CN114523105B - High-crosslinking-degree organosilicon polymer/metal composite microsphere and preparation method thereof - Google Patents
High-crosslinking-degree organosilicon polymer/metal composite microsphere and preparation method thereof Download PDFInfo
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- CN114523105B CN114523105B CN202111682811.0A CN202111682811A CN114523105B CN 114523105 B CN114523105 B CN 114523105B CN 202111682811 A CN202111682811 A CN 202111682811A CN 114523105 B CN114523105 B CN 114523105B
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- crosslinking
- organosilicon polymer
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- microsphere
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- 239000004005 microsphere Substances 0.000 title claims abstract description 194
- 229920001558 organosilicon polymer Polymers 0.000 title claims abstract description 114
- 239000002905 metal composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 104
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- 239000002184 metal Substances 0.000 claims abstract description 67
- 238000005576 amination reaction Methods 0.000 claims abstract description 43
- 238000007747 plating Methods 0.000 claims abstract description 43
- 239000000126 substance Substances 0.000 claims abstract description 29
- 238000004132 cross linking Methods 0.000 claims abstract description 28
- 239000007822 coupling agent Substances 0.000 claims abstract description 23
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000004913 activation Effects 0.000 claims abstract description 21
- 238000012986 modification Methods 0.000 claims abstract description 15
- 230000004048 modification Effects 0.000 claims abstract description 15
- 239000002798 polar solvent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003929 acidic solution Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 43
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 40
- 238000001914 filtration Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000012266 salt solution Substances 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 229910052763 palladium Inorganic materials 0.000 claims description 20
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012190 activator Substances 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 11
- SHHGHQXPESZCQA-UHFFFAOYSA-N oxiran-2-ylmethylsilicon Chemical compound [Si]CC1CO1 SHHGHQXPESZCQA-UHFFFAOYSA-N 0.000 claims description 11
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 10
- 238000007772 electroless plating Methods 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 8
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 claims description 6
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 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
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 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 5
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 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
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 239000008098 formaldehyde solution Substances 0.000 claims description 3
- -1 glycidoxymethyl Chemical group 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- YAHRDLICUYEDAU-UHFFFAOYSA-N methylhexaneamine Chemical compound CCC(C)CC(C)N YAHRDLICUYEDAU-UHFFFAOYSA-N 0.000 claims description 3
- 229950000752 methylhexaneamine Drugs 0.000 claims description 3
- 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
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- APXBXAJWVZTKSE-UHFFFAOYSA-N pyridine-2,3,4-triamine Chemical compound NC1=CC=NC(N)=C1N APXBXAJWVZTKSE-UHFFFAOYSA-N 0.000 claims description 3
- IRNVCLJBFOZEPK-UHFFFAOYSA-N pyridine-2,3,6-triamine Chemical compound NC1=CC=C(N)C(N)=N1 IRNVCLJBFOZEPK-UHFFFAOYSA-N 0.000 claims description 3
- UIQHHOMREHEPJX-UHFFFAOYSA-N pyridine-3,4,5-triamine Chemical compound NC1=CN=CC(N)=C1N UIQHHOMREHEPJX-UHFFFAOYSA-N 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
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- 239000003377 acid catalyst Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
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- 238000006068 polycondensation reaction Methods 0.000 claims description 2
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- 239000004094 surface-active agent Substances 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 9
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
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- 238000001000 micrograph Methods 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 8
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
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- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
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- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
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- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
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- 235000011130 ammonium sulphate Nutrition 0.000 description 1
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- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 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
- 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
- 239000000203 mixture Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000001393 triammonium citrate Substances 0.000 description 1
- 235000011046 triammonium citrate Nutrition 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
The invention provides a preparation method of a high-crosslinking-degree organosilicon polymer/metal composite microsphere, 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 organosilicon polymer microspheres and the amino inorganic nanoparticles into an acidic solution system, and uniformly mixing to obtain the high-crosslinking-degree organosilicon polymer microspheres coated with the amino inorganic nanoparticles; (3) And (3) carrying out activation treatment and chemical plating on the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nanoparticle obtained in the step (2) to obtain the high-crosslinking-degree organosilicon polymer/metal composite microsphere. The high-crosslinking-degree organosilicon 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 coating of a metal layer, firm adhesion and difficult falling.
Description
Technical Field
The invention relates to the technical field of functional microspheres, in particular to a high-crosslinking-degree organosilicon polymer/metal composite microsphere and a preparation method thereof.
Background
The resin core conductive microsphere is formed by taking the resin microsphere as a base material and plating a conductive metal material. The conductive microsphere has good conductive performance by compounding the high polymer microsphere and the metal, greatly reduces the metal consumption, has the advantages of metal materials and high polymer resin microsphere, and is widely applied to the technical field of 3C.
In the preparation process of the traditional resin core conductive microsphere, the resin microsphere needs to be subjected to multiple steps of degreasing, coarsening, sensitization, activation, chemical plating and the like, and the preparation process is complicated. Patent application number CN202011488043.0 discloses roughening polystyrene microsphere by using roughening solution (mixture of chromium trioxide and concentrated sulfuric acid) to improve adhesion capability of PS microsphere surface, but this method has serious environmental pollution; patent application numbers CN201210154648.5 and CN201110162698.3 both disclose that metal ions are directly adsorbed on the surfaces of polymer microspheres and gold-plated particles are prepared by chemical deposition, so that the thickness of a plating layer of the prepared conductive particles is limited, the cost is high, and the used polymer microspheres are non-high-crosslinking polymer microspheres, so that the prepared conductive microspheres have the defect of intolerance to solvent swelling. Therefore, there is an urgent need to prepare a resin core conductive composite microsphere with good monodispersity, high crosslinking degree, stable chemical properties, corrosion resistance, high temperature resistance, and excellent anti-aging and anti-solvent swelling properties.
Disclosure of Invention
The embodiment of the invention provides a high-crosslinking-degree organosilicon polymer/metal composite microsphere and a preparation method thereof, which can provide 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.
In a first aspect, the present invention provides a method for preparing a high crosslinking degree silicone polymer/metal composite microsphere, the method comprising the steps of:
(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 organosilicon polymer microspheres and the amination inorganic nanoparticles into an acidic solution system, and uniformly mixing to obtain the high-crosslinking-degree organosilicon polymer microspheres coated with the amination inorganic nanoparticles;
(3) And (3) carrying out activation treatment and chemical plating on the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nanoparticle obtained in the step (2) to obtain the high-crosslinking-degree organosilicon polymer/metal composite microsphere.
Preferably, in the step (1), the modification is performed in a nitrogen atmosphere, the reaction temperature is 50-100 ℃, and the reaction time is 12-48 hours; preferably, the modification reaction temperature is 65-80 ℃ and the reaction time is 24 hours.
Preferably, the mass ratio of the inorganic nano particles, the polar solvent and the aminosilane coupling agent is 1:100 (0.01-0.5); preferably 1:100, (0.05-0.35).
Preferably, in step (1), the inorganic nanoparticles are one or more selected from silica, magnesia, ferroferric oxide, titania, alumina, zinc oxide, kaolin; preferably one or more of silica, titania, alumina, zinc oxide; more preferably one or more of silica and titania.
The particle size of the inorganic nanoparticles is 5 to 500nm, preferably 10 to 50nm.
Preferably, in step (1), the polar solvent is one or more selected from ethanol, methanol, isopropanol, N-dimethylformamide, acetonitrile, dimethylsulfoxide, 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, acetonitrile. More preferably ethanol.
Preferably, in step (1), the aminosilane coupling agent is prepared by the steps of:
Dissolving glycidyl silane 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, the anhydrous alcohol and the active hydrogen-containing organic amine is 1:100 (0.1-1); preferably 1:100, (0.2-0.6);
preferably, in the step (1), the reaction temperature of the reaction 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 silane containing compound has the chemical formula (RO) 3 SiP 1 Wherein R is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably a methyl group or an ethyl group; p (P) 1 Is gamma-glycidoxypropyl or glycidoxymethyl;
preferably, 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, para-aminopyridine, 2,3, 4-triaminopyridine, 3,4, 5-triaminopyridine, 2,3, 6-triaminopyridine, imidazole, or 2-phenylimidazole; preferably ethylenediamine, diethylamine or para-aminopyridine; more preferably ethylenediamine.
Preferably, in step (2), the mass ratio of the high crosslinking degree silicone polymer microspheres to the aminated inorganic nanoparticles is (1 to 100): 1, preferably (40 to 80): 1;
preferably, in the step (2), the particle size of the high-crosslinking-degree silicone polymer microsphere is 1-15 μm;
the particle size of the amination inorganic nano particles is 5-500 nm, preferably 10-50 nm;
preferably, in step (2), the pH of the acidic solution system is preferably 2.0 to 6.5, more preferably 3.0 to 5.0.
Preferably, in step (3), the activation treatment comprises the following sub-steps:
adding the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nano particles into a Bigley palladium activator PL-5, then adding the water into a sodium hypophosphite aqueous solution after washing and filtering, and then washing and filtering to finish the activation treatment;
the mass ratio of the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nano particles, the Biglepalladium activator PL-5 and the sodium hypophosphite aqueous solution is (1-10): 50:10, preferably 3:50:10.
Preferably, in step (3), the electroless plating comprises the following sub-steps:
dispersing the activated high-crosslinking-degree organosilicon polymer microspheres coated with the amination inorganic nanoparticles into a metal salt solution, and then adding a reducing solution for reaction to obtain the high-crosslinking-degree organosilicon polymer/metal composite microspheres; wherein, the thickness of the metal layer of the high crosslinking degree organosilicon polymer/metal composite microsphere is 30-200 nm;
Preferably, in the step (3), the reaction temperature of the reaction 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 step (3), the number of electroless plating is 2 to 8, preferably 2 to 5, more preferably 3.
Preferably, in the step (3), the mass ratio of the activated high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nano particles 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%, preferably 3-8%;
more preferably, in the step (3), the mass ratio of the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nanoparticle after the activation treatment 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 prepared by the preparation method in any one of the first aspects.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The invention provides a preparation method of a high-crosslinking-degree organosilicon polymer/metal composite microsphere, which comprises the steps of modifying inorganic nano particles to obtain amino inorganic nano particles, adsorbing the amino inorganic nano particles on the surface of the micron-level high-crosslinking-degree organosilicon polymer microsphere through electrostatic action, and finally plating a uniform metal layer on the surface of the microsphere through chemical plating to obtain the high-crosslinking-degree organosilicon 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 organosilicon polymer microsphere through electrostatic action, so that roughening treatment on the surface of the high-crosslinking-degree organosilicon polymer microsphere is realized, a large amount of amino groups are carried on the surface of the microsphere, and a metal layer coated on the surface of the microsphere is more compact and firmly attached; the thickness of the metal layer is controllable by controlling the metal plating times on the surface of the microsphere; meanwhile, the surface of various inorganic nano particles can be subjected to amination modification and then coated on the surface of the high-crosslinking-degree organosilicon polymer microsphere, and then the plating requirements of different metal layers can be met.
(3) The high-crosslinking-degree organosilicon polymer microsphere in the preparation method provided by the invention has the advantages of good monodispersity, swelling resistance, aging resistance and corrosion resistance; and the roughening treatment method does not need chromic anhydride, concentrated sulfuric acid or hydrofluoric acid, and is environment-friendly compared with the traditional roughening method.
(4) The invention provides the high-crosslinking-degree organosilicon polymer/metal composite microsphere 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 coating of a metal layer, 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 that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
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 present invention.
FIG. 3 is a scanning electron microscope image of the high crosslinking degree organosilicon polymer/nickel composite microsphere prepared in example 4 of the present invention.
FIG. 4 is a scanning electron microscope image of the high crosslinking degree organosilicon polymer/metal composite microsphere prepared in example 5 of the present invention.
FIG. 5 is a scanning electron microscope image of the high crosslinking degree organosilicon polymer/silver composite microsphere prepared in comparative example 1 of the present invention.
FIG. 6 is a scanning electron microscope image of the high crosslinking degree silicone polymer/silver composite microsphere prepared in comparative example 2 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
The invention provides a preparation method of a high-crosslinking-degree organosilicon polymer/metal composite microsphere, 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 organosilicon polymer microspheres and the amination inorganic nanoparticles into an acidic solution system, and uniformly mixing to obtain the high-crosslinking-degree organosilicon polymer microspheres coated with the amination inorganic nanoparticles;
(3) And (3) carrying out activation treatment and chemical plating on the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nanoparticle obtained in the step (2) to obtain the high-crosslinking-degree organosilicon polymer/metal composite microsphere.
The preparation method of the high-crosslinking-degree organosilicon polymer microsphere is referred to in patent application No. CN 202110292742.6. The high-crosslinking-degree organosilicon polymer microsphere has excellent semi-inorganic and semi-organic properties, including stable chemical properties, no toxicity, environmental friendliness, solvent swelling resistance, corrosion resistance, high temperature resistance, aging resistance and the like, and is widely applied to the fields of light scattering materials, catalyst carriers, plastics, rubber, coatings, adsorption materials, ceramic materials, biological medicines and the like.
Specifically, the preparation method of the high-crosslinking-degree organosilicon 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 (3) dropwise adding an alkaline catalyst into the reaction system containing the prepolymer obtained in the step (i) to perform an alkaline catalytic polycondensation reaction to obtain the micron-sized organosilicon microsphere with high crosslinking degree (namely the organosilicon polymer microsphere with high crosslinking degree). The high-crosslinking-degree organosilicon polymer microsphere has narrow sphere diameter distribution and good sphericity, can still maintain higher monodispersity within the range of 1-15 mu m, and can effectively solve the problem of wide microsphere diameter distribution.
According to the preparation method, firstly, an amino modified inorganic nanoparticle is prepared, the pH of a solution system is regulated to be acidic, so that the surface of the inorganic nanoparticle is positively charged, then the nanoparticle is adsorbed on the surface of a negatively charged high-crosslinking-degree organosilicon polymer microsphere through electrostatic interaction, the high-crosslinking-degree organosilicon polymer microsphere (namely, a modified high-crosslinking-degree organosilicon polymer microsphere) coated with the amino modified inorganic nanoparticle is obtained, and finally, a uniform metal layer is plated on the surface of the modified high-crosslinking-degree organosilicon polymer microsphere through electroless plating, so that the high-crosslinking-degree organosilicon polymer/metal composite microsphere is obtained.
The high-crosslinking-degree organosilicon polymer/metal composite microsphere prepared by the method 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 coating of a metal layer, firm adhesion and difficult falling.
According to some preferred embodiments, in step (1), the modification is carried out with a nitrogen atmosphere at a reaction temperature of 50-100 ℃ (e.g. may be 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃) for a reaction time of 12-48 hours (e.g. may be 12 hours, 18 hours, 24 hours, 30 hours, 35 hours, 40 hours or 48 hours); the modification reaction temperature is preferably 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 step (1), the mass ratio of the inorganic nanoparticles, the polar solvent, and the aminosilane coupling agent is 1:100 (0.01 to 0.5) (e.g., 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 step (1), the mass ratio of the inorganic nanoparticles, the polar solvent, and the aminosilane coupling agent is 1:100 (0.05-0.35) (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, titania, alumina, zinc oxide, kaolin; preferably one or more of silica, titania, alumina, zinc oxide; more preferably one or more of silica and titania.
According to some preferred embodiments, the particle size of the inorganic nanoparticles is 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 particle size of the inorganic nanoparticles is 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, dimethylsulfoxide, 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; more preferably ethanol.
According to some preferred embodiments, in step (1), the aminosilane coupling agent is prepared by:
dissolving glycidyl silane in absolute ethyl alcohol, and then adding organic amine containing active hydrogen to react to obtain the aminosilane coupling agent;
the organic amine containing active hydrogen is added under a nitrogen atmosphere.
According to some preferred embodiments, in step (1), the mass ratio of the glycidyl silane, the anhydrous alcohol, and the active hydrogen-containing organic amine is 1:100 (0.1-1) (e.g., 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 step (1), the mass ratio of the glycidyl silane, the anhydrous alcohol, and the active hydrogen containing organic amine is 1:100 (0.2-0.6) (e.g., 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 step (1), the reaction temperature of the reaction is 50-100 ℃ (e.g., may be 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃), and the reaction time is 6-60 hours (e.g., may be 6 hours, 15 hours, 25 hours, 35 hours, 45 hours, 55 hours or 60 hours).
According to some more preferred embodiments, in step (1), the reaction temperature of the reaction is 60 to 75 ℃ (e.g., may be 60 ℃, 64 ℃, 68 ℃, 70 ℃, 72 ℃, or 75 ℃), and the reaction time is 10 to 20 hours (e.g., may be 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, or 20 hours). Too low a temperature does not react or reacts too slowly; the temperature is too high, which is unfavorable for the stable reaction.
According to some preferred embodiments, in step (1), the glycidyl silane-containing compound has the general chemical formula (RO) 3 SiP 1 Wherein R is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably a methyl group or an ethyl group; p1 is gamma-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, para-aminopyridine, 2,3, 4-triaminopyridine, 3,4, 5-triaminopyridine, 2,3, 6-triaminopyridine, imidazole, or 2-phenylimidazole; preferably ethylenediamine, diethylamine or para-aminopyridine; more preferably ethylenediamine.
According to some preferred embodiments, in step (2), the mass ratio of the high degree of crosslinking silicone polymer microspheres and the aminated inorganic nanoparticles is (1-100): 1 (e.g., 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 step (2), the mass ratio of the high degree of crosslinking silicone polymer microspheres and the aminated inorganic nanoparticles is (40 to 80): 1 (e.g., may be 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, or 80:1);
According to some preferred embodiments, in step (2), the particle size of the aminated inorganic nanoparticle is 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, in step (2), the particle size of the aminated inorganic nanoparticles is 10-50 nm; (e.g., 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, or 50 nm).
According to some preferred embodiments, in step (2), the high degree of crosslinking silicone polymer microspheres have a particle size of 1 to 15 μm (e.g., may be 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 between 2.0 and 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 between 3.0 and 5.0 (e.g., may be 3.0, 3.2, 3.5, 3.8, 4.0, 4.5, 4.8 or 5.0).
The pH of the acidic solution system in step (2) was <7.
In the step (2), after dispersing the high-crosslinking-degree organosilicon polymer microspheres and the amination inorganic nanoparticles into deionized water and uniformly mixing, adjusting the pH to be less than 7 by adding hydrochloric acid, stirring for 60min at normal temperature, washing with water, filtering, and drying to obtain the high-crosslinking-degree organosilicon polymer microspheres coated with the amination inorganic nanoparticles; the pH value in the process is controlled in the range, so that the aminated inorganic nano particles can be positively charged, and the subsequent adsorption on the surface of the high-crosslinking-degree organosilicon polymer microsphere through electrostatic action is facilitated.
In the invention, experiments prove that when the mass ratio of the high-crosslinking-degree organosilicon polymer microsphere to the amino inorganic nano-particles is less than 1:1, the amino groups on the surface of the microsphere are less due to the less amino inorganic nano-particles, the roughness of the surface of the high-crosslinking-degree organosilicon polymer microsphere cannot be ensured, and the adhesive force between the metal layer and the surface of the microsphere can be further weakened; when the mass ratio of the high-crosslinking-degree organosilicon polymer microsphere to the aminated inorganic nanoparticle is more than 100:1, the aminated inorganic nanoparticle is loose on the surface of the high-crosslinking-degree organosilicon polymer microsphere, the bonding is not tight, and the bonding force between the metal layer and the microsphere surface can be weakened. Similarly, when the particle size of the aminated inorganic nano particles is smaller than 5nm, the particle size of the aminated inorganic nano particles is too small, the surface roughness of the high-crosslinking-degree organosilicon polymer microsphere is poor, and the metal layer cannot be tightly coated on the surface of the microsphere in the plating process; when the particle size of the amination inorganic nano particles is larger than 500nm, the amination inorganic nano particles cannot be tightly coated on the surface of the high-crosslinking-degree organosilicon polymer microsphere under the action of static electricity, so that the adhesion force of the metal layer on the surface of the microsphere is weakened, and the metal layer on the surface of the microsphere is easy to drop.
According to some preferred embodiments, in step (3), the activation treatment comprises the following sub-steps:
and adding the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nano particles into a Bigley palladium activator PL-5, then adding the water into a sodium hypophosphite aqueous solution after washing and filtering, and then washing and filtering to finish the activation treatment.
More specifically, in the step (3), the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nano-particles is added into a Bigley palladium activator PL-5 for adsorption activation, the microsphere with colloid palladium adsorbed on the surface is obtained, and after water washing and filtration, a sodium hypophosphite aqueous solution with the mass ratio of 1% is added, stirring is carried out for 10min at room temperature (for example, 25 ℃), and then the activation treatment is carried out by water washing and filtration, thus obtaining the activated microsphere.
According to some preferred embodiments, the ratio of the mass of the high crosslinking degree silicone polymer microsphere coated with the aminated inorganic nanoparticle, the specific glair palladium activator PL-5 and the aqueous sodium hypophosphite solution is (1 to 10): 50:10 (for example, may be 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), preferably 3:50:10).
According to some preferred embodiments, the electroless plating comprises the following sub-steps:
dispersing the activated high-crosslinking-degree organosilicon polymer microspheres coated with the amination inorganic nanoparticles into a metal salt solution, and then adding a reducing solution for reaction to obtain the high-crosslinking-degree organosilicon polymer/metal composite microspheres; wherein the thickness of the metal layer of the high crosslinking degree organosilicon 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 of the reaction is 20 to 100 ℃ (for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃), and the reaction time is 1 to 12 hours (for example, 1 hour, 3 hours, 5 hours, 8 hours, 9 hours, 10 hours or 12 hours).
According to some more preferred embodiments, the reaction temperature in the electroless plating is 30 to 85 ℃ (e.g., may be 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, or 85 ℃) and the reaction time is 3 to 5 hours (e.g., may be 3 hours, 3.2 hours, 3.6 hours, 3.8 hours, 4 hours, 4.5 hours, or 5 hours).
The activated microspheres are directly dispersed into a metal salt solution, a reducing solution is dripped under mechanical stirring at 20-100 ℃, and after the reaction is carried out for 1-12 hours, the solution is filtered to finish the surface metal plating; and then repeating the surface plating, and sequentially filtering, washing and drying to obtain the micron-sized high-crosslinking-degree organosilicon polymer/metal composite microsphere. Meanwhile, the thickness of the surface metal layer of the high-crosslinking-degree organosilicon polymer/metal composite microsphere is regulated and controlled by the times of metal plating.
According to some preferred embodiments, the electroless plating is performed 2 to 8 times (e.g., 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, or 8 times), preferably 2 to 5 times (e.g., 2 times, 3 times, 4 times, or 5 times), and more preferably 3 times.
The electroless plating process further comprises the steps of filtering, washing and drying.
According to some preferred embodiments, the mass ratio of the high crosslinking degree organosilicon polymer microsphere coated with the amination inorganic nanoparticle after the activation treatment 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 high crosslinking degree silicone polymer microsphere coated with the aminated inorganic nanoparticle after the activation treatment to the metal salt in the metal salt solution is 1 (1.2-2) (for example, may be 1:1.2, 1:1.4, 1:1.5, 1:1.6, 1:1.8 or 1:2); wherein the mass fraction of the metal salt in the metal salt solution is 3-8% (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. The 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; wherein, the complexing agent can improve the activity and stability of the plating solution, can stably realize metal plating, and the metal plating is uniformly coated.
The invention also provides the high-crosslinking-degree organosilicon polymer/metal composite microsphere which is prepared by adopting the preparation method in any aspect.
According to the preparation method of the high-crosslinking-degree organosilicon polymer/metal composite microsphere, the surfaces of various inorganic nano-particles are subjected to amination modification and then coated on the surfaces of the high-crosslinking-degree organosilicon polymer microsphere, so that various metal layers are plated on the surfaces of the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nano-particles; the obtained high-crosslinking-degree organosilicon polymer/metal composite microsphere has the advantages of good monodispersity, high crosslinking degree, excellent ageing resistance and solvent swelling resistance, uniform coating of a surface metal layer, controllable thickness, firm adhesion and difficult falling.
In order to more clearly illustrate the technical scheme and advantages of the present invention, the present invention will be further described below with reference to examples.
Example 1:
(1) And (3) amination modification: dispersing 0.5g of gamma-glycidoxypropyl triethoxysilane into 50g of absolute ethyl alcohol under the condition of introducing nitrogen, adding 0.1g of ethylenediamine, reacting for 20 hours at 70 ℃, 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 at 80 ℃ for 24 hours, and washing and drying by centrifugation-ethanol twice to obtain aminated silicon dioxide nano particles;
(2) Coating: adding 3g of high-crosslinking-degree organosilicon polymer microspheres with an average particle size of 5.8 mu m and 0.05g of the aminated silicon dioxide nanoparticles obtained in the step (1) into 50g of deionized water, uniformly mixing, then dropwise adding dilute hydrochloric acid to adjust the pH=4.5, stirring for 60min at normal temperature, filtering, washing with water, and drying to obtain the high-crosslinking-degree organosilicon polymer microspheres coated with the aminated inorganic nanoparticles;
(3) Activating: adding the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nano particles obtained in the step (2) into 50g of a Biglai palladium activator PL-5 for activation to obtain microsphere with colloidal palladium adsorbed on the surface, filtering, washing with water, adding into 10g of 1% sodium hypophosphite aqueous solution, stirring at room temperature for 10min at a rotating speed of 100r/min, and filtering and washing with water twice to obtain activated microsphere;
(4) Plating: dissolving 5g of silver nitrate in 90g of water, dropwise adding 25% ammonia water until precipitation disappears (silver ammonia solution is obtained), then adding the activated microsphere obtained in the step (3), stirring at a rotating speed of 55 ℃ and 300r/min, dropwise adding 6g of 50% hydrazine hydrate solution while stirring, continuing to react for 60min after the dropwise adding is finished, and filtering to finish primary surface chemical plating;
and re-dispersing the microspheres subjected to chemical plating into the silver ammonia solution, repeating the chemical plating step for 3 times, and sequentially filtering, washing and drying to obtain the high-crosslinking-degree organosilicon 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) And (3) amination modification: dispersing 0.5g of gamma-glycidoxypropyl trimethoxy silane into 50g of absolute ethyl alcohol under the condition of introducing nitrogen, adding 0.15g of diethylamine, reacting for 18 hours at 65 ℃, 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 for 30 hours at 80 ℃, and then washing and drying by centrifugation-ethanol twice to obtain aminated titanium dioxide nano particles;
(2) Coating: weighing 3g of high-crosslinking-degree organosilicon polymer microspheres with the average particle diameter of 8.0 mu m and 0.07g of the aminated titanium dioxide nanoparticles obtained in the step (1) into 50g of deionized water, uniformly mixing, dripping dilute hydrochloric acid to adjust the pH value to be 3.5, stirring for 60min at normal temperature, filtering, washing with water, and drying to obtain the high-crosslinking-degree organosilicon polymer microspheres coated with the aminated inorganic nanoparticles;
(3) Activating: adding the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nano particles obtained in the step (2) into 50g of a Biglai palladium activator PL-5 for activation to obtain microsphere with colloidal palladium adsorbed on the surface, filtering, washing with water, adding into 10g of 1% sodium hypophosphite aqueous solution, stirring at room temperature for 10min at a rotating speed of 100r/min, and filtering and washing with water twice to obtain activated microsphere;
(4) Plating: dissolving 3g of silver nitrate in 90g of water, dropwise adding 25% ammonia water until precipitation disappears (silver ammonia solution is obtained), then adding the activated microsphere obtained in the step (3), stirring at 50 ℃ and a 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 finish primary surface chemical plating;
and re-dispersing the microspheres subjected to chemical plating into the silver ammonia solution, repeating the chemical plating step for 2 times, and sequentially filtering, washing and drying to obtain the high-crosslinking-degree organosilicon 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 figure 2.
Example 3:
(1) And (3) amination modification: dispersing 0.5g of gamma-glycidoxypropyl trimethoxy silane into 50g of absolute ethyl alcohol under the condition of introducing nitrogen, adding 0.3g of 2,6-2 aminopyridine, reacting at 70 ℃ for 18 hours, and then 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 the prepared aminosilane coupling agent, reacting for 24 hours at 80 ℃, and then washing and drying by centrifugation-ethanol twice to obtain the aminated titanium dioxide nano-particles.
(2) Coating: weighing 3g of high-crosslinking-degree organosilicon polymer microspheres with the average particle diameter of 3.0 mu m and 0.1g of the 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 be=5.0, stirring for 60min at normal temperature, filtering, washing with water, and drying to obtain the high-crosslinking-degree organosilicon polymer microspheres coated with the aminated inorganic nanoparticles;
(3) Activating: adding the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nano particles obtained in the step (2) into 50g of a Biglai palladium activator PL-5 for activation to obtain microsphere with colloidal palladium adsorbed on the surface, filtering, washing with water, adding into 10g of 1% sodium hypophosphite aqueous solution, stirring at room temperature for 10min at a rotating speed of 100r/min, and filtering and washing with water twice to obtain activated microsphere;
(4) Plating: 4g NiCl 2 ·6H 2 Dissolving 0.4g of sodium citrate in 60g of water, fully dissolving to obtain a mixed solution, adding the activated microsphere obtained in the step (3), stirring at the temperature of 70 ℃ and the 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 re-dispersing the microspheres subjected to chemical plating into the mixed solution, repeating the plating step for 1 time, and sequentially filtering, washing and drying to obtain the high-crosslinking-degree organosilicon polymer/metal composite microspheres with the surface nickel layer thickness of 80 nm.
Example 4:
(1) And (3) amination modification: dispersing 0.5g of gamma-glycidoxypropyl triethoxysilane into 50g of absolute ethyl alcohol under the condition of introducing nitrogen, adding 0.15g of diethylamine, reacting for 20 hours at 60 ℃, 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 ℃, and performing centrifugation-ethanol washing and drying twice to obtain aminated silicon dioxide nano particles;
(2) Coating: weighing 3g of high-crosslinking-degree organosilicon polymer microspheres with an average particle size of 5.8 mu m and 0.15g of the aminated silicon dioxide nanoparticles obtained in the step (1) in 50g of deionized water, uniformly mixing, dripping dilute hydrochloric acid to adjust the pH value to be 4.0, stirring for 60min at normal temperature, filtering, washing with water, and drying to obtain the high-crosslinking-degree organosilicon polymer microspheres coated with the aminated inorganic nanoparticles;
(3) Activating: adding the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nano particles obtained in the step (2) into 50g of a Biglai palladium activator PL-5 for activation to obtain microsphere with colloidal palladium adsorbed on the surface, filtering, washing with water, adding into 10g of 1% sodium hypophosphite aqueous solution, stirring at room temperature for 10min at a rotating speed of 100r/min, and filtering and washing with water twice to obtain activated microsphere;
(4) Plating: 4g NiCl 2 ·6H 2 Dissolving 0.4g of sodium citrate in 60g of water, fully dissolving to obtain a mixed solution, adding the activated microsphere obtained in the step (3), stirring at the temperature of 80 ℃ and the 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 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 organosilicon 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 figure 3.
Example 5:
example 5 is substantially the same as example 4 except that: in the step (4), after the primary surface chemical plating is completed, the microspheres plated once are dispersed to 5.5g AuCl 3 Dissolving in 90g of aqueous solution, stirring at a speed of 300r/min at 35 ℃, dropwise adding saturated sodium sulfite solution while stirring until no gas appears, filtering, washing and drying after the dropwise adding is finished and the reaction is continued for 60min, so as to obtain the high-crosslinking-degree organosilicon polymer/metal composite microsphere with a surface metal layer (nickel layer and gold layer) thickness of 100nm, wherein a scanning electron microscope diagram of the composite microsphere is shown in figure 4.
Comparative example 1:
weighing 3g of high-crosslinking-degree organosilicon polymer microspheres with an average particle size of 6.0 mu m and 0.1g of 15nm silicon dioxide in 50g of deionized water, uniformly mixing, dripping dilute hydrochloric acid to adjust the pH value to be 6.0, stirring at normal temperature for 60min, and filtering and washing; adding the washed particles into 50g of Biglai palladium activator PL-5 for activation, then adding 10g of 1% sodium hypophosphite aqueous solution after twice filtration and water washing to obtain microspheres with colloidal palladium adsorbed on the surfaces, stirring for 10min at the room temperature at the rotating speed of 100r/min, and obtaining activated microspheres after twice filtration and water washing; then 3g of silver nitrate is dissolved in 90g of water, 25% ammonia water is dripped until precipitation disappears, activated microspheres are added into the silver ammonia solution, 30g of 10% glucose solution is dripped under the stirring of 300r/min at 55 ℃, and the reaction is continued for 60min after the dripping is finished, so that the surface plating is completed; 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 figure 5.
Comparative example 2:
weighing 3g of high-crosslinking-degree organosilicon polymer microspheres with an average particle size of 6.3 mu m, washing with water, adding the microspheres into 50g of Biglai palladium activator PL-5 for activation, then adding 10g of 1% sodium hypophosphite aqueous solution after twice filtration and washing with water to obtain microspheres with colloidal palladium adsorbed on the surfaces, stirring for 10min at room temperature of 100r/min, and obtaining activated microspheres after twice filtration and washing with water; then 5g of silver nitrate is dissolved in 90g of water, 25% ammonia water is dripped until precipitation disappears, activated microspheres are added into the silver ammonia solution, 20g of 20% glucose solution is dripped under the stirring of 300r/min at 55 ℃, and the reaction is continued for 60min after the dripping is finished, so that the surface plating is completed; and re-dispersing the plated microspheres into the solution, repeating the plating step for 2 times, and sequentially filtering, washing and drying to obtain the composite microspheres with the surface silver layer thickness of 100nm, as shown in figure 6.
As can be seen from the scanning electron microscope pictures of the comparative example and the examples, compared with the comparative example, the amino modification is carried out on the surfaces of the nano particles, and the nano particles are adsorbed on the organosilicon polymer microspheres and then are subjected to chemical plating, so that the metal layer on the surfaces of the composite microspheres has good dispersibility, more uniform coating, stronger adhesive force, less falling and more compactness. In the comparative example 1, a layer of inorganic nano particles is adsorbed on the surface of the high-crosslinking-degree organosilicon polymer microsphere to enable the surface of the microsphere to be rough, and then the microsphere is subjected to chemical plating, so that the surface of the obtained composite microsphere is provided with a relatively uniform metal layer, but the binding force between the inorganic nano particles and the high-crosslinking-degree organosilicon polymer microsphere is relatively weak, the binding force between the microsphere and the metal layer is relatively weak, and the surface metal particles are easy to fall off; comparative example 2 was directly plated with metal on the surface of the high crosslinking degree organosilicon polymer microsphere, and the metal layer was not firmly adhered to the microsphere surface and was liable to drop.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (19)
1. The preparation method of the high-crosslinking-degree organosilicon polymer/metal composite microsphere is characterized by comprising the following steps of:
(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 organosilicon polymer microspheres and the amination inorganic nanoparticles into an acidic solution system, and uniformly mixing to obtain the high-crosslinking-degree organosilicon polymer microspheres coated with the amination inorganic nanoparticles; the mass ratio of the high-crosslinking-degree organosilicon polymer microspheres to the amination inorganic nanoparticles is (1-100) 1; the particle size of the high-crosslinking-degree organosilicon polymer microsphere is 1-15 mu m; the particle size of the amination inorganic nano particles is 5-500 nm; the pH value of the acid solution system is 2.0-6.5;
The preparation method of the high-crosslinking-degree organosilicon 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) Dropwise adding an alkaline catalyst into the reaction system containing the prepolymer obtained in the step (i) to perform an alkaline catalytic polycondensation reaction to obtain the high-crosslinking-degree organosilicon polymer microsphere;
(3) Activating and chemically plating the high-crosslinking-degree organic silicon polymer microsphere coated with the amination inorganic nano particles obtained in the step (2) to obtain the high-crosslinking-degree organic silicon polymer/metal composite microsphere;
the aminosilane coupling agent is prepared by the following steps:
dissolving glycidyl silane 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, the absolute ethyl alcohol and the active hydrogen-containing organic amine is 1:100 (0.1-1);
the reaction temperature of the reaction is 50-100 ℃ and the reaction time is 6-60 h;
the chemical general formula of the glycidyl silane is (RO) 3 SiP 1 Wherein R is an aliphatic hydrocarbon group having 1 to 30 carbon atoms; p (P) 1 Is gamma-glycidoxypropyl or glycidoxymethyl.
2. The method of claim 1, wherein in step (1):
the modification is to adopt nitrogen atmosphere, the reaction temperature is 50-100 ℃, and the reaction time is 12-48 h; and/or
The mass ratio of the inorganic nano particles to the polar solvent to the aminosilane coupling agent is 1:100 (0.01-0.5).
3. The preparation method according to claim 1, wherein the modified reaction temperature is 65-80 ℃ and the reaction time is 24 hours; and/or
The mass ratio of the inorganic nano particles to the polar solvent to the aminosilane coupling agent is 1:100 (0.05-0.35).
4. The method of 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;
the particle size of the inorganic nano particles is 5-500 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.
5. The method of claim 4, wherein the inorganic nanoparticles are one or more of silica, titania, alumina, and zinc oxide;
the particle size of the inorganic nano particles is 10-50 nm; and/or
The polar solvent is one or more of methanol, ethanol, isopropanol, acetone and acetonitrile.
6. The preparation method according to claim 5, wherein the inorganic nanoparticles are one or more of silica and titania; and/or
The polar solvent is ethanol.
7. The method of claim 1, wherein in step (1):
the mass ratio of the glycidyl silane, the absolute ethyl alcohol and the active hydrogen-containing organic amine is 1:100 (0.2-0.6);
the reaction temperature of the reaction is 60-75 ℃, and the reaction time is 10-20 h.
8. The method of claim 1, wherein R is methyl or ethyl;
the organic amine containing active hydrogen is methylamine, ethylenediamine, hexamethylenediamine, isopropylamine, p-phenylenediamine, diethylamine, diphenylamine, methylethylamine, 2-amino-4-methylhexane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, para-aminopyridine, 2,3, 4-triaminopyridine, 3,4, 5-triaminopyridine, 2,3, 6-triaminopyridine, imidazole or 2-phenylimidazole.
9. The method according to claim 8, wherein the active hydrogen-containing organic amine is ethylenediamine, diethylamine or para-aminopyridine.
10. The method according to claim 9, wherein the active hydrogen-containing organic amine is ethylenediamine.
11. The method of claim 1, wherein in step (2):
the mass ratio of the high-crosslinking-degree organosilicon polymer microspheres to the amination inorganic nanoparticles is (40-80) 1;
the particle size of the amination inorganic nano particles is 10-50 nm;
the pH value of the acidic solution system is 3.0-5.0.
12. The method according to claim 1, wherein in step (3), the activation treatment comprises the sub-steps of:
adding the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nano particles into a Bigley palladium activator PL-5, then adding the water into a sodium hypophosphite aqueous solution after washing and filtering, and then washing and filtering to finish the activation treatment;
the mass ratio of the high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nano particles, the Bigley palladium activator PL-5 and the sodium hypophosphite aqueous solution is (1-10): 50:10.
13. The preparation method according to claim 12, wherein the mass ratio of the high crosslinking degree silicone polymer microsphere coated with the aminated inorganic nanoparticle, the specific gurley palladium activator PL-5 and the sodium hypophosphite aqueous solution is 3:50:10.
14. The method of claim 1, wherein in step (3):
the electroless plating comprises the following substeps:
dispersing the activated high-crosslinking-degree organosilicon polymer microspheres coated with the amination inorganic nanoparticles into a metal salt solution, and then adding a reducing solution for reaction to obtain the high-crosslinking-degree organosilicon polymer/metal composite microspheres; wherein the thickness of the metal layer of the high-crosslinking-degree organosilicon polymer/metal composite microsphere is 30-200 nm;
the reaction temperature of the reaction is 20-100 ℃ and the reaction time is 1-12 h; and/or
The times of the chemical plating are 2-8 times.
15. The preparation method according to claim 14, wherein the reaction temperature of the reaction is 30-85 ℃ and the reaction time is 3-5 h; and/or
The times of the chemical plating are 2-5 times.
16. The method of claim 15, wherein the number of electroless plating is 3.
17. The method of manufacturing according to claim 14, wherein:
the mass ratio of the activated high-crosslinking-degree organosilicon polymer microsphere coated with the amination inorganic nano particles 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%;
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.
18. The preparation method of the metal salt solution according to claim 17, wherein the mass ratio of the activated high-crosslinking-degree organosilicon polymer microsphere coated with the aminated inorganic nanoparticle 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%.
19. A high crosslinking degree organosilicon polymer/metal composite microsphere, which is characterized in that the microsphere is prepared by the preparation method of any one of claims 1 to 18.
Priority Applications (1)
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