CN102307952B - 无溶剂水溶性的硅烷改性硅酸盐 - Google Patents
无溶剂水溶性的硅烷改性硅酸盐 Download PDFInfo
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- CN102307952B CN102307952B CN201080006652.6A CN201080006652A CN102307952B CN 102307952 B CN102307952 B CN 102307952B CN 201080006652 A CN201080006652 A CN 201080006652A CN 102307952 B CN102307952 B CN 102307952B
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- Prior art keywords
- silane
- aqueous solution
- solution
- radical
- component
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- 150000004760 silicates Chemical class 0.000 title abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 229910000077 silane Inorganic materials 0.000 claims abstract description 17
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 11
- -1 phosphate radical Chemical class 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229940071182 stannate Drugs 0.000 claims description 2
- 125000005402 stannate group Chemical group 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 235000019353 potassium silicate Nutrition 0.000 description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000004111 Potassium silicate Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052913 potassium silicate Inorganic materials 0.000 description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 238000013022 venting Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 description 1
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- AGUIILSGLFUTKG-UHFFFAOYSA-N CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] Chemical compound CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] AGUIILSGLFUTKG-UHFFFAOYSA-N 0.000 description 1
- VPFMOTZBTOCCPO-UHFFFAOYSA-N CC1C(O1)OCO[Si](OC)(OC)CCCCCC Chemical compound CC1C(O1)OCO[Si](OC)(OC)CCCCCC VPFMOTZBTOCCPO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ATGKAFZFOALBOF-UHFFFAOYSA-N cyclohexyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCCC1 ATGKAFZFOALBOF-UHFFFAOYSA-N 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- VLWUKSRKUMIQAX-UHFFFAOYSA-N diethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[SiH](OCC)CCCOCC1CO1 VLWUKSRKUMIQAX-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- FIHCECZPYHVEJO-UHFFFAOYSA-N ethoxy-dimethyl-phenylsilane Chemical compound CCO[Si](C)(C)C1=CC=CC=C1 FIHCECZPYHVEJO-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical class [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical class [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 238000002103 osmometry Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- IFHVCUGTUBHOML-UHFFFAOYSA-N trimethyl (3-methyloxiran-2-yl) silicate Chemical compound CC1C(O1)O[Si](OC)(OC)OC IFHVCUGTUBHOML-UHFFFAOYSA-N 0.000 description 1
- XFVUECRWXACELC-UHFFFAOYSA-N trimethyl oxiran-2-ylmethyl silicate Chemical compound CO[Si](OC)(OC)OCC1CO1 XFVUECRWXACELC-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical class [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
- C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
- C01B33/325—After-treatment, e.g. purification or stabilisation of solutions, granulation; Dissolution; Obtaining solid silicate, e.g. from a solution by spray-drying, flashing off water or adding a coagulant
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/04—Alkali metal or ammonium silicate cements ; Alkyl silicate cements; Silica sol cements; Soluble silicate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Abstract
本发明涉及改性硅酸盐水溶液,其中所述溶液没有有机溶剂,该溶液通过(a)制备通式M2O·nSiO2的硅酸盐的溶液,其中M为选自Li+、Na+、K+、NY4 +的阳离子,其中Y为氢原子和/或有1-22个碳原子的烷基或链烯基,并使其在5-100℃的温度与(b)至少一种通式(i)的硅烷,其中X彼此独立地为基团CH3、OCH3、OC2H5、OC3H7、OCOCH3、H或Cl;R为饱和或不饱和、线形或支化或环形基团,具有至少一个氧和/或氮原子和至少2个碳原子;n为从1到3,反应,然后除去转化中形成的醇而获得。R-(CH2)n-Si-(X)3 (i)。
Description
本发明涉及在水溶液中制备有机和无机改性的溶解性硅酸盐。这些硅酸盐为无溶剂的混杂无机-有机低聚物。
存在大量基于硅的产品溶液,这些溶液在作为涂料施用之后使基材表面在耐火性、抗划伤性、耐腐蚀性等方面有改进的性能。原则上,需要使用非常薄的无不利现象如VOCs(使用中溶剂蒸发)或AOX废水污染(有机氯物质)的便宜材料层,如果可能为溶液形式(避免灰尘),并且优选水溶液。施用应尤其可通过常见的简单方法进行,如喷涂、辊涂、刮刀式涂布等,以避免昂贵的表面改性方法,例如溅射。应该可以使这种液体涂料材料的配制剂与各种基材匹配。
现在已发现特定的改性溶解性硅酸盐以卓越的方式满足上述要求。
本申请提供改性硅酸盐的水溶液,所述溶液不含有机溶剂,其可通过使
(a)通式M2O·nSiO2的硅酸盐的初始带电水溶液,其中M为选自Li+、Na+、K+、NY4 +的阳离子,其中Y为氢原子和/或有1-10个碳原子的烷基或链烯基,与
(b)至少一种通式(I)的有机硅化合物
R-(CH2)n-Si-(X)3 (I)
其中X在每种情况下独立地为CH3、OCH3、OC2H5、OC3H7、OCOCH3、H或Cl基团且R为饱和或不饱和、线形或支化、或环状基团,具有至少一个氧和/或氮原子和至少2个碳原子,n为从1到3,
在温度5-100℃下反应,然后除去反应中形成的醇而获得。
组分(a)
这里可能的组分(a)尤其包括称为水玻璃的物质。水玻璃是已经从熔体固化的似玻璃的、水溶性碱金属硅酸盐(即硅酸的盐),或其粘性水溶液。水玻璃中通常每1摩尔碱金属氧化物(M2O)有1-4摩尔的SiO2,因此,例如,也常常以SiO2/碱金属氧化物的质量比或摩尔比和该水溶液的密度来表征钠水玻璃和钾水玻璃。他们包含带有碱金属作为相反离子的低聚硅酸盐阴离子(例如,带有M=K或Na)。尤其优选作为反应组分(a)的水玻璃为钠或钾水玻璃。优选那些水玻璃的SiO2∶M2O摩尔比为2-5,优选2.5-3.5。尤其特别优选2.7-3.4。水玻璃优选作为水溶液使用,其包含15-50重量%固体(溶解形式),特别优选含量为25-40重量%的溶液。
组分(b)
组分(b)包括同样为已知的有机硅化合物。这些优选包括硅烷。这基本是硅-氢化合物的组名。
然而,在本发明中,仅由通式(i)的那些硅烷改性反应组分(a)的溶解性硅酸盐:
R-(CH2)n-Si-(X)3 (i)
其中X在每种情况下独立地为CH3、OCH3、OC2H5、OC3H7、OCOCH3、或Cl基团而R为饱和或不饱和、线形或支化、或环状基团,具有至少一个氧和/或氮原子和至少2个碳原子,n为从1到3。本文中尤其优选通式(ii)R-(CH2)n-Si-(CH3)(X)2的硅烷,其中X和n分别定义如上。
适合的硅烷为,例如,三(三甲氧基)硅烷、辛基三乙氧基硅烷、甲基三乙氧基硅烷、甲基三甲氧基硅烷;异氰酸酯基硅烷如三[3-(三甲氧基甲硅烷基)丙基]异氰脲酸酯;γ-巯基丙基三甲氧基硅烷、二(3-[三乙氧基甲硅烷基]丙基)多硫化物、β-(3,4-环氧环己基)乙基三甲氧基硅烷、环氧硅烷、环氧丙氧基-和/或环氧丙氧丙基三甲氧基硅烷、γ-环氧丙氧丙基甲基二乙氧基硅烷、(3-环氧丙氧丙基)三甲氧基硅烷、(3-环氧丙氧丙基)己基三甲氧基硅烷、β-(3,4-环氧环己基)乙基三乙氧基硅烷;含乙烯基团的硅烷如乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、乙烯基甲基二甲氧基硅烷、乙烯基三异丙氧基硅烷;γ-异丁烯酰基氧基丙基三甲氧基硅烷、γ-异丁烯酰基氧基丙基三异丙氧基硅烷、γ-异丁烯酰基氧基丙基三乙氧基硅烷、辛基三甲基氧基硅烷、乙基三甲氧基硅烷、丙基三乙氧基硅烷、苯基三甲氧基硅烷、3-巯基丙基三乙氧基硅烷、环己基三甲氧基硅烷、环己基三乙氧基硅烷、二甲基二甲氧基硅烷、3-氯丙基三乙氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、异丁基三乙氧基硅烷,三甲基乙氧基硅烷、苯基二甲基乙氧基硅烷、六甲基二硅氧烷、三甲基甲硅烷基氯化物、乙烯基三乙氧基硅烷、六甲基二硅氮烷及其混合物。US4,927,749在表2,第9栏第10行至第11栏第23行,公开了更适合的硅烷,它们也发现可用于本发明的技术内容。本发明技术内容上下文中尤其优选的硅烷选自带有甲基、乙基、丙基和/或丁基的烷基烷氧基硅烷,优选三烷氧基硅烷。还优选其烷基链插入有杂原子如O或N的那些三烷氧基硅烷。优选的硅烷为N-(2-氨乙基)-3-氨丙基硅烷或3-氨丙基三乙氧基硅烷或3-缩水甘油基氧基丙基三甲氧基-或3-缩水甘油基氧基丙基三乙氧基硅烷。有机硅化合物可各自单独使用或作为混合物,否则为释放的醇可能在先减少的其部分水解产物(or else the partial hydrolyzates thereof with possible priorreduction of the alcohol released)。
组分(c)
在一个实施方案中,组分(a)和(b)的上述转化在用于低聚物无机改性的另一(其它)组分(c)的存在下实现;使用酸性氧化物的水溶性盐(玻璃网成型剂)。
组分(c)可由通用经验式(Cat)x(An)yOz表示,其中“Cat”指单价阳离子,“An”指形成玻璃的元素,(An)yOz二价或多价阴离子;指数x、y和z产生于整体中性的组分(c)的必要电荷平衡,其中指数可以为整数或可以不为整数。
优选铵、钠和钾作为单价阳离子,与选自硼酸根、磷酸根、铝酸根、钼酸根、钨酸根、高铁酸根、锗酸根、钛酸根、锡酸根或其氧代多阴离子(oxo polyanions)的阴离子结合,这些阴离子也可相互混合。
特别优选钠和钾作为阳离子,硼酸根和多磷酸根作为阴离子。
组分(c)优选以固体形式使用。
反应机制
溶解性硅酸盐组分(a)优选用作商业的熔融玻璃基水玻璃溶液。使用任选组分(c)时,将其溶于水中,与组分(a)分开。然后溶液(a)与溶液(c)搅拌混合至成为澄清溶液。可选地,在40-250℃且尤其是120-200℃范围内于碱金属氢氧化物溶液中混合固体二氧化硅源与氧化物(AnvOw)或含氧硅酸盐(AndSieOf)并且其热液溶解之后,也可能产生在(a)水玻璃溶液中的无机改性的(c)。然后向(a)溶液中的无机(c)中逐滴计量加入液态硅烷组分(b)。
优选在室温(20℃)下制备为本发明主题的改性硅酸盐低聚物,如果需要在至多80℃的升高的温度下,尤其优选温度范围为20-50℃,以转化为有机-无机混杂物。选择合适的反应温度取决于硅烷组分反应性。优选在室温下转化甲氧基硅烷,而乙氧基硅烷优选在40-50℃。另一方面,反应中的温度不宜选择在过高水平,因为大多数硅烷反应物确实具有显著挥发性。完成所有组分混合之后,继续搅拌直至形成透明水溶液。
仅此以后将混合物再加热至60-100℃,优选70-80℃,以单独或与水一起蒸发掉化学反应中产生的醇;可通过减小压力(应用减压)促进蒸发(蒸馏去除)。
如前文所述,除去反应中形成的醇为本发明的必要特征。原则上可通过任何方法除去醇,优选可以在标准压力或减压下进行的蒸馏去除。在蒸馏去除过程中,去除醇也有效自动地蒸馏掉水。可能有必要在该蒸馏步骤之后进一步计量加入水以使溶液不会过度浓缩和胶凝。
组分(a)和(b)的反应产物中来自(a)的SiO2与来自(b)的SiO2的重量比率为30∶1至2∶1。特别优选的比率为20∶1至5∶1。非常特别优选12∶1至6∶1的比率。来自(a)的SiO2与来自(c)的无机多晶型物AnyOz的总量的关系为1000∶1至5∶1,优选500∶1至10∶1。
依照本发明制备的低聚物平均摩尔质量(通过渗透压测定法在稀水溶液中测量)优选为150-800且尤其为350-650。改性硅酸盐的低聚阴离子优选粒度为20-200nm,主要为75-100nm。
本说明书的改性硅酸盐混合物优选作为如涂料材料使用。为改进基材润湿性,可建议加入少量(<1%)润湿剂,例如醇乙氧基化物或表面活性剂。与改性硅酸盐一起使用的适合的表面活性剂为阴离子型、阳离子型、两性型或非离子型表面活性剂。优选非离子型表面活性剂。表面活性剂分子优选每分子含少于12个碳原子。为影响干燥特性,可加入水溶助长剂,例如甘油或糖。如果需要同样可以用增稠剂如改性纤维素(CMC、HEC)、瓜尔胶或黄原胶将溶液增稠。
应用
本发明改性硅酸盐的水溶液无VOC(这是其以后应用的非常核心点)(本领域技术人员理解VOCs指的是挥发性有机化合物)。这是由于已经发现,本发明关键特征(其在于除去组分(a)和(b)转化中形成的醇)的忽略导致在涂料应用中效果较差的硅酸盐溶液。更特别地,依照本发明制备的当然无有机溶剂的硅酸盐溶液尤其适于涂覆目的(表面亲水化),优选用于高温涂覆。基于依据本发明制备的硅酸盐溶液的涂料也有显著良好的耐化学性(耐酸和耐碱),并且与含醇(作为有机溶剂)的相应产品相比它们也具有较好的耐龟裂形成性。
用以防腐蚀的金属涂层或作为中间层用于更多涂层,天然石料或工业生产的石料或矿物成型体处理、颜料表面改性。
实施例
缩写:
MR-SiO2/Na2O摩尔比3.9
SC-固含量
制备本发明的硅酸盐溶液:
实施例1:
将81份硅酸钾水溶液(SiO2/K2O摩尔比3.15;固含量:41重量%)与12份水混合,随后室温下向其中逐滴加入7份3-缩水甘油基氧基丙基三甲氧基硅烷(GLYMO),滴加结束后,将混合物在室温下再搅拌15分钟。将该澄清溶液加热到70℃,于温和真空下除去约10体积%馏出物(甲醇/水);为了冷却,向溶液中再加入相同量的蒸馏水。
实施例2:
将67份硅酸钾水溶液(SiO2/K2O摩尔比2.9;固含量:42重量%)与27份水混合,室温下向其中逐滴加入1份3-氨丙基三乙氧基硅烷,然后将混合物加热到40℃。在40℃,加入6份3-缩水甘油基氧基丙基三甲氧基硅烷。将混合物进一步加热到80℃,并经由通过惰性氮气料流使溶液浓缩10体积%。为了冷却,混合物再补充10%的水。
实施例3:
在室温下将5份4,7,10-三氮杂癸基三乙氧基硅烷(TRIAMO)逐滴加入96份硅酸钠水溶液(SiO2/Na2O摩尔比3.9;固含量:28重量%)中。滴加结束后,在室温下再继续搅拌15分钟,然后在80℃使澄清溶液浓缩10体积%,然后再加入10%的水以冷却。
实施例4:
在水中搅拌KBO2形成40%溶液。向硅酸钾溶液(MR 3,SC 30%)中逐滴加入9份GLYMO(来自Evonik),然后将混合物加热至80℃,然后排去约15体积份馏出物。为了冷却,混合物再补充15份水并搅拌加入该硼酸钾溶液。
实施例5:
在室温下,将9份磷酸三钾(K3PO4)溶于140份硅酸钾水溶液(MR 4,SC20%)。向该初级混合物中逐滴加入8份GLYMO(来自Evonik),在70℃排去约20份馏出物,将该混合物再补充水。
实施例6:
向158份17%氢氧化四甲基铵(TEAH)溶液中逐滴加入66份40%硅溶胶(Koestrosol 1040),将该混合物加热至40℃。向所得季硅酸盐(quaternary silicate)溶液中逐滴加入5份GLYMO(来自Evonik),在60℃于温和真空下排去10重量份馏出物,然后冷却该混合物。
实施例7:
在搅拌下将70份氢氧化锂水合物溶于700份水中,并通过热液反应在70℃下将235g沉淀二氧化硅(Sipernat 700,来自Evonik)溶于其中。最后,将5份AMEO(来自Evonik)逐滴加入敞口容器中,在70℃将混合物再搅拌30分钟,然后不再加热并边搅拌边冷却。
实施例8:
将500份石英砂、2份沉淀氧化铝和1份锐钛矿多晶型二氧化钛混合并在高压釜中与500份浓氢氧化钾溶液(50%)和500份水在200℃下热液反应以产生无机改性的钾水玻璃溶液,通过添加1000份水将热反应混合物冷却至80℃,并在1小时内向敞口容器中逐滴加入50份Geniosil CF20(来自Momentive)。不再加热,使混合物冷却同时再搅拌5小时。
N.B.:
以上实施例1-8的所有情况中,溶液的顶空气相色谱分析表明它们无VOCs(VOC=挥发性有机化合物含量)。对已经预先冻干的溶液做1H,13C,29Si NMR测量,可能会发现硅烷和硅氧烷与无机多阴离子在溶液中反应生成混合低聚物。
Claims (3)
1.无有机溶剂的改性硅酸盐水溶液,其可通过使
(a)通式M2O·nSiO2的硅酸盐的初始带电水溶液,其中M为选自Li+、Na+、K+、NY4 +的阳离子,其中Y为氢原子和/或有1-22个碳原子的烷基或链烯基,与
(b)至少一种通式(i)的硅烷
R-(CH2)n-Si-(X)3 (i)
其中X在每种情况下独立地为OCH3、OC2H5、OC3H7、OCOCH3基团且R为饱和或不饱和、线形或支化、或环状基团,具有至少一个氧和/或氮原子和至少2个碳原子,n为从1到3,
在温度5-100℃下反应,然后除去反应中形成的醇而获得,
其中(a)与(b)的反应在组分(c)的存在下进行,其中组分(c)具有通式
(Cat)x(An)yOz,
其中“Cat”指单价阳离子,“An”指形成玻璃的元素,(An)yOz为二价或多价阴离子;指数x、y和z产生于整体中性的组分(c)的必要电荷平衡,其中指数为整数或不为整数,
其中单价阳离子选自铵、钠和钾,
(An)yOz选自硼酸根、磷酸根、铝酸根、钼酸根、钨酸根、高铁酸根、锗酸根、钛酸根、锡酸根或其氧代多阴离子,或它们的互相混合物。
2.如权利要求1所述的改性硅酸盐水溶液用于表面亲水化的用途。
3.如权利要求2所述的用途,其用于高温涂料。
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EP20090001740 EP2216371A1 (de) | 2009-02-07 | 2009-02-07 | Lösemittelfreie wasserlösliche Silan modifizierte Silikate |
EP09001740.1 | 2009-02-07 | ||
PCT/EP2010/000530 WO2010089053A1 (de) | 2009-02-07 | 2010-01-29 | Lösemittelfreie wasserlösliche silan modifizierte silikate |
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WO2014049000A1 (de) * | 2012-09-28 | 2014-04-03 | Henkel Ag & Co. Kgaa | Passivierende alkalische zusammensetzung basierend auf wasserglas |
FR2996220B1 (fr) * | 2012-09-28 | 2014-09-26 | Centre Nat Rech Scient | Procede de preparation d'une composition comprenant des particules minerales silicatees colorees et composition comprenant des particules minerales silicatees colorees |
DE102013215441A1 (de) | 2013-08-06 | 2015-02-12 | Henkel Ag & Co. Kgaa | Metallvorbehandlungszusammensetzungen umfassend Silane und Organophosphonsäuren |
DE102013215440A1 (de) | 2013-08-06 | 2015-02-12 | Henkel Ag & Co. Kgaa | Metallvorbehandlung mit sauren wasserhaltigen Zusammensetzungen umfassend Silane |
ES2732264T3 (es) | 2014-02-13 | 2019-11-21 | Doerken Ewald Ag | Procedimiento para la preparación de un sustrato provisto de una pasivación libre de cobalto y libre de cromo-VI |
KR101615713B1 (ko) * | 2014-07-25 | 2016-04-26 | 양철호 | 친환경 무기질계 코팅제 조성물 및 이의 제조방법 |
CN104263020A (zh) * | 2014-09-19 | 2015-01-07 | 常熟市康佳涂料装饰工程有限公司 | 耐高温防氧化涂料 |
EP3040445B1 (de) | 2014-12-30 | 2019-02-06 | Ewald Dörken Ag | Passivierungszusammensetzung aufweisend eine silanmodifizierte Silikatverbindung |
DE102015211812A1 (de) * | 2015-06-25 | 2016-12-29 | Wacker Chemie Ag | Wirtschaftliches Verfahren zur Herstellung von organisch modifizierten Lyo- oder Aerogelen |
JP6918825B2 (ja) * | 2016-07-27 | 2021-08-11 | ワッカー ケミー アクチエンゲゼルシャフトWacker Chemie AG | 改質沈降シリカの製造方法および改質沈降シリカを含有する組成物 |
CN113736292A (zh) * | 2021-09-10 | 2021-12-03 | 上海保耐舒新材料技术有限公司 | 无机纳米长效防雾自洁涂料及其制备方法和应用 |
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US3721574A (en) * | 1968-08-06 | 1973-03-20 | R Schneider | Silicate coatings compositions |
DE4418846A1 (de) * | 1994-05-30 | 1995-12-07 | Henkel Kgaa | Siliciumorganisch modifizierte wasserlösliche amorphe Alkalimetallsilicate |
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DE2343026A1 (de) * | 1973-08-25 | 1975-03-06 | Dynamit Nobel Ag | Verfahren zur herstellung waessriger alkalipolysilikatloesungen |
US4120938A (en) * | 1973-08-25 | 1978-10-17 | Dynamit Nobel Aktiengesellschaft | Aqueous solutions of alkali polysilicates |
JPS5880355A (ja) * | 1981-11-06 | 1983-05-14 | Daikin Ind Ltd | 親水性皮膜形成用組成物 |
DE3151680C2 (de) * | 1981-12-28 | 1985-09-26 | Dynamit Nobel Ag, 5210 Troisdorf | Gelbildendes Gemisch auf Alkalisilicat-Basis |
DE3606313A1 (de) * | 1986-02-27 | 1987-09-03 | Dynamit Nobel Ag | Dichtmasse fuer bodenabdichtungen |
US4927749A (en) | 1986-04-09 | 1990-05-22 | Jeanette Simpson | Reagent for cell separation |
DE4443824A1 (de) * | 1994-12-09 | 1996-06-13 | Huels Chemische Werke Ag | Organopolysiloxan-haltige Zusammensetzungen auf Wasserbasis, Verfahren zu deren Herstellung sowie deren Verwendung |
JP2953658B1 (ja) * | 1998-07-24 | 1999-09-27 | 株式会社神戸製鋼所 | 表面処理金属板およびその製造方法 |
WO2003022940A1 (en) * | 2001-09-11 | 2003-03-20 | Akzo Nobel Coatings International B.V. | Coating composition for metal substrates |
DE102004037045A1 (de) * | 2004-07-29 | 2006-04-27 | Degussa Ag | Wässrige Silan-Nanokomposite |
TWI477565B (zh) * | 2007-04-19 | 2015-03-21 | Akzo Nobel Coatings Int Bv | 用於金屬基材之塗料組合物 |
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US3721574A (en) * | 1968-08-06 | 1973-03-20 | R Schneider | Silicate coatings compositions |
DE4418846A1 (de) * | 1994-05-30 | 1995-12-07 | Henkel Kgaa | Siliciumorganisch modifizierte wasserlösliche amorphe Alkalimetallsilicate |
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