CN106479338B - A kind of preparation method with hydrophobic cationic acrylate resin cathode electrophoresis dope - Google Patents
A kind of preparation method with hydrophobic cationic acrylate resin cathode electrophoresis dope Download PDFInfo
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- CN106479338B CN106479338B CN201610872247.1A CN201610872247A CN106479338B CN 106479338 B CN106479338 B CN 106479338B CN 201610872247 A CN201610872247 A CN 201610872247A CN 106479338 B CN106479338 B CN 106479338B
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- 238000001962 electrophoresis Methods 0.000 title claims abstract description 70
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 25
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 23
- -1 cation fluorine modified acrylic ester Chemical class 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 31
- 239000011737 fluorine Substances 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 29
- 239000004971 Cross linker Substances 0.000 claims abstract description 27
- 150000002148 esters Chemical class 0.000 claims abstract description 27
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 27
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 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 13
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- 238000004438 BET method Methods 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 5
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 claims description 4
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 4
- 229960004194 lidocaine Drugs 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000002966 varnish Substances 0.000 claims description 3
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000008367 deionised water Substances 0.000 abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 abstract description 10
- 239000003973 paint Substances 0.000 abstract description 4
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000007812 deficiency Effects 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 230000037452 priming Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 238000004070 electrodeposition Methods 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 7
- 238000013019 agitation Methods 0.000 description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 6
- 239000006210 lotion Substances 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 230000003075 superhydrophobic effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 241001465382 Physalis alkekengi Species 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000023555 blood coagulation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
Classifications
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—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
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/4465—Polyurethanes
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- 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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
- C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
-
- 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
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1803—C3-(meth)acrylate, e.g. (iso)propyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Molecular Biology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of preparation methods with hydrophobic cationic acrylate resin cathode electrophoresis dope, first prepare the preparation of cation fluorine modified acrylic ester resin and Totally-enclosed-type polyisocyanate crosslinker, it will be acidified after cation fluorine modified acrylic ester resin and the reaction of Totally-enclosed-type polyisocyanate crosslinker, it is carried out after being sufficiently mixed preparation with hydrophobic oxide particle, is eventually adding deionized water dispersion and cathode electrophoresis dope is prepared.Fluorin modified crylic acid ester monomer is introduced into acrylate cathode electrophoresis dope by the present invention, utilize the excellent chemical resistance and low-surface-energy of fluorine resin, to be effectively improved the hydrophobic performance of film, meanwhile acrylate and epoxy resin perfect combination getting up, acrylate is because of its excellent weatherability and good guarantor's color, gloss retention, it is only suitable for doing the deficiency of priming paint to compensate for epoxy resin, properties of product are excellent, and the service life is long, can be widely used for all kinds of high-quality hardwares.
Description
Technical field
The present invention relates to a kind of preparation processes of new material, specifically, being a kind of with hydrophobic cationic acrylamide
The preparation method of acid ester resin cathode electrophoresis dope.
Background technique
In recent years, super-hydrophobic (contact angle is greater than 150 °) in nature causes the research of people emerging with self-cleaning phenomenon
Interest.Manually preparing super hydrophobic surface can be used for the antifouling of automotive window, the windowpane of building and glass outer wall, be used for thunder
Reach, signal is decayed caused by antenna surface can be prevented due to precipitation adhesion, the surface super hydrophobic of material can inhibit micro- life
Object inhibits the blood coagulation phenomenon of polymer surfaces in the adherency of body surface, can reduce fluid resistance for water delivery, oil transportation inner tubal wall
Deng.The research of super hydrophobic surface has become hot subject, is related to botany, chemistry, materialogy, engineering mechanics etc. more
Section.
Cathodic Electrophoretic Painting Technology, due to its coating uniformity and excellent corrosion resistance and low pollution the advantages that,
Application field is growing, it has also become one of indispensable method of field of coating.Since first generation cathode electrophoresis dope is developed
Since succeeding and being applied, by development in more than 40 years, the research of domestic and international cathode electrophoresis dope and application field occurred
Very big variation, has researched and developed the 6th generation, the 7th generation or even eighth generation product.Cathode electrophoresis dope belongs to environment friend
Good type water paint, from now on, during cathode electro-coating new technology development, coating process should be towards the saving energy, reduction
Labor intensity and production cost, reduce environmental pollution, heavy metal free, low VOC, VOC, reduce solidification temperature,
The directions such as high performance are developed.
Since 1971, PPG company, the U.S. developed first generation cathode electrophoresis dope, and electrophoretic coating enters one quickly
The track of development, especially cathode electrophoresis dope, because corrosion resistance is 3-4 times high compared with anode electrophoresis dope for it, permeability ratio is high
1.3-1.5 times, and metal surface is not easy to be ionized and eluted when electro-deposition, solves workpiece surface etching problem, thus obtain
Be widely applied, gradually comprehensively instead of anode electrophoresis dope, cathode electrophoresis dope shows several major sects at present: i.e. with
PPG company, the U.S. is the anti-corrosion cation electrophoretic coating at beginning；It is used with German Hocehst company for the car truck of pioneer
Cation electrophoretic coating；Using the western paint company in day Benshen Dongguan as the modified cation electrophoretic coating of representative.Some skills
The leading cathode electrophoresis dope company of art has developed corner rust-proof type, yin of weather-proof and the 5th generation of low temperature curing type forth generation
Pole electrophoretic coating, while in the six, the seven generations, also developed in laboratory research.The May 4th research institute, weapons portion (five or nine institute) at home,
Shanghai coating research institute and coating research institute, the Ministry of Chemical Industry develop cathode electrophoresis dope the eighties in succession, and some Paint Factories are also confused
The confused Introduced from Japan Northwest, Austrian Stollack, U.S. PPG, the technologies such as German BASF carry out the production of electrophoretic coating, and
The matrix resin generally used has epoxy resin, polyester resin, epoxy-polyurethane etc..But it is poor often to there is weatherability, and heating is easy
Xanthochromia, solidification temperature are high, it is difficult to the problems such as coloured silkization.And acrylic cathodic electrophoretic coating is because of its excellent guarantor's light, weather-proof, uvioresistant
The performances such as line aging, high decoration and be widely used in bottom surface unification electrophoretic painting.
In recent years, high-performance hardware especially lamps and lanterns, fittings of bathroom, the rapid development of metal handicrafts and electrophoresis
The continuous development and progress of application techniques propose performance especially hydrophobicity, weatherability and the dicoration of coating higher
It is required that.After traditional aqueous cathode electrophoresis dope film forming, the comprehensive performance of film especially hydrophobicity, weatherability and dicoration are owed
It is good, it is not able to satisfy the new demand that high-grade hardware proposes aqueous cathode electrophoresis dope.CN101993576 provides one kind
Hydrophobicity cathode electrophoresis dope resin emulsion and preparation method thereof.The resin emulsion is by cation fluorine carbon resin and contains active hydrogen
Organic compound is to be acidified after the Totally-enclosed-type polyisocyanate crosslinker of sealer reacts, and deionized water dispersion preparation is added
Obtain, the resin emulsion of the invention after being configured to cathode electrophoresis dope varnish film forming, the contact angle 100 of film and water~
120 °, the biggish hydrophobicity for improving aqueous cathode electrophoresis dope, weatherability and dicoration.CN103333596A has registered one
Kind fluorinated silicone modified acrylic cathodic electrophoretic coating of automatically cleaning and preparation method thereof, it is modified to use semiclosed aliphatic isocyanates
Fluorine silicon acrylic cationic resin and nano-titanium dioxide modified mill base are prepared, and the contact angle of film coated surface and water reaches
130°。
Although having there is many progress in hydrophobicity, the comprehensive performance of existing film especially hydrophobicity,
Weatherability and the decorative new demand for being not met by high-grade hardware and aqueous cathode electrophoresis dope being proposed, it is especially super
The requirement of hydrophobic performance.Therefore further the cathode electrophoresis dope of development function type is current research hotspot.
Summary of the invention
The present invention is exactly directed to various shortcomings existing in the prior art, provide it is a kind of have hydrophobic sun from
The preparation method of sub- acrylate cathode electrophoresis dope.
The present invention is technical solution in this way to realize in order to achieve the above objectives:
The invention discloses a kind of preparation method with hydrophobic cationic acrylate resin cathode electrophoresis dope,
The preparation for first preparing cation fluorine modified acrylic ester resin and Totally-enclosed-type polyisocyanate crosslinker, cation fluorine is modified
It is acidified, is carried out with hydrophobic oxide particle sufficiently mixed after acrylate and the reaction of Totally-enclosed-type polyisocyanate crosslinker
It closes after preparing, is eventually adding deionized water dispersion and cathode electrophoresis dope is prepared.
As a further improvement, of the present invention, specific preparation process is as follows: in a kettle, solvent and part is added
Initiator azodiisobutyronitrile, at 85-100 DEG C by crylic acid ester mixture monomer and fluorinated acrylate monomer mixture and
Partial initiator azodiisobutyronitrile solution is added drop-wise in reaction kettle, is dripped off in 2-4 hours, is continued insulation reaction 2 hours, drop
Cation fluorine modified acrylic ester resin is obtained after temperature；Prepare Totally-enclosed-type polyisocyanate crosslinker, by it is a certain amount of sun from
Sub- fluorin modified crylic acid ester resin, Totally-enclosed-type polyisocyanate crosslinker and ethylene glycol monobutyl ether, organic acid and hydrophobicity oxygen
Compound particle is uniformly mixed, and be acidified 1-2 hours at 50-70 DEG C, is then added a certain amount of deionized water, under high-speed stirred, is divided
Scattered 15-30min obtains having hydrophobic cationic acrylate resin cathode electrophoresis dope, and control pH is 5.0-6.5.
As a further improvement, of the present invention there is hydrophobic cationic acrylate resin ability cathode electrophoresis to apply
The preparation method of material, which is characterized in that the preparation method of the Totally-enclosed-type polyisocyanate crosslinker be in a kettle,
Isophorone diisocyanate is added slowly butyl is added drop-wise in reaction kettle under agitation, drip within 1 hour
It adds, is heated to 70 DEG C, react 2-4 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
As a further improvement, fluorinated acrylate monomer of the present invention is Hexafluorobutyl mathacrylate, third
Olefin(e) acid hexafluoro butyl ester, dodecafluoroheptyl methacrylate, ten trifluoro monooctyl ester of methacrylic acid, perluorooctyl acrylate and perfluor
One of alkyl ethylmethyl acrylate is a variety of.
As a further improvement, crylic acid ester mixture monomer of the present invention includes tertiary amino acrylic ester monomer
With general acrylic ester monomer, wherein tertiary amino acrylic ester monomer includes dimethylaminoethyl methacrylate, acrylic acid two
Ethylamino propyl ester, dimethylaminoethyl acrylate, dimethylaminoethyl propyl ester, methacrylic acid lignocaine propyl ester,
One of dimethylaminoethyl methacrylate, dimethylaminoethyl propyl ester are a variety of；General esters of acrylic acid list
Body includes styrene, methyl methacrylate, ethyl methacrylate, butyl acrylate, isopropyl acrylate, acrylic acid -2-
One of hydroxy methacrylate, methacrylic acid -2- hydroxy methacrylate and methacrylic acid -2- hydroxy propyl ester are a variety of.
As a further improvement, in cation fluorine modified acrylic ester resin of the present invention, tertiary amino acrylic acid
Esters monomer 10-20 parts by weight, general acrylic ester monomer 40-70 parts by weight, fluorinated acrylate monomer 10-30 weight
Part, initiator azodiisobutyronitrile 0.5-2 parts by weight and solvent 10-30 parts by weight, organic acid are formic acid, acetic acid, lactic acid and ammonia
Base sulfonic acid it is one or more.
As a further improvement, hydrophobic oxide particle of the present invention is hydrophobic silica, it is primary flat
Equal partial size is 3-100nm, and the specific surface area measured with BET method is 50-300 m2/g。
As a further improvement, having trimethylsilyl on its surface of hydrophobic silica of the present invention.
As a further improvement, cathode electrophoresis dope each group of the present invention is divided into cation fluorine modification acrylate
Resin 50-60 parts by weight, Totally-enclosed-type polyisocyanate crosslinker 20-25 parts by weight, hydrophobic oxide particle 2-10 weight
Part.
As a further improvement, cathode electrophoresis dope obtained by the present invention is after varnish film forming, film and water are connect
Feeler is 145-160 degree.
Beneficial effects of the present invention are as follows:
1, the present invention provides one kind to have hydrophobic cathode electrophoresis dope cationic acrylate resin and its preparation
Method.Conventional propylene acid resin cathode electrophoresis dope does not have hydrophobic performance, and the present invention introduces fluorin modified crylic acid ester monomer
In acrylate cathode electrophoresis dope, using the excellent chemical resistance and low-surface-energy of fluorine resin, to be effectively improved
The hydrophobic performance of film.
Specific embodiment
The invention discloses one kind to have hydrophobic cationic acrylate resin cathode electrophoresis dope and its preparation side
Method, the present invention make detailed description further to technical solution of the present invention combined with specific embodiments below, but of the invention
Range is not limited to embodiment.
Embodiment 1
(1) preparation of cation fluorine modified acrylic ester resin
In the reaction kettle equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
0.2 parts by weight of 10 parts by weight of butyl acetate and initiator azodiisobutyronitrile, by crylic acid ester mixture monomer (propylene at 85 DEG C
Sour 10 parts by weight of dimethylamino propyl ester, 10 parts by weight of methyl methacrylate, 20 parts by weight of butyl acrylate, acrylic acid -2- hydroxyl
10 parts by weight of base ethyl ester) and 10 parts by weight of fluorinated acrylate monomer perfluor alkyl ethide methacrylate and initiator it is even
0.3 parts by weight solution of nitrogen bis-isobutyronitrile is added drop-wise in reaction kettle, is dripped off in 2 hours, is continued insulation reaction 2 hours.After cooling
To cation fluorine modified acrylic ester resin.
(2) preparation of Totally-enclosed-type polyisocyanate crosslinker
In the reaction kettle equipped with agitating device, constant pressure funnel and reflux condensing tube, two isocyanide of isophorone is added
About 75 parts by weight of butyl are slowly added drop-wise in reaction kettle by 50 parts by weight of acid esters under agitation, are dripped within 1 hour
It adds.70 DEG C are heated to, is reacted 4 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 50 parts by weight, 20 parts of Totally-enclosed-type polyisocyanate crosslinker
With the hydrophobic silicas of 20 parts by weight of ethylene glycol monobutyl ether, quantitative acetic acid and 2 parts by weight (average grain diameter is 3nm,
The specific surface area measured with BET method has trimethylsilyl for 300 m2/g on its surface of hydrophobic silica), mixing
Uniformly, it is acidified 2 hours at 50 DEG C.Then it is added the deionized water of 40 parts by weight, under high-speed stirred, dispersion 15-30min is had
There is hydrophobic cationic acrylate resin cathode electrophoresis dope, control pH is 5.0.
The electrophoresis lotion made from the present embodiment, directly progress cathode electro-coating, electrophoretic voltage 250V, electrophoresis temperature 30
DEG C, electrophoresis time 5 minutes.Gained film toasts 30 minutes at 160 DEG C, gained appearance of film uniform ground, film and water
Contact angle is 145 °, other performances of film meet product standard.
Embodiment 2
(1) preparation of cation fluorine modified acrylic ester resin
In the reaction kettle equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
1 parts by weight of 30 parts by weight of butyl acetate and initiator azodiisobutyronitrile, by crylic acid ester mixture monomer (methyl at 100 DEG C
20 parts by weight of dimethylaminoethyl methacrylate, 20 parts by weight of ethyl methacrylate, 30 parts by weight of isopropyl acrylate, methyl-prop
20 parts by weight of olefin(e) acid -2- hydroxy propyl ester) and 30 parts by weight of fluorinated acrylate monomer hexafluorobutyl acrylate and initiator it is even
1 parts by weight solution of nitrogen bis-isobutyronitrile is added drop-wise in reaction kettle, is dripped off in 4 hours, is continued insulation reaction 2 hours.It is obtained after cooling
Cation fluorine modified acrylic ester resin.
(2) preparation of Totally-enclosed-type polyisocyanate crosslinker
In the reaction kettle equipped with agitating device, constant pressure funnel and reflux condensing tube, two isocyanide of isophorone is added
About 75 parts by weight of butyl are slowly added drop-wise in reaction kettle by 50 parts by weight of acid esters under agitation, are dripped within 1 hour
It adds.70 DEG C are heated to, is reacted 2 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 60 parts by weight, 25 parts of Totally-enclosed-type polyisocyanate crosslinker
(average grain diameter is with the hydrophobic silicas of 20 parts by weight of ethylene glycol monobutyl ether, quantitative lactic acid and 10 parts by weight
100nm, the specific surface area measured with BET method have trimethylsilyl for 50 m2/g on its surface of hydrophobic silica),
It is uniformly mixed, is acidified 1 hour at 70 DEG C.Then it is added the deionized water of 60 parts by weight, under high-speed stirred, dispersion 15-30min is obtained
To with hydrophobic cationic acrylate resin cathode electrophoresis dope, controlling pH is 6.5.
The electrophoresis lotion made from the present embodiment, directly progress cathode electro-coating, electrophoretic voltage 250V, electrophoresis temperature 30
DEG C, electrophoresis time 5 minutes.Gained film toasts 30 minutes at 160 DEG C, gained appearance of film uniform ground, film and water
Contact angle is 155 °, other performances of film meet product standard.
Embodiment 3
(1) preparation of cation fluorine modified acrylic ester resin
In the reaction kettle equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
0.5 parts by weight of 20 parts by weight of butyl acetate and initiator azodiisobutyronitrile, by crylic acid ester mixture monomer (propylene at 95 DEG C
Sour 15 parts by weight of dimethylaminoethyl, 5 parts by weight of styrene, 10 parts by weight of ethyl methacrylate, 30 weight of isopropyl acrylate
Measure part, 15 parts by weight of methacrylic acid -2- hydroxy methacrylate) and ten trifluoro monooctyl ester of fluorinated acrylate monomer methacrylic acid, 20 weight
Amount part and 0.5 parts by weight solution of initiator azodiisobutyronitrile are added drop-wise in reaction kettle, are dripped off in 3 hours, and it is anti-to continue heat preservation
It answers 2 hours.Cation fluorine modified acrylic ester resin is obtained after cooling.
(2) preparation of Totally-enclosed-type polyisocyanate crosslinker
In the reaction kettle equipped with agitating device, constant pressure funnel and reflux condensing tube, two isocyanide of isophorone is added
About 75 parts by weight of butyl are slowly added drop-wise in reaction kettle by 50 parts by weight of acid esters under agitation, are dripped within 1 hour
It adds.70 DEG C are heated to, is reacted 3 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 55 parts by weight, 23 parts of Totally-enclosed-type polyisocyanate crosslinker
With the hydrophobic silicas of 20 parts by weight of ethylene glycol monobutyl ether, quantitative formic acid and 6 parts by weight (average grain diameter is 7nm,
The specific surface area measured with BET method has trimethylsilyl for 220 m2/g on its surface of hydrophobic silica), mixing
Uniformly, it is acidified 1 hour at 70 DEG C.Then it is added the deionized water of 50 parts by weight, under high-speed stirred, dispersion 15-30min is had
There is hydrophobic cationic acrylate resin cathode electrophoresis dope, control pH is 5.5.
The electrophoresis lotion made from the present embodiment, directly progress cathode electro-coating, electrophoretic voltage 250V, electrophoresis temperature 30
DEG C, electrophoresis time 5 minutes.Gained film toasts 30 minutes at 160 DEG C, gained appearance of film uniform ground, film and water
Contact angle is 160 °, other performances of film meet product standard.
Embodiment 4
(1) preparation of cation fluorine modified acrylic ester resin
In the reaction kettle equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
1 parts by weight of 20 parts by weight of butyl acetate and initiator azodiisobutyronitrile, by crylic acid ester mixture monomer (methyl-prop at 85 DEG C
10 parts by weight of olefin(e) acid dimethylaminoethyl, 10 parts by weight of methyl methacrylate, 20 parts by weight of butyl acrylate, acrylic acid -2-
10 parts by weight of hydroxy methacrylate) and 10 parts by weight of fluorinated acrylate monomer Hexafluorobutyl mathacrylate and initiator azo two
1 parts by weight solution of isobutyronitrile is added drop-wise in reaction kettle, is dripped off in 2 hours, is continued insulation reaction 2 hours.Obtained after cooling sun from
Sub- fluorin modified crylic acid ester resin.
(2) preparation of Totally-enclosed-type polyisocyanate crosslinker
In the reaction kettle equipped with agitating device, constant pressure funnel and reflux condensing tube, two isocyanide of isophorone is added
About 75 parts by weight of butyl are slowly added drop-wise in reaction kettle by 50 parts by weight of acid esters under agitation, are dripped within 1 hour
It adds.70 DEG C are heated to, is reacted 4 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 50 parts by weight, 20 parts of Totally-enclosed-type polyisocyanate crosslinker
(average grain diameter is with the hydrophobic silicas of 20 parts by weight of ethylene glycol monobutyl ether, quantitative sulfamic acid and 8 parts by weight
12nm, the specific surface area measured with BET method have trimethylsilyl for 180 m2/g on its surface of hydrophobic silica),
It is uniformly mixed, is acidified 2 hours at 50 DEG C.Then it is added the deionized water of 40 parts by weight, under high-speed stirred, dispersion 15-30min is obtained
To with hydrophobic cationic acrylate resin cathode electrophoresis dope, controlling pH is 6.0.
The electrophoresis lotion made from the present embodiment, directly progress cathode electro-coating, electrophoretic voltage 250V, electrophoresis temperature 30
DEG C, electrophoresis time 5 minutes.Gained film toasts 30 minutes at 160 DEG C, gained appearance of film uniform ground, film and water
Contact angle is 158 °, other performances of film meet product standard.
Embodiment 5
(1) preparation of cation fluorine modified acrylic ester resin
In the reaction kettle equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
0.5 parts by weight of 20 parts by weight of butyl acetate and initiator azodiisobutyronitrile, by crylic acid ester mixture monomer (third at 100 DEG C
20 parts by weight of olefin(e) acid lignocaine propyl ester, 20 parts by weight of ethyl methacrylate, 30 parts by weight of isopropyl acrylate, metering system
20 parts by weight of acid -2- hydroxy propyl ester) and 30 parts by weight of fluorinated acrylate monomer dodecafluoroheptyl methacrylate and initiation
1 parts by weight solution of agent azodiisobutyronitrile is added drop-wise in reaction kettle, is dripped off in 4 hours, is continued insulation reaction 2 hours.After cooling
Obtain cation fluorine modified acrylic ester resin.
(2) preparation of Totally-enclosed-type polyisocyanate crosslinker
In the reaction kettle equipped with agitating device, constant pressure funnel and reflux condensing tube, two isocyanide of isophorone is added
About 75 parts by weight of butyl are slowly added drop-wise in reaction kettle by 50 parts by weight of acid esters under agitation, are dripped within 1 hour
It adds.70 DEG C are heated to, is reacted 2 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 60 parts by weight, 25 parts of Totally-enclosed-type polyisocyanate crosslinker
(average grain diameter is with the hydrophobic silicas of 20 parts by weight of ethylene glycol monobutyl ether, quantitative acetic acid and 4 parts by weight
20nm, the specific surface area measured with BET method have trimethylsilyl for 150 m2/g on its surface of hydrophobic silica),
It is uniformly mixed, is acidified 1 hour at 70 DEG C.Then it is added the deionized water of 60 parts by weight, under high-speed stirred, dispersion 15-30min is obtained
To with hydrophobic cationic acrylate resin cathode electrophoresis dope, controlling pH is 5.5.
The electrophoresis lotion made from the present embodiment, directly progress cathode electro-coating, electrophoretic voltage 250V, electrophoresis temperature 30
DEG C, electrophoresis time 5 minutes.Gained film toasts 30 minutes at 160 DEG C, gained appearance of film uniform ground, film and water
Contact angle is 153 °, other performances of film meet product standard.
Embodiment 6
(1) preparation of cation fluorine modified acrylic ester resin
In the reaction kettle equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
0.5 parts by weight of 10 parts by weight of butyl acetate and initiator azodiisobutyronitrile, by crylic acid ester mixture monomer (methyl at 85 DEG C
10 parts by weight of dimethylaminoethyl methacrylate, 10 parts by weight of methyl methacrylate, 20 parts by weight of butyl acrylate, acrylic acid-
10 parts by weight of 2- hydroxy methacrylate) and 10 parts by weight of fluorinated acrylate monomer perluorooctyl acrylate and initiator azo two
0.5 parts by weight solution of isobutyronitrile is added drop-wise in reaction kettle, is dripped off in 2 hours, is continued insulation reaction 2 hours.Sun is obtained after cooling
Ion fluorin modified crylic acid ester resin.
(2) preparation of Totally-enclosed-type polyisocyanate crosslinker
In the reaction kettle equipped with agitating device, constant pressure funnel and reflux condensing tube, two isocyanide of isophorone is added
About 75 parts by weight of butyl are slowly added drop-wise in reaction kettle by 50 parts by weight of acid esters under agitation, are dripped within 1 hour
It adds.70 DEG C are heated to, is reacted 4 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 50 parts by weight, 20 parts of Totally-enclosed-type polyisocyanate crosslinker
With the hydrophobic silicas of 20 parts by weight of ethylene glycol monobutyl ether, quantitative acetic acid and 5 parts by weight (average grain diameter is 7nm,
The specific surface area measured with BET method has trimethylsilyl for 220 m2/g on its surface of hydrophobic silica), mixing
Uniformly, it is acidified 2 hours at 50 DEG C.Then it is added the deionized water of 40 parts by weight, under high-speed stirred, dispersion 15-30min is had
There is hydrophobic cationic acrylate resin cathode electrophoresis dope, control pH is 5.5.
The electrophoresis lotion made from the present embodiment, directly progress cathode electro-coating, electrophoretic voltage 250V, electrophoresis temperature 30
DEG C, electrophoresis time 5 minutes.Gained film toasts 30 minutes at 160 DEG C, gained appearance of film uniform ground, film and water
Contact angle is 160 °, other performances of film meet product standard.
Finally, it should also be noted that the above enumerated are only specific embodiments of the present invention son.Obviously, the present invention is not
It is limited to above embodiment, acceptable there are many deformations.Those skilled in the art can be straight from present disclosure
All deformations for connecing export or associating, are considered as protection scope of the present invention.
Claims (7)
1. a kind of preparation method with hydrophobic cationic acrylate resin cathode electrophoresis dope, which is characterized in that first
Cation fluorine modified acrylic ester resin and Totally-enclosed-type polyisocyanate crosslinker are prepared, by cation fluorine modification acrylate
Resin and Totally-enclosed-type polyisocyanate crosslinker are acidified after being sufficiently mixed with hydrophobic oxide particle, are eventually adding
Cathode electrophoresis dope is prepared in ion water dispersion, and specific preparation process is as follows:
In a kettle, solvent and part initiator azodiisobutyronitrile is added, by crylic acid ester mixture list at 85-100 DEG C
Body and fluorinated acrylate monomer mixture and partial initiator azodiisobutyronitrile solution are added drop-wise in reaction kettle, 2-4
It is dripped off in hour, continues insulation reaction 2-4 hours, cation fluorine modified acrylic ester resin is obtained after cooling；Wherein, acrylic acid
Ester mix monomer includes tertiary amino acrylic ester monomer and general acrylic ester monomer, the general esters of acrylic acid list
Body includes styrene, methyl methacrylate, ethyl methacrylate, butyl acrylate, isopropyl acrylate, acrylic acid -2-
One of hydroxy methacrylate, methacrylic acid -2- hydroxy methacrylate and methacrylic acid -2- hydroxy propyl ester are a variety of；
Totally-enclosed-type polyisocyanate crosslinker is prepared, in a kettle, isophorone diisocyanate is added, in stirring condition
Under, slowly butyl is added drop-wise in reaction kettle, is dripped within 1 hour, is heated to 70 DEG C, is reacted 2-4 hours, measurement trip
When being lower than 0.5% from NCO content, cooling discharge obtains Totally-enclosed-type polyisocyanate crosslinker；
By a certain amount of cation fluorine modified acrylic ester resin, Totally-enclosed-type polyisocyanate crosslinker and ethylene glycol only son
Ether, organic acid and hydrophobic oxide particle are uniformly mixed, and are acidified 1-2 hours at 50-70 DEG C, be then added it is a certain amount of go from
Sub- water, under high-speed stirred, dispersion 15-30min obtains having hydrophobic cationic acrylate resin cathode electrophoresis dope, controls
PH processed is 5.0-6.5；Wherein, hydrophobic oxide particle is the hydrophobic silica with trimethylsilyl.
2. the preparation side according to claim 1 with hydrophobic cationic acrylate resin cathode electrophoresis dope
Method, which is characterized in that the fluorinated acrylate monomer is Hexafluorobutyl mathacrylate, hexafluorobutyl acrylate, methyl
Dodecafluorhe-ptylacrylate, ten trifluoro monooctyl ester of methacrylic acid, perluorooctyl acrylate and perfluor alkyl ethide metering system
One of acid esters is a variety of.
3. the preparation side according to claim 2 with hydrophobic cationic acrylate resin cathode electrophoresis dope
Method, which is characterized in that the tertiary amino acrylic ester monomer includes dimethylaminoethyl methacrylate, acrylic acid lignocaine
Propyl ester, dimethylaminoethyl acrylate, dimethylaminoethyl propyl ester, methacrylic acid lignocaine propyl ester, methyl-prop
One of olefin(e) acid dimethylaminoethyl is a variety of.
4. the system according to claim 1 or 2 or 3 with hydrophobic cationic acrylate resin cathode electrophoresis dope
Preparation Method, which is characterized in that in the cation fluorine modified acrylic ester resin, tertiary amino acrylic ester monomer 10-20
Parts by weight, general acrylic ester monomer 40-70 parts by weight, fluorinated acrylate monomer 10-30 parts by weight, initiator azo two
Isobutyronitrile 0.5-2 parts by weight and solvent 10-30 parts by weight, the organic acid are one kind of formic acid, acetic acid, lactic acid and sulfamic acid
Or it is a variety of.
5. the system according to claim 1 or 2 or 3 with hydrophobic cationic acrylate resin cathode electrophoresis dope
Preparation Method a, which is characterized in that average grain diameter of the hydrophobic silica is 3-100nm, the ratio measured with BET method
Surface area is 50-300m2/g。
6. the system according to claim 1 or 2 or 3 with hydrophobic cationic acrylate resin cathode electrophoresis dope
Preparation Method, which is characterized in that the cathode electrophoresis dope each group is divided into cation fluorine modified acrylic ester resin 50-60 weight
Part, Totally-enclosed-type polyisocyanate crosslinker 20-25 parts by weight, hydrophobic oxide particle 2-10 parts by weight.
7. the preparation side according to claim 6 with hydrophobic cationic acrylate resin cathode electrophoresis dope
Method, which is characterized in that for obtained cathode electrophoresis dope after varnish film forming, the contact angle of film and water is 145-160 degree.
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| CN109988497B (en) * | 2019-04-17 | 2021-02-12 | 广州希森美克新材料科技股份有限公司 | High-wear-resistance high-hardness easy-to-clean electrophoretic color nano coating and preparation method thereof |
| CN109970928B (en) * | 2019-04-17 | 2021-08-27 | 广州希森美克新材料科技有限公司 | High-performance resin for electrophoretic paint and synthetic method thereof |
| CN111041440B (en) * | 2019-12-20 | 2021-08-31 | 浙江中杭新材料科技有限公司 | Surface protection method of neodymium iron boron permanent magnet |
| CN112662104B (en) * | 2020-12-10 | 2022-04-15 | 中电保力（北京）科技有限公司 | Composite test material based on graphene oxide and preparation method and application thereof |
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