CN113136034B - Preparation method of core-shell fluorine-containing hydrophobic and oleophobic emulsion - Google Patents
Preparation method of core-shell fluorine-containing hydrophobic and oleophobic emulsion Download PDFInfo
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- CN113136034B CN113136034B CN202110259644.2A CN202110259644A CN113136034B CN 113136034 B CN113136034 B CN 113136034B CN 202110259644 A CN202110259644 A CN 202110259644A CN 113136034 B CN113136034 B CN 113136034B
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- emulsion
- oleophobic
- fluorine
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- shell
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- 239000000839 emulsion Substances 0.000 title claims abstract description 137
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 47
- 239000011737 fluorine Substances 0.000 title claims abstract description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 42
- 239000011258 core-shell material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- -1 octadecyl ester Chemical class 0.000 claims description 30
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 20
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 238000009210 therapy by ultrasound Methods 0.000 claims description 19
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 17
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 5
- FBKBIOOBMXQNBA-UHFFFAOYSA-N propane-2-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)S(O)(=O)=O FBKBIOOBMXQNBA-UHFFFAOYSA-N 0.000 claims description 5
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- RZBSVYZMOJXQJU-UHFFFAOYSA-N [Na].CCCO Chemical compound [Na].CCCO RZBSVYZMOJXQJU-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([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
- CLHYKAZPWIRRRD-UHFFFAOYSA-N 1-hydroxypropane-1-sulfonic acid Chemical compound CCC(O)S(O)(=O)=O CLHYKAZPWIRRRD-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 3
- 238000000576 coating method Methods 0.000 abstract description 20
- 239000011248 coating agent Substances 0.000 abstract description 18
- 239000010702 perfluoropolyether Substances 0.000 abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 229920006243 acrylic copolymer Polymers 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 229920000184 poly(octadecyl acrylate) Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 239000004753 textile Substances 0.000 abstract description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 18
- 229920000056 polyoxyethylene ether Polymers 0.000 description 18
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 17
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 16
- 235000011130 ammonium sulphate Nutrition 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 11
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 8
- 102100041003 Glutamate carboxypeptidase 2 Human genes 0.000 description 7
- 101000892862 Homo sapiens Glutamate carboxypeptidase 2 Proteins 0.000 description 7
- 229920001481 poly(stearyl methacrylate) Polymers 0.000 description 7
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 6
- 229920002313 fluoropolymer Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004811 fluoropolymer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229940005605 valeric acid Drugs 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 230000003075 superhydrophobic effect Effects 0.000 description 3
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000015205 orange juice Nutrition 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 235000013555 soy sauce Nutrition 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- QTRSWYWKHYAKEO-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(1,1,2,2,2-pentafluoroethoxy)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QTRSWYWKHYAKEO-UHFFFAOYSA-N 0.000 description 1
- DVMSVWIURPPRBC-UHFFFAOYSA-N 2,3,3-trifluoroprop-2-enoic acid Chemical class OC(=O)C(F)=C(F)F DVMSVWIURPPRBC-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GZBAUYZREARCNR-UHFFFAOYSA-N C(CCCCCCCCC)[Si](OC)(OC)OC.[F] Chemical compound C(CCCCCCCCC)[Si](OC)(OC)OC.[F] GZBAUYZREARCNR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- PXUULQAPEKKVAH-UHFFFAOYSA-N perfluorohexanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PXUULQAPEKKVAH-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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Classifications
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The invention discloses a preparation method of core-shell fluorine-containing hydrophobic and oleophobic emulsion, which takes poly (octadecyl acrylate) or poly (octadecyl methacrylate) as a core, an acrylic copolymer as a first shell and poly (perfluoropolyether acrylate) for surface modification of the shell. The core-shell fluorine-containing hydrophobic and oleophobic emulsion prepared by the invention is environment-friendly, stable in storage and excellent in hydrophobic and oleophobic performances. The amphiphobic coating material is green and environment-friendly, can be cured in a wider temperature range, and is suitable for substrates made of various materials, such as textiles, metals, glass, steel plates and high polymer materials.
Description
Technical Field
The invention relates to the technical field of preparation of hydrophobic and oleophobic coatings, in particular to a preparation method of a core-shell fluorine-containing hydrophobic and oleophobic emulsion.
Background
Since the amphiphobic (hydrophobic and oleophobic) surface has very low surface energy, excellent properties are exhibited in terms of self-cleaning, oil-water separation, stain resistance, antifogging, anti-icing, drag reduction, organic liquid transport, corrosion prevention, etc., and fabrics treated by the amphiphobic surface have various applications such as medical uniforms, packaging, fashion clothing, extreme sport wear, and military equipment.
C8 fluoropolymer refers to a polymer containing 8 to 12 carbon atoms containing fluoroalkyl chains, all or most of whose hydrogen atoms are substituted with fluorine (known as C8 chemistry). The surface free energy of the C8 fluorine-containing polymer is very low and is 10-15 mN/m. These long fluorinated chains are important for amphiphobic surfaces, their amphiphobic properties depending on the number of fluorinated carbon atoms. Although the C8 fluorinated polymer has good amphiphobic performance, the C-F bond is stable in property and difficult to hydrolyze, photolyze and biodegrade, and generates perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) which are harmful to human bodies in the environment, so that the C-F bond is eliminated abroad. In order to replace the C8 fluoropolymers, researchers developed short chain fluoropolymers containing C.ltoreq.6 fluorinated carbon atoms (referred to as C6 chemistry). To date, the new generation of C6 fluoropolymers is considered environmentally friendly because they can be degraded to non-toxic perfluorohexanoic acid (PFHxA), with high biological clearance.
Chinese patent CN111019482A (application No. 201911348754.5) discloses the preparation and application of super hydrophobic/oleophobic coating with excellent performance. Dispersing nano particles and cellulose in an alcoholic solution containing alkaline substances, and adding tetraethyl orthosilicate and fluorine-containing organosilane for hydrolysis coating to form a solution A; dispersing epoxy resin in an alcohol solution to form a solution B; uniformly mixing the solution A and the solution B, and then adding tetraethyl orthosilicate and fluorine-containing organosilane to react to generate polysiloxane, namely solution C; dissolving amine compounds containing fluorine in an alcohol solution, and obtaining a solution D; and uniformly mixing the solution C and the solution D, spraying the mixture on a substrate, and curing to obtain the coating. This patent has constructed a multistage micro-nano hierarchical structure, and chemical stability is good, can reach the effect of complete rejection to N, N-dimethylformamide liquid drop (34.4mN/m), is 120 to the contact angle of N-hexadecane (27.1mN/m), but the process is comparatively complicated loaded down with trivial details, and the fluorine-containing organosilane of chooseing for use is seventeen fluorine decyl trimethoxy silane etc. moreover, exists the threat to the environment.
Chinese patent CN111154344A (application No. 202010067754.4) discloses a super-hydrophobic and super-oleophobic coating and a preparation method thereof. Adding deionized water, styrene, an acrylic monomer, an initiator and divinyl benzene into a container, uniformly stirring, heating to 40-90 ℃, and preserving heat for 1-10 hours to obtain white St-AA copolymer emulsion; adding a solvent, orthosilicate and St-AA copolymer emulsion into a container, and stirring to obtain uniform emulsion; and then adding ammonia water into the uniform emulsion, stirring and heating to 30-80 ℃, keeping the temperature for 0.5-8 h, then adding fluorosilicone, and keeping the temperature for 0.5-8 h to obtain the super-hydrophobic and super-oleophobic coating. The fluorosilicone adopts perfluorodecyl triethoxysilane, and is also not friendly to the environment.
The limited use of the C8 fluorine-containing polymer greatly restricts the selection of raw materials in the synthesis of the amphiphobic material, and although the C6 fluorine-containing polymer does not have the problem of environmental unfriendliness, the prepared amphiphobic coating has the performance which is still inferior to that of the C8. Therefore, the invention provides a preparation method of the core-shell type hydrophobic and oleophobic emulsion to achieve the aim of preparing the high-performance hydrophobic and oleophobic coating.
Disclosure of Invention
The invention aims to solve the problem that the use of C8 fluorine-containing reagent is limited in the preparation of the existing high-performance double-hydrophobic coating, and provides a preparation method of a core-shell fluorine-containing hydrophobic and oleophobic emulsion. The amphiphobic coating material is green and environment-friendly, can be cured in a wider temperature range, and is suitable for substrates made of various materials, such as textiles, metals, glass, steel plates and high polymer materials.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of core-shell fluorine-containing hydrophobic and oleophobic emulsion comprises the following steps:
1) carrying out ultrasonic treatment on an octadecyl ester monomer, an emulsifier, an initiator and deionized water in an ultrasonic cell crusher under the ice bath condition to obtain a miniemulsion, filling the obtained miniemulsion into a reactor, introducing protective gas nitrogen, and reacting for 4-6 h at the temperature of 80-95 ℃ to obtain a homopolymer emulsion, wherein the homopolymer is used as the core of the fluorine-containing hydrophobic and oleophobic emulsion;
2) stirring an acrylic mixed monomer, an emulsifier, an initiator and deionized water to obtain a pre-emulsion, dropwise adding the obtained pre-emulsion into the emulsion containing the homopolymer in the step 1), and dropwise adding the pre-emulsion for 2-3 hours at the temperature of 60-80 ℃ to obtain a copolymer emulsion, wherein the copolymer serves as a shell of the fluorine-containing hydrophobic and oleophobic emulsion;
3) and (2) stirring a fluorine-containing monomer, an emulsifier, an initiator and deionized water to form an emulsion, dropwise adding the obtained emulsion into the copolymer emulsion obtained in the step 2), and dropwise adding the emulsion for 2-3 hours at 70-90 ℃ to prepare the core-shell fluorine-containing hydrophobic and oleophobic emulsion.
Wherein the emulsifier is one of Sodium Dodecyl Benzene Sulfonate (SDBS), alkylphenol polyoxyethylene ether (OP-10), Sodium Vinyl Sulfonate (SVS), 2-allyl ether-3-hydroxypropyl alkyl-1-sodium sulfonate (UCAN-1), allyl ether hydroxypropane sodium sulfonate (UCAN-8088), alcohol ether succinate sodium salt (NRS-138), acrylamide isopropyl sulfonate (A-2405) and allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86);
the initiator is one of azobisisobutyronitrile, potassium persulfate, ammonium persulfate, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline or azobiscyanovaleric acid.
In the step 1), the octadecyl monomer is one of octadecyl acrylate and octadecyl methacrylate;
the dosage ratio of the octadecyl ester monomer, the emulsifier, the initiator and the deionized water is 5-10 g: 0.1 g-0.2 g: 0.025 g-0.06 g: 40-60 g.
The ultrasonic conditions are as follows: and carrying out ultrasonic treatment for 2-4 s, and carrying out intermittent treatment for 3-6 s for 10-20 min.
In the step 2), the acrylic monomers are at least two of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate and methyl methacrylate;
the dosage ratio of the acrylic monomer, the emulsifier, the initiator and the deionized water is 30-60 g: 0.35 g-1.4 g: 0.15 g-0.36 g: 120-200 g.
In the step 3), the fluorine-containing monomer is at least one of perfluoropolyether-methacrylate PFPE-MMA-1000, PFPE-MMA-1600, PFPE-MMA-2000 and PFPE-MMA-3000;
the using amount ratio of the fluorine-containing monomer to the emulsifier to the initiator to the deionized water is 5-10 g: 0.1 g-0.2 g: 0.025 g-0.06 g: 40-60 g.
Methacrylate (octadecyl acrylate (SA) and octadecyl methacrylate (SMA)) containing long-chain alkyl ester (n is more than 12), wherein alkyl side chains in the polymer can be crystallized and have low activity, when the surface of the polymer is contacted with polar liquid such as water and the like, the surface reconstruction phenomenon cannot occur, the dynamic water repellency is good, and the durable, stable and low surface energy can be obtained, so the acrylic acid/acrylic acid copolymer has the advantages of good water repellency and good water resistanceThe coating prepared by using poly (octadecyl acrylate) (PSA) or poly (octadecyl methacrylate) (PSMA) as the core of the core-shell emulsion has hydrophobic property. Because PAS or PSMA has higher crystallinity, the formed coating becomes brittle and affects the performance, so the invention takes the acrylic copolymer as the shell of the core-shell emulsion to regulate and control the performance of the coating after film forming. The side chain of PSA or PSMA contains only long-chain alkyl ester, its hydrocarbon (-CH)3) The surface tension of the coating is about 24mN/m, and the oil-repellent performance is difficult to realize, so that the fluorine-containing polymer (about 10-15 mN/m) with lower surface energy is introduced to be used as the modification of the shell of the core-shell type emulsion, and the coating has the oil-repellent performance. In the invention, the perfluoropolyether acrylate with short fluorocarbon chain is selected as a polymerization monomer, wherein the main chain of the fluorine-containing group is formed by-CF2-O-CF2-such ether chain formation, with-CF2-CF2-CF2The perfluoroolefin chains of such C8 polymers, unlike one another, are degradable in the environment. Meanwhile, the poly (perfluoropolyether acrylate) with stable performance is used for modifying the shell layer of the core-shell type emulsion, so that the prepared emulsion can be stored for a long time.
In general, perfluoroacrylates synthesized by free radical polymerization are difficult to crystallize only when they have a long perfluoroalkyl side chain (C) which is rigidnF2n+1N is more than or equal to 8), so that the polymer is induced to crystallize, and a layered stacking structure can be formed after the crystallization of the linear side chain. The short perfluoroalkyl side chain cannot crystallize per se, and is difficult to form a stable crystalline structure, the obtained polymer surface cannot form a durable low-surface-energy coating, and the polymer surface can generate moving and reconstruction phenomena in the process of contacting polar substances. Therefore, the core-shell fluorine-containing hydrophobic and oleophobic emulsion prepared by the invention takes PSA or PSMA which is easy to crystallize as a core, acrylic copolymer as a shell and poly (perfluoropolyether acrylate) as a modified shell layer. Higher crystallinity PSAs or PSMAs may limit the short chain-CF in polyperfluoropolyether acrylates3Activity and reconstitution of-CF in coatings prepared with emulsions of the present invention3Can be closely packed, thereby showing excellent hydrophobic and oleophobic performances.
Compared with the prior art, the invention has the following advantages:
1. the core-shell structure selected by the invention takes PSA or PSMA with excellent hydrophobic property as a core and acrylic copolymer as a shell to regulate and control the performance of the coating, and the polyperfluoropolyether acrylate is used for modifying the shell layer to provide oleophobic property, thereby fully playing the performance characteristics of various substances.
2. The invention limits short chain-CF in poly (perfluoropolyether acrylate) by PSA or PSMA with higher crystallinity3The core-shell fluorine-containing hydrophobic and oleophobic emulsion prepared by the method is environment-friendly, stable in storage and excellent in performance (hydrophobic and oleophobic).
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the emulsion prepared in example 6.
FIG. 2 is a graph showing the effect of testing the hydrophobic and oleophobic properties of the emulsions prepared in examples 1-6 and comparative examples 1-2, which were sprayed on a woven fabric to form a coating, using a copper sulfate solution, orange juice, milk, soy sauce, vegetable oil, and hexadecane.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
5g of octadecyl acrylate (SA), 0.1g of Sodium Dodecyl Benzene Sulfonate (SDBS), 0.025g of azodiisobutyronitrile and 40g of deionized water, carrying out ultrasonic treatment (ultrasonic treatment for 3s, intermittent treatment for 3s and continuous treatment for 15min) in an ultrasonic cell crusher under the ice bath condition to obtain a miniemulsion, filling the obtained emulsion into a reactor, introducing protective gas nitrogen, and reacting at 80 ℃ for 4h to obtain an emulsion 1; 15g of methyl methacrylate, 15g of butyl acrylate, 0.35g of Sodium Vinyl Sulfonate (SVS), 0.15g of azobisisobutyronitrile and 120g of deionized water, stirring at a high speed to form a pre-emulsion, adding the obtained pre-emulsion into the emulsion 1 by a dropwise adding method, and dropwise adding for 3 hours at the temperature of 80 ℃ to obtain an emulsion 2; 5g of perfluoropolyether methyl methacrylate (PFPE-MMA-1000), 0.1g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.025g of azodiisobutyronitrile and 40g of deionized water are stirred at a high speed to form a pre-emulsion, the obtained pre-emulsion is added into the emulsion 2 dropwise, and the pre-emulsion is added dropwise for 2 hours at 80 ℃ to prepare the core-shell fluorine-containing hydrophobic and oleophobic emulsion.
Example 2
5g of octadecyl methacrylate (SMA), 0.1g of alkylphenol polyoxyethylene ether (OP-10), 0.025g of potassium persulfate and 40g of deionized water, carrying out ultrasonic treatment (ultrasonic treatment for 3s, intermittent treatment for 3s, and continuous treatment for 15min) in an ultrasonic cell crusher under the ice bath condition to obtain miniemulsion, filling the obtained emulsion into a reactor, introducing protective gas nitrogen, and reacting at 80 ℃ for 4h to obtain emulsion 1; 20g of methyl acrylate, 20g of methacrylic acid, 0.50g of 2-allyl ether-3-hydroxypropyl alkane-1-sodium sulfonate (UCAN-1), 0.20g of potassium persulfate and 140g of deionized water are stirred at a high speed to form a pre-emulsion, the obtained pre-emulsion is added into the emulsion 1 by a dropping method, and the pre-emulsion is dropped for 3 hours at the temperature of 80 ℃ to obtain an emulsion 2; 5g of perfluoropolyether methyl methacrylate (PFPE-MMA-1000), 0.1g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.025g of azodiisobutyronitrile and 40g of deionized water are stirred at a high speed to form a pre-emulsion, the obtained pre-emulsion is added into the emulsion 2 dropwise, and the pre-emulsion is added dropwise for 2 hours at 80 ℃ to prepare the core-shell fluorine-containing hydrophobic and oleophobic emulsion.
Example 3
10g of octadecyl acrylate (SA), 0.2g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.06g of ammonium persulfate and 60g of deionized water, carrying out ultrasonic treatment (ultrasonic treatment for 3s, intermittent treatment for 3s and continuous treatment for 15min) in an ultrasonic cell crusher under the ice bath condition to obtain miniemulsion, filling the obtained emulsion into a reactor, introducing protective gas nitrogen, and reacting at 80 ℃ for 4h to obtain emulsion 1; 25g of methyl methacrylate, 25g of ethyl acrylate, 1.00g of alcohol ether succinate sodium salt (NRS-138), 0.25g of potassium persulfate and 160g of deionized water, stirring at a high speed to form a pre-emulsion, adding the obtained pre-emulsion into the emulsion 1 by a dropwise adding method, and dropwise adding for 3 hours at the temperature of 80 ℃ to obtain an emulsion 2; 5g of perfluoropolyether methyl methacrylate (PFPE-MMA-2000), 0.1g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.025g of azodiisobutyronitrile and 40g of deionized water are stirred at a high speed to form a pre-emulsion, the obtained pre-emulsion is added into the emulsion 2 dropwise, and the pre-emulsion is added dropwise for 2 hours at 80 ℃ to prepare the core-shell fluorine-containing hydrophobic and oleophobic emulsion.
Example 4
8g of octadecyl methacrylate (SMA), 0.16g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.04g of azodicyano valeric acid and 50g of deionized water, carrying out ultrasonic treatment (ultrasonic treatment for 3s, intermittent treatment for 3s, and continuous treatment for 15min) in an ultrasonic cell crusher under an ice bath condition to obtain a fine emulsion, filling the obtained emulsion into a reactor, introducing protective gas nitrogen, and carrying out reaction for 4h at 90 ℃ to obtain an emulsion 1; 25g of methyl methacrylate, 25g of butyl acrylate, 1.00g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.25g of potassium persulfate and 160g of deionized water, stirring at a high speed to form a pre-emulsion, adding the pre-emulsion into the emulsion 1 by a dropwise adding method, and dropwise adding at the temperature of 80 ℃ for 3 hours to obtain an emulsion 2; 10g of perfluoropolyether methyl methacrylate (PFPE-MMA-1000), 0.2g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.05g of azodicyano valeric acid and 60g of deionized water are stirred at a high speed to form a pre-emulsion, the obtained pre-emulsion is added into the emulsion 2 by a dropwise adding method, and the core-shell type fluorine-containing hydrophobic and oleophobic emulsion is prepared by dropwise adding for 3h at 85 ℃.
Example 5
10g of octadecyl methacrylate (SMA), 0.10g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.05g of azodiisobutyronitrile and 60g of deionized water, carrying out ultrasonic treatment (ultrasonic treatment for 3s, intermittent treatment for 3s, and continuous treatment for 15min) in an ultrasonic cell crusher under an ice bath condition to obtain a miniemulsion, filling the obtained emulsion into a reactor, introducing protective gas nitrogen, and carrying out reaction for 4h at 95 ℃ to obtain an emulsion 1; 30g of methyl methacrylate, 30g of butyl acrylate, 0.60g of sodium allyl ether hydroxypropanesulfonate (UCAN-8088), 0.30g of ammonium persulfate and 200g of deionized water are stirred at a high speed to form a pre-emulsion, the pre-emulsion is added into the emulsion 1 by a dropping method, and the pre-emulsion is dropped for 3 hours at the temperature of 80 ℃ to obtain an emulsion 2; 10g of perfluoropolyether methyl methacrylate (PFPE-MMA-3000), 0.2g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.05g of azodicyano valeric acid and 60g of deionized water are stirred at a high speed to form a pre-emulsion, the obtained pre-emulsion is added into the emulsion 2 by a dropwise adding method, and the core-shell type fluorine-containing hydrophobic and oleophobic emulsion is prepared by dropwise adding for 3h at 85 ℃.
Example 6
10g of octadecyl methacrylate (SMA), 0.10g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.05g of azodiisobutyronitrile and 40g of deionized water, carrying out ultrasonic treatment (ultrasonic treatment for 3s, intermittent treatment for 3s, and continuous treatment for 15min) in an ultrasonic cell crusher under an ice bath condition to obtain a miniemulsion, filling the obtained emulsion into a reactor, introducing protective gas nitrogen, and reacting at 85 ℃ for 4h to obtain an emulsion 1; 30g of methyl methacrylate, 30g of butyl acrylate, 0.50g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.30g of azodiisobutyronitrile and 180g of deionized water, stirring at a high speed to form a pre-emulsion, adding the obtained pre-emulsion into the emulsion 1 by a dropwise adding method, and dropwise adding for 3 hours at the temperature of 80 ℃ to obtain an emulsion 2; 10g of perfluoropolyether methyl methacrylate (PFPE-MMA-1000), 0.2g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.05g of azodicyano valeric acid and 40g of deionized water are stirred at a high speed to form a pre-emulsion, the obtained pre-emulsion is added into the emulsion 2 by a dropwise adding method, and the core-shell type fluorine-containing hydrophobic and oleophobic emulsion is prepared by dropwise adding for 3h at 90 ℃.
Comparative example 1
The method comprises the following steps of preparing a fine emulsion by ultrasonic treatment in an ultrasonic cell crusher under the ice bath condition, wherein the fine emulsion is prepared by the steps of 5g of octadecyl acrylate (SA), 15g of methyl methacrylate, 15g of butyl acrylate, 5g of perfluoropolyether methyl methacrylate (PFPE-MMA-1000), 2.00g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.20g of azobisisobutyronitrile and 200g of deionized water, loading the fine emulsion into a reactor, introducing protective gas nitrogen, and reacting for 6 hours at 85 ℃ to obtain the emulsion.
Comparative example 2
5g of octadecyl methacrylate (SMA), 0.10g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.025g of azodiisobutyronitrile and 50g of deionized water, carrying out ultrasonic treatment (ultrasonic treatment for 3s, intermittent treatment for 3s, and continuous treatment for 15min) in an ultrasonic cell crusher under an ice bath condition to obtain a miniemulsion, filling the obtained emulsion into a reactor, introducing protective gas nitrogen, and reacting at 85 ℃ for 4h to obtain an emulsion 1; 15g of methyl methacrylate, 15g of butyl acrylate, 5g of perfluoropolyether methyl methacrylate (PFPE-MMA-1000), 1.50g of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate (DNS-86), 0.175g of azobisisobutyronitrile and 150g of deionized water are stirred at a high speed to form a pre-emulsion, the obtained pre-emulsion is added into the emulsion 1 by a dropping method, and the pre-emulsion is dropped for 3 hours at the temperature of 85 ℃ to obtain the emulsion.
The emulsions prepared in examples 1 to 6 and comparative examples 1 to 2 were sprayed on a woven cloth to form a coating layer, and the contact angles of water (copper sulfate solution, orange juice, milk, soy sauce) and oil (vegetable oil, Hexadecane (HD)) were tested, and table 1 is data of the contact angles. As can be seen from the data in the table, the core-shell type emulsion prepared by the method of the invention has excellent hydrophobic and oleophobic properties.
FIG. 1 is a TEM image of example 6, from which it can be seen that the prepared emulsion has a core-shell structure. The hydrophobic and oleophobic performance effect graph of fig. 2 corresponds to the data in table 1, and further verifies that the core-shell fluorine-containing hydrophobic and oleophobic emulsion prepared by the invention has excellent performance.
TABLE 1
Claims (8)
1. A preparation method of core-shell fluorine-containing hydrophobic and oleophobic emulsion is characterized by comprising the following steps:
1) carrying out ultrasonic treatment on an octadecyl ester monomer, an emulsifier, an initiator and deionized water in an ultrasonic cell crusher under the ice bath condition to obtain a miniemulsion, filling the obtained miniemulsion into a reactor, introducing protective gas nitrogen, and reacting for 4-6 h at the temperature of 80-95 ℃ to obtain a homopolymer emulsion, wherein the homopolymer is used as the core of the fluorine-containing hydrophobic and oleophobic emulsion;
the octadecyl monomer is one of octadecyl acrylate and octadecyl methacrylate;
2) stirring an acrylic mixed monomer, an emulsifier, an initiator and deionized water to obtain a pre-emulsion, dropwise adding the obtained pre-emulsion into the emulsion containing the homopolymer in the step 1), and dropwise adding the pre-emulsion for 2-3 hours at the temperature of 60-80 ℃ to obtain a copolymer emulsion, wherein the copolymer serves as a shell of the fluorine-containing hydrophobic and oleophobic emulsion;
the acrylic mixed monomer is at least two of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate and methyl methacrylate;
3) stirring a fluorine-containing monomer, an emulsifier, an initiator and deionized water to form an emulsion, dropwise adding the obtained emulsion into the copolymer emulsion obtained in the step 2), and dropwise adding the emulsion for 2-3 hours at 70-90 ℃ to prepare a core-shell fluorine-containing hydrophobic and oleophobic emulsion;
the fluorine-containing monomer is at least one of perfluoropolyether-methacrylate PFPE-MMA-1000, PFPE-MMA-1600, PFPE-MMA-2000 and PFPE-MMA-3000.
2. The method for preparing the core-shell fluorine-containing hydrophobic and oleophobic emulsion according to claim 1, characterized in that in step 1), the emulsifier is one of sodium dodecyl benzene sulfonate, alkylphenol polyoxyethylene, sodium vinyl sulfonate, 2-allyl ether-3-hydroxypropyl alkyl-1-sodium sulfonate, allyl ether hydroxypropane sodium sulfonate, alcohol ether succinate sodium salt, acrylamide isopropyl sulfonate, and allyloxy nonylphenol polyoxyethylene ammonium sulfate;
the initiator is one of azobisisobutyronitrile, potassium persulfate, ammonium persulfate, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline or azobiscyanovaleric acid.
3. The preparation method of the core-shell fluorine-containing hydrophobic and oleophobic emulsion according to claim 1, characterized in that in step 1), the usage ratio of the octadecyl monomer, the emulsifier, the initiator and the deionized water is 5-10 g: 0.1 g-0.2 g: 0.025 g-0.06 g: 40-60 g.
4. The method for preparing the core-shell fluorine-containing hydrophobic and oleophobic emulsion according to claim 1, characterized in that in step 2), the emulsifier is one of sodium dodecyl benzene sulfonate, alkylphenol polyoxyethylene, sodium vinyl sulfonate, 2-allyl ether-3-hydroxypropyl alkyl-1-sodium sulfonate, allyl ether hydroxypropane sodium sulfonate, alcohol ether succinate sodium salt, acrylamide isopropyl sulfonate, and allyloxy nonylphenol polyoxyethylene ammonium sulfate;
the initiator is one of azobisisobutyronitrile, potassium persulfate, ammonium persulfate, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline or azobiscyanovaleric acid.
5. The preparation method of the core-shell fluorine-containing hydrophobic and oleophobic emulsion according to claim 1, characterized in that in step 2), the usage ratio of the acrylic mixed monomer, the emulsifier, the initiator and the deionized water is 30-60 g: 0.35 g-1.4 g: 0.15 g-0.36 g: 120-200 g.
6. The method for preparing the core-shell fluorine-containing hydrophobic and oleophobic emulsion according to claim 1, characterized in that in step 3),
the emulsifier is one of sodium dodecyl benzene sulfonate, alkylphenol polyoxyethylene, sodium vinylsulfonate, 2-allyl ether-3-hydroxypropyl alkyl-1-sodium sulfonate, sodium allyl ether hydroxypropane sulfonate, alcohol ether succinate sodium salt, acrylamide isopropyl sulfonate and allyloxy nonylphenol polyoxyethylene ammonium sulfate;
the initiator is one of azobisisobutyronitrile, potassium persulfate, ammonium persulfate, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline or azobiscyanovaleric acid.
7. The preparation method of the core-shell fluorine-containing hydrophobic and oleophobic emulsion according to claim 1, characterized in that in step 3), the usage ratio of the fluorine-containing monomer, the emulsifier, the initiator and the deionized water is 5-10 g: 0.1 g-0.2 g: 0.025 g-0.06 g: 40-60 g.
8. The method for preparing the core-shell fluorine-containing hydrophobic and oleophobic emulsion according to claim 1, characterized in that in step 1), the ultrasonic conditions are as follows: and carrying out ultrasonic treatment for 2-4 s, and carrying out intermittent treatment for 3-6 s for 10-20 min.
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| CN108250350B (en) * | 2018-02-08 | 2020-02-07 | 江南大学 | Preparation and application of short-chain fluorine-containing copolymer water-repellent and oil-repellent finishing agent |
| WO2019172021A1 (en) * | 2018-03-08 | 2019-09-12 | Ａｇｃ株式会社 | Method for producing water-and-oil repellent composition, and method for producing water-and-oil repellent article |
| CN109281172B (en) * | 2018-08-15 | 2020-11-10 | 浙江理工大学 | Core-shell type fluorine-free waterproof finishing agent and preparation method and application thereof |
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