CN113583534A - Oleic acid grafted zinc acrylate epoxy resin-based paint and preparation method thereof - Google Patents
Oleic acid grafted zinc acrylate epoxy resin-based paint and preparation method thereof Download PDFInfo
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- CN113583534A CN113583534A CN202110686857.3A CN202110686857A CN113583534A CN 113583534 A CN113583534 A CN 113583534A CN 202110686857 A CN202110686857 A CN 202110686857A CN 113583534 A CN113583534 A CN 113583534A
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- epoxy resin
- oleic acid
- acid grafted
- zinc acrylate
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 51
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 51
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 title claims abstract description 41
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000005642 Oleic acid Substances 0.000 title claims abstract description 41
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 title claims abstract description 41
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003973 paint Substances 0.000 title claims description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 43
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 32
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 29
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 29
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 25
- 239000000049 pigment Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000002519 antifouling agent Substances 0.000 claims abstract description 16
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 16
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 16
- 239000004014 plasticizer Substances 0.000 claims abstract description 16
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011717 all-trans-retinol Substances 0.000 claims description 3
- 235000019169 all-trans-retinol Nutrition 0.000 claims description 3
- 239000011280 coal tar Substances 0.000 claims description 3
- QHNCWVQDOPICKC-UHFFFAOYSA-N copper;1-hydroxypyridine-2-thione Chemical compound [Cu].ON1C=CC=CC1=S.ON1C=CC=CC1=S QHNCWVQDOPICKC-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229940117955 isoamyl acetate Drugs 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- XNFIRYXKTXAHAC-UHFFFAOYSA-N tralopyril Chemical compound BrC1=C(C(F)(F)F)NC(C=2C=CC(Cl)=CC=2)=C1C#N XNFIRYXKTXAHAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 229940043810 zinc pyrithione Drugs 0.000 claims description 3
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000013505 freshwater Substances 0.000 abstract description 18
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 8
- 238000005336 cracking Methods 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 230000003204 osmotic effect Effects 0.000 abstract description 4
- 230000002159 abnormal effect Effects 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 3
- 230000003373 anti-fouling effect Effects 0.000 description 18
- 239000013535 sea water Substances 0.000 description 7
- 238000010276 construction Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
Images
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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Abstract
The invention provides an oleic acid grafted zinc acrylate epoxy resin-based coating and a preparation method thereof, wherein the coating is prepared by dispersing materials in a solvent medium by an oleic acid grafted zinc acrylate polymer, epoxy resin, rosin liquid, cuprous oxide, zinc oxide, an auxiliary antifouling agent, a pigment, a thixotropic agent and a plasticizer through a dispersion process, so that the materials are uniformly mixed, and the fineness reaches below 80 mu m; meanwhile, a small amount of epoxy resin is added to eliminate stress generated after resin hydrolysis, such as resin/pigment filler interface stress and calcified resin skeleton interface stress after hydrolysis, so that abnormal phenomena of cracking and the like caused by large osmotic pressure change of a coating in a fresh water environment are avoided, and stable durability of the coating is ensured.
Description
Technical Field
The invention relates to the technical field of chemical materials, is suitable for ship antifouling coatings, and particularly relates to an oleic acid grafted zinc acrylate epoxy resin-based coating and a preparation method thereof.
Background
At present, shipbuilding factories in mainland areas in China are generally positioned in fresh water river water areas near sea entrances, ships need to be built in the fresh water areas for a long time in an upper-layer building process in the ship building process, and as the osmotic pressure of fresh water is far higher than that of seawater, the antifouling paint often has the adverse phenomena of falling, bubbling and cracking in the fresh water, so that the ships need to be docked and then coated and repaired after the construction is finished, the construction period is influenced, and the construction cost is increased.
Aiming at the problem of special water areas for ship construction in China continental area, relevant researches are carried out by foreign coating huge heads. The self-polishing antifouling paint which adopts acrylic silane polymer as resin base material is developed by the Japan intermediate coat industry, and the water absorption of the coating is reduced by adding hydrophobic alicyclic compound, so that the self-polishing antifouling paint has the applicability of fresh water resistance; the Nippon paint company and Mitsubishi company jointly develop the antifouling paint which takes vinyl resin as a resin base material, and the water absorption of the coating is reduced by utilizing the hydrophobicity of the vinyl resin, so that the fresh water applicability of the antifouling paint is endowed.
Disclosure of Invention
In order to solve the problems, the invention provides the oleic acid grafted zinc acrylate epoxy resin-based paint and the preparation method thereof, the antifouling paint is suitable for a freshwater environment, the problems of easy falling, cracking, foaming and the like caused by freshwater soaking of an antifouling coating are solved, and the long-term freshwater resistance requirement of the antifouling paint is realized.
The technical scheme adopted by the invention for solving the technical problems is as follows: an oleic acid grafted zinc acrylate epoxy resin-based paint comprises the following components in parts by weight: 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 30-40 parts of cuprous oxide, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment, 0.5-1 part of thixotropic agent, 2-4 parts of plasticizer and 5-8 parts of solvent.
Furthermore, rosin is dissolved in a solvent xylene to obtain a rosin solution with mass solubility of 55-65%, and the rosin is one or a combination of more of rosin and modified rosin.
Further, the epoxy resin is one or a combination of E51 epoxy resin and E44 epoxy resin.
Furthermore, the cuprous oxide has a water content of less than 0.1%; the zinc oxide has water content and water soluble matter content less than 0.15%.
Furthermore, the auxiliary antifouling agent is one or a combination of several of ECONEA, copper pyrithione, zinc pyrithione and zineb.
Further, the pigment is permanent red, the thixotropic agent is polyamide wax, and one or a combination of more of plasticizers R40 chlorinated paraffin and R70 chlorinated paraffin.
Further, the solvent is one or a combination of more of xylene, n-butanol, ethyl acetate, coal tar, cyclohexanone, acetophenone, isobutanol, isopropanol, methyl acetate and isoamyl acetate.
A preparation method of an oleic acid grafted zinc acrylate epoxy resin-based paint comprises the following preparation steps:
weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment and 2-4 parts of plasticizer according to the mass parts, adding the materials into a dispersion tank in the above order, and performing first high-speed dispersion by using a high-speed dispersion machine for 2-4 hours until the particle size is less than or equal to 80 mu m;
continuously adding 30-40 parts of cuprous oxide and 5-8 parts of solvent into a dispersion tank, and performing secondary high-speed dispersion for 25-35 min until the particle size is smaller than or equal to 80 mu m;
and step three, adding 0.5-1 part of thixotropic agent into the dispersion tank, continuously dispersing for 5-20 min until the thixotropic agent is uniformly dispersed, filtering and discharging.
A preparation method of an oleic acid grafted zinc acrylate epoxy resin-based paint comprises the following preparation steps:
weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 30-40 parts of cuprous oxide, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment, 2-4 parts of plasticizer and 5-8 parts of solvent, adding the materials into a dispersion tank according to the sequence, and performing ball milling for 20-30 hours until the particle size is less than or equal to 80 mu m;
and step two, adding 0.5-1 part of thixotropic agent into a dispersion tank, continuously performing ball milling until the thixotropic agent is uniformly dispersed, filtering and discharging.
A preparation method of an oleic acid grafted zinc acrylate epoxy resin-based paint comprises the following preparation steps:
weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment and 2-4 parts of plasticizer according to the mass parts, adding the materials into a dispersion tank in the sequence, and performing sand grinding dispersion by using a sand mill for 0.8-1.8 hours until the particle size is less than or equal to 80 mu m;
continuously adding 30-40 parts of cuprous oxide and 5-8 parts of solvent into a dispersion tank, and performing secondary sanding dispersion for 20-40 min until the particle size is smaller than or equal to 80 mu m;
and step three, adding 0.5-1 part of thixotropic agent into the dispersion tank, continuously dispersing for 20-40 min until the thixotropic agent is uniformly dispersed, filtering and discharging.
The invention has the beneficial effects that: according to the preparation method of the fresh water-resistant self-polishing antifouling paint based on the oleic acid grafted zinc acrylate/epoxy resin matrix, the long-chain oleic acid grafted zinc acrylate polymer is used as a main film forming agent of a coating, so that the flexibility of the paint film is improved, and the stress of the coating is eliminated; meanwhile, a small amount of epoxy resin is added to eliminate stress generated after resin hydrolysis, such as resin/pigment filler interface stress and calcified resin skeleton interface stress after hydrolysis, so that abnormal phenomena of cracking and the like caused by large osmotic pressure change of a coating in a fresh water environment are avoided, and stable durability of the coating is ensured.
Drawings
FIG. 1 is a graph showing the test condition of the antifouling paint of the present invention after being soaked in fresh water for 12 months;
FIG. 2 is a graph showing the antifouling paint of the present invention without seawater alternation between wetting and drying;
FIG. 3 is a graph showing the test results of the antifouling paint of the present invention after seawater wetting and drying alternation for 8 months.
Detailed Description
The embodiments of the present invention are described in detail with reference to the accompanying drawings, and the embodiments and specific operations of the embodiments are provided on the premise of the technical solution of the present invention, but the scope of the present invention is not limited to the following embodiments.
An oleic acid grafted zinc acrylate epoxy resin-based paint comprises the following components in parts by weight: 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 30-40 parts of cuprous oxide, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment, 0.5-1 part of thixotropic agent, 2-4 parts of plasticizer and 5-8 parts of solvent.
Furthermore, rosin is dissolved in a solvent xylene to obtain a rosin solution with mass solubility of 55-65%, and the rosin is one or a combination of more of rosin and modified rosin.
Further, the epoxy resin is one or a combination of E51 epoxy resin and E44 epoxy resin.
Furthermore, the cuprous oxide has a water content of less than 0.1%; the zinc oxide has water content and water soluble matter content less than 0.15%.
Furthermore, the auxiliary antifouling agent is one or a combination of several of ECONEA, copper pyrithione, zinc pyrithione and zineb.
Further, the pigment is permanent red, the thixotropic agent is polyamide wax, and one or a combination of more of plasticizers R40 chlorinated paraffin and R70 chlorinated paraffin.
Further, the solvent is one or a combination of more of xylene, n-butanol, ethyl acetate, coal tar, cyclohexanone, acetophenone, isobutanol, isopropanol, methyl acetate and isoamyl acetate.
The molecular formula of the resin base material oleic acid grafted zinc acrylate polymer is as follows:
a preparation method of an oleic acid grafted zinc acrylate epoxy resin-based paint adopts a high-speed dispersion method and comprises the following preparation steps:
weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment and 2-4 parts of plasticizer according to the mass parts, adding the materials into a dispersion tank in the above sequence, and performing first high-speed dispersion by using a high-speed dispersion machine for 3 hours until the particle size is less than or equal to 80 mu m;
continuously adding 30-40 parts of cuprous oxide and 5-8 parts of solvent into a dispersion tank, and performing secondary high-speed dispersion for 30min until the particle size is less than or equal to 80 mu m;
and step three, adding 0.5-1 part of thixotropic agent into the dispersion tank, continuously dispersing for 10min until the thixotropic agent is uniformly dispersed, filtering and discharging.
A preparation method of an oleic acid grafted zinc acrylate epoxy resin-based paint adopts a ball milling method and comprises the following preparation steps:
weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 30-40 parts of cuprous oxide, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment, 2-4 parts of plasticizer and 5-8 parts of solvent, adding the materials into a dispersion tank according to the sequence, and performing ball milling for 24 hours until the particle size is less than or equal to 80 mu m;
and step two, adding 0.5-1 part of thixotropic agent into a dispersion tank, continuously performing ball milling until the thixotropic agent is uniformly dispersed, filtering and discharging.
A preparation method of an oleic acid grafted zinc acrylate epoxy resin-based paint adopts a sanding dispersion method, and comprises the following preparation steps:
weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment and 2-4 parts of plasticizer according to the mass parts, adding the materials into a dispersion tank in the above sequence, and performing sand grinding dispersion by using a basket type sand mill or a horizontal sand mill for 1h until the particle size is less than or equal to 80 mu m;
continuously adding 30-40 parts of cuprous oxide and 5-8 parts of solvent into a dispersion tank, and performing secondary sanding dispersion for 30min until the particle size is smaller than or equal to 80 mu m;
and step three, adding 0.5-1 part of thixotropic agent into the dispersion tank, continuously dispersing for 20-40 min until the thixotropic agent is uniformly dispersed, filtering and discharging.
The invention discloses a preparation method of a freshwater-resistant self-polishing antifouling coating based on oleic acid grafted zinc acrylate/epoxy resin, which adopts a long-chain oleic acid grafted zinc acrylate polymer as a main film-forming agent of a coating, improves the flexibility of the coating and eliminates the stress of the coating; simultaneously, a small amount of epoxy resin is added to eliminate stress generated after resin hydrolysis, and the action schematic diagram of the epoxy resin for reducing the stress of the coating is as follows:
such as resin/pigment filler interface stress and calcified resin skeleton interface stress after hydrolysis, avoids abnormal phenomena of cracking and the like of the coating due to large osmotic pressure change in a fresh water environment, and ensures that the coating has stable durability.
Example 1
The ingredients of this example are shown in table 1, and the coating is prepared by a ball milling method in this example;
example 2
The ingredients of this example are shown in table 1, and the coating is prepared by a high-speed dispersion method in this example;
example 3
The ingredients of this example are shown in table 1, and the coating is prepared by a sand milling method;
the addition amounts of the substances in the examples in Table 1 are parts by mass;
table 1 formulation of the coatings of the different examples
1) The surface change of the paint prepared by the invention is shown in figure 1 when the paint is coated on a sample plate and soaked in fresh water for 12 months, and as can be seen from figure 1, the antifouling paint prepared by the invention does not have obvious phenomena of shedding, cracking and foaming on the surface after being soaked in fresh water for 12 months, which shows that the antifouling paint prepared by the invention has good fresh water soaking resistance.
2) The coating prepared by the invention is coated on a sample plate, and is soaked in seawater for 8 months of seawater wet-dry alternation, the sample figure before soaking is shown in figure 2, the surface change situation is shown in figure 3, and figure 3 shows that the antifouling coating prepared by the invention has no obvious phenomena of shedding, cracking and foaming on the surface after 8 months of seawater wet-dry alternation, which indicates that the antifouling coating prepared by the invention has good seawater wet-dry alternation resistance.
The above embodiments are merely to illustrate the technical solutions of the present invention and not to limit the present invention, and the present invention has been described in detail with reference to the preferred embodiments. It will be understood by those skilled in the art that various modifications and equivalent arrangements may be made without departing from the spirit and scope of the present invention and it should be understood that the present invention is to be covered by the appended claims.
Claims (10)
1. An oleic acid grafted zinc acrylate epoxy resin-based paint is characterized in that: the coating comprises the following components in parts by mass: 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 30-40 parts of cuprous oxide, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment, 0.5-1 part of thixotropic agent, 2-4 parts of plasticizer and 5-8 parts of solvent.
2. The oleic acid grafted zinc acrylate epoxy resin-based coating of claim 1, wherein: the rosin solution is obtained by dissolving rosin in a solvent xylene, wherein the mass solubility of the rosin is 55-65%, and the rosin is one or a combination of rosin and modified rosin.
3. The oleic acid grafted zinc acrylate epoxy resin-based coating of claim 1, wherein: the epoxy resin is one or a combination of E51 epoxy resin and E44 epoxy resin.
4. The oleic acid grafted zinc acrylate epoxy resin-based coating of claim 1, wherein: cuprous oxide with water content less than 0.1%; the zinc oxide has water content and water soluble matter content less than 0.15%.
5. The oleic acid grafted zinc acrylate epoxy resin-based coating of claim 1, wherein: the auxiliary antifouling agent is one or a combination of several of ECONEA, copper pyrithione, zinc pyrithione and zineb.
6. The oleic acid grafted zinc acrylate epoxy resin-based coating of claim 1, wherein: the pigment is permanent red, the thixotropic agent is polyamide wax, and the plasticizer is one or a combination of more of R40 chlorinated paraffin and R70 chlorinated paraffin.
7. The oleic acid grafted zinc acrylate epoxy resin-based coating of claim 1, wherein: the solvent is one or more of xylene, n-butanol, ethyl acetate, coal tar, cyclohexanone, acetophenone, isobutanol, isopropanol, methyl acetate, and isoamyl acetate.
8. The preparation method of the oleic acid grafted zinc acrylate epoxy resin-based paint according to any one of claims 1 to 7, characterized by comprising the following steps: the preparation method comprises the following preparation steps:
weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment and 2-4 parts of plasticizer according to the mass parts, adding the materials into a dispersion tank in the above order, and performing first high-speed dispersion by using a high-speed dispersion machine for 2-4 hours until the particle size is less than or equal to 80 mu m;
continuously adding 30-40 parts of cuprous oxide and 5-8 parts of solvent into a dispersion tank, and performing secondary high-speed dispersion for 25-35 min until the particle size is smaller than or equal to 80 mu m;
and step three, adding 0.5-1 part of thixotropic agent into the dispersion tank, continuously dispersing for 5-20 min until the thixotropic agent is uniformly dispersed, filtering and discharging.
9. The preparation method of the oleic acid grafted zinc acrylate epoxy resin-based paint according to any one of claims 1 to 7, characterized by comprising the following steps: the preparation method comprises the following preparation steps:
weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 30-40 parts of cuprous oxide, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment, 2-4 parts of plasticizer and 5-8 parts of solvent, adding the materials into a dispersion tank according to the sequence, and performing ball milling for 20-30 hours until the particle size is less than or equal to 80 mu m;
and step two, adding 0.5-1 part of thixotropic agent into a dispersion tank, continuously performing ball milling until the thixotropic agent is uniformly dispersed, filtering and discharging.
10. The preparation method of the oleic acid grafted zinc acrylate epoxy resin-based paint according to any one of claims 1 to 7, characterized by comprising the following steps: the preparation method comprises the following preparation steps:
weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment and 2-4 parts of plasticizer according to the mass parts, adding the materials into a dispersion tank in the sequence, and performing sand grinding dispersion by using a sand mill for 0.8-1.8 hours until the particle size is less than or equal to 80 mu m;
continuously adding 30-40 parts of cuprous oxide and 5-8 parts of solvent into a dispersion tank, and performing secondary sanding dispersion for 20-40 min until the particle size is smaller than or equal to 80 mu m;
and step three, adding 0.5-1 part of thixotropic agent into the dispersion tank, continuously dispersing for 20-40 min until the thixotropic agent is uniformly dispersed, filtering and discharging.
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