CN115785761A - Preparation method of fluorinated epoxy resin coating and fluorinated epoxy resin coating - Google Patents
Preparation method of fluorinated epoxy resin coating and fluorinated epoxy resin coating Download PDFInfo
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- CN115785761A CN115785761A CN202211491876.1A CN202211491876A CN115785761A CN 115785761 A CN115785761 A CN 115785761A CN 202211491876 A CN202211491876 A CN 202211491876A CN 115785761 A CN115785761 A CN 115785761A
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- epoxy resin
- coating
- fluorinated
- thiolactone
- fluorinated epoxy
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- 238000000576 coating method Methods 0.000 title claims abstract description 111
- 239000011248 coating agent Substances 0.000 title claims abstract description 105
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 51
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OROGUZVNAFJPHA-UHFFFAOYSA-N 3-hydroxy-2,4-dimethyl-2H-thiophen-5-one Chemical class CC1SC(=O)C(C)=C1O OROGUZVNAFJPHA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003973 paint Substances 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000002585 base Substances 0.000 claims abstract description 9
- -1 mercaptan compound Chemical class 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- 229920006334 epoxy coating Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 claims description 3
- VLCCKNLIFIJYOQ-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] 2,2,3,3-tetrakis(sulfanyl)propanoate Chemical compound OCC(CO)(CO)COC(=O)C(S)(S)C(S)S VLCCKNLIFIJYOQ-UHFFFAOYSA-N 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- QMUNTDPZNPLSPB-UHFFFAOYSA-N 2,3-dihydroxypropyl 3,3,3-tris(sulfanyl)propanoate Chemical compound OCC(O)COC(=O)CC(S)(S)S QMUNTDPZNPLSPB-UHFFFAOYSA-N 0.000 claims description 2
- MYEWQUYMRFSJHT-UHFFFAOYSA-N 2-(2-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1N MYEWQUYMRFSJHT-UHFFFAOYSA-N 0.000 claims description 2
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 2
- 235000013824 polyphenols Nutrition 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- 230000003373 anti-fouling effect Effects 0.000 abstract description 51
- 239000004593 Epoxy Substances 0.000 abstract description 18
- 239000007788 liquid Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000005507 spraying Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
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- 239000002253 acid Substances 0.000 abstract description 4
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- 230000032683 aging Effects 0.000 abstract description 3
- 230000001680 brushing effect Effects 0.000 abstract description 2
- 230000006378 damage Effects 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910052731 fluorine Inorganic materials 0.000 description 17
- 239000011737 fluorine Substances 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 10
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 125000003396 thiol group Chemical group [H]S* 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 210000002268 wool Anatomy 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000003075 superhydrophobic effect Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 210000004243 sweat Anatomy 0.000 description 3
- HBZFBSFGXQBQTB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HBZFBSFGXQBQTB-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012650 click reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- QUKRIOLKOHUUBM-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C QUKRIOLKOHUUBM-UHFFFAOYSA-N 0.000 description 1
- ZMFWTUBNIJBJDB-UHFFFAOYSA-N 6-hydroxy-2-methylquinoline-4-carboxylic acid Chemical compound C1=C(O)C=CC2=NC(C)=CC(C(O)=O)=C21 ZMFWTUBNIJBJDB-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
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- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a preparation method of a fluorinated epoxy antifouling paint and a fluorinated epoxy resin paint prepared by the method. The preparation method comprises the following steps: firstly, preparing a fluorinated thiolactone prepolymer with a branched fluoroalkane chain, and uniformly dispersing the fluorinated thiolactone prepolymer, an amine curing agent and epoxy resin to obtain a fluorinated epoxy resin coating solution. And spraying or brushing the prepared fluorinated epoxy resin coating on the surface of a substrate, naturally airing, and curing at 120 ℃ for 2 hours to obtain the fluorinated epoxy antifouling coating. The coating formed by the fluorinated epoxy resin coating is acid and alkali resistant, ultraviolet aging resistant, strong in base material adhesive force, and has good fingerprint resistance, and good rolling resistance of ink, paint and liquid. After chemical destruction, the coating can be heated for a short time to restore its antifouling properties.
Description
Technical Field
The invention belongs to the technical field of hydrophobic and oleophobic antifouling coating materials, and particularly relates to a preparation method of a fluorinated epoxy resin coating and the fluorinated epoxy resin coating.
Background
Transparent hydrophobic, oleophobic (amphiphobic) antifouling coatings have attracted extensive research in the past decade to meet the ever-increasing demands of applications. The transparent antifouling paint has great application requirements in the fields of display screens, automotive interiors, photovoltaic solar systems and the like, and enables our lives to be more comfortable, healthy and energy-saving. Generally, the antifouling performance of the amphiphobic coating depends on the enrichment degree of substances with low surface energy on the surface, but the properties of environmental protection, low cost, good weather resistance, high mechanical strength, high transparency and the like are considered, so that great challenges still exist. In addition, polydimethylsiloxane (PDMS) based antifouling coatings have been widely reported to form similar liquid surfaces enriched with low surface energy siloxane segments. The surface can make the pollutant quickly separate in a liquid-liquid contact mode to realize an antifouling effect. However, surface enrichment of PDMS generally makes the surface wet and greasy, which tends to create fingerprints and affect the feel after touch. In addition, PDMS monomers that are chemically inert are very energy consuming in the manufacturing process and can induce strong phase separation, which affects the transparency. Fluorinated epoxy antifouling coatings are expected to overcome the above disadvantages and help achieve excellent mechanical strength. However, the reported fluorinated epoxy resin coatings still have the problems of severe phase separation, low transparency, too high fluorine content, no self-healing and poor weatherability. In summary, it is still a difficult point in the art to design and obtain a fluorinated epoxy antifouling coating with high efficiency, good weather resistance, self-healing, low fluorine content (environmental protection) and excellent antifouling property.
Disclosure of Invention
In order to avoid the defects of the prior art, the invention provides a preparation method of a fluorinated epoxy resin coating and the fluorinated epoxy resin coating prepared by the method.
According to one aspect of the present invention, there is provided a method for preparing a fluorinated epoxy resin coating, characterized by the steps of:
step 1, preparation of fluorinated thiolactone prepolymer: dispersing a multifunctional thiol compound, fluoroacrylate and double-bond end-capped thiolactone in a solvent, adding a photoinitiator, and stirring and reacting for 10-60 minutes under the conditions of ultraviolet illumination and normal temperature to obtain a fluorinated thiolactone prepolymer, wherein the mass ratio of the multifunctional thiol compound, the fluoroacrylate, the double-bond end-capped thiolactone to the photoinitiator is 1.2-2;
step 2, preparing the fluorinated epoxy resin coating: dissolving an amine curing agent, a fluorinated thiolactone prepolymer and an alkali catalyst in a solvent, fully stirring and reacting, then adding epoxy resin, and continuously stirring to obtain a uniform and transparent fluorinated epoxy resin coating, wherein the mass ratio of the amine curing agent to the fluorinated thiolactone prepolymer to the alkali catalyst to the epoxy resin is 0.2-0.6.
Wherein the polyfunctional thiol compounds include, but are not limited to: glycerol trimercaptopropionate, trimethylolpropane trimercaptopropyl ester, isocyanuric acid trimercaptocarboxylate, pentaerythritol tetramercaptopropionate, or dipentaerythritol hexa (3-mercaptopropionate).
The fluoroacrylate is a perfluoro (methyl) acrylate compound CH 2 CH(CH 3 )COO-(CH 2 ) 2 -(CF 2 ) n CF 3 Wherein n is a natural number of 3 to 10.
The double-bond end-capped thiolactone is an acrylamide end-capped thiolactone or an allyl formate end-capped thiolactone.
Wherein the solvent in step 1 and step 2 may be tetrahydrofuran, acetone, dioxane, N-dimethylacetamide, dimethyl sulfoxide or dimethyl carbonate, and the solvent used in step 1 and step 2 may be different. In addition, the hydrosolvent needs to be dewatered before use.
The photoinitiator includes a uv photoinitiator 1173, 184, 907, 369, 1490, or 1700.
The amine-based curing agents include, but are not limited to: 4-amino-alpha, alpha-4-trimethyl-cyclohexanemethylamine, isophorone diamine, m-phenylenediamine, aminophenylsulfone, 4,4' -diaminodiphenylmethane, polyamide, dicyandiamide. Part of the highly active aliphatic chain amine catalysts cannot be used.
The base catalyst includes, but is not limited to: 1,8-diazabicycloundecen-7-ene (DBU), 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), triethylamine, triethylenediamine, diethylenetriamine, hexylamine, cyclohexylamine, imidazole.
The epoxy resin comprises: bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin.
According to another aspect of the present invention, there is also provided a fluorinated epoxy resin coating prepared by the above preparation method.
Based on the prepared fluorinated epoxy resin coating, the method for preparing the fluorinated epoxy antifouling coating comprises the following steps: adding a solvent, preparing the fluorinated epoxy resin coating into a solution with a solid content of 20-60 percent (wt%), spraying or brushing the solution on the surface of the base material, naturally airing the solution for 6-12 hours at room temperature, and then placing the solution in a 120 ℃ oven for curing for 2-4 hours to obtain the transparent fluorinated epoxy antifouling coating.
The coating formed by the fluorinated epoxy resin coating disclosed by the invention is high in transparency and good in weather resistance, has excellent oil-proof paint, ink handwriting resistance and fingerprint resistance, and has better acid resistance, alkali resistance, sweat corrosion resistance and ultraviolet aging resistance.
Drawings
Fig. 1 shows the appearance of a coating formed according to example 1 of the present invention after 20 rubs of steel wool (fig. 1 a) and the results of a cross-hatch test (fig. 1 b).
FIG. 2 shows the rolling behavior (with roll angle, liquid surface tension) of water, glycol, and hexadecane droplets on the surface of a coating formed in accordance with example 1 of the present invention
FIG. 3 shows the ink writing, fingerprint, and paint resistance of a coating formed according to example 1 of the present invention.
FIG. 4 shows the alkali damage and self-healing antifouling performance of coatings formed according to example 1 of the present invention.
FIG. 5 shows the antifouling property of the coating formed according to example 1 of the present invention after UV irradiation for 100 hours.
Detailed Description
For a clearer understanding of the objects, technical solutions and advantages of the present invention, the present invention will be described in further detail below with reference to the accompanying drawings and embodiments.
The invention provides a preparation method of a fluorinated epoxy antifouling coating. The invention firstly prepares the thiolactone-terminated fluorinated prepolymer by high-efficiency thiol click reaction. The introduction of the thiolactone group effectively reduces the polarity difference of the original sulfhydryl and fluoroalkane chain segments, inhibits the formation of micelles and the occurrence of phase separation, ensures the high transparency of the coating, and simultaneously protects the sulfhydryl which is easy to be oxidized. In addition, after the subsequent thiolactone ring-opening reaction, the re-appeared sulfydryl can continue to efficiently perform click reaction with the epoxy resin. The thiolactone fluorine-containing prepolymer has small molecular weight and does not contain large steric hindrance groups, so that the thiolactone fluorine-containing prepolymer has strong surface migration capability, and therefore, under the condition of extremely low addition amount, fluorine-containing alkane chain segments can still be enriched on the surface of a coating, so that the surface free energy is obviously reduced. Thanks to the high fluorine content and compact epoxy crosslinking structure on the surface, the coating not only has excellent oil-proof paint, ink handwriting resistance and fingerprint resistance, but also has better acid resistance, alkali resistance, sweat corrosion resistance and ultraviolet aging resistance. The extremely strong surface migration of the fluoroalkane chain enables the coating to quickly recover the antifouling performance after short-time high-temperature treatment. The invention provides a new idea and a new method for preparing the high-transparency high-strength epoxy antifouling coating.
It should be noted that the antifouling property of the coating was evaluated by observing the change and residue of industrial paint, oil-based ink and fingerprint on the surface of the coating, and the rolling state of different surface energy liquids on the surface of the coating. The mechanical properties of the coating were characterized by constant pressure cyclic friction (10 kPa) and cross-hatch adhesion test method (ASTM D3359-2002) for #000 type steel wool. The change of the antifouling property of the coating is judged by observing the state of the ink handwriting on the surface of the coating.
Example 1: super-hydrophobic coating for coating glass surface
(1) Glass surface pretreatment: the glass was sonicated in distilled water and methanol for 10 minutes, respectively. And finally, washing the mixture for a plurality of times by using distilled water, and airing the mixture in an oven for later use.
(2) Preparation of fluorinated thiolactone prepolymer: 1.22g of pentaerythritol tetramercaptopropionate, 2.41g of 2- (perfluorooctyl) ethyl methacrylate, 1.31g of acrylamide thiolactone, 0.04g of 184-photoinitiator, and 20g of acetone were added in this order to a reaction flask, and the mixture was stirred well for 30 minutes under ultraviolet irradiation at room temperature. Infrared and nuclear magnetic tests show that the double bond and mercapto characteristic peaks disappear after the reaction is finished, and prove that the fluoro-thiolactone prepolymer is successfully prepared.
(3) Preparation of fluorinated epoxy resin coating: into a new reaction flask, 0.58g of 4,4' -diaminodiphenylmethane was charged and sufficiently dissolved with 2g of tetrahydrofuran, and 0.15g of the fluorinated thiolactone prepolymer prepared in (2) and 5mg of a base catalyst DBU were added to the solution. After stirring and reacting for 10 minutes, 1g of aliphatic glycidyl ether epoxy resin (2,2' - [ [ 2-ethyl-2- [ (epoxyethylmethoxy) methyl ] -1,3-dipropyl ] bis (oxymethylene) ] diepoxy ethane) is added, and stirring is continued for 30 minutes to obtain a uniform and transparent fluorinated epoxy resin solution.
(4) Preparation of fluorinated epoxy antifouling coating: and (4) diluting the resin solution obtained in the step (3) to 30% of solid content, and spraying the diluted resin solution on the glass surface. And (3) airing the coating for 6 hours at room temperature, and then curing the coating for 2 hours in an oven at 120 ℃ to obtain the fluorinated epoxy antifouling coating.
(5) Testing antifouling property, mechanical property, chemical resistance and self-repairing property of the coating: the coating had no apparent scratches after 20 cycles of steel wool rubbing (fig. 1 a). The cross-hatch test method showed good adhesion of the coating to the substrate (fig. 1 b). The roll angles of the coating for water, ethylene glycol, and hexadecane were 33 °,28 °,10 °, respectively, and the time required for the liquid to slide over 2/3 of the slide length was 12 seconds, 11 seconds, and 3 seconds, respectively (fig. 2). The ink traces shrink into small droplets on the coating surface and the paint can shrink rapidly and slide away with less than 10% of fingerprint residue traces (figure 3). The antifouling property was maintained after the coating was subjected to soda-soaking for 12 hours, and disappeared after 14 hours (fig. 4). The coating recovered antifouling properties after heating at 130 ℃ for 30 minutes (fig. 4). The coating still maintained antifouling properties after 100 hours of uv irradiation (figure 5).
Example 2: super-hydrophobic coating for coating Polycarbonate (PC) plate surface
(1) Preparation of fluorinated thiolactone prepolymer: 1.22g of trimethylolpropane trimercaptopropyl ester, 0.25g of perfluorooctyl ethyl acrylate, 1.63g of acrylamide thiolactone, 0.02g of 1173-photoinitiator and 20g of tetrahydrofuran are sequentially added into a reaction bottle, and the mixture is fully stirred for 60 minutes under the conditions of ultraviolet irradiation and room temperature. Infrared and nuclear magnetic tests show that the double bond and mercapto characteristic peaks disappear after the reaction is finished, and prove that the fluoro-thiolactone prepolymer is successfully prepared.
(2) Preparation of fluorinated epoxy resin coating: to a new reaction flask, 0.44g of dicyandiamide was added and sufficiently dissolved with 2g of tetrahydrofuran, and to the solution were added 0.4g of the fluorinated thiolactone prepolymer prepared in (1), and 10mg of a basic catalyst TBD. After 5 minutes of stirring reaction, 1g of bisphenol A epoxy resin (E51) was added and stirring was continued for 20 minutes to obtain a uniform and clear fluorinated epoxy resin solution.
(3) Preparation of fluorinated epoxy antifouling coating: and (3) diluting the resin solution obtained in the step (2) to 20% of solid content, and spraying the diluted resin solution on the surface of a polycarbonate plate. And after the coating is dried at room temperature for 12 hours, curing the coating in an oven at 120 ℃ for 3 hours to obtain the fluorinated epoxy antifouling coating.
(4) Testing antifouling property, mechanical property, chemical resistance and self-repairing property of the coating: the coating has no obvious scratch on the appearance after the steel wool is circularly rubbed for 20 times. The cross hatch test method shows good adhesion of the coating to the substrate. The roll angles of the coating to water, ethylene glycol and hexadecane were 35 deg., 28 deg., 8 deg., respectively, and the time required for the liquid to slide over 2/3 of the slide length was 14 seconds, 12 seconds and 3 seconds, respectively. Ink traces shrink into small droplets on the surface of the coating, the paint can shrink rapidly and slide away, and fingerprint residual traces are less than 10%. The antifouling property of the coating is maintained after the coating is subjected to alkali soaking for 13 hours, and the antifouling property disappears after 14 hours. The coating recovered antifouling properties after heating at 130 ℃ for 30 minutes. The coating still maintains antifouling performance after 20 hours of ultraviolet irradiation.
Example 3: super-hydrophobic coating layer coating polyethylene glycol terephthalate (PET) plate surface
(1) Preparation of fluorinated thiolactone prepolymer: 1.22g of dipentaerythritol hexa (3-mercaptopropionate), 1.83g of 2- (perfluorooctyl) ethyl methacrylate, 1.52g of thioacrylamide lactone, 0.03g of 1173-photoinitiator, and 25g of dioxane were sequentially added to a reaction flask, and the mixture was sufficiently stirred under ultraviolet irradiation at room temperature for 20 minutes. Infrared and nuclear magnetic tests show that the double bond and mercapto characteristic peaks disappear after the reaction is finished, and prove that the fluoro-thiolactone prepolymer is successfully prepared.
(2) Preparation of fluorinated epoxy resin coating: 0.24g of isophorone diamine was added to a new reaction flask and sufficiently dissolved with 2g of tetrahydrofuran, and then 0.05g of the fluorinated thiolactone prepolymer prepared in (1) and 6mg of the alkali catalyst TBD were added to the solution. After stirring and reacting for 20 minutes, 1g of bisphenol A epoxy resin (E44) was added, and stirring was continued for 10 minutes to obtain a uniform and clear fluorinated epoxy resin solution.
(3) Preparation of fluorinated epoxy antifouling coating: and (3) diluting the resin solution obtained in the step (2) to 50% of solid content, and spraying the diluted resin solution on the surface of a polycarbonate plate. And after the coating is dried at room temperature for 6 hours, the coating is placed in a 120 ℃ oven for curing for 4 hours, and the fluorinated epoxy antifouling coating is obtained.
(4) Testing antifouling property, mechanical property, chemical resistance and self-repairing property of the coating: the coating has no obvious scratch on the appearance after the steel wool is circularly rubbed for 20 times. The cross hatch test method shows good adhesion of the coating to the substrate. The roll angles of the coating to water, ethylene glycol and hexadecane were 32 deg., 29 deg., 11 deg., respectively, and the time required for the liquid to slide over 2/3 of the slide length was 13 seconds, 12 seconds and 4 seconds, respectively. Ink traces shrink into small droplets on the surface of the coating, the paint can shrink rapidly and slide away, and fingerprint residual traces are less than 10%. The antifouling property of the coating is maintained after the coating is subjected to alkali soaking for 14 hours, and the antifouling property disappears after 16 hours. The coating recovered antifouling properties after heating at 130 ℃ for 30 minutes. The coating still keeps antifouling performance after 30 hours of ultraviolet irradiation.
Example 4 (comparative example 1):
the reaction sequence or recipe in examples 1-3 was varied: dispersing fluoroacrylate and polyfunctional mercaptan into a solvent, adding an initiator, reacting for 60 minutes under the conditions of ultraviolet irradiation and normal temperature to obtain a mercaptan terminated fluorine-containing prepolymer, and then adding double-bond terminated thiolactone for reaction, wherein the subsequent reaction is the same as that in the embodiment 1-3; or directly using the thiol-terminated fluorine-containing prepolymer to participate in the subsequent reaction with the epoxy resin. Because the polarity difference between the mercaptan functional group of the mercaptan-terminated fluorine-containing prepolymer and the fluoroalkyl chain is large, a micelle structure is easily formed, the reaction efficiency with other components is low, and micelles cannot disappear in the whole process. The resulting coating phase separates severely and is poorly transparent. This example demonstrates the importance of the reaction sequence (timing of thiolactone incorporation) and the incorporation of thiolactones.
Example 5 (comparative example 2):
the reaction monomers in examples 1-3 were varied: an aliphatic chain amine curing agent is used to react with a fluorinated thiolactone prepolymer and an epoxy resin, such as diethylenetriamine. The prepared resin generates dregs-like precipitation, and a transparent antifouling coating cannot be obtained. This is because the reactivity of the aliphatic chain type amine curing agent is too high, and a large amount of mercapto groups are rapidly generated and oxidized to form disulfide bonds after opening a thiolactone ring. These disulfide bond-containing products are hardly dissolved in a solvent and are precipitated. This example demonstrates the importance of monomer activity control during resin preparation.
Example 6 (comparative example 3):
the formulations in examples 1-3 were varied: and (2) uniformly dispersing the polyfunctional mercaptan, the fluoroacrylate and the epoxy in a solvent, adding an alkali catalyst, spraying, and curing at high temperature to obtain the fluorinated epoxy coating. The coating has low hardness, no abrasion loss and poor adhesion of the base material. This example illustrates the importance of amine curing agents for coating mechanical properties and substrate adhesion.
Compared with the prior art, the invention has the advantages that:
1. the thiolactone-terminated fluorine-containing prepolymer is efficiently prepared through click chemistry, thiolactone effectively protects easily-oxidized sulfydryl, prevents the fluorine-containing prepolymer from forming a micelle structure in a solution and initiating phase separation, and ensures high transparency of a coating.
2. The thiolactone-terminated fluorine-containing prepolymer has small molecular weight and does not contain rigid large steric hindrance groups, so that the thiolactone-terminated fluorine-containing prepolymer has flexible surface migration capability. And a small amount of fluorine-containing prepolymer is introduced to ensure high surface fluorine content and excellent antifouling property of the coating.
3. Unlike the antifouling coating based on polydimethylsiloxane, the surface of the fluorine-containing resin is dry and not greasy, is not easy to leave fingerprints, and is comfortable to touch.
4. The thiolactone reacts with the amine curing agent, active amino is introduced while the sulfhydryl is released again, and the sulfhydryl and the amino react with the epoxy efficiently, so that the effective grafting of the fluoroalkane chain is ensured.
5. The fluorine-containing alkane chains enriched on the surface and the highly crosslinked epoxy structure enable the antifouling paint to have excellent antifouling performance. After the coating is chemically damaged, the fluorocarbon chain inside the coating migrates to the surface through high-temperature treatment, so that the antifouling performance is repaired.
6. The monomers without unsaturated bonds are selected to react, so that the coating can be endowed with more excellent weather resistance.
7. Fluorinated epoxy coatings have been designed as highly transparent antifouling coatings with relatively little research. The technology provides a feasible preparation method of the fluorinated epoxy coating with excellent performance.
8. The antifouling coating can be prepared on various base materials in a large range, the curing process is simple, and the base material adhesion is excellent.
9. The super-hydrophobic coating has a roll angle of about 33 DEG to distilled water; roll angle to hexadecane is less than 10 °; the rolling angle to the glycol is less than 30 degrees; the residual area of the fingerprint is less than 10%, paint and ink are difficult to adhere to the surface, and the self-cleaning performance is good.
10. The coating has good mechanical properties and chemical stability: the pencil hardness is 5H, and no obvious scratch is formed on the surface of the steel wool after the steel wool is rubbed for 20 times; the coating can maintain antifouling performance after being subjected to 16 hours of high-temperature sweat vapor corrosion, 6 hours of strong acid corrosion, 12 hours of strong base corrosion and 100 hours of high-strength ultraviolet radiation.
11. The coating was able to recover the destroyed anti-fouling properties after heating at 130 ℃ for 30 minutes.
Claims (10)
1. A preparation method of fluorinated epoxy resin paint is characterized by comprising the following steps:
step 1, dispersing a polyfunctional mercaptan compound, fluoroacrylate and double-bond end-capped thiolactone in a solvent, adding a photoinitiator, and stirring to react under ultraviolet irradiation and normal temperature conditions to obtain a fluorinated thiolactone prepolymer, wherein the mass ratio of the polyfunctional mercaptan compound, the fluoroacrylate, the double-bond end-capped thiolactone to the photoinitiator is (1.2-1);
and 2, dissolving an amine curing agent, a fluorinated thiolactone prepolymer and an alkali catalyst in a solvent, fully stirring and reacting, then adding epoxy resin, and continuously stirring to obtain a uniform and transparent fluorinated epoxy resin coating, wherein the mass ratio of the amine curing agent to the fluorinated thiolactone prepolymer to the alkali catalyst to the epoxy resin is 0.2-0.6.
2. The method according to claim 1, wherein the polyfunctional thiol compound is selected from the group consisting of glycerol trimercaptopropionate, trimethylolpropane trimercaptopropyl ester, trimercaptocarboxylate isocyanurate, pentaerythritol tetramercaptopropionate, and dipentaerythritol hexa (3-mercaptopropionate).
3. The process according to claim 1, wherein the fluoroacrylate is a perfluoro (meth) acrylate compound CH 2 CH(CH 3 )COO-(CH 2 ) 2 -(CF 2 ) n CF 3 Wherein n is a natural number of 3 to 10.
4. The production method according to claim 1, wherein the double bond-terminated thiolactone is an acrylamide-terminated thiolactone or an allyl formate-terminated thiolactone.
5. The process according to claim 1, wherein the solvent is selected from tetrahydrofuran, acetone, dioxane, N, N-dimethylacetamide, dimethyl sulfoxide or dimethyl carbonate.
6. The method of claim 1, wherein the photoinitiator is an ultraviolet photoinitiator 1173, 184, 907, 369, 1490 or 1700.
7. The method according to claim 1, wherein the amine-based curing agent is selected from the group consisting of 4-amino- α, α -4-trimethyl-cyclohexanemethylamine, isophorone diamine, m-phenylenediamine, aminophenylsulfone, 4,4' -diaminodiphenylmethane, polyamide and dicyandiamide.
8. The process of claim 1 wherein the base catalyst is selected from the group consisting of 1,8-diazabicycloundecen-7-ene, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, triethylamine, triethylenediamine, diethylenetriamine, hexylamine, cyclohexylamine and imidazole.
9. The production method according to claim 1, wherein the epoxy resin is selected from a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a polyphenol type glycidyl ether epoxy resin, an aliphatic glycidyl ether epoxy resin, a glycidyl ester type epoxy resin or a glycidyl amine type epoxy resin.
10. A fluorinated epoxy coating, wherein the fluorinated epoxy coating is prepared by the method of claim 1.
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