CN116515389B - Blending complexing modified organic silicon marine antifouling paint and preparation method thereof - Google Patents
Blending complexing modified organic silicon marine antifouling paint and preparation method thereof Download PDFInfo
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- CN116515389B CN116515389B CN202310428101.8A CN202310428101A CN116515389B CN 116515389 B CN116515389 B CN 116515389B CN 202310428101 A CN202310428101 A CN 202310428101A CN 116515389 B CN116515389 B CN 116515389B
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 43
- 239000003973 paint Substances 0.000 title claims abstract description 36
- 238000002156 mixing Methods 0.000 title claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 17
- 239000010703 silicon Substances 0.000 title claims abstract description 17
- 230000000536 complexating effect Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 27
- 238000004132 cross linking Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000002086 nanomaterial Substances 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 230000002209 hydrophobic effect Effects 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000049 pigment Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- -1 polydimethylsiloxane Polymers 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 230000003993 interaction Effects 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000013535 sea water Substances 0.000 abstract description 5
- 238000010668 complexation reaction Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000002464 physical blending Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 238000010276 construction Methods 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 244000236521 Bupleurum rotundifolium Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 241000194024 Streptococcus salivarius Species 0.000 description 1
- 102000004142 Trypsin Human genes 0.000 description 1
- 108090000631 Trypsin Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001332 colony forming effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
- 239000001974 tryptic soy broth Substances 0.000 description 1
- 108010050327 trypticase-soy broth Proteins 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- 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
- C09D5/1675—Polyorganosiloxane-containing compositions
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to a blending complexing modified organic silicon marine antifouling paint and a preparation method thereof. The invention realizes that the hydroxyl-rich polymer and the metal oxide cluster generate dense supermolecular interaction through simple physical blending, thereby realizing hydrogen bond complexation interaction. The prepared coating is suitable for marine ship surface antifouling, the surface of the coating still has the antifouling property of the organosilicon low-surface-energy coating while the excellent bonding strength with a substrate is maintained, and the coating can be suitable for equipment immersed in a seawater environment for a long time.
Description
Technical Field
The invention belongs to the technical field of marine antifouling paint and underwater paint, and particularly relates to a blending complexing modified organic silicon marine antifouling paint for releasing antifouling on the surface of a marine ship and a preparation method thereof.
Background
The development of the marine transportation industry greatly promotes the economic culture communication of all countries in the world, and particularly for China, china is the largest marine industry country in the world and the largest marine vessel production and manufacturing base in the world at present. Each year, more than 60% of new ocean capacity is transported to china. The development of the ocean industry greatly promotes the economic development of China.
However, in the development of the marine and maritime industry, it is inevitable to face the marine biofouling problem. Marine biofouling refers to the process of indiscriminate adhesion of marine fouling organisms to substrates immersed in a seawater environment, which can lead to corrosion of metal substrates and degradation of nonmetallic substrates, thereby seriously jeopardizing equipment construction and use stability and human life safety. Currently, the most efficient and economical solution is to paint marine antifouling paint. With the development of science and technology and the improvement of environmental protection consciousness of human society, the traditional toxic agent release type marine antifouling paint is gradually forbidden, so that the alternative type environment-friendly marine antifouling paint is developed and gradually popularized and applied in the marine and maritime industries.
The organosilicon low-surface-energy marine antifouling paint is an important part of an environment-friendly pollution-release type antifouling technology, and can inhibit adhesion of marine fouling organisms by physical means based on the characteristics of low surface free energy and low elastic modulus of organosilicon materials, even if the adhesion is not firm, the fouling organisms can be released into a seawater environment again by means of flushing of seawater, so that the environment-friendly pollution-release type antifouling aim is achieved. However, the antifouling dominant properties of conventional silicone low surface energy marine antifouling paints, silicone materials, in turn, can lead to adverse effects on the application. Because the organosilicon material belongs to a nonpolar material, the bonding force to the polar ship base material is poor, and the organosilicon material is easy to collide and fall off in the actual use process, so that the commercialization application of the product is greatly limited. Currently, the vast majority of improvements are the synthesis of specific modified polysiloxane materials by chemical modification, although many beneficial results have emerged. However, the chemical synthesis modification mode has high requirements on the research and development technology of enterprises and strict production conditions, and can only be developed in large-scale and powerful chemical enterprises. Technical barriers, production requirements, etc. limit the further application of such modified silicone marine antifouling coatings.
Disclosure of Invention
Aiming at the problems that the organic silicon low-surface-energy marine antifouling paint has low bonding strength with a polar substrate, is easy to collide and fall off and the like, the invention provides the marine antifouling paint which is physically blended to generate hydrogen bond complexation interaction so as to improve the bonding force of the coating and the polar substrate. In particular, the coating super strong adhesion derives from the dense supermolecular interaction between the hydroxyl-containing polymer blend and the sub-nanostructure metal oxide, and the hydrogen bond complexing interaction based on the supermolecular interaction can effectively ignore cohesive stress generated by the polymer in the curing process and provide higher energy dissipation capability, thereby ensuring that the cured coating still maintains excellent binding force. The polymer/sub-nanoparticle composite coating is constructed by simple physical blending, the preparation process is simple, and the excellent antifouling property of the organosilicon low-surface-energy coating is maintained.
The technical scheme of the invention is as follows: the blending complexing modified organic silicon marine antifouling paint for fouling release and antifouling on the surface of a marine vessel comprises the following components in parts by weight: (1) 20-30 parts of A component; (2) 3-6 parts of component B; (3) 1-2 parts of component C;
wherein, the liquid crystal display device comprises a liquid crystal display device,
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
3.0 to 10.0 portions of cross-linking curing agent
10.0 to 25.0 parts of a second solvent
The component C comprises the following components in parts by weight:
1.0 to 3.0 portions of crosslinking catalyst
And 5.0 to 10.0 parts of a third solvent.
Preferably, the hydrophobic silicone resin is one of an alpha, omega-dihydroxypolysiloxane, an alpha, omega-dihydroxypolydimethylsiloxane, and an alpha, omega-dihydroxypolymethylsiloxane resin.
Preferably, the pigment additive is not particularly limited, and the micro-nano powder commonly applied to the marine antifouling paint can be any one of barium sulfate, ferrous sulfate, calcium carbonate, nano silicon dioxide, gas phase silicon dioxide and nano zinc oxide as a preferable scheme.
Preferably, the metal oxide cluster having a sub-nanostructure is any one of 1nm silicotungstic acid and 1nm phosphotungstic acid.
Preferably, the polyvinyl alcohol is one with hydrolysis degree greater than 99% and relative molecular weight of 50000-100000.
Preferably, the first solvent is any one of ethanol and isopropanol.
Preferably, the auxiliary agent is at least one of a flatting agent, a defoaming agent and a wetting dispersant, and as a preferable scheme, the flatting agent is any one of BYK333, BYK306 and 837 of the self company; the defoamer is any one of BYK066N, BYK022, BYK039 and 6500 and 6600 of the court of the Dety company; the wetting dispersant is any one of BYK161 and BYK163 of Pick corporation.
Preferably, the crosslinking curing agent is any one of methyltriacetoxysilane, aminopropyl triethoxysilane and tetraethoxysilane.
Preferably, the second solvent is any one of xylene, acetone, toluene and ethanol.
Preferably, the crosslinking catalyst is any one of dibutyl tin dilaurate, stannous octoate and organic bismuth.
Preferably, the third solvent is any one of acetylacetone, acetone and butanone.
The invention relates to a preparation method of a blending complexing modified organic silicon marine antifouling paint,
wherein, the component A is prepared by the following steps:
(1) Stirring polyvinyl alcohol and 50% by weight of a first solvent in 200-300 rpm for 10-20 min by using a dispersing stirrer, uniformly mixing, and then sealing and preserving;
(2) Stirring hydrophobic organic silicon resin, pigment filler and auxiliary agent in 200-400 rpm for 20-40 min by using a dispersing stirrer, then adding metal oxide clusters with sub-nano structure and 50% by weight of first solvent into the system, and stirring in 100-200 rpm for 30-60 min;
(3) Adding the mixed solution obtained in the step (1) into the system obtained in the step (2) by using a dispersing stirrer, and stirring for 20-50 min at 100-200 rpm;
wherein, B, C component is prepared by the following steps:
the components in the B, C component are uniformly mixed according to parts by weight by using a dispersing device, the dispersing device is not particularly limited, the rotating speed and the dispersing time are also not particularly limited, and the components B and C which are uniformly mixed can be finally obtained according to actual conditions.
When in use, the component A and the component B are uniformly mixed according to the weight parts, and the mixture is stood for at least 30min, then the component C is added and uniformly mixed, then the construction is carried out in a conventional manner, and the coating is prepared through crosslinking and curing.
Compared with the existing organosilicon low-surface-energy marine antifouling paint, the invention has the following beneficial effects:
1. the marine antifouling paint with excellent bonding effect is prepared by simple physical blending and complexing, no new polymer is needed to be synthesized, the preparation process is simple, and the construction efficiency is high.
2. Through dense supermolecular interaction constructed by polyvinyl alcohol and sub-nanometer metal oxide clusters, cohesive stress generated by volume shrinkage of the polyvinyl alcohol in the curing process can be effectively overcome, and higher energy dissipation capacity is provided, so that strong hydrogen bond interaction between hydroxyl groups of the polyvinyl alcohol and polar substrates is ensured, and the binding force between the coating and the substrates is improved.
3. The metal oxide clusters with the sub-nano structure also have high-density surface hydrogen bond sites, can form simple complexation with the polar polymer polyvinyl alcohol, and provide high-density hydrogen bonds as enhanced physical crosslinking points so as to ensure that the coating is firmly adhered on the surfaces of various polar substrates.
4. In the cured coating, the polar polyvinyl alcohol is segregated based on the difference of the molecular structure of the nonpolar cured silicone elastomer, and is mainly concentrated in the coating-substrate area, so that the surface of the coating still maintains excellent hydrophobicity, and the excellent antifouling performance of the coating is ensured.
Detailed Description
The present invention will be described with reference to the following specific examples, but the present invention is not limited to the following specific examples, and various modifications are possible within the scope of the present invention, and these modifications are included in the technical scope of the present invention.
According to the blending complexing modified organic silicon marine antifouling paint and the preparation method thereof, the component A is used as a main film forming material component to play a role in final curing and film forming, the component B is used as a crosslinking curing agent component to play a role in ensuring the crosslinking and curing of the component A, and the component C is used as a crosslinking catalyst to ensure that the component A and the component B can undergo a curing and crosslinking chemical reaction.
< raw materials used >
The substances listed in table 1 are representative of various embodiments of the present invention, but are not limited to those listed in table 1 in the actual implementation. Corresponding commercial or chemical materials can be selected according to the foregoing description, and the related substances are not particularly limited to manufacturers. The chemicals used in the examples were all commercially available chemicals.
The hydrophobic silicone resins listed in Table 1 were selected from the alpha, omega-dihydroxy polydimethyl siloxane available from DY series, viscosity (25 ℃ C.) from Shandong Dayi chemical Co., ltd.). 10000 mpa.s, but the hydrophobic silicone resin selected for use in the practice of the invention is not limited to the manufacturer and specific performance parameters thereof.
TABLE 1
Example 1-example 4
The formulation is shown in Table 2, and the specific preparation process is the same as follows:
(1) Stirring polyvinyl alcohol and 50% by weight of a first solvent at 260rpm for 10min, uniformly mixing, and then sealing and preserving;
(2) Stirring the hydrophobic organic silicon resin, the pigment filler and the auxiliary agent in 200rpm for 40min, then adding 50% weight part of the first solvent with the metal oxide clusters with the sub-nano structure into the system, and stirring in 100rpm for 60min;
(3) Adding the mixed solution obtained in the step (1) into the system obtained in the step (2), and stirring for 50min at 180 rpm;
(4) Stirring the components in B, C components in parts by weight at 150rpm for 10min by using a dispersing stirrer, and sequentially and uniformly mixing;
(5) Uniformly mixing the component A and the component B according to parts by weight, standing for at least 30min, then adding and uniformly mixing the component C, then adopting a spraying mode for construction, and preparing a coating through crosslinking and curing, wherein the thickness is controlled to be 200-300 mu m.
TABLE 2
[ example 5 ]
The formulation is the same as that of example 1, and the specific preparation process is as follows
(1) Stirring polyvinyl alcohol and 50% by weight of a first solvent at 200rpm for 20min, uniformly mixing, and then sealing and preserving;
(2) Stirring the hydrophobic organic silicon resin, the pigment filler and the auxiliary agent for 20min at 350rpm, then adding 50% weight part of the first solvent with the metal oxide clusters with the sub-nano structures into the system, and stirring for 45min at 100 rpm;
(3) Adding the mixed solution obtained in the step (1) into the system obtained in the step (2), and stirring for 45min at 100 rpm;
(4) Stirring the components in B, C components in parts by weight at 150rpm for 10min by using a dispersing stirrer, and sequentially and uniformly mixing;
(5) Uniformly mixing the component A and the component B according to parts by weight, standing for at least 30min, then adding and uniformly mixing the component C, then adopting a spraying mode for construction, and preparing a coating through crosslinking and curing, wherein the thickness is controlled to be 200-300 mu m.
[ example 6 ]
The formulation is the same as that of example 1, and the specific preparation process is as follows
(1) Stirring polyvinyl alcohol and 50% by weight of a first solvent at 300rpm for 15min, uniformly mixing, and then sealing and preserving;
(2) Stirring the hydrophobic organic silicon resin, the pigment filler and the auxiliary agent for 25min at 400rpm, then adding 50% weight part of the first solvent with the metal oxide clusters with the sub-nano structures into the system, and stirring for 30min at 200 rpm;
(3) Adding the mixed solution obtained in the step (1) into the system obtained in the step (2), and stirring for 20min at 200 rpm;
(4) Stirring the components in B, C components in parts by weight at 150rpm for 10min by using a dispersing stirrer, and sequentially and uniformly mixing;
(5) Uniformly mixing the component A and the component B according to parts by weight, standing for at least 30min, then adding and uniformly mixing the component C, then adopting a spraying mode for construction, and preparing a coating through crosslinking and curing, wherein the thickness is controlled to be 200-300 mu m.
[ example 7 ]
The formulation is the same as that of example 1, and the specific preparation process is as follows
(1) Stirring polyvinyl alcohol and 50% by weight of a first solvent at 220rpm for 15min, uniformly mixing, and then sealing and preserving;
(2) Stirring the hydrophobic organic silicon resin, the pigment filler and the auxiliary agent for 25min at 300rpm, then adding 50% weight part of the first solvent with the metal oxide clusters with the sub-nano structures into the system, and stirring for 30min at 120 rpm;
(3) Adding the mixed solution obtained in the step (1) into the system obtained in the step (2), and stirring for 20min at 200 rpm;
(4) Stirring the components in B, C components in parts by weight at 150rpm for 10min by using a dispersing stirrer, and sequentially and uniformly mixing;
(5) Uniformly mixing the component A and the component B according to parts by weight, standing for at least 30min, then adding and uniformly mixing the component C, then adopting a spraying mode for construction, and preparing a coating through crosslinking and curing, wherein the thickness is controlled to be 200-300 mu m.
Comparative example 1 (common organosilicon Low surface energy marine antifouling paint)
The common organosilicon low-surface-energy marine antifouling paint comprises the following raw materials in parts by weight: 100.0 parts of polysiloxane resin, 20.0 parts of pigment and filler, 3.0 parts of crosslinking curing agent, 1.0 part of catalyst, 1.0 part of auxiliary agent and 30.0 parts of solvent.
The polysiloxane resin is alpha, omega-dihydroxy polydimethylsiloxane with 10000 mPa.s viscosity; the pigment is selected from industrial cuprous oxide; the cross-linking curing agent is selected from ethyl orthosilicate; the catalyst is dibutyl tin dilaurate; the auxiliary agent is 0.5 part of BYK163 dispersing agent of the Pick company and 0.5 part of 6500 defoamer of the modesty company; the solvent is selected from dimethylbenzene.
The preparation method of the common organosilicon low-surface-energy marine antifouling paint comprises the following steps:
(1) Adding 100.0 parts of alpha, omega-dihydroxypolydimethylsiloxane with 10000 mPas viscosity and 20.0 parts of industrial cuprous oxide into a dispersing machine, dispersing at a high speed for 30min at 500rpm, adding 0.5 part of BYK163 dispersing agent of Pick company and 0.5 part of defoaming agent of De-Qian company 6500 into the dispersing machine at 200rpm for 20min, grinding to fineness less than 40 mu m by a sand mill, preparing pre-dispersed slurry, and canning for later use;
(2) 3.0 parts of ethyl orthosilicate and 15.0 parts of dimethylbenzene are uniformly mixed to prepare a cross-linking curing agent component, and then the cross-linking curing agent component is canned for standby, and 1.0 part of dibutyltin dilaurate and 15.0 parts of dimethylbenzene are uniformly mixed to prepare a catalyst component, and then the catalyst component is canned for standby;
(3) Before use, the pre-dispersed slurry, the cross-linking curing agent component and the catalyst component are uniformly stirred according to the proportion, and the obtained coating is coated and cured in a spraying mode to obtain the common organosilicon low-surface-energy marine antifouling coating, wherein the thickness is controlled between 200 and 300 mu m.
Comparative example 2
The formulation does not contain metal oxide clusters with sub-nanostructures, and the remainder is the same as in example 1, and the specific preparation process is the same as in example 1.
[ comparative example 3 ]
The formulation does not contain polyvinyl alcohol, and the rest is the same as in example 1, and the specific preparation process is the same as in example 1.
< specific test conditions >
Test 1: surface free energy
The contact angles of deionized water and diiodomethane on the surface of the coating were measured using an XG-CAMC3 type full-automatic contact angle measuring instrument manufactured by Shanghai Xuan standard instruments, inc. The surface energy of the coating was then calculated according to the Owens two-fluid method.
Test 2: drawing method for measuring adhesive force (Steel plate, aluminum plate, epoxy intermediate paint)
The BGD500 digital display semiautomatic adhesive force tester produced by Guangzhou Bidada precision instruments is used for measuring the adhesive force of a coating painted on a corresponding substrate or epoxy intermediate paint, the steel plate and the aluminum plate need to be polished by 800-mesh sand paper before being used, and the used epoxy intermediate paint is the epoxy cloud iron intermediate paint produced by Shanghai gold emperor. The adhesion of the coating was tested on standing for 100 days in sterilized aged seawater.
Test 3: test of antifouling Property
Dispersing a mixture of at least 108 units of Streptococcus salivarius in 20ml of tryptic Soy Broth at 38deg.C, 5% CO 2 Is cultured for 2 hours. The suspension was then further diluted and inoculated into agar supplemented with 5% sheep blood and at 38℃with 5% CO 2 After 48 hours of culture, the units containing six colony forming units were dispersed in 10mL of trypsin soybean broth. 20mL of the above bacterial suspension was then covered on a 10X 5cm range of coating and at 38℃with 5% CO 2 Is cultured for 24 hours. After the completion of the incubation, each sample was subjected to a spin rinse in 45mL of distilled water for 30 seconds, and then rinsed with 50mL of distilled water to remove non-stick substances, and surface-adhered bacteria were observed using a Simga300 scanning electron microscope manufactured by Karl Seiss, germany.
TABLE 3 Properties of the coatings prepared in examples and comparative examples
As can be seen from table 3, the blended complex modified silicone marine antifouling coating prepared in the examples also has excellent antifouling effects compared to the comparative examples. More importantly, the coating of the embodiment has excellent binding force on steel plates, aluminum plates and epoxy intermediate paint, and is exponentially increased compared with the comparative example. This highlights the disadvantage that the blending complexation modified organosilicon marine antifouling paint can significantly improve the bonding force between the organosilicon low surface energy marine antifouling paint and polar base material.
Variations and modifications to the above would be obvious to those skilled in the art to which the invention pertains, from the foregoing description of the invention. The invention is not limited to the specific embodiments described above, but modifications thereto are intended to fall within the scope of the claims.
Claims (6)
1. The blending complexing modified organic silicon marine antifouling paint is characterized by comprising the following components in parts by weight: (1) 20-30 parts of a component A; (2) 3-6 parts of a component B; (3) 1-2 parts of component C;
wherein, the liquid crystal display device comprises a liquid crystal display device,
the component A comprises the following components in parts by weight:
60.0-100.0 parts of hydrophobic organic silicon resin
Pigment and filler 0.0-20.0 parts
4.0-10.0 parts of metal oxide cluster with sub-nano structure
10.0-20.0 parts of polyvinyl alcohol
30.0-60.0 parts of a first solvent
0.0-3.0 parts of auxiliary agent
The component B comprises the following components in parts by weight:
3.0-10.0 parts of cross-linking curing agent
10.0 to 25.0 parts of a second solvent
The component C comprises the following components in parts by weight:
1.0-3.0 parts of crosslinking catalyst
5.0-10.0 parts of a third solvent;
wherein the hydrophobic organic silicon resin is alpha, omega-dihydroxy polydimethylsiloxane;
the metal oxide cluster with the sub-nano structure is any one of 1nm silicotungstic acid and 1nm phosphotungstic acid;
the polyvinyl alcohol has a hydrolysis degree of more than 99% and a relative molecular weight of 50000-100000.
2. The marine antifouling paint according to claim 1, wherein the crosslinking curing agent is any one of methyltriacetoxysilane, aminopropyl triethoxysilane, and tetraethyl orthosilicate.
3. The marine antifouling paint according to claim 1, wherein the crosslinking catalyst is any one of dibutyltin dilaurate, stannous octoate, and organic bismuth.
4. The marine antifouling paint according to claim 1, wherein the auxiliary agent is at least one of a leveling agent, an antifoaming agent, and a wetting dispersant.
5. A method of preparing a marine antifouling paint according to any of claims 1 to 4, wherein the a component is prepared by:
(1) Uniformly mixing polyvinyl alcohol and 50% by weight of a first solvent at 200-300 rpm for 10-20 min, and then sealing and preserving;
(2) Stirring hydrophobic organic silicon resin, pigment and filler and auxiliary agent for 20-40 min at 200-400 rpm, adding 50% by weight of first solvent and metal oxide clusters with sub-nano structures into the system, and stirring for 30-60 min at 100-200 rpm;
(3) And (3) adding the mixed solution obtained in the step (1) into the system obtained in the step (2), and stirring for 20-50 min at 100-200 rpm.
6. The coating prepared from the marine antifouling paint according to any of claims 1 to 4, wherein the coating is prepared by uniformly mixing the component A and the component B in parts by weight, standing for at least 30min, adding and uniformly mixing the component C, coating the mixture on a substrate, and curing the mixture by crosslinking.
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