CN106928844A - 一种含氟超疏水有机硅涂层复合物及其制备方法 - Google Patents
一种含氟超疏水有机硅涂层复合物及其制备方法 Download PDFInfo
- Publication number
- CN106928844A CN106928844A CN201710027048.5A CN201710027048A CN106928844A CN 106928844 A CN106928844 A CN 106928844A CN 201710027048 A CN201710027048 A CN 201710027048A CN 106928844 A CN106928844 A CN 106928844A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- organic silicon
- hydrophobic organic
- silicon coating
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 55
- 239000011737 fluorine Substances 0.000 title claims abstract description 55
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011248 coating agent Substances 0.000 title claims abstract description 50
- 238000000576 coating method Methods 0.000 title claims abstract description 50
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 45
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 43
- 239000010703 silicon Substances 0.000 title claims abstract description 43
- 150000001875 compounds Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000007711 solidification Methods 0.000 claims abstract 2
- 230000008023 solidification Effects 0.000 claims abstract 2
- -1 alkoxy silane Chemical compound 0.000 claims description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 229910000077 silane Inorganic materials 0.000 claims description 33
- 229920001296 polysiloxane Polymers 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000013517 stratification Methods 0.000 claims description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 239000013522 chelant Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 4
- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 3
- KUGBQWBWWNPMIT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentan-1-ol Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(O)(F)F KUGBQWBWWNPMIT-UHFFFAOYSA-N 0.000 claims description 3
- YIHRGKXNJGKSOT-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluorobutan-1-ol Chemical compound CC(F)(F)C(F)(F)C(O)(F)F YIHRGKXNJGKSOT-UHFFFAOYSA-N 0.000 claims description 3
- CSUFEOXMCRPQBB-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropan-1-ol Chemical compound CC(F)(F)C(O)(F)F CSUFEOXMCRPQBB-UHFFFAOYSA-N 0.000 claims description 3
- VUYQBMXVCZBVHP-UHFFFAOYSA-N 1,1-difluoroethanol Chemical compound CC(O)(F)F VUYQBMXVCZBVHP-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 3
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 3
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 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 claims description 3
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012675 alcoholic extract Substances 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 229960004217 benzyl alcohol Drugs 0.000 claims description 2
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 238000004807 desolvation Methods 0.000 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000002210 silicon-based material Substances 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 2
- IUJVSGPNAKIWKG-UHFFFAOYSA-N C(CC)(=O)OC(C)C.[Ti] Chemical compound C(CC)(=O)OC(C)C.[Ti] IUJVSGPNAKIWKG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RBIILJCATVGHHI-UHFFFAOYSA-N [diethoxy(phenyl)silyl]methanamine Chemical compound NC[Si](OCC)(OCC)C1=CC=CC=C1 RBIILJCATVGHHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 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
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
本发明涉及有机硅复合物领域,为解决现有超疏水涂层耐温耐候性差、制备工艺复杂、制备时浓度非常稀、只在较低浓度下才有超疏水性能等缺点,本发明提出了一种含氟超疏水有机硅涂层复合物及其制备方法,所述的有机硅涂层复合物经10~40℃,固化3~48后硬度为3H~6H,水接触角150~165º,滚动角小于10 º。该超疏水涂层不使用污染环境的催化剂,可实现大批量生产,产品具有含氟有机硅材料的耐温耐候、耐溶剂腐蚀等优点。
Description
技术领域
本发明涉及有机硅复合物领域,具体涉及一种超疏水有机硅涂层及其制备方法。
背景技术
超疏水材料是指表面的水接触角大于150°,并且滚动角小于10°的材料,在汽车和飞机等挡风玻璃、高层建筑墙玻璃、眼镜等的表面改性领域具有广阔的应用潜力。Bravo等[Langmuir,2007,23 (13):7293-7298]使用氟硅烷改性剂、SiO2纳米粒子与聚苯乙烯磺酸钠等自组装制备了160°水接触角的透明超疏水涂膜。Xu 等[J Mater Chem,2009,19:655-660]用无皂乳液聚合合成了聚苯乙烯微球,再将此微球与无机SiO2粒子共混,超声振荡后涂膜,在500 ℃高温下产生相分离并得到形似火山口的微观结构,经氟硅烷偶联剂表面修饰后得到可见光透过率在90% 以上、水接触角达160°的透明超疏水涂膜。这些方法工艺过于复杂,涂层耐温耐候性差,制约了其推广应用。
中国发明专利申请CN103469184A公开了一种超疏水铋涂层的制备方法,它是通过化学镀层技术,在锌片上镀上一层金属铋。金属铋层具有羽毛状的微纳结构,经长链脂肪族醇疏水改性后表现出超疏水性能。该方法适合于金属表面电镀,污染大。
叶文波等(应用化学,29(10):1123-1129)以甲基三乙氧基硅烷( MTES) 为有机硅前驱体,通过酸-碱催化水解-缩合得到聚有机硅氧烷凝胶,经浸涂-提拉成膜技术在玻璃表面制备超疏水聚硅氧烷涂层。虽然涂层的接触角可达160°,但是涂层溶液非常稀,难以满足大规模使用要求。李恒等(广东化工 2016,43(1):38-39)利用有机硅对单分散性SiO2纳米球疏水改性,通过浸涂提拉法和加热固化交联制得接触角可达155°的超疏水涂层,但该方法制备的涂层只在有机硅含量很低的时候才显示出超疏水性能。
发明内容
为解决现有超疏水涂层耐温耐候性差、制备工艺复杂、制备时浓度非常稀、只在较低浓度下才有超疏水性能等缺点,本发明提出了一种含氟超疏水有机硅涂层复合物及其制备方法,该超疏水涂层不使用污染环境的催化剂,可实现大批量生产,产品具有含氟有机硅材料的耐温耐候、耐溶剂腐蚀等优点。
本发明是通过以下技术方案实现的:一种含氟超疏水有机硅涂层复合物,所述的有机硅涂层复合物在10~40℃固化3~48 h后硬度为3H~6H,水接触角150~165º,滚动角小于10 º。
所述的含氟超疏水有机硅涂层复合物的制备方法为以下步骤:
(1)采用带异氰酸酯基的三官能烷氧基硅烷与含氟醇反应,制备三官能含氟烷氧基硅烷;
带异氰酸酯的三官能烷氧基硅烷与含氟醇按照异氰酸酯与醇羟基摩尔比1:1投料,在20~80℃下进行水解反应0.5~12h。作为优选,反应条件为30~60℃下反应2~8h。
所述带异氰酸酯基的三官能烷氧基硅烷选自3-异氰酸酯基丙基三甲氧基硅烷、3-异氰酸酯基丙基三乙氧基硅烷、3-异氰酸酯基丙基三异丙氧基硅烷、异氰酸酯三甲氧基硅烷,异氰酸酯三乙氧基硅烷中的一种或几种。
所述含氟醇选自二氟乙醇、三氟乙醇、四氟丙醇、六氟丁醇、六氟异丙醇、八氟戊醇、四氟对苯二苄醇中的一种或几种。
(2)将包括步骤(1)制备得到的三官能含氟烷氧基硅烷、烷氧基硅烷组成的有机硅原料与纳米二氧化硅的进行原位共水解缩合反应,制备含氟硅树脂复合物;
将有机硅原料与纳米二氧化硅在反应溶剂中与酸催化剂在20~78℃反应0.5~72h,作为优选,在40~78℃反应1~12 h。反应完毕后,中和到中性后静置分层,将水层分出后,将油相与原位改性的纳米二氧化硅混合物经50~140℃/20mmHg脱除溶剂、低分子和残留水份后,获得含氟硅树脂复合物。
作为优选, 水的使用量为使反应充分进行的量。
有机硅原料由三官能含氟烷氧基硅烷、烷氧基硅烷组成,其中烷氧基硅烷选自二甲基二甲氧基硅烷、二甲基二乙氧基硅烷、甲基苯基二甲氧基硅烷、甲基苯基二乙氧基硅烷、二苯基二甲氧基硅烷、二苯基二乙氧基硅烷、 辛基三甲氧基硅烷、辛基三乙氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、苯基三甲氧基硅烷、苯基三乙氧基硅烷、正硅酸甲酯、正硅酸乙酯中的一种或几种,烷氧基硅烷质量为有机硅原料质量的0~50%,三官能含氟烷氧基硅烷质量为有机硅原料质量的50%~100%。
所述纳米二氧化硅选自气相法二氧化硅、沉淀法二氧化硅中一种,粒径为5~400nm,纳米二氧化硅质量为所有有机硅原料质量的0.5~25%。
反应溶剂选自甲苯、二甲苯、三甲苯、石油醚、四氢呋喃、乙酸乙酯、乙酸丁酯中的一种或几种,使用量为使溶质溶解的量,优选其使用量为有机硅原料质量的0.3~4倍。
酸催化剂选自醋酸、盐酸、硫酸、三氟甲磺酸、对甲苯磺酸、苯磺酸中的一种或几种,酸催化剂使用量为有机硅原料质量的0.1%~10%。
(3)将含氟硅树脂复合物与溶解溶剂、固化催化剂混合,得到一种超疏水有机硅涂层复合物。作为优选,混合物在密闭、20~30℃下混合。
所述溶解溶剂选自乙酸乙酯、乙酸丁酯、丙二醇甲醚醋酸酯、丙酮中的一种或几种,溶解溶剂的使用量为使含氟超疏水有机硅涂层复合物溶液固含量为8%~60%。
所述固化催化剂选自钛酸异丙酯、钛酸异丙酯的乙酰丙酮螯合物、钛酸正丁酯、钛酸正丁酯的乙酰丙酮螯合物中的一种或几种,使用量为含氟硅树脂复合物质量的0.5%~10%。
所述的超疏水涂层不使用污染环境的催化剂,具有耐温耐候、耐溶剂腐蚀等优点,可用于家具漆、厨房用具、汽车、高层建筑墙玻璃、眼镜等。
与现有技术相比,本发明的有益效果是:本发明的超疏水涂层不使用污染环境的催化剂,可实现大批量生产,产品具有含氟有机硅材料的耐温耐候、耐溶剂腐蚀等优点。
具体实施方式
下面通过实施例对本发明作进一步详细说明,但实施例不是对本发明保护范围的限制。
实施例中所用原料均可市购或采用常规方法制备,实施例中纳米二氧化硅市购为气相法二氧化硅,如瓦克N20,N40;株洲兴隆新材料股份有限公司ZQ356,ZQ135等国内外厂家的气相法白炭黑和沉淀法白炭黑产品,其粒径为5~400nm。
实施例1
(1)用3-异氰酸酯基丙基三甲氧基硅烷205.28g与二氟乙醇82.05g在40℃下反应24h,获得三官能含氟烷氧基硅烷287.33g;
(2)用(1)中所得三官能含氟烷氧基硅烷100g、纳米二氧化硅5g甲苯105g的混合物中,滴加80g去离子水和1g醋酸的混合物,0.5h内滴加完毕,并在78℃下反应4h后,静置分层,除去水相,在60℃/20mmHg下减压除去甲苯和残留水份,获得含氟硅树脂复合物68g。
(3)将(2)中所得含氟硅树脂复合物68g、乙酸乙酯68g、钛酸异丙酯1.36g混合均匀,密闭、在30℃下保存,即为一种含氟超疏水有机硅涂层复合物1。
将含氟超疏水有机硅涂层复合物1在25℃下经24h固化,涂层硬度5H,水接触角164o,滚动角5o。
实施例2
(1)用3-异氰酸酯基丙基三乙氧基硅烷247g与三氟乙醇100 g在30℃下反应48h,获得三官能含氟烷氧基硅烷347g;
(2)用(1)中所得三官能含氟烷氧基硅烷100g、纳米二氧化硅15g、二甲苯460g的混合物中,滴加80g去离子水和1g硫酸的混合物,0.5h内滴加完毕,并在20℃下反应24 h后,静置分层,除去水相,在140℃/20mmHg下减压除去二甲苯和残留水份,获得含氟硅树脂复合物72g。
(3)将(2)中所得含氟硅树脂复合物72g、乙酸乙酯36g、丙二醇甲醚醋酸酯108g,钛酸异丙酯10.8g混合均匀,密闭、在25℃下保存,即为一种含氟超疏水有机硅涂层复合物2。
将含氟超疏水有机硅涂层复合物2在25℃下经24h固化,涂层硬度5H,水接触角158o,滚动角8o。
实施例3
(1)用3-异氰酸酯基丙基三甲氧基硅烷205.28g与四氟丙醇132 g在40℃下反应72 h,获得三官能含氟烷氧基硅烷337.28 g;
(2)用(1)中所得三官能含氟烷氧基硅烷100g、纳米二氧化硅1g,乙酸乙酯31 g的混合物中,滴加100g去离子水和5g对甲苯磺酸的混合物,0.5h内滴加完毕,并在40℃下反应0.5h后,静置分层,除去水相,在100℃/20mmHg下减压除去乙酸乙酯和残留水份,获得含氟硅树脂复合物52 g。
(3)将(2)中所得含氟硅树脂复合物52 g、乙酸乙酯520g、钛酸异丙酯的乙酰丙酮螯合物1.36g混合均匀,密闭、在20℃下保存,即为一种含氟超疏水有机硅涂层复合物3。
将含氟超疏水有机硅涂层复合物3在25℃下经24h固化,涂层硬度4H,水接触角153o,滚动角9o。
实施例4
(1)用3-异氰酸酯基丙基三异丙氧基硅烷205.28g与六氟丁醇182.06g在50℃下反应24h,获得三官能含氟烷氧基硅烷387.34g;
(2)用(1)中所得三官能含氟烷氧基硅烷100g、纳米二氧化硅25g,三甲苯105g的混合物中,滴加80g去离子水和1g磷酸的混合物,0.5h内滴加完毕,并在60 ℃下反应4h后,静置分层,除去水相,在140℃/20mmHg下减压除去三甲苯和残留水份,获得含氟硅树脂复合物75g。
(3)将(2)中所得含氟硅树脂复合物75g、乙酸乙酯75g、丙二醇甲醚醋酸酯75g,钛酸异丙酯4 g混合均匀,密闭、在22℃下保存,即为一种超疏水有机硅涂层。
将所得超疏水有机硅涂层在25℃下经24h固化,涂层硬度5H,水接触角162o,滚动角7o。
实施例5
(1)用异氰酸酯三甲氧基硅烷205.28g与六氟异丙醇168.04 g在30℃下反应48h,获得三官能含氟烷氧基硅烷370.34g;
(2)用(1)中所得三官能含氟烷氧基硅烷148g、二甲基二乙氧基硅烷148g,纳米二氧化硅10g,四氢呋喃105g的混合物中,滴加120g去离子水和1g三氟甲磺酸的混合物,0.5h内滴加完毕,并在78℃下反应12h后,静置分层,除去水相,在60℃/20mmHg下减压除去四氢呋喃和残留水份,获得含氟硅树脂复合物83 g。
(3)将(2)中所得含氟硅树脂复合物83 g、乙酸丁酯249g、钛酸丁酯乙酰丙酮螯合物3.49 g混合均匀,密闭、在28℃下保存,即为一种超疏水有机硅涂层。
将所得超疏水有机硅涂层在10℃下经48h固化,涂层硬度6H,水接触角156o,滚动角9o。
实施例6
(1)用异氰酸酯三乙氧基硅烷205.28g与八氟戊醇232 g在50℃下反应48 h,获得三官能含氟烷氧基硅烷437.283g;
(2)用(1)中所得三官能含氟烷氧基硅烷210g、甲基苯基二乙氧基硅烷100g,纳米二氧化硅10 g,石油醚330 g的混合物中,滴加90g去离子水和33g醋酸的混合物,0.5h内滴加完毕,并在78℃下反应8h后,静置分层,除去水相,在60℃/20mmHg下减压除去石油醚和残留水份,获得含氟硅树脂复合物156g。
(3)将(2)中所得含氟硅树脂复合物156 g、乙酸乙酯322g、乙酸丁酯322g,钛酸异丙酯15.6 g混合均匀,密闭、在25℃下保存,即为一种超疏水有机硅涂层。
将所得超疏水有机硅涂层在40 ℃下经5h固化,涂层硬度4H,水接触角152o,滚动角6o。
实施例7
(1)用3-异氰酸酯基丙基三甲氧基硅烷205.28g与八氟戊醇232g在40℃下反应24h,获得三官能含氟烷氧基硅烷437.28g;
(2)用(1)中所得三官能含氟烷氧基硅烷280g、纳米二氧化硅2g,甲基三甲氧基硅烷40g,正硅酸四乙酯20.8g,二苯基二乙氧基硅烷21g,二甲基二甲氧基硅烷20g,甲苯800g的混合物中,滴加250g去离子水和26g苯磺酸的混合物,1 h内滴加完毕,并在78℃下反应8h后,静置分层,除去水相,在120℃/20mmHg下减压除去甲苯和残留水份,获得含氟硅树脂复合物380g。
(3)将(2)中所得含氟硅树脂复合物100g、乙酸乙酯400g、钛酸异丙酯0.5g混合均匀,密闭、在27℃下保存,即为一种超疏水有机硅涂层。
将所得超疏水有机硅涂层在25℃下经24h固化,涂层硬度4H,水接触角152o,滚动角8o。
Claims (10)
1.一种含氟超疏水有机硅涂层复合物,其特征在于,所述的有机硅涂层复合物在10~40℃固化3~48 h后硬度为3H~6H,水接触角150~165º,滚动角小于10 º。
2.一种如权利要求1所述的含氟超疏水有机硅涂层复合物的制备方法,其特征在于,所述制备方法为以下步骤:
(1)采用带异氰酸酯基的三官能烷氧基硅烷与含氟醇反应,制备三官能含氟烷氧基硅烷;
(2)将包括步骤(1)制备得到的三官能含氟烷氧基硅烷、烷氧基硅烷组成的有机硅原料与纳米二氧化硅进行原位共水解缩合反应,制备含氟硅树脂复合物;
(3)将含氟硅树脂复合物与溶解溶剂、固化催化剂混合,得到一种超疏水有机硅涂层复合物。
3.根据权利要求2所述的一种含氟超疏水有机硅涂层复合物的制备方法,其特征在于,步骤(1)中带异氰酸酯的三官能烷氧基硅烷与含氟醇按照异氰酸酯与醇羟基摩尔比1:1投料,在20~80℃下反应0.5~12h。
4.根据权利要求2或3所述的一种含氟超疏水有机硅涂层复合物的制备方法,其特征在于,步骤(1)中所述带异氰酸酯基的三官能烷氧基硅烷选自3-异氰酸酯基丙基三甲氧基硅烷、3-异氰酸酯基丙基三乙氧基硅烷、3-异氰酸酯基丙基三异丙氧基硅烷、异氰酸酯三甲氧基硅烷,异氰酸酯三乙氧基硅烷中的一种或几种;
所述含氟醇选自二氟乙醇、三氟乙醇、四氟丙醇、六氟丁醇、六氟异丙醇、八氟戊醇、四氟对苯二苄醇中的一种或几种。
5.根据权利要求2所述的一种含氟超疏水有机硅涂层复合物的制备方法,其特征在于,步骤(2)将有机硅原料和纳米二氧化硅在反应溶剂中与酸催化剂、在20~78℃进行水解反应0.5~72h,反应完毕后,中和到中性后静置分层,将水层分出后,将油相与原位改性的纳米二氧化硅混合物经50~140℃/20mmHg脱除溶剂、低分子和残留水份后,获得含氟硅树脂复合物。
6.根据权利要求2或5所述的一种含氟超疏水有机硅涂层复合物的制备方法,其特征在于,步骤(2)中有机硅原料由三官能含氟烷氧基硅烷、烷氧基硅烷组成,其中所述烷氧基硅烷选自二甲基二甲氧基硅烷、二甲基二乙氧基硅烷、甲基苯基二甲氧基硅烷、甲基苯基二乙氧基硅烷、二苯基二甲氧基硅烷、二苯基二乙氧基硅烷、 辛基三甲氧基硅烷、辛基三乙氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、苯基三甲氧基硅烷、苯基三乙氧基硅烷、正硅酸甲酯、正硅酸乙酯中的一种或几种,烷氧基硅烷质量为有机硅原料质量的0~50%。
7.根据权利要求2或5所述的一种含氟超疏水有机硅涂层复合物的制备方法,其特征在于,步骤(2)所述纳米二氧化硅选自气相法二氧化硅、沉淀法二氧化硅中一种,粒径为5~400nm,纳米二氧化硅质量为有机硅原料质量的0.5~25%。
8.根据权利要求5所述的一种含氟超疏水有机硅涂层复合物的制备方法,其特征在于,反应溶剂选自甲苯、二甲苯、三甲苯、石油醚、四氢呋喃、乙酸乙酯、乙酸丁酯中的一种或几种;酸催化剂选自醋酸、盐酸、硫酸、三氟甲磺酸、对甲苯磺酸、苯磺酸中的一种或几种,酸催化剂使用量为有机硅原料质量的0.1%~10%。
9.根据权利要求2所述的一种含氟超疏水有机硅涂层复合物的制备方法,其特征在于,步骤(3)中所述溶解溶剂选自乙酸乙酯、乙酸丁酯、丙二醇甲醚醋酸酯、丙酮中的一种或几种,溶解溶剂的使用量为使含氟超疏水有机硅涂层复合物溶液固含量为8%~60%。
10.根据权利要求2所述的一种含氟超疏水有机硅涂层复合物的制备方法,其特征在于,步骤(3)中所述固化催化剂选自钛酸异丙酯、钛酸异丙酯的乙酰丙酮螯合物、钛酸正丁酯、钛酸正丁酯的乙酰丙酮螯合物中的一种或几种,使用量为含氟硅树脂复合物质量的0.5%~10%。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710027048.5A CN106928844B (zh) | 2017-01-15 | 2017-01-15 | 一种含氟超疏水有机硅涂层复合物及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710027048.5A CN106928844B (zh) | 2017-01-15 | 2017-01-15 | 一种含氟超疏水有机硅涂层复合物及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106928844A true CN106928844A (zh) | 2017-07-07 |
CN106928844B CN106928844B (zh) | 2019-06-25 |
Family
ID=59444730
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710027048.5A Expired - Fee Related CN106928844B (zh) | 2017-01-15 | 2017-01-15 | 一种含氟超疏水有机硅涂层复合物及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106928844B (zh) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107629492A (zh) * | 2017-09-11 | 2018-01-26 | 东南大学 | 一种超疏水涂料的制备方法及其所得涂料和制备高透明超疏水涂层的应用 |
CN108395115A (zh) * | 2018-02-01 | 2018-08-14 | 阿尔特汽车技术股份有限公司 | 汽车后视镜 |
CN109289337A (zh) * | 2018-09-30 | 2019-02-01 | 李明珠 | 一种吸油降噪材料、其制备方法及应用 |
WO2019062083A1 (zh) * | 2017-09-28 | 2019-04-04 | 洛阳尖端技术研究院 | 超疏水涂层及其制备方法和应用 |
CN109867990A (zh) * | 2017-12-01 | 2019-06-11 | 洛阳尖端技术研究院 | 一种透明超疏水涂层及其制备方法和应用 |
CN110204780A (zh) * | 2019-06-24 | 2019-09-06 | 鲁东大学 | 一种耐用型超疏水聚氨酯泡沫材料的制备方法 |
KR20200055780A (ko) * | 2017-10-31 | 2020-05-21 | 다이킨 고교 가부시키가이샤 | 경화성 조성물 |
CN111925525A (zh) * | 2020-08-28 | 2020-11-13 | 东莞市溢美材料科技有限公司 | 一种氨基氟硅树脂及其组合物的制备方法与应用 |
CN112724829A (zh) * | 2020-12-28 | 2021-04-30 | 苏州德达材料科技有限公司 | 一种抗指纹材料及其制备方法和应用 |
CN114249871A (zh) * | 2021-09-09 | 2022-03-29 | 中昊北方涂料工业研究设计院有限公司 | 一种氟硅烷改性耐磨聚氨酯树脂及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104073116A (zh) * | 2014-07-08 | 2014-10-01 | 深圳大学 | 一种超双疏涂层的制备方法 |
CN104987520A (zh) * | 2015-07-09 | 2015-10-21 | 北京航空航天大学 | 一种超疏水纳米透明涂层及其制备方法 |
-
2017
- 2017-01-15 CN CN201710027048.5A patent/CN106928844B/zh not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104073116A (zh) * | 2014-07-08 | 2014-10-01 | 深圳大学 | 一种超双疏涂层的制备方法 |
CN104987520A (zh) * | 2015-07-09 | 2015-10-21 | 北京航空航天大学 | 一种超疏水纳米透明涂层及其制备方法 |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107629492A (zh) * | 2017-09-11 | 2018-01-26 | 东南大学 | 一种超疏水涂料的制备方法及其所得涂料和制备高透明超疏水涂层的应用 |
CN107629492B (zh) * | 2017-09-11 | 2019-10-11 | 东南大学 | 一种超疏水涂料的制备方法及其所得涂料和制备高透明超疏水涂层的应用 |
WO2019062083A1 (zh) * | 2017-09-28 | 2019-04-04 | 洛阳尖端技术研究院 | 超疏水涂层及其制备方法和应用 |
JPWO2019088117A1 (ja) * | 2017-10-31 | 2020-07-02 | ダイキン工業株式会社 | 硬化性組成物 |
US11629254B2 (en) | 2017-10-31 | 2023-04-18 | Daikin Industries, Ltd. | Curable composition |
KR102447150B1 (ko) | 2017-10-31 | 2022-09-26 | 다이킨 고교 가부시키가이샤 | 경화성 조성물 |
JP7089189B2 (ja) | 2017-10-31 | 2022-06-22 | ダイキン工業株式会社 | 硬化性組成物 |
KR20200055780A (ko) * | 2017-10-31 | 2020-05-21 | 다이킨 고교 가부시키가이샤 | 경화성 조성물 |
CN109867990A (zh) * | 2017-12-01 | 2019-06-11 | 洛阳尖端技术研究院 | 一种透明超疏水涂层及其制备方法和应用 |
CN109867990B (zh) * | 2017-12-01 | 2021-07-13 | 洛阳尖端技术研究院 | 一种透明超疏水涂层及其制备方法和应用 |
CN108395115B (zh) * | 2018-02-01 | 2022-05-13 | 阿尔特汽车技术股份有限公司 | 汽车后视镜 |
CN108395115A (zh) * | 2018-02-01 | 2018-08-14 | 阿尔特汽车技术股份有限公司 | 汽车后视镜 |
CN109289337A (zh) * | 2018-09-30 | 2019-02-01 | 李明珠 | 一种吸油降噪材料、其制备方法及应用 |
CN110204780A (zh) * | 2019-06-24 | 2019-09-06 | 鲁东大学 | 一种耐用型超疏水聚氨酯泡沫材料的制备方法 |
CN111925525A (zh) * | 2020-08-28 | 2020-11-13 | 东莞市溢美材料科技有限公司 | 一种氨基氟硅树脂及其组合物的制备方法与应用 |
CN112724829A (zh) * | 2020-12-28 | 2021-04-30 | 苏州德达材料科技有限公司 | 一种抗指纹材料及其制备方法和应用 |
CN114249871A (zh) * | 2021-09-09 | 2022-03-29 | 中昊北方涂料工业研究设计院有限公司 | 一种氟硅烷改性耐磨聚氨酯树脂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN106928844B (zh) | 2019-06-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106928844B (zh) | 一种含氟超疏水有机硅涂层复合物及其制备方法 | |
CN102061112B (zh) | 复合金属有机骨架材料胶体溶液的制备方法及其在光学涂层上的应用 | |
CN102653628B (zh) | 一种纳米溶胶改性水性聚氨酯乳液的制备方法及应用 | |
CN102795786B (zh) | 超疏水自清洁涂层及其制备方法 | |
KR102088630B1 (ko) | 규소 산화물 나노 입자와 실세스퀴옥산 중합체의 복합체 및 그의 제조 방법, 및 그 복합체를 사용하여 제조한 복합 재료 | |
CN104629617B (zh) | 一种无机‑有机杂化型超亲水自清洁涂层及其生产方法 | |
CN103524049B (zh) | 一种单层SiO2增透膜的制备方法 | |
CN101955728A (zh) | 一种用于光学塑料表面增强的有机-无机杂化耐磨透明涂料 | |
CN106752121B (zh) | 二氧化硅包覆型铝颜料的制备方法 | |
CN103113825A (zh) | 纳米复合防护涂料及制作方法 | |
CN102358822B (zh) | 一种复合透明硬涂层的制备方法 | |
CN111995889A (zh) | 一种可喷涂疏水材料的制备方法 | |
CN102766333B (zh) | 铝卷涂布用硅树脂复合物及其制备和在铝卷上的涂布方法 | |
CN106243988A (zh) | 高固含量水性紫外光固化透明隔热涂料及其制备方法 | |
CN110157329A (zh) | 一种纳米复合涂层材料 | |
CN103409029A (zh) | 一种疏水耐候性涂料及其制备方法 | |
CN103122214B (zh) | 一种耐高温、耐腐蚀含氟有机硅/SiO2纳米杂化涂层的制备方法 | |
CN104910805B (zh) | 一种用于汽车外表面的陶瓷涂料及其制备方法和应用 | |
CN103508681A (zh) | 超亲水增透涂层的制备方法及超亲水增透涂层 | |
CN101935457A (zh) | 一种高折射率TiO2/有机硅杂化涂层的制作方法 | |
CN105273622B (zh) | 低折射率膜形成用组合物及其制法、低折射率膜的形成法 | |
CN102002268A (zh) | 采用溶胶-凝胶杂化技术制备的超硬不粘硅炊具涂料 | |
CN104087162A (zh) | 多级微纳米粒子增强硅橡胶涂料的制备及其梯度涂覆工艺 | |
CN103664003A (zh) | 一种隔热防雾膜剂的制备方法 | |
CN101168645A (zh) | 一种透明有机硅增硬涂料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20211216 Address after: 315400 No. 28, Maosheng Road, Lianghui Economic Development Zone, Yuyao City, Ningbo City, Zhejiang Province Patentee after: Yuyao Far East Chemical Co.,Ltd. Address before: 2318 yuhangtang Road, Cangqian street, Yuhang District, Hangzhou City, Zhejiang Province Patentee before: Hangzhou Normal University |
|
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190625 |