CN114523105A - High-crosslinking-degree organic silicon polymer/metal composite microsphere and preparation method thereof - Google Patents
High-crosslinking-degree organic silicon polymer/metal composite microsphere and preparation method thereof Download PDFInfo
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- CN114523105A CN114523105A CN202111682811.0A CN202111682811A CN114523105A CN 114523105 A CN114523105 A CN 114523105A CN 202111682811 A CN202111682811 A CN 202111682811A CN 114523105 A CN114523105 A CN 114523105A
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- Prior art keywords
- crosslinking
- organic silicon
- silicon polymer
- degree
- microspheres
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- 239000004005 microsphere Substances 0.000 title claims abstract description 194
- 229920001558 organosilicon polymer Polymers 0.000 title claims abstract description 112
- 239000002905 metal composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 96
- 229910052751 metal Inorganic materials 0.000 claims abstract description 62
- 239000002184 metal Substances 0.000 claims abstract description 62
- 238000007747 plating Methods 0.000 claims abstract description 41
- 238000004132 cross linking Methods 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 29
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 239000000243 solution Substances 0.000 claims description 43
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 6
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
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- -1 glycidoxymethyl Chemical group 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
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- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
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- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical group Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229940076131 gold trichloride Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
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- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001393 triammonium citrate Substances 0.000 description 1
- 235000011046 triammonium citrate Nutrition 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of high-crosslinking-degree organic silicon polymer/metal composite microspheres, which comprises the following steps: (1) dispersing inorganic nano particles into a polar solvent, and then adding an aminosilane coupling agent for modification to obtain aminated inorganic nano particles; (2) adding the high-crosslinking-degree organic silicon polymer microspheres and the aminated inorganic nanoparticles into an acidic solution system and uniformly mixing to obtain the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles; (3) and (3) carrying out activation treatment and chemical plating on the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nano-particles obtained in the step (2) to obtain the high-crosslinking-degree organic silicon polymer/metal composite microspheres. The high-crosslinking-degree organic silicon polymer/metal composite microsphere prepared by the invention has the advantages of good monodispersity, stable chemical property, high crosslinking degree, excellent ageing resistance and solvent swelling resistance, uniform metal layer coating, firm attachment and difficult falling.
Description
Technical Field
The invention relates to the technical field of functional microspheres, in particular to an organic silicon polymer/metal composite microsphere with high crosslinking degree and a preparation method thereof.
Background
The resin core conductive microsphere is a conductive microsphere formed by plating a conductive metal material on a resin microsphere serving as a base material. The conductive microspheres are compounded with the high-molecular polymer microspheres and the metal, so that the conductive microspheres have good conductive performance, greatly reduce the metal consumption, and have the advantages of metal materials and high-molecular resin microspheres, so that the conductive microspheres are widely applied to the technical field of 3C.
In the traditional preparation process of the resin core conductive microspheres, a plurality of steps such as deoiling, coarsening, sensitizing, activating, chemical plating and the like are needed to be carried out on the resin microspheres, and the preparation process is complicated. Patent application No. CN202011488043.0 discloses that polystyrene microspheres are roughened by using a roughening solution (a mixture of chromium trioxide and concentrated sulfuric acid) to improve the surface adhesion capability of PS microspheres, but the method is relatively serious in environmental pollution; patent application nos. CN201210154648.5 and CN201110162698.3 both disclose that metal ions are directly adsorbed on the surface of polymer microspheres and gold-plated particles are prepared by chemical deposition, so that the thickness of the plated layer of the prepared conductive particles is limited, the cost is high, and the used polymer microspheres are non-highly crosslinked polymer microspheres, which results in the defect that the prepared conductive microspheres are not resistant to solvent swelling. Therefore, it is urgently needed to prepare a resin core conductive composite microsphere with good monodispersity, high crosslinking degree, stable chemical property, corrosion resistance, high temperature resistance and excellent ageing resistance and solvent swelling resistance.
Disclosure of Invention
The embodiment of the invention provides an organic silicon polymer/metal composite microsphere with a high crosslinking degree and a preparation method thereof, and can provide a resin core conductive composite microsphere with good monodispersity, high crosslinking degree, stable chemical properties, corrosion resistance, high temperature resistance, excellent ageing resistance and excellent solvent swelling resistance.
In a first aspect, the present invention provides a preparation method of a high crosslinking degree organosilicon polymer/metal composite microsphere, wherein the preparation method comprises the following steps:
(1) dispersing inorganic nano particles into a polar solvent, and then adding an aminosilane coupling agent for modification to obtain aminated inorganic nano particles;
(2) adding the high-crosslinking-degree organic silicon polymer microspheres and the aminated inorganic nanoparticles into an acidic solution system and uniformly mixing to obtain the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles;
(3) and (3) carrying out activation treatment and chemical plating on the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nano-particles obtained in the step (2) to obtain the high-crosslinking-degree organic silicon polymer/metal composite microspheres.
Preferably, in the step (1), the modification is carried out in a nitrogen atmosphere, the reaction temperature is 50-100 ℃, and the reaction time is 12-48 h; preferably, the modification reaction temperature is 65-80 ℃, and the reaction time is 24 h.
Preferably, the mass ratio of the inorganic nanoparticles to the polar solvent to the aminosilane coupling agent is 1:100 (0.01-0.5); preferably 1:100 (0.05-0.35).
Preferably, in the step (1), the inorganic nanoparticles are one or more selected from silica, magnesia, ferroferric oxide, titanium dioxide, alumina, zinc oxide and kaolin; preferably one or more of silicon dioxide, titanium dioxide, aluminum oxide and zinc oxide; more preferably one or more of silica and titania.
The particle size of the inorganic nano-particles is 5-500 nm, preferably 10-50 nm.
Preferably, in the step (1), the polar solvent is one or more selected from ethanol, methanol, isopropanol, N-dimethylformamide, acetonitrile, dimethyl sulfoxide, hexamethylphosphoramide, cyclohexanone, acetone, N-butanol, tetrahydrofuran, methyl N-butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; preferably one or more of methanol, ethanol, isopropanol, acetone, acetonitrile. Ethanol is more preferred.
Preferably, in step (1), the aminosilane coupling agent is prepared by:
dissolving silane containing glycidol in absolute ethyl alcohol, and then adding organic amine containing active hydrogen to react to obtain the aminosilane coupling agent;
preferably, in the step (1), the mass ratio of the glycidyl silane to the anhydrous ethanol to the organic amine containing active hydrogen is 1:100 (0.1-1); preferably 1:100 (0.2-0.6);
preferably, in the step (1), the reaction temperature is 50-100 ℃, and the reaction time is 6-60 h; preferably, the reaction temperature is 60-75 ℃, and the reaction time is 10-20 h.
Preferably, the glycidyl group-containing silane has the general chemical formula (RO)3SiP1Wherein R is an aliphatic alkyl group with 1-30 carbon atoms, preferably methyl or ethyl; p1Is gamma-glycidoxypropyl or glycidoxymethyl;
preferably, in the step (1), the active hydrogen-containing organic amine is methylamine, ethylenediamine, hexamethylenediamine, isopropylamine, p-phenylenediamine, diethylamine, diphenylamine, methylethylamine, 2-amino-4-methylhexane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, p-aminopyridine, 2,3, 4-triaminopyridine, 3,4, 5-triaminopyridine, 2,3, 6-triaminopyridine, imidazole or 2-phenylimidazole; preferably ethylenediamine, diethylamine or p-aminopyridine; more preferably ethylenediamine.
Preferably, in the step (2), the mass ratio of the high-crosslinking-degree organosilicon polymer microspheres to the aminated inorganic nanoparticles is (1-100): 1, preferably (40-80): 1;
preferably, in the step (2), the particle size of the high crosslinking degree organosilicon polymer microsphere is 1-15 μm;
the particle size of the aminated inorganic nanoparticles is 5-500 nm, preferably 10-50 nm;
preferably, in the step (2), the pH value of the acidic solution system is preferably 2.0-6.5, and more preferably 3.0-5.0.
Preferably, in step (3), the activation process includes the sub-steps of:
adding the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles into a Pegley palladium activator PL-5, washing with water, filtering, adding into a sodium hypophosphite aqueous solution, washing with water, and filtering to complete the activation treatment;
the mass ratio of the aminated inorganic nanoparticle-coated high-crosslinking-degree organosilicon polymer microsphere to the Pegley palladium activator PL-5 to the sodium hypophosphite aqueous solution is (1-10): 50:10, preferably 3:50: 10.
Preferably, in step (3), the electroless plating includes the substeps of:
dispersing the activated high-crosslinking-degree organic silicon polymer microspheres coated with aminated inorganic nano-particles into a metal salt solution, and then adding a reducing solution for reaction to obtain the high-crosslinking-degree organic silicon polymer/metal composite microspheres; wherein the thickness of the metal layer of the high-crosslinking-degree organic silicon polymer/metal composite microsphere is 30-200 nm;
preferably, in the step (3), the reaction temperature is 20-100 ℃, and the reaction time is 1-12 h; preferably, the reaction temperature is 30-85 ℃, and the reaction time is 3-5 h.
Preferably, in the step (3), the number of times of the electroless plating is 2 to 8 times, preferably 2 to 5 times, and more preferably 3 times.
Preferably, in the step (3), the mass ratio of the activated high-crosslinking-degree organosilicon polymer microspheres coated with aminated inorganic nanoparticles to the metal salt in the metal salt solution is 1 (1-3), wherein the mass fraction of the metal salt in the metal salt solution is 1-10%, and preferably 3-8%;
more preferably, in the step (3), the mass ratio of the activated high crosslinking degree silicone polymer microspheres coated with aminated inorganic nanoparticles to the metal salt in the metal salt solution is 1 (1.2-2); wherein the mass fraction of the metal salt in the metal salt solution is 3-8%.
The metal salt solution comprises one or more of nickel salt, silver salt and gold salt;
the metal salt solution further comprises a complexing agent; wherein the complexing agent is ammonia, ammonium salt or sodium citrate;
the reducing solution is hydrazine hydrate solution, glucose solution, sodium hypophosphite aqueous solution, formaldehyde solution, acetaldehyde solution, sodium borohydride solution, potassium borohydride solution or saturated sodium sulfite solution.
In a second aspect, the invention provides a high-crosslinking-degree organosilicon polymer/metal composite microsphere, which is prepared by the preparation method of any one of the first aspect.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention provides a preparation method of a high-crosslinking-degree organic silicon polymer/metal composite microsphere, which comprises the steps of modifying inorganic nanoparticles to obtain aminated inorganic nanoparticles, adsorbing the aminated inorganic nanoparticles on the surface of a micron-level high-crosslinking-degree organic silicon polymer microsphere through electrostatic action, and plating a uniform metal layer on the surface of the microsphere through chemical plating to obtain the high-crosslinking-degree organic silicon polymer/metal composite microsphere.
(2) According to the preparation method provided by the invention, the aminated inorganic nano particles are adsorbed on the surface of the high-crosslinking-degree organic silicon polymer microsphere through electrostatic action, so that the surface of the high-crosslinking-degree organic silicon polymer microsphere is coarsened and is provided with a large amount of amino groups, and further, a metal layer coated on the surface of the microsphere is tighter and more firmly adhered; the metal plating frequency on the surface of the microsphere is controlled, so that the thickness of the metal layer is controllable; meanwhile, the surfaces of various inorganic nano particles can be coated on the surface of the organic silicon polymer microsphere with high crosslinking degree after amination modification, and then the requirements of plating different metal layers are met.
(3) The high-crosslinking-degree organic silicon polymer microspheres prepared by the preparation method provided by the invention have the advantages of good monodispersity, swelling resistance, aging resistance and corrosion resistance; and the roughening treatment method does not need to use chromic anhydride, concentrated sulfuric acid or hydrofluoric acid, and is environment-friendly compared with the traditional roughening method.
(4) The invention provides an organosilicon polymer/metal composite microsphere with high crosslinking degree, which has the advantages of good monodispersity, high crosslinking degree, stable chemical property, corrosion resistance, high temperature resistance, excellent ageing resistance and solvent swelling resistance, uniform metal layer coating, firm adhesion and difficult falling.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a scanning electron microscope image of the high crosslinking degree organosilicon polymer/silver composite microsphere prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the high crosslinking degree organosilicon polymer/silver composite microsphere prepared in example 2 of the invention.
Fig. 3 is a scanning electron microscope picture of the high crosslinking degree organic silicon polymer/nickel composite microsphere prepared in example 4 of the present invention.
Fig. 4 is a scanning electron microscope picture of the high crosslinking degree organic silicon polymer/metal composite microsphere prepared in example 5 of the present invention.
FIG. 5 is a scanning electron microscope picture of the high crosslinking degree organosilicon polymer/silver composite microsphere prepared in comparative example 1 of the invention.
FIG. 6 is a scanning electron microscope picture of the high crosslinking degree organosilicon polymer/silver composite microsphere prepared in comparative example 2 of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention, and based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative efforts belong to the scope of the present invention.
The invention provides a preparation method of high-crosslinking-degree organic silicon polymer/metal composite microspheres, which comprises the following steps:
(1) dispersing inorganic nano particles into a polar solvent, and then adding an aminosilane coupling agent for modification to obtain aminated inorganic nano particles;
(2) adding the high-crosslinking-degree organic silicon polymer microspheres and the aminated inorganic nanoparticles into an acidic solution system and uniformly mixing to obtain the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles;
(3) and (3) carrying out activation treatment and chemical plating on the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nano-particles obtained in the step (2) to obtain the high-crosslinking-degree organic silicon polymer/metal composite microspheres.
The preparation method of the high crosslinking degree organic silicon polymer microsphere refers to patent with application number of CN 202110292742.6. The high-crosslinking-degree organic silicon polymer microspheres have excellent semi-inorganic and semi-organic performances, including stable chemical properties, no toxicity, environmental friendliness, solvent swelling resistance, corrosion resistance, high temperature resistance, aging resistance and the like, so that the high-crosslinking-degree organic silicon polymer microspheres are widely applied to the fields of light scattering materials, catalyst carriers, plastics, rubbers, coatings, adsorbing materials, ceramic materials, biological medicines and the like.
Specifically, the preparation method of the high crosslinking degree organic silicon polymer microsphere comprises the following steps: (i) dissolving a reactive organic silicon surfactant and a silicon-containing monomer in a mixed solvent formed by water and lower alcohol, adding an acid catalyst to perform an acid catalytic reaction, and heating and polymerizing to obtain a prepolymer; (ii) and (i) dropwise adding an alkaline catalyst into the reaction system containing the prepolymer obtained in the step (i) to perform an alkaline catalytic polycondensation reaction, thereby obtaining the micron-scale high-crosslinking-degree organosilicon microspheres (namely the high-crosslinking-degree organosilicon polymer microspheres). The high-crosslinking-degree organic silicon polymer microsphere is narrow in sphere diameter distribution and good in sphericity, can still keep high monodispersity within the range of 1-15 mu m, and can effectively solve the problem of wide particle size distribution of the microsphere.
The invention firstly prepares an amination modified inorganic nano-particle, the surface of the inorganic nano-particle is positively charged by adjusting the pH value of a solution system to be acidic, then the nano-particle is absorbed on the surface of a high-crosslinking-degree organic silicon polymer microsphere with negative charge through electrostatic interaction to obtain the high-crosslinking-degree organic silicon polymer microsphere (namely the modified high-crosslinking-degree organic silicon polymer microsphere) coated with the amination inorganic nano-particle, and finally, a uniform metal layer is plated on the surface of the modified high-crosslinking-degree organic silicon polymer microsphere through chemical plating to obtain the high-crosslinking-degree organic silicon polymer/metal composite microsphere.
The high-crosslinking-degree organosilicon polymer/metal composite microspheres prepared by the method have the advantages of good monodispersity, high crosslinking degree, stable chemical properties, corrosion resistance, high temperature resistance, excellent ageing resistance and solvent swelling resistance, uniform metal layer coating, firm adhesion and difficulty in falling.
According to some preferred embodiments, in the step (1), the modification is performed by using a nitrogen atmosphere, the reaction temperature is 50 to 100 ℃ (for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃), and the reaction time is 12 to 48 hours (for example, 12 hours, 18 hours, 24 hours, 30 hours, 35 hours, 40 hours or 48 hours); preferably, the modification reaction temperature is 65 to 80 ℃ (for example, 65 ℃, 68 ℃, 70 ℃, 74 ℃, 76 ℃ or 80 ℃), and the reaction time is 24 hours.
According to some preferred embodiments, in the step (1), the ratio of the mass of the inorganic nanoparticles, the polar solvent, and the aminosilane coupling agent is 1:100 (0.01 to 0.5) (for example, may be 1:100:0.01, 1:100:0.05, 1:100:0.12, 1:100:0.2, 1:100:0.3, 1:100:0.4, or 1:100: 0.5);
according to some more preferred embodiments, in the step (1), the ratio of the mass of the inorganic nanoparticles, the polar solvent, and the aminosilane coupling agent is 1:100 (0.05 to 0.35) (e.g., may be 1:100:0.05, 1:100:0.1, 1:100:0.15, 1:100:0.2, 1:100:0.25, 1:100:0.3, or 1:100: 0.35).
According to some preferred embodiments, in step (1), the inorganic nanoparticles are one or more selected from silica, magnesia, ferroferric oxide, titanium dioxide, alumina, zinc oxide, kaolin; preferably one or more of silicon dioxide, titanium dioxide, aluminum oxide and zinc oxide; more preferably one or more of silica and titania.
According to some preferred embodiments, the inorganic nanoparticles have a particle size of 5 to 500nm (e.g., may be 5nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, or 500 nm).
According to some more preferred embodiments, the inorganic nanoparticles have a particle size of 10 to 50nm (e.g., may be 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, or 50 nm).
According to some preferred embodiments, in step (1), the polar solvent is one or more selected from the group consisting of ethanol, methanol, isopropanol, N-dimethylformamide, acetonitrile, dimethyl sulfoxide, hexamethylphosphoramide, cyclohexanone, acetone, N-butanol, tetrahydrofuran, methyl N-butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether; preferably one or more of methanol, ethanol, isopropanol, acetone and acetonitrile; ethanol is more preferred.
According to some preferred embodiments, in step (1), the aminosilane coupling agent is prepared by:
dissolving silane containing glycidyl into absolute ethyl alcohol, and then adding organic amine containing active hydrogen to react to obtain the aminosilane coupling agent;
it should be noted that organic amine containing active hydrogen is added under nitrogen atmosphere.
According to some preferred embodiments, in step (1), the mass ratio of the glycidylsilane, the anhydrous ethanol, and the active hydrogen-containing organic amine is 1:100 (0.1 to 1) (for example, may be 1:100:0.1, 1:100:0.2, 1:100:0.3, 1:100:0.4, 1:100:0.5, 1:100:0.6, 1:100:0.7, 1:100:0.8, 1:100:0.9, or 1:100: 1).
According to some more preferred embodiments, in the step (1), the mass ratio of the glycidyl group-containing silane to the anhydrous ethanol to the active hydrogen-containing organic amine is 1:100 (0.2 to 0.6) (for example, may be 1:100:0.2, 1:100:0.25, 1:100:0.3, 1:100:0.35, 1:100:0.4, 1:100:0.45, 1:100:0.5, 1:100:0.55, or 1:100: 0.6);
according to some preferred embodiments, in the step (1), the reaction temperature of the reaction is 50 to 100 ℃ (for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃) and the reaction time is 6 to 60 hours (for example, 6 hours, 15 hours, 25 hours, 35 hours, 45 hours, 55 hours or 60 hours).
According to some more preferred embodiments, in the step (1), the reaction temperature of the reaction is 60 to 75 ℃ (for example, 60 ℃, 64 ℃, 68 ℃, 70 ℃, 72 ℃ or 75 ℃) and the reaction time is 10 to 20 hours (for example, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours or 20 hours). The temperature is too low to react or the reaction is too slow; the temperature is too high, which is not favorable for the smooth reaction.
According to some preferred embodiments, in step (1), the glycidyl-containing silane has the general chemical formula (RO)3SiP1Wherein R is an aliphatic alkyl group with 1-30 carbon atoms, preferably methyl or ethyl; p1 is γ -glycidoxypropyl or glycidoxymethyl;
according to some preferred embodiments, in step (1), the active hydrogen-containing organic amine is methylamine, ethylenediamine, hexamethylenediamine, isopropylamine, p-phenylenediamine, diethylamine, diphenylamine, methylethylamine, 2-amino-4-methylhexane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, p-aminopyridine, 2,3, 4-triaminopyridine, 3,4, 5-triaminopyridine, 2,3, 6-triaminopyridine, imidazole or 2-phenylimidazole; preferably ethylenediamine, diethylamine or p-aminopyridine; more preferably ethylenediamine.
According to some preferred embodiments, in the step (2), the mass ratio of the high crosslinking degree silicone polymer microspheres to the aminated inorganic nanoparticles is (1-100: 1) (for example, may be 1:1, 5:1, 10:1, 15:1, 25:1, 35:1, 45:1, 55:1, 65:1, 75:1, 85:1, 95:1, or 100: 1).
According to some more preferred embodiments, in the step (2), the mass ratio of the high crosslinking degree silicone polymer microspheres to the aminated inorganic nanoparticles is (40-80: 1) (for example, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, or 80:1 may be used);
according to some preferred embodiments, in the step (2), the particle size of the aminated inorganic nanoparticles is 5 to 500nm (for example, may be 5nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, or 500 nm).
According to some more preferred embodiments, in the step (2), the aminated inorganic nanoparticles have a particle size of 10 to 50 nm; (for example, it may be 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm or 50 nm).
According to some preferred embodiments, in the step (2), the particle size of the high crosslinking degree silicone polymer microsphere is 1 to 15 μm (for example, 1 μm, 2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm or 15 μm);
according to some preferred embodiments, in step (2), the pH of the acidic solution system is 2.0 to 6.5 (e.g., may be 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, or 6.5).
According to some more preferred embodiments, in step (2), the pH of the acidic solution system is 3.0 to 5.0 (e.g., may be 3.0, 3.2, 3.5, 3.8, 4.0, 4.5, 4.8, or 5.0).
It should be noted that the pH of the acidic solution system in step (2) is < 7.
In the step (2), dispersing the high-crosslinking-degree organic silicon polymer microspheres and the aminated inorganic nanoparticles into deionized water, uniformly mixing, adjusting the pH to be less than 7 by adding hydrochloric acid, stirring at normal temperature for 60min, washing with water, filtering, and drying to obtain the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles; when the pH value is controlled in the range, the aminated inorganic nano particles can be positively charged, and the subsequent adsorption on the surface of the organic silicon polymer microsphere with high crosslinking degree through electrostatic action is facilitated.
In the invention, experiments prove that when the mass ratio of the high-crosslinking-degree organic silicon polymer microspheres to the aminated inorganic nanoparticles is less than 1:1, the amino groups on the surfaces of the microspheres are fewer due to fewer aminated inorganic nanoparticles, the roughness of the surfaces of the high-crosslinking-degree organic silicon polymer microspheres cannot be ensured, and the adhesion between the metal layer and the surfaces of the microspheres can be further weakened; when the mass ratio of the high-crosslinking-degree organic silicon polymer microspheres to the aminated inorganic nanoparticles is greater than 100:1, the aminated inorganic nanoparticles are too many and are loose on the surfaces of the high-crosslinking-degree organic silicon polymer microspheres and are not tightly bonded, so that the bonding force between the metal layer and the surfaces of the microspheres is weakened. Similarly, when the particle size of the aminated inorganic nanoparticles is less than 5nm, the particle size of the aminated inorganic nanoparticles is too small, the surface roughness of the high-crosslinking-degree organosilicon polymer microspheres is poor, and a metal layer cannot be tightly coated on the surfaces of the microspheres in the plating process; when the particle size of the aminated inorganic nano-particles is larger than 500nm, the aminated inorganic nano-particles are too large in particle size and cannot be tightly coated on the surface of the high-crosslinking-degree organic silicon polymer microspheres under the action of static electricity, so that the adhesion of the metal layer on the surfaces of the microspheres is weakened, and the metal layer on the surfaces of the microspheres is easy to drop.
According to some preferred embodiments, in step (3), the activation process comprises the following sub-steps:
and adding the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nano particles into a Pegley palladium activator PL-5, washing with water, filtering, adding into a sodium hypophosphite aqueous solution, washing with water, and filtering to complete the activation treatment.
More specifically, in step (3), the high crosslinking degree silicone polymer microspheres coated with the aminated inorganic nanoparticles are added into a bigelia palladium activator PL-5 for adsorption and activation, the microspheres with colloidal palladium adsorbed on the surface are washed with water, filtered, added with a sodium hypophosphite aqueous solution with the mass ratio of 1%, stirred at room temperature (for example, 25 ℃) for 10min, filtered and washed with water to complete the activation treatment, and the activated microspheres are obtained.
According to some preferred embodiments, the mass ratio of the aminated inorganic nanoparticle-coated silicone polymer microsphere with high degree of crosslinking, the pegalladium activator PL-5 and the sodium hypophosphite aqueous solution is (1-10): 50:10 (for example, 1:50:10, 2:50:10, 3:50:10, 4:50:10, 5:50:10, 6:50:10, 7:50:10, 8:50:10, 9:50:10 or 10:50:10), and preferably 3:50: 10.
According to some preferred embodiments, the electroless plating comprises the sub-steps of:
dispersing the activated high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles into a metal salt solution, and then adding a reducing solution to react to obtain the high-crosslinking-degree organic silicon polymer/metal composite microspheres; the thickness of the metal layer of the high-crosslinking-degree organic silicon polymer/metal composite microsphere is 30-200 nm (for example, 30nm, 40nm, 50nm, 60nm, 80nm, 100nm, 120nm, 150nm, 180nm or 200 nm);
the reaction temperature is 20-100 ℃ (for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃), and the reaction time is 1-12 h (for example, 1h, 3h, 5h, 8h, 9h, 10h or 12 h).
According to some more preferred embodiments, the reaction temperature in the electroless plating is 30 to 85 ℃ (for example, may be 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃ or 85 ℃), and the reaction time is 3 to 5 hours (for example, may be 3 hours, 3.2 hours, 3.6 hours, 3.8 hours, 4 hours, 4.5 hours or 5 hours).
The method comprises the following steps of directly dispersing activated microspheres into a metal salt solution, dropwise adding a reducing solution under mechanical stirring at 20-100 ℃, reacting for 1-12 hours, and filtering to complete surface metal plating; and then repeating the surface plating, and sequentially filtering, washing and drying to obtain the micron-scale high-crosslinking-degree organic silicon polymer/metal composite microspheres. Meanwhile, the thickness of the surface metal layer of the high-crosslinking-degree organic silicon polymer/metal composite microsphere is regulated and controlled through the number of times of metal plating.
According to some preferred embodiments, the electroless plating is performed 2 to 8 times (for example, 2,3,4, 5, 6, 7 or 8 times), preferably 2 to 5 times (for example, 2,3,4 or 5 times), and more preferably 3 times.
It should be noted that the electroless plating also includes the steps of filtering, washing, and drying.
According to some preferred embodiments, the mass ratio of the activated high crosslinking degree silicone polymer microspheres coated with aminated inorganic nanoparticles to the metal salt in the metal salt solution is 1 (1-3) (for example, 1:1, 1:1.5, 1:2, 1:2.5 or 1: 3); wherein the mass fraction of the metal salt in the metal salt solution is 1-10% (for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%);
the metal salt solution comprises one or more of nickel salt, silver salt and gold salt;
the metal salt solution further comprises a complexing agent; wherein the complexing agent is ammonia, ammonium salt or sodium citrate;
the reducing solution is hydrazine hydrate solution, glucose solution, sodium hypophosphite aqueous solution, formaldehyde solution, acetaldehyde solution, sodium borohydride solution, potassium borohydride solution or saturated sodium sulfite solution.
According to some more preferred embodiments, the mass ratio of the activated high crosslinking degree silicone polymer microspheres coated with aminated inorganic nanoparticles to the metal salt in the metal salt solution is 1 (1.2-2) (for example, 1:1.2, 1:1.4, 1:1.5, 1:1.6, 1:1.8, or 1: 2); wherein the metal salt solution contains 3-8% by mass of metal salt (for example, 3%, 4%, 5%, 6%, 7% or 8%).
The nickel salt is one or more of nickel sulfate, nickel chloride, nickel acetate and nickel sulfamate; the silver salt is silver nitrate; the gold salt is gold trichloride. Ammonia in the complexing agent is ammonia gas or ammonia molecules in ammonia water, and the ammonium salt is one or more of ammonium phosphate, ammonium sulfate, ammonium nitrate, ammonium acetate, ammonium carbonate, ammonium sulfonate, ammonium citrate and triammonium citrate; the complexing agent can improve the activity and stability of the plating solution, can stably realize metal plating, and the metal plating layer is uniformly coated.
The invention also provides the high-crosslinking-degree organic silicon polymer/metal composite microsphere which is prepared by the preparation method in any aspect.
The preparation method of the high-crosslinking-degree organic silicon polymer/metal composite microspheres, provided by the invention, comprises the steps of coating the surfaces of various inorganic nano-particles on the surfaces of the high-crosslinking-degree organic silicon polymer microspheres after amination modification, and further coating various metal layers on the surfaces of the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nano-particles; the obtained high-crosslinking-degree organic silicon polymer/metal composite microspheres have good monodispersity, high crosslinking degree, excellent aging resistance and solvent swelling resistance, and meanwhile, the surface metal layer is uniformly coated, the thickness is controllable, the adhesion is firm, and the microspheres are not easy to fall off.
In order to more clearly illustrate the technical solutions and advantages of the present invention, the present invention is further described below with reference to the following embodiments.
Example 1:
(1) amination modification: dispersing 0.5g of gamma-glycidyloxypropyltriethoxysilane into 50g of absolute ethanol under the condition of introducing nitrogen, adding 0.1g of ethylenediamine, reacting at 70 ℃ for 20 hours, and distilling under reduced pressure to obtain an aminosilane coupling agent; dispersing 1g of silicon dioxide with the average particle size of 8nm into 100g of methanol, adding 0.15g of prepared aminosilane coupling agent, reacting for 24 hours at 80 ℃, centrifuging twice, washing with ethanol, and drying to obtain aminated silicon dioxide nanoparticles;
(2) coating: adding 3g of high-crosslinking-degree organic silicon polymer microspheres with the average particle size of 5.8 microns and 0.05g of aminated silicon dioxide nanoparticles obtained in the step (1) into 50g of deionized water, uniformly mixing, dropwise adding dilute hydrochloric acid to adjust the pH value to 4.5, stirring at normal temperature for 60min, filtering, washing with water, and drying to obtain the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles;
(3) and (3) activation: adding the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nano particles obtained in the step (2) into 50g of Pegelai palladium activator PL-5 for activation to obtain microspheres with colloidal palladium adsorbed on the surface, filtering, washing, adding into 10g of 1% sodium hypophosphite aqueous solution, stirring for 10min at the rotating speed of 100r/min at room temperature, and filtering and washing twice to obtain activated microspheres;
(4) plating: dissolving 5g of silver nitrate in 90g of water, dropwise adding 25% ammonia water until the precipitate disappears (to obtain a silver ammonia solution), then adding the activated microspheres obtained in the step (3), stirring at 55 ℃ and 300r/min, dropwise adding 6g of 50% hydrazine hydrate solution while stirring, continuing to react for 60min after dropwise adding is finished, and filtering to finish primary surface chemical plating;
and (3) dispersing the microspheres subjected to chemical plating into the silver ammonia solution again, repeating the chemical plating step for 3 times, and sequentially filtering, washing and drying to obtain the high-crosslinking-degree organic silicon polymer/metal composite microspheres with the surface silver layer thickness of 200nm, wherein a scanning electron microscope image of the composite microspheres is shown in figure 1.
Example 2:
(1) amination modification: dispersing 0.5g of gamma-glycidyloxypropyltrimethoxysilane into 50g of absolute ethyl alcohol under the condition of introducing nitrogen, adding 0.15g of diethylamine, reacting at 65 ℃ for 18h, and distilling under reduced pressure to obtain an aminosilane coupling agent; dispersing 1g of titanium dioxide with the average particle size of 15nm into 100g of methanol, adding 0.1g of prepared aminosilane coupling agent, reacting at 80 ℃ for 30h, centrifuging twice, washing with ethanol, and drying to obtain aminated titanium dioxide nanoparticles;
(2) coating: weighing 3g of high-crosslinking-degree organic silicon polymer microspheres with the average particle size of 8.0 microns and 0.07g of aminated titanium dioxide nanoparticles obtained in the step (1) in 50g of deionized water, uniformly mixing, dropwise adding dilute hydrochloric acid to adjust the pH value to 3.5, stirring at normal temperature for 60min, filtering, washing with water, and drying to obtain the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles;
(3) and (3) activation: adding the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles obtained in the step (2) into 50g of Pegelai palladium activator PL-5 for activation to obtain microspheres with colloidal palladium adsorbed on the surface, filtering, washing, adding into 10g of 1% sodium hypophosphite aqueous solution, stirring for 10min at the rotating speed of 100r/min at room temperature, and filtering and washing twice to obtain activated microspheres;
(4) plating: dissolving 3g of silver nitrate in 90g of water, dropwise adding 25% ammonia water until the precipitate disappears (to obtain a silver ammonia solution), then adding the activated microspheres obtained in the step (3), stirring at the temperature of 50 ℃ and the rotating speed of 300r/min, dropwise adding 30g of 10% glucose solution while stirring, continuing to react for 60min after the dropwise adding is finished, and filtering to complete primary surface chemical plating;
and (3) dispersing the microspheres coated with the chemical plating into the silver ammonia solution again, repeating the chemical plating step for 2 times, and sequentially filtering, washing and drying to obtain the high-crosslinking-degree organic silicon polymer/metal composite microspheres with the surface silver layer thickness of 100nm, wherein a scanning electron microscope image of the composite microspheres is shown in fig. 2.
Example 3:
(1) amination modification: dispersing 0.5g of gamma-glycidyloxypropyl trimethoxy silane into 50g of absolute ethanol under the condition of introducing nitrogen, adding 0.3g of 2,6-2 aminopyridine, reacting at 70 ℃ for 18h, and distilling under reduced pressure to obtain an aminosilane coupling agent; dispersing 1g of titanium dioxide with the average particle size of 8nm into 100g of methanol, adding 0.08g of prepared aminosilane coupling agent, reacting for 24 hours at 80 ℃, centrifuging twice, washing with ethanol, and drying to obtain the aminated titanium dioxide nanoparticles.
(2) Coating: weighing 3g of high-crosslinking-degree organic silicon polymer microspheres with the average particle size of 3.0 microns and 0.1g of aminated titanium dioxide nanoparticles obtained in the step (1), adding into 50g of deionized water, uniformly mixing, dropwise adding dilute hydrochloric acid to adjust the pH value to 5.0, stirring at normal temperature for 60min, filtering, washing with water, and drying to obtain the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles;
(3) and (3) activation: adding the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles obtained in the step (2) into 50g of Pegelai palladium activator PL-5 for activation to obtain microspheres with colloidal palladium adsorbed on the surface, filtering, washing, adding into 10g of 1% sodium hypophosphite aqueous solution, stirring for 10min at the rotating speed of 100r/min at room temperature, and filtering and washing twice to obtain activated microspheres;
(4) plating: 4g of NiCl2·6H2Dissolving 0.4g of sodium citrate in 60g of water, fully dissolving to obtain a mixed solution, then adding the activated microspheres obtained in the step (3), stirring at 70 ℃ and a rotating speed of 300r/min, dropwise adding 10g of 30% sodium hypophosphite aqueous solution while stirring, continuously reacting for 60min after the dropwise adding is finished, and filtering to finish primary surface chemical plating;
and dispersing the microspheres subjected to chemical plating into the mixed solution again, repeating the plating step for 1 time, and sequentially filtering, washing and drying to obtain the high-crosslinking-degree organic silicon polymer/metal composite microspheres with the surface nickel layer thickness of 80 nm.
Example 4:
(1) amination modification: dispersing 0.5g of gamma-glycidyloxypropyltriethoxysilane into 50g of absolute ethanol under the condition of introducing nitrogen, adding 0.15g of diethylamine, reacting at 60 ℃ for 20 hours, and distilling under reduced pressure to obtain an aminosilane coupling agent; dispersing 1g of silicon dioxide with the average particle size of 13nm into 100g of acetone, adding 0.12g of prepared aminosilane coupling agent, reacting for 20 hours at 80 ℃, centrifuging twice, washing with ethanol, and drying to obtain aminated silicon dioxide nanoparticles;
(2) coating: weighing 3g of high-crosslinking-degree organic silicon polymer microspheres with the average particle size of 5.8 microns and 0.15g of aminated silicon dioxide nanoparticles obtained in the step (1) in 50g of deionized water, uniformly mixing, dropwise adding dilute hydrochloric acid to adjust the pH value to 4.0, stirring at normal temperature for 60min, filtering, washing with water, and drying to obtain the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles;
(3) and (3) activation: adding the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles obtained in the step (2) into 50g of Pegelai palladium activator PL-5 for activation to obtain microspheres with colloidal palladium adsorbed on the surface, filtering, washing, adding into 10g of 1% sodium hypophosphite aqueous solution, stirring for 10min at the rotating speed of 100r/min at room temperature, and filtering and washing twice to obtain activated microspheres;
(4) plating: 4g of NiCl2·6H2Dissolving 0.4g of sodium citrate in 60g of water, fully dissolving to obtain a mixed solution, then adding the activated microspheres obtained in the step (3), stirring at 80 ℃ and a rotating speed of 300r/min, dropwise adding 10g of 30% sodium hypophosphite aqueous solution while stirring, continuing to react for 60min after the dropwise adding is finished, and filtering to finish primary surface chemical plating;
and (3) re-dispersing the microspheres subjected to chemical plating into the mixed solution, repeating the plating step for 2 times, and sequentially filtering, washing and drying to obtain the high-crosslinking-degree organic silicon polymer/metal composite microspheres with the surface nickel layer thickness of 120nm, wherein a scanning electron microscope image of the composite microspheres is shown in fig. 3.
Example 5:
example 5 is essentially the same as example 4, except that: in step (4), after one surface chemical plating is completed, the once-plated microspheres are dispersed in 5.5g of AuCl3Dissolving in 90g of water solution, stirring at the rotating speed of 300r/min at the temperature of 35 ℃, dropwise adding saturated sodium sulfite solution while stirring until no gas appears, continuing to react for 60min after dropwise adding, filtering, washing and drying to obtain the high-crosslinking-degree organic silicon polymer/metal composite microspheres with the surface metal layers (nickel layers and gold layers) of 100nm in thickness, wherein a scanning electron microscope image of the composite microspheres is shown in FIG. 4.
Comparative example 1:
weighing 3g of high-crosslinking-degree organic silicon polymer microspheres with the average particle size of 6.0 mu m and 0.1g of 15nm silicon dioxide in 50g of deionized water, uniformly mixing, dropwise adding dilute hydrochloric acid to adjust the pH value to 6.0, stirring at normal temperature for 60min, and filtering and washing with water; adding the washed particles into 50g of a Pegley palladium activator PL-5 for activation, then filtering and washing the microspheres with the surface adsorbing colloidal palladium twice, adding the microspheres into 10g of 1% sodium hypophosphite aqueous solution, stirring for 10min at room temperature at the rotating speed of 100r/min, and filtering and washing twice to obtain activated microspheres; then dissolving 3g of silver nitrate in 90g of water, dropwise adding 25% ammonia water until the precipitate disappears, adding the activated microspheres into the silver-ammonia solution, dropwise adding 30g of 10% glucose solution under stirring at the temperature of 55 ℃ at 300r/min, continuing to react for 60min after the dropwise adding is finished, and finishing surface plating; and re-dispersing the plated microspheres into the solution, repeating the plating step for 1 time, filtering, washing and drying to obtain the composite microspheres with the surface nickel layer thickness of 50nm, as shown in FIG. 5.
Comparative example 2:
weighing 3g of high-crosslinking-degree organic silicon polymer microspheres with the average particle size of 6.3 mu m, washing with water, adding the washed microspheres into 50g of Pegelai palladium activator PL-5 for activation, filtering and washing the microspheres with the surface adsorbed with colloidal palladium for two times, adding the microspheres into 10g of 1% sodium hypophosphite aqueous solution, stirring for 10min at room temperature at 100r/min, and filtering and washing for two times to obtain activated microspheres; then dissolving 5g of silver nitrate in 90g of water, dropwise adding 25% ammonia water until the precipitate disappears, adding the activated microspheres into the silver-ammonia solution, dropwise adding 20g of 20% glucose solution under stirring at the temperature of 55 ℃ at 300r/min, continuing to react for 60min after the dropwise adding is finished, and finishing surface plating; and re-dispersing the plated microspheres into the solution, repeating the plating step for 2 times, and then sequentially filtering, washing and drying to obtain the composite microspheres with the surface silver layer thickness of 100nm, as shown in fig. 6.
By comparing the scanning electron microscope images of the embodiment and the comparative example, it can be known that, compared with the comparative example, the embodiment performs amino modification on the surface of the nano-particles, adsorbs the nano-particles onto the organic silicon polymer microspheres, and then performs chemical plating, so that the metal layer on the surface of the composite microspheres has good dispersibility, more uniform coating, stronger adhesion, difficulty in dropping and more compactness. Comparative example 1 a layer of inorganic nanoparticles is adsorbed on the surface of a high-crosslinking-degree organic silicon polymer microsphere to roughen the surface of the microsphere, and then the microsphere is subjected to chemical plating, so that the surface of the obtained composite microsphere has a uniform metal layer, but the bonding force between the inorganic nanoparticles and the high-crosslinking-degree organic silicon polymer microsphere is weak, the bonding force between the microsphere and the metal layer is weak, and the surface metal particles are easy to fall off; comparative example 2 the metal is directly plated on the surface of the high crosslinking degree organic silicon polymer microsphere, and the metal layer is not firmly adhered on the surface of the microsphere and is easy to drop.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of high-crosslinking-degree organic silicon polymer/metal composite microspheres is characterized by comprising the following steps:
(1) dispersing inorganic nano particles into a polar solvent, and then adding an aminosilane coupling agent for modification to obtain aminated inorganic nano particles;
(2) adding the high-crosslinking-degree organic silicon polymer microspheres and the aminated inorganic nanoparticles into an acidic solution system and uniformly mixing to obtain the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles;
(3) and (3) carrying out activation treatment and chemical plating on the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nano-particles obtained in the step (2) to obtain the high-crosslinking-degree organic silicon polymer/metal composite microspheres.
2. The production method according to claim 1, wherein in step (1):
the modification is carried out in a nitrogen atmosphere, the reaction temperature is 50-100 ℃, and the reaction time is 12-48 h;
preferably, the reaction temperature of the modification is 65-80 ℃, and the reaction time is 24 h; and/or
The mass ratio of the inorganic nanoparticles to the polar solvent to the aminosilane coupling agent is 1:100 (0.01-0.5), and preferably 1:100 (0.05-0.35).
3. The production method according to claim 1, wherein in step (1):
the inorganic nano particles are one or more selected from silicon dioxide, magnesium oxide, ferroferric oxide, titanium dioxide, aluminum oxide, zinc oxide and kaolin; preferably one or more of silicon dioxide, titanium dioxide, aluminum oxide and zinc oxide; more preferably one or more of silicon dioxide and titanium dioxide;
the particle size of the inorganic nano-particles is 5-500 nm, preferably 10-50 nm; and/or
The polar solvent is one or more selected from ethanol, methanol, isopropanol, N-dimethylformamide, acetonitrile, dimethyl sulfoxide, hexamethylphosphoramide, cyclohexanone, acetone, N-butanol, tetrahydrofuran, methyl N-butanone methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; preferably one or more of methanol, ethanol, isopropanol, acetone and acetonitrile; ethanol is more preferred.
4. The production method according to claim 1, characterized in that, in step (1):
the amino silane coupling agent is prepared by the following steps:
dissolving silane containing glycidol in absolute ethyl alcohol, and then adding organic amine containing active hydrogen to react to obtain the aminosilane coupling agent;
the mass ratio of the glycidyl silane to the absolute ethyl alcohol to the organic amine containing active hydrogen is 1:100 (0.1-1); preferably 1:100 (0.2-0.6);
the reaction temperature is 50-100 ℃, and the reaction time is 6-60 h; preferably, the reaction temperature is 60-75 ℃, and the reaction time is 10-20 h.
5. The method of claim 4, wherein:
the chemical formula of the glycidyl silane is (RO)3SiP1Wherein R is an aliphatic alkyl group with 1-30 carbon atoms, preferably methyl or ethyl; p1Is gamma-glycidoxypropyl or glycidoxymethyl;
the organic amine containing active hydrogen is methylamine, ethylenediamine, hexamethylenediamine, isopropylamine, p-phenylenediamine, diethylamine, diphenylamine, methylethylamine, 2-amino-4-methylhexane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, p-aminopyridine, 2,3, 4-triaminopyridine, 3,4, 5-triaminopyridine, 2,3, 6-triaminopyridine, imidazole or 2-phenylimidazole; preferably ethylenediamine, diethylamine or p-aminopyridine; more preferably ethylenediamine.
6. The production method according to claim 1, wherein in step (2):
the mass ratio of the high-crosslinking-degree organic silicon polymer microspheres to the aminated inorganic nanoparticles is (1-100): 1, and preferably (40-80): 1;
the particle size of the high-crosslinking-degree organic silicon polymer microspheres is 1-15 mu m;
the particle size of the aminated inorganic nanoparticles is 5-500 nm, preferably 10-50 nm;
the pH value of the acidic solution system is preferably 2.0-6.5, and more preferably 3.0-5.0.
7. The method of claim 1, wherein:
in step (3), the activation process includes the substeps of:
adding the high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles into a Pegley palladium activator PL-5, washing with water, filtering, adding into a sodium hypophosphite aqueous solution, washing with water, and filtering to complete the activation treatment;
the mass ratio of the aminated inorganic nanoparticle-coated high-crosslinking-degree organosilicon polymer microsphere to the Pegley palladium activator PL-5 to the sodium hypophosphite aqueous solution is (1-10): 50:10, preferably 3:50: 10.
8. The production method according to claim 1, wherein in step (3):
the electroless plating includes the substeps of:
dispersing the activated high-crosslinking-degree organic silicon polymer microspheres coated with aminated inorganic nano-particles into a metal salt solution, and then adding a reducing solution for reaction to obtain the high-crosslinking-degree organic silicon polymer/metal composite microspheres; wherein the thickness of the metal layer of the high-crosslinking-degree organic silicon polymer/metal composite microsphere is 30-200 nm;
the reaction temperature is 20-100 ℃, and the reaction time is 1-12 h; preferably, the reaction temperature is 30-85 ℃, and the reaction time is 3-5 h; and/or
The number of times of the electroless plating is 2 to 8 times, preferably 2 to 5 times, and more preferably 3 times.
9. The method of claim 8, wherein:
the mass ratio of the activated high-crosslinking-degree organic silicon polymer microspheres coated with the aminated inorganic nanoparticles to the metal salt in the metal salt solution is 1 (1-3), and preferably 1 (1.2-2); wherein the mass fraction of the metal salt in the metal salt solution is 1-10%, preferably 3-8%;
the metal salt solution comprises one or more of nickel salt, silver salt and gold salt;
the metal salt solution further comprises a complexing agent; wherein the complexing agent is ammonia, ammonium salt or sodium citrate;
the reducing solution is hydrazine hydrate solution, glucose solution, sodium hypophosphite aqueous solution, formaldehyde solution, acetaldehyde solution, sodium borohydride solution, potassium borohydride solution or saturated sodium sulfite solution.
10. An organosilicon polymer/metal composite microsphere with high crosslinking degree, which is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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| CN116903990A (en) * | 2023-08-31 | 2023-10-20 | 江苏汉光实业股份有限公司 | Modified ABS composite plastic particle and preparation method thereof |
| CN116903990B (en) * | 2023-08-31 | 2024-01-30 | 江苏汉光实业股份有限公司 | Modified ABS composite plastic particle and preparation method thereof |
| CN117327474A (en) * | 2023-09-27 | 2024-01-02 | 大庆永铸石油技术开发有限公司 | High-temperature-resistant dual-nano-inlay collapse-prevention drilling fluid |
| CN117327474B (en) * | 2023-09-27 | 2024-04-23 | 大庆永铸石油技术开发有限公司 | High-temperature-resistant dual-nano-inlay collapse-prevention drilling fluid |
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