scale from several nanometers to several hundred nanometers, the Nano silver grain reported at present
Including shapes such as silver nanoparticle ball, Silver nanorod, silver nanoparticle cube, Nano silver piece and silver nanoparticle polyhedrons.Nano silver grain exists
Local surface plasma resonance characteristic is shown under external electromagnetic field effect, surface plasma body resonant vibration signal is by nanoparticle
The influence of the size, shape, composition, aggregation extent and surrounding dielectric environment of son.Under normal conditions, spherical Nano silver grain
Near 420 nm, with the increase of particle size red shift occurs for surface plasmon absorption peak；Silver nanorod, Yin Na
The anisotropic Nano silver grains such as rice piece have two or more surface plasmon absorption peaks.Due to surface plasma
The optical characteristics that resonance body phenomenon generates has a good application prospect Nano silver grain as optically active material.This
Outside, Nano silver grain heterogeneous catalysis, Surface enhanced Raman spectroscopy, energy conversion and in terms of had it is extensive
Using.
In the prior art, the research of silver nano particle composite material achieves certain progress, such as Nano silver grain is compound
The composite materials such as polyvinylpyrrolidone film, organic glass (polymethyl methacrylate), alkyd resin.But due to this
300 are usually no more than a bit with the thermal decomposition temperature of carbon alkane polymer as main componentoC causes these Nano silver grains multiple
Condensation material is not applied for hot environment, is especially easy under laser irradiation ablated.
Organic siliconresin is that the height of organic group is had on the silicon atom of part using Si-O-Si key as general chemical structure
Half inorganic polymer of crosslinking is a kind of inertia, nontoxic, nonflammable material, and has high light transmittance and high-weatherability, height
The features such as temperature tolerance, aerospace, electronic apparatus, building, in terms of be widely used.By Nano silver grain with
Organic siliconresin is compound, obtains a kind of silver nano particle composite material with high temperature resistance, improves the energy of resistance to laser ablation
Power has main application advantage.
On the other hand, the preparation of Nano silver grain generallys use in-situ preparation method in the prior art, obtained silver nanoparticle
Particle size distribution is very wide (from 1 nanometer or less to several hundred nanometers), and the homogeneity of composite material obtained is bad, limits material
The application range of material.
Summary of the invention
The purpose of the invention is to find it is a kind of meet that at low cost, equipment is simple, the method for the requirements such as environmental-friendly, system
The composite material and coating material that standby novel Nano silver grain and organic siliconresin are formed, Nano silver grain prepared by the present invention
Composite silicone resin material have high light transmittance, high-weatherability and high temperature tolerance, and have antistatic effect, antibacterial ability and
Special optical property, has broad application prospects as nonlinear optical material or optical coating material.And use this hair
The Nano silver grain narrow size distribution of bright method preparation, can form uniform dispersion in organic siliconresin matrix, obtain
The composite material homogeneity obtained is good.
To achieve the above object, the method comprises the steps of firstly, preparing the Nano silver grain of silica shell cladding and organosilicon trees
Then rouge performed polymer is prepared for Nano silver grain Composite silicone resin material by the recombination process that solvent assists.
In addition, the Nano silver grain 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 Nano silver grain Composite silicone resin, comprising the following steps:
(1) Nano silver grain is prepared using the seed mediated growth method under surfactant protection；
(2) using Nano silver grain obtained in step (1), silica shell cladding is prepared using Stoeber Hydrolyze method
Nano silver grain；
(3) organic-silicone prepolymer is prepared；
(4) the organosilicon tree prepared in the Nano silver grain and step (3) of the silica shell cladding prepared in step (2) is taken
Rouge performed polymer prepares Nano silver grain Composite silicone resin material by the recombination process that solvent assists.
Preferably, the step (1) are as follows:
Silver nanoparticle seed solution is prepared using sodium borohydride reduction silver nitrate under sodium citrate protection；
Silver nanoparticle seed solution is added to containing cetyl trimethylammonium bromide (0.01-0.2 mol/L), silver nitrate
In the growth-promoting media of (0.1-0.5 mmol/L), ascorbic acid (0.5-5 mmol/L) and sodium hydroxide (5-20 mmol/L), stirring
Reaction；
After reaction, reaction product centrifugation, washing are precipitated, Nano silver grain is obtained, by silver nanoparticle dispersion in water
It saves backup.
Preferably, by changing the concentration of cetyl trimethylammonium bromide in growth-promoting media, coming in the step (1)
Adjust the shape of Nano silver grain；When preparing silver nanoparticle ball, the concentration of cetyl trimethylammonium bromide is 0.04-0.05
Mol/L, the size uniformity of gained silver nanoparticle ball, control reaction condition adjust silver nanoparticle ball average diameter 10-100 nm it
Between；When preparing Nano silver piece, the concentration of cetyl trimethylammonium bromide is 0.09-0.15 mol/L, and gained Nano silver piece is
Triangular plate, hexagonal piece or subcircular piece, diameter can be adjusted between 50-200 nm, and thickness is between 10-50 nm.
Preferably, the step (2) are as follows:
Mercaptopropyl trimethoxysilane solution is added into Nano silver grain obtained in step (1), passes through silver atoms and sulfydryl
Between effect by mercaptopropyl trimethoxysilane be fixed to Nano silver grain surface；
Ethyl orthosilicate is added into system, sodium hydroxide is added after mixing is lauched siloxy key in weak basic condition
Solution is silicone hydroxyl, forms silicon oxygen silicon key by the polycondensation between silicone hydroxyl, forms layer of silicon dioxide on Nano silver grain surface；
Product obtains the Nano silver grain of silica shell cladding after being centrifuged, washing, by silica shell cladding
Silver nanoparticle dispersion saves backup in tetrahydrofuran.
Coated with silica Nano silver grain is used in the step (2), wherein the thickness of silicon dioxide layer is by positive silicic acid
The conditions control such as the dosage and hydrolysis time of ethyl ester, the dosage of sodium hydroxide, is generally adjusted between 2-50 nm.Use dioxy
The purpose of SiClx cladding Nano silver grain is the interface energy reduced between Nano silver grain and organic siliconresin matrix, prevents from making
The reunion of Nano silver grain in standby composite material, improves Nano silver grain and organic-silicone prepolymer carries out solvent auxiliary
Mixing when dispersibility.
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 ] and mercaptopropyl trimethoxysilane etc. be used as organic siliconresin predecessor, be stirred to react, organic siliconresin predecessor occurs
Hydrolysis, polycondensation reaction；
After reaction, revolving removing solvent and water arrive the organic-silicone prepolymer that organic group is R ' to thick,
Tetrahydrofuran dilution is added into organic-silicone prepolymer to save.
Alkylalkoxy silane [(RO) used in the step (3)4-nSiR’n], wherein R group include methyl and
Ethyl etc., R ' group include methyl, ethyl, phenyl etc., n 1-2.
Preferably, the step (4) are as follows:
It takes the silver nanoparticle dispersion of the silica shell prepared in step (2) cladding in tetrahydrofuran solvent, step is added
Suddenly the organic-silicone prepolymer prepared in (3), being sufficiently stirred mixes Nano silver grain with organic-silicone prepolymer, is formed
Uniform dispersion；
Then revolving removes solvent to thick, and aminopropyl triethoxysilane is added, pours into mold after mixing evenly, vacuum
Gas and residual solvent, curing molding are removed, Nano silver grain Composite silicone resin material is obtained.
Preferably, the Nano silver grain as described in step (1) is silver nanoparticle ball or Nano silver piece；
Wherein silver nanoparticle ball specific the preparation method comprises the following steps:
The preparation of seed solution: taking sodium citrate solution to be added in silver nitrate solution, sodium borohydride solution be added after being stirred,
It is stirred to react 10-20 min and obtains silver nanoparticle seed solution；
The concentration of sodium citrate, silver nitrate and sodium borohydride is respectively 1-1.5 mmol/L, 0.2-0.25 in entire reaction solution
Mmol/L and 0.25-0.3 mmol/L；
The preparation of silver nanoparticle ball: silver nanoparticle seed solution is added in growth-promoting media, 25-28o10-30 is stirred to react under C
Then reaction system centrifugation, washing are precipitated, obtain silver nanoparticle ball, silver nanoparticle ball is dispersed in water and is saved backup by min；
In the growth-promoting media, cetyl trimethylammonium bromide, silver nitrate, ascorbic acid and sodium hydroxide are dense in growth-promoting media
Degree is respectively 0.04-0.05 mol/L, 0.20-0.25 mmol/L, 4-5 mmol/L and 6-6.5 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,；
Nano silver piece specific the preparation method comprises the following steps:
The preparation of seed solution: taking sodium citrate solution to be added in silver nitrate solution, sodium borohydride solution be added after being stirred,
It is stirred to react 10-20 min and obtains silver nanoparticle seed solution；
The concentration of sodium citrate, silver nitrate and sodium borohydride is respectively 1-1.5 mmol/L, 0.2-0.25 in entire reaction solution
Mmol/L and 0.25-0.3 mmol/L；
The preparation of Nano silver piece: silver nanoparticle seed solution is added in growth-promoting media, 25-28oReaction 10-30 min is stood under C,
Then reaction system centrifugation, washing are precipitated, obtains Nano silver piece, Nano silver piece is dispersed in water and is saved backup；
In the growth-promoting media, cetyl trimethylammonium bromide, silver nitrate, ascorbic acid and sodium hydroxide are dense in growth-promoting media
Degree is respectively 0.09-0.15 mol/L, 0.25-0.3 mmol/L, 6-7 mmol/L and 10-15 mmol/L；
The percentage that the volume for the seed solution being wherein added into growth-promoting media accounts for growth-promoting media volume is 1-2%.
Preferably, the step (2) specifically:
The Nano silver grain prepared in step (1) is taken, mercaptopropyl trimethoxysilane is added, in 25-30o4-5 h is stirred under C；
Then pH to 9-10 is adjusted with NaOH solution, ethyl orthosilicate ethanol solution is added dropwise, be stirred to react after 10-15 h and be centrifuged, use water
Washing precipitating, obtain silica shell cladding Nano silver grain, silicon dioxide layer with a thickness of 2-50 nm, by titanium dioxide
The silver nanoparticle dispersion of silicon shell cladding saves backup in tetrahydrofuran (THF)；
The Nano silver grain amount of addition is 1-2 mg, the amount of the substance of the mercaptopropyl trimethoxysilane and ethyl orthosilicate of addition
Respectively 1-5 mmol and 30-100 mmol.
Preferably, the step (3) specifically:
Dilute hydrochloric acid is added into pure water and adjusts pH to 3-4, ethyl orthosilicate, alkylalkoxy silane and mercapto propyl trimethoxy is added
Base silane is heated to 40-70oHigh-speed stirred reacts 4-6 h under the conditions of C；Then revolving removes solvent and water to residual substrate is
It is thick to get arrive organic-silicone prepolymer, be added THF dilution after save；
Pure water, ethyl orthosilicate, alkylalkoxy silane and mercaptopropyl trimethoxysilane volume ratio be 1:0.1-0.5:
0.1-0.5:0.003-0.02；
The molecular formula of the alkylalkoxy silane is (RO)4-nSiR’n, wherein R is methyl, ethyl etc., R ' be methyl, ethyl,
Phenyl etc..
Preferably, in the step (4), Nano silver grain, the organic-silicone prepolymer of silica shell cladding
Quality with aminopropyl triethoxysilane is respectively 0.02-2 mg, 0.3-1.0 g and 2-20 mg.
Beneficial effect
The invention discloses it is a kind of it is at low cost, equipment is simple, the preparation of environmental-friendly Nano silver grain Composite silicone resin
Method.The method comprises the steps of firstly, preparing the Nano silver grains and organic-silicone prepolymer of silica shell cladding, then prepare
Dispersion of finely dispersed, the stable Nano silver grain in organic-silicone prepolymer, finally obtains by solidification
The solid-state sol material of Nano silver grain Composite silicone resin.
The Nano silver grain narrow size distribution prepared using the method for the present invention can be formed in organic siliconresin matrix
The solid-state colloidal sol composite material homogeneity of one dispersion, acquisition is good.
In preparation method of the present invention, using coated with silica Nano silver grain, can reduce Nano silver grain with
Interface energy between organic siliconresin matrix, prevents the reunion of the Nano silver grain in preparation composite material, improves silver and receives
Rice corpuscles and organic-silicone prepolymer carry out the dispersibility when mixing of solvent auxiliary.
The main silver nanoparticle by using of the optical property of Nano silver grain Composite silicone resin material prepared by the present invention
The optical property of particle determines that the absorbance and light transmittance of absorption spectrum are controlled by the amount of added Nano silver grain.
The composite material has broad application prospects in optical material field, such as plasma material, nonlinear optical material and laser
Protective materials etc..Moreover, the high weatherability of the composite material combination organic siliconresin and the high stability of metal nanoparticle,
Color has long-time stability in usual environment, and has antibacterial ability and antistatic effect.
Detailed description of the invention
Transmission electron microscope (TEM) photo of Fig. 1 silver nanoparticle ball；
Transmission electron microscope (TEM) photo of the silver nanoparticle ball of Fig. 2 coated with silica；
The Fourier transform infrared spectroscopy figure (FT-IR) of Fig. 3 organic-silicone prepolymer；
The photo of Fig. 4 silver nanoparticle ball Composite silicone resin material；
The UV-vis spectrogram of Fig. 5 silver nanoparticle ball Composite silicone resin material；
The thermal weight loss spectrogram of Fig. 6 silver nanoparticle ball Composite silicone resin material
Transmission electron microscope (TEM) photo of Fig. 7 Nano silver piece；
Transmission electron microscope (TEM) photo of the Nano silver piece of Fig. 8 coated with silica
The photo of Fig. 9 Nano silver piece Composite silicone resin material；
The UV-vis spectrogram of Figure 10 Nano silver piece 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 preparation method of silver nanoparticle ball Composite silicone resin, comprising the following steps:
(1) silver nanoparticle ball is prepared for using seed mediated growth method.
The preparation of (1-1) seed solution: taking 20 mL sodium citrate solutions (1.25 mmol/L), and 0.1 mL nitric acid is added
Silver-colored solution (50 mmol/L), is added 1.2 ml sodium borohydride solutions (5 mmol/L), is stirred to react 10 min and obtains after being stirred
To silver nanoparticle seed solution.
The preparation of (1-2) silver nanoparticle ball: taking 20 mL cetyl trimethylammonium bromide solutions (0.05 mol/L), is added
In 0.1 mL silver nitrate (50 mmol/L), 1 mL ascorbic acid (0.1 mol/L) and 1.5 mL above-mentioned steps (1-1) silver
Nanometer seed solution, is then added 0.14 mL sodium hydroxide solution (1 mol/L), 27oIt is stirred to react 15 min under C, then will
Reaction system centrifugation, washing precipitating, and silver nanoparticle ball precipitating is re-dispersed into water.
(2) coated with silica of silver nanoparticle ball.20 mL(of silver nanoparticle ball solution prepared in above-mentioned steps (1-2) is taken to contain
0.5 mg of silver), it is added 0.2 mL mercaptopropyl trimethoxysilane (10.8 mmol/L), 27o5 h are stirred under C heating water bath.
Then adjusting pH with 0.1 mol/L NaOH solution is 9-10, and 0.16 mL ethyl orthosilicate ethanol solution (0.9 mol/ is added dropwise
L), it is stirred to react after 12 h and is centrifuged, precipitating is washed with water, then is distributed in THF after washing precipitating with THF.
(3) preparation of organic-silicone prepolymer.It takes the ultrapure water of 33.75 mL in the single-necked flask of 50 mL, is added
0.04 mL dilute hydrochloric acid (0.1 mol/L) is adjusted to faintly acid, and 5 mL ethyl orthosilicates, 10 mL methyltriethoxysilane are added
With 0.2 mL mercaptopropyl trimethoxysilane, 60o5 h are stirred to react under C heating water bath.Then revolving removes second alcohol and water extremely
Residual substrate is thick to get organic-silicone prepolymer is arrived, and is saved after THF dilution is added.
(4) preparation of silver nanoparticle ball Composite silicone resin.Take THF points of the silver nanoparticle ball of a certain amount of Silica-coated
(then step (3) are added in argentiferous 0.27,0.45 mg respectively, counter sample a, b), centrifugal concentrating to 1 mL of volume for granular media system
In the made THF solution containing 1 g organic-silicone prepolymer, after being uniformly mixed, being evaporated in vacuo most of solvent makes body
System becomes thick, and 10 mg aminopropyl trimethoxysilanes are then added, 0.3 g is taken to be transferred to polytetrafluoroethyl-ne after being sufficiently stirred
In alkene mold, vacuum removal gas and residual solvent, solidification obtains Nano silver grain Composite silicone resin material at room temperature.
The transmission electron microscope photo that silver nanoparticle ball is obtained in the present embodiment step (1-2) is as shown in Figure 1.It can from figure
Out, the size of gained Nano silver grain is between 15-40 nm, 30 nm of average out to.
The transmission electron microscope photo that coated with silica silver nanoparticle ball is obtained in the present embodiment step (2) is as shown in Figure 2.From figure
In it can be seen that silica shell average thickness be 15 nm.
The FT-IR spectrum of organic-silicone prepolymer obtained in the present embodiment step (3) is as shown in Figure 3.It can from figure
To find out, 3443 cm-1Place corresponds to the absorption of hydroxyl, 2970,2934 and 1273 cm-1Place corresponds to the absorption of methyl,
1000-1124 cm-1Between broad peak correspond to the absorption of this Si-O-Si key.
The photo of silver nanoparticle ball Composite silicone resin material is as shown in figure 4, by sample obtained in the present embodiment step (4)
Product are placed on the bottom plate with letter, it can be seen that and preferably, sample a, b are yellow transparent solid body to the transparency of sample, with
Silver nanoparticle ball content improves color burn；Its corresponding UV-vis spectrogram is as shown in figure 5, its absorption peak center is 450
Nm, wherein the absorbance of sample a is 0.38, and the absorbance of sample b is 0.66.
The thermogravimetric curve of silver nanoparticle ball Composite silicone resin under nitrogen atmosphere obtained in the present embodiment step (4)
As shown in Figure 6.From curve as can be seen that sample is 200oC weight-loss ratio below is about 2.5%, until 700oWeight-loss ratio when C is about
7%。
Embodiment 2
The preparation method of Nano silver piece Composite silicone resin, comprising the following steps:
(1) Nano silver piece is prepared using seed mediated growth method.
The preparation of (1-1) seed solution: taking 20 ml sodium citrate solutions (1.25 mmol/L), and 0.1 mL nitric acid is added
Silver-colored solution (50 mmol/L), is added 1.2 ml sodium borohydride solutions (5 mmol/L), is stirred to react 10-20 after being stirred
Min obtains silver nanoparticle seed solution.
The preparation of (1-2) Nano silver piece: taking 30 mL cetyl trimethylammonium bromide solutions (0.1 mol/L), is added
0.2 mL silver nitrate solution (50 mmol/L), 2 mL ascorbic acid solutions (0.1 mol/L), in 0.5 mL above-mentioned steps (1-1)
Silver nanoparticle seed solution, be then added 0.44 mL sodium hydroxide (1 mol/L), 27oReaction 10-30 min is stood under C,
Reaction system centrifugation, washing are precipitated again, Nano silver piece is obtained and is re-dispersed into water.
(2) coated with silica of Nano silver piece.The Nano silver grain prepared in 20 mL above-mentioned steps (1-3) is taken, is added
0.2 mL mercaptopropyl trimethoxysilane (10.8 mmol/L), 27o5 h are stirred under C heating water bath.Then with 0.1 mol/L
It is 9-10 that NaOH solution, which adjusts pH, and 0.16 mL ethyl orthosilicate ethanol solution (0.9 mol/L) is added dropwise, is stirred to react 12 h
After be centrifuged, be washed with water precipitating, then be distributed in THF after washing precipitating with THF.
(3) preparation of organic-silicone prepolymer.It takes the ultrapure water of 33.75 mL in the single-necked flask of 50 mL, is added
0.04 mL dilute hydrochloric acid (0.1 mol/L) is adjusted to faintly acid, and 8 mL ethyl orthosilicates, 7 mL methyltriethoxysilane are added
With 0.3 mL mercaptopropyl trimethoxysilane, 60o5 h are stirred to react under C heating water bath.Then revolving removes second alcohol and water extremely
Residual substrate is thick to get organic-silicone prepolymer is arrived, and is saved after THF dilution is added.
(4) preparation of Nano silver piece Composite silicone resin.Take the Nano silver piece THF of the Silica-coated of certain volume
(argentiferous is respectively 0.18 mg, 0.36 mg to dispersion, counter sample c, d), then step is added in centrifugal concentrating to 1 mL of volume
Suddenly the THF solution containing 1 g organic-silicone prepolymer made in (3), after being uniformly mixed, vacuum evaporating solvent makes system
Become thick, aminopropyl trimethoxysilane is then added, 0.3 g is gone to be transferred to Teflon mould after being sufficiently stirred
In, vacuum removal gas and residual solvent, solidification obtains Nano silver grain Composite silicone resin material at room temperature.
The transmission electron microscope photo that Nano silver piece is obtained in the present embodiment step (1-2) is as shown in Figure 7.It can from figure
Out, the size range of gained Nano silver piece is 80-110 nm.
The transmission electron microscope photo that coated with silica Nano silver piece is obtained in the present embodiment step (2) is as shown in Figure 8.From figure
In as can be seen that the thickness of silica shell is about 5 nm.
The photo of Nano silver piece Composite silicone resin material is obtained in the present embodiment step (4) as shown in figure 9, by sample
It being placed on the bottom plate with letter, it can be seen that preferably, gained sample c, d are blue-tinted transparent solid to the transparency of sample, with
Nano silver piece content improve color burn.Its corresponding UV-vis spectrogram is as shown in Figure 10.It can be seen from the figure that sample exists
350 nm are 620 nm to there is relatively strong absorption, absorption maximum peak position between 700 nm, and corresponding c sample absorbance is
0.21, d sample absorbance is 0.32.
Claims (10)
1. a kind of preparation method of Nano silver grain Composite silicone resin, which comprises the following steps:
(1) Nano silver grain is prepared using the seed mediated growth method under surfactant protection；
(2) using Nano silver grain obtained in step (1), silica shell cladding is prepared using Stoeber Hydrolyze method
Nano silver grain；
(3) organic-silicone prepolymer is prepared；
(4) the organosilicon tree prepared in the Nano silver grain and step (3) of the silica shell cladding prepared in step (2) is taken
Rouge performed polymer prepares Nano silver grain Composite silicone resin material by the recombination process that solvent assists.
2. the preparation method of Nano silver grain Composite silicone resin according to claim 1, which is characterized in that the step
Suddenly (1) are as follows:
Silver nanoparticle seed solution is prepared using sodium borohydride reduction silver nitrate under sodium citrate protection；
Silver nanoparticle seed solution is added to containing cetyl trimethylammonium bromide, silver nitrate, ascorbic acid and sodium hydroxide
Growth-promoting media in, be stirred to react；
After reaction, reaction product centrifugation, washing are precipitated, Nano silver grain is obtained, by silver nanoparticle dispersion in water
It saves backup.
3. the preparation method of Nano silver grain 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 Nano silver grain obtained in step (1), positive silicic acid second is then added
Ester, sodium hydroxide is added after mixing makes system in weak basic condition, is stirred to react；
After reaction, product obtains the Nano silver grain of silica shell cladding after being centrifuged, washing, by silica
The silver nanoparticle dispersion of shell cladding saves backup in tetrahydrofuran.
4. the preparation method of Nano silver grain 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 Nano silver grain Composite silicone resin according to claim 1, which is characterized in that the step
Suddenly (4) are as follows:
The Nano silver grain for taking the silica shell cladding being scattered in tetrahydrofuran solvent prepared in step (2), is added
The tetrahydrofuran solution of the organic-silicone prepolymer prepared in step (3), being sufficiently stirred makes Nano silver grain and organosilicon tree
The mixing of rouge performed polymer, forms uniform dispersion；
Then revolving removes solvent to thick, and aminopropyl triethoxysilane is added, pours into mold after mixing evenly, vacuum
Gas and residual solvent, curing molding are removed, Nano silver grain Composite silicone resin material is obtained.
6. the preparation method of Nano silver grain Composite silicone resin according to claim 1, which is characterized in that the step
Suddenly Nano silver grain described in (1) is silver nanoparticle ball, Nano silver piece；
Wherein silver nanoparticle ball specific the preparation method comprises the following steps:
The preparation of seed solution: taking sodium citrate solution to be added in silver nitrate solution, sodium borohydride solution be added after being stirred,
It is stirred to react 10-20 min and obtains silver nanoparticle seed solution；
The concentration of sodium citrate, silver nitrate and sodium borohydride is respectively 1-1.5 mmol/L, 0.2-0.25 in entire reaction solution
Mmol/L and 0.25-0.3 mmol/L；
The preparation of silver nanoparticle ball: silver nanoparticle seed solution is added in growth-promoting media, 25-28o10-30 min is stirred to react under C,
Then reaction system centrifugation, washing are precipitated, obtains silver nanoparticle ball, silver nanoparticle ball is dispersed in water and is saved backup；
In the growth-promoting media, cetyl trimethylammonium bromide, silver nitrate, ascorbic acid and sodium hydroxide are dense in growth-promoting media
Degree is respectively 0.04-0.05 mol/L, 0.20-0.25mmol/L, 4-5mmol/L and 6-6.5mmol/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,；
Nano silver piece specific the preparation method comprises the following steps:
The preparation of seed solution: taking sodium citrate solution to be added in silver nitrate solution, sodium borohydride solution be added after being stirred,
It is stirred to react 10-20 min and obtains silver nanoparticle seed solution；
The concentration of sodium citrate, silver nitrate and sodium borohydride is respectively 1-1.5 mmol/L, 0.2-0.25 in entire reaction solution
Mmol/L and 0.25-0.3 mmol/L；
The preparation of Nano silver piece: silver nanoparticle seed solution is added in growth-promoting media, 25-28oReaction 10-30 min is stood under C,
Then reaction system centrifugation, washing are precipitated, obtains Nano silver piece, Nano silver piece is dispersed in water and is saved backup；
In the growth-promoting media, cetyl trimethylammonium bromide, silver nitrate, ascorbic acid and sodium hydroxide are dense in growth-promoting media
Degree is respectively 0.09-0.15 mol/L, 0.25-0.3 mmol/L, 6-7 mmol/L and 10-15 mmol/L；
The percentage that the volume for the seed solution being wherein added into growth-promoting media accounts for growth-promoting media volume is 1-2%.
7. the preparation method of Nano silver grain Composite silicone resin according to claim 1, which is characterized in that the step
Suddenly (2) specifically:
The Nano silver grain prepared in step (1) is taken, mercaptopropyl trimethoxysilane is added, in 25-30o4-5 h is stirred under C；So
PH to 9-10 is adjusted with NaOH solution afterwards, ethyl orthosilicate ethanol solution is added dropwise, is stirred to react after 10-15 h and is centrifuged, is washed with water
Wash precipitating, obtain silica shell cladding Nano silver grain, silicon dioxide layer with a thickness of 2-50 nm, by silica
The silver nanoparticle dispersion of shell cladding saves backup in tetrahydrofuran；
The amount of the Nano silver grain of addition is 1-2 mg, the substance of the mercaptopropyl trimethoxysilane and ethyl orthosilicate of addition
Amount is respectively 1-5 mmol and 30-100 mmol.
8. the preparation method of Nano silver grain Composite silicone resin according to claim 1, which is characterized in that the step
Suddenly (3) specifically:
Dilute hydrochloric acid is added into pure water and adjusts pH to 3-4, ethyl orthosilicate, alkylalkoxy silane and mercapto propyl trimethoxy is added
Base silane is heated to 40-70oHigh-speed stirred reacts 4-6 h under the conditions of C；Then revolving removes solvent and water to residual substrate is
It is thick to get arrive organic-silicone prepolymer, be added tetrahydrofuran (THF) dilution after save；
Pure water, ethyl orthosilicate, alkylalkoxy silane and mercaptopropyl trimethoxysilane volume ratio be 1:0.1-0.5:
0.1-0.5: 0.003-0.02.
9. the preparation method of Nano silver grain 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 0.02-2 mg, 0.3-1.0 g and 2-20 mg.
10. a kind of Nano silver grain 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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