CN116814153A - Organic silicon marine antifouling paint with hydrogen bond complexation effect and preparation method thereof - Google Patents
Organic silicon marine antifouling paint with hydrogen bond complexation effect and preparation method thereof Download PDFInfo
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 30
- 239000003973 paint Substances 0.000 title claims abstract description 30
- 239000001257 hydrogen Substances 0.000 title claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 14
- 239000010703 silicon Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 230000000694 effects Effects 0.000 title abstract description 9
- 238000010668 complexation reaction Methods 0.000 title abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- 238000004132 cross linking Methods 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 230000000536 complexating effect Effects 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002086 nanomaterial Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 28
- 238000001723 curing Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 16
- -1 (methyl) acryloyloxy group Chemical group 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000010907 mechanical stirring Methods 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- WOCGAOBSWOEOTH-UHFFFAOYSA-N 2,2-dihydroxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)O WOCGAOBSWOEOTH-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 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
- 238000005507 spraying Methods 0.000 claims description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 claims description 2
- GIEMHYCMBGELGY-UHFFFAOYSA-N 10-undecen-1-ol Chemical compound OCCCCCCCCCC=C GIEMHYCMBGELGY-UHFFFAOYSA-N 0.000 claims 1
- 238000007761 roller coating Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 230000003993 interaction Effects 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- 230000021715 photosynthesis, light harvesting Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 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
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000002002 slurry Substances 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
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000009924 canning Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000282414 Homo sapiens Species 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
- 241000656145 Thyrsites atun Species 0.000 description 1
- 102000004142 Trypsin Human genes 0.000 description 1
- 108090000631 Trypsin Proteins 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 230000001332 colony forming effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 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
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- 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 description 1
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Abstract
The invention relates to an organic silicon marine antifouling paint with a hydrogen bond complexing effect and a preparation method thereof. According to the invention, through synthesizing the modified curing agent rich in hydroxyl groups, in the process of realizing crosslinking and curing of the organosilicon coating, dense supermolecular interaction is generated with the metal oxide clusters with the sub-nano structures, and hydrogen bond complexation interaction is realized, so that cohesive stress generated by a polymer in the coating curing process is effectively avoided, and higher energy dissipation capacity is maintained, and excellent bonding effect of the cured coating and various polar substrates is ensured. The coating may be suitable for equipment immersed in a marine environment for a long period of time.
Description
Technical Field
The invention belongs to the technical field of marine antifouling paint and underwater paint, and particularly relates to an organic silicon marine antifouling paint with a hydrogen bond complexing effect, which can keep lasting and excellent bonding effect after being immersed in a seawater environment for a long time, and a preparation method thereof.
Background
The development of the marine industry greatly promotes the economic development and cultural communication of all countries around the world, and the earth enters the ocean age. Today, china has become the most important industrial production and manufacturing base for ships worldwide, with more than 60% of new annual capacity worldwide being transported to China. The prosperous marine economy inevitably faces the trouble of marine biofouling organisms. Marine fouling refers to the indiscriminate adhesive failure of a substrate immersed in sea water by marine organisms, which can lead to corrosion of metallic substrates and degradation of nonmetallic substrates, thereby leading to equipment damage and personnel life and property damage. In addition, the adhering marine organisms also lead to increased fuel consumption of the vessel, thereby leading to the emission of large amounts of greenhouse gases and toxic and harmful gases.
At present, the most effective prevention and treatment measures are to paint marine antifouling paint, and the traditional marine antifouling paint kills marine fouling organisms through the release of toxic agents or heavy metal ions, so that the excellent prevention and treatment effects are achieved, meanwhile, the damage to the marine ecological environment is unavoidable, and finally, the safety of human beings is endangered through the food chain enrichment effect. At present, environmental-friendly marine antifouling paints are developed widely in all countries around the world, and are mainly classified into fouling release type, fouling degradation type and fouling inhibition type.
The organosilicon marine antifouling paint belongs to the technical field of fouling release antifouling, and physical prevention and removal of fouling organisms are realized through low surface energy and low elastic modulus, however, the non-polar characteristic of an organosilicon material leads to poor adhesion with a polar substrate, and serious falling off can occur in the process of external impact or long-term use, so that the commercialized application of the organosilicon marine antifouling paint is limited. The common mode is to endow the organic silicon material with polar property through modification of polar functional groups and generate hydrogen bond or chemical bond combination, so that the bonding force of the coating and the polar substrate is improved. However, polymers have limited application to polar substrate surfaces due to reduced or even lost adhesion effects caused by the tendency of shrinkage to build up internal stress during curing and crosslinking.
Disclosure of Invention
Aiming at the defect of poor binding force between the traditional organic silicon marine antifouling paint and various polar substrates, the invention provides the organic silicon marine antifouling paint with the hydrogen bond complexing effect and the preparation method thereof, and the cured coating can realize the hydrogen bond complexing interaction through the supermolecular interaction between hydroxyl groups and metal oxide clusters with sub-nano structures, thereby effectively avoiding the cohesive stress generated by the polymer in the curing process of the coating, keeping higher energy dissipation capacity and ensuring that the cured coating and various polar substrates keep excellent binding effect. In addition, the copolymer synthesized by the component B does not adversely affect the surface energy and the elastic modulus of the cured coating when the curing agent is crosslinked, so that the excellent antifouling scope is maintained, and the physical prevention and treatment of marine fouling organisms are realized.
The invention is realized by the following technical scheme:
the organic silicon marine antifouling paint with the hydrogen bond complexing effect is characterized by comprising, by weight, 10-30 parts of (1) a component A; (2) 5-10 parts of component B; (3) 1-3 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:
the component C comprises the following components in parts by weight
5-10 parts of cross-linking catalyst
15-30 parts of a third solvent
Preferably, the silicone hydrophobic resin is one of an alpha, omega-dihydroxypolysiloxane, an alpha, omega-dihydroxypolydimethylsiloxane, and an alpha, omega-dihydroxypolymethylsiloxane resin.
Preferably, the pigment and filler is not particularly limited, and can be micro-nano powder commonly applied to organosilicon marine antifouling paint, and the pigment and filler is one of kaolin, titanium dioxide, heavy calcium powder, iron oxide red and white carbon black as a preferable scheme.
Preferably, the auxiliary agent is at least one of a flatting agent, a defoaming agent and a wetting dispersant, and the flatting agent is one of BYK333, BYK306 and 432 of the Pike company as a preferable scheme; the defoamer is one of BYK066N, BYK022, BYK039 and 7015 and 6600 of the court of the Dety company; the wetting dispersant is one of BYK161 and BYK163 of Pick company.
Preferably, the metal oxide cluster with the sub-nano structure is one of silicotungstic acid with the particle size of 1 nanometer and phosphotungstic acid with the particle size of 1 nanometer.
Preferably, the first solvent is one of ethanol and isopropanol.
Preferably, the monomer having a hydroxyl group and an unsaturated double bond group is one of phenylacrylic acid, 4-hydroxy butyl acrylate, hydroxyethyl acrylate, dihydroxyethyl methacrylate, undecylenic acid alcohol.
Preferably, the silane monomer having a (meth) acryloyloxy group is one of gamma-methacryloxypropyl triisopropoxysilane, gamma-methacryloxypropyl methyldimethoxysilane and 3-methacryloxypropyl trimethyloxysilane.
Preferably, the initiator is azobisisobutyronitrile.
Preferably, the second solvent is one of ethanol, butanone, ethyl acetate, toluene and xylene.
Preferably, the crosslinking catalyst is one of dibutyl tin dilaurate, stannous octoate and organic bismuth.
Preferably, the third solvent is one of acetylacetone, acetone, xylene and isopropanol.
The invention relates to a preparation method of an organic silicon marine antifouling paint with hydrogen bond complexation,
wherein, the component A is prepared by the following steps:
the components in the component A are sequentially and uniformly mixed according to parts by weight by using dispersing equipment, the dispersing equipment is not particularly limited, the rotating speed and the dispersing time are also not particularly limited, and the component A which is uniformly mixed can be finally obtained according to actual conditions.
Wherein the component B is prepared by the following steps:
(1) Mixing a monomer with a hydroxyl group and an unsaturated double bond group, a silane monomer with a (methyl) acryloyloxy group and 50% by weight of a second solvent for 10-30 min under 100-300 rpm by mechanical stirring in a light-proof environment;
(2) Simultaneously, mixing the initiator and 50% by weight of the second solvent for 10-20 min under 100-200 rpm by mechanical stirring;
(3) Subsequently, the two mixtures of the step (1) and the step (2) are placed in a reaction kettle, kept in a nitrogen protection state and reacted for 4 to 7 hours at the temperature of 45 to 65 ℃.
Wherein, the component C is prepared by the following steps:
the components in the component C are sequentially and uniformly mixed according to parts by weight by using dispersing equipment, the dispersing equipment is not particularly limited, the rotating speed and the dispersing time are also not particularly limited, and the component C can be finally obtained after uniform mixing according to actual conditions.
Before coating, the component A and the component B are mixed evenly by hand, kept stand for at least 30min, then the component C is added, mixed evenly by hand, the coating is prepared by brush coating, spraying or rolling coating method construction and crosslinking solidification.
Compared with the traditional organic silicon marine antifouling paint, the invention has the following beneficial effects:
1. the core of the invention is that a modified polysiloxane copolymer (curing agent) with hydroxyl groups and acyloxy groups is synthesized through free radical polymerization, the curing agent can participate in the crosslinking curing reaction of polysiloxane resin, and the modification of the main film forming polysiloxane resin in the component A is avoided through modifying the curing agent, so that the difficulty of synthesizing modified organic silicon resin is effectively reduced.
2. Through the dense supermolecule interaction constructed by the polymer rich in hydroxyl groups and the metal oxide clusters with the sub-nano structures, the cohesive stress generated by volume shrinkage of the polymer in the curing process can be effectively overcome, and higher energy dissipation capacity is provided, so that the strong hydrogen bond interaction between the polymer containing hydroxyl groups and the polar substrate is ensured, and the binding force between the coating and the substrate is improved.
3. The metal oxide clusters with the sub-nano structures also have high-density surface hydrogen bond sites, can form simple complexation with polar polymers containing hydroxyl groups, provide high-density hydrogen bonds as enhanced physical crosslinking points, and further ensure that the coating is firmly adhered to the surfaces of various polar substrates.
4. The curing agent rich in hydroxyl plays a role in curing and crosslinking in the final cured coating, so that the properties of low surface energy, low elastic modulus and the like of the film-forming organosilicon elastomer are not affected, and the prepared coating can still keep excellent antifouling performance.
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 realize final curing and film forming, the component B is used as a crosslinking curing agent component to perform chemical crosslinking and curing reaction with the component A, and the component C is used as a crosslinking catalyst to ensure that the component A and the component B can perform 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 silicone hydrophobic resins listed in table 1 were purchased from DY series, eastern chemical industry limited, but the silicone hydrophobic resins selected for use in the practice of the present invention are 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) Mixing a monomer having a hydroxyl group and an unsaturated double bond group, a silane-based monomer having a (meth) acryloyloxy group, 50% by weight of a second solvent by mechanical stirring at 300rpm for 25 minutes in a dark environment;
(2) Simultaneously, mixing the initiator and 50% by weight of the second solvent by mechanical stirring at 200rpm for 10min;
(3) Subsequently, the two mixtures of the step (1) and the step (2) are placed in a reaction kettle, kept in a nitrogen protection state and reacted for 5 hours at 60 ℃;
(4) The component B can be obtained after the temperature of the reaction product is reduced to the room temperature, and the component B is taken out and stored in a dark place;
(5) Mixing the components in A, C components in parts by weight with dispersing equipment at 100rpm for 8min, and sequentially and uniformly mixing;
(6) And (3) mixing the component A and the component B by hand uniformly, standing for at least 30min, then adding the component C, mixing by hand uniformly, constructing by adopting a brush coating method, and preparing the coating with the thickness of 100-150 mu m by crosslinking and curing.
TABLE 2
[ example 5 ]
The formulation was the same as in example 1, and the specific preparation process was as follows:
(1) Mixing a monomer having a hydroxyl group and an unsaturated double bond group, a silane-based monomer having a (meth) acryloyloxy group, 50% by weight of a second solvent by mechanical stirring at 200rpm for 10min in a dark environment;
(2) Simultaneously, mixing the initiator and 50% by weight of the second solvent by mechanical stirring at 100rpm for 15min;
(3) Subsequently, placing the two mixtures in the step (1) and the step (2) in a reaction kettle, keeping a nitrogen protection state, and carrying out reaction for 4 hours at 65 ℃;
(4) The component B can be obtained after the temperature of the reaction product is reduced to the room temperature, and the component B is taken out and stored in a dark place;
(5) Mixing the components in A, C components in parts by weight with dispersing equipment at 100rpm for 8min, and sequentially and uniformly mixing;
(6) And (3) mixing the component A and the component B by hand uniformly, standing for at least 30min, then adding the component C, mixing by hand uniformly, constructing by adopting a brush coating method, and preparing the coating with the thickness of 100-150 mu m by crosslinking and curing.
[ example 6 ]
The formulation was the same as in example 1, and the specific preparation process was as follows:
(1) Mixing a monomer having a hydroxyl group and an unsaturated double bond group, a silane-based monomer having a (meth) acryloyloxy group, 50% by weight of a second solvent by mechanical stirring at 100rpm for 30min in a dark environment;
(2) Simultaneously, mixing the initiator and 50% parts by weight of the second solvent by mechanical stirring at 120rpm for 20min;
(3) Subsequently, the two mixtures of the step (1) and the step (2) are placed in a reaction kettle, kept in a nitrogen protection state and reacted for 7 hours at 45 ℃;
(4) The component B can be obtained after the temperature of the reaction product is reduced to the room temperature, and the component B is taken out and stored in a dark place;
(5) Mixing the components in A, C components in parts by weight with dispersing equipment at 100rpm for 8min, and sequentially and uniformly mixing;
(6) And (3) mixing the component A and the component B by hand uniformly, standing for at least 30min, then adding the component C, mixing by hand uniformly, constructing by adopting a brush coating method, and preparing the coating with the thickness of 100-150 mu m by crosslinking and curing.
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: 90.0 parts of polysiloxane resin, 30.0 parts of pigment and filler, 4.0 parts of crosslinking curing agent, 1.5 parts of catalyst, 0.5 part of auxiliary agent and 0.0 part of third solvent.
The polysiloxane resin is alpha, omega-dihydroxy polydimethylsiloxane with 10000 mPa.s viscosity; the pigment is selected from micron-sized zinc 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 BYK161 dispersing agent of Pick company; the solvent is selected from dimethylbenzene.
(1) 90.0 parts of alpha, omega-dihydroxypolydimethylsiloxane with 10000 mPas viscosity and 30.0 parts of micron-sized zinc oxide are added into a dispersing machine, dispersed at a high speed for 30min at 300rpm, then 0.5 part of BYK161 dispersing agent of Pick company is added into the dispersing machine at 200rpm for 30min, and then the mixture is ground to a fineness less than 40 mu m through a sand mill to prepare pre-dispersed slurry, and the pre-dispersed slurry is canned for standby;
(2) Uniformly mixing 4.0 parts of ethyl orthosilicate and 10.0 parts of dimethylbenzene to prepare a cross-linking curing agent component, canning for later use, uniformly mixing 1.5 parts of dibutyltin dilaurate and 20.0 parts of dimethylbenzene to prepare a catalyst component, and canning for later use;
(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 to obtain the common organosilicon low-surface-energy marine antifouling coating with the thickness of 100-150 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.
< 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, compared with the comparative example, the silicone marine antifouling paint with hydrogen bond complexing effect prepared in the example maintains excellent combination effect with various polar substrates (steel plate, aluminum plate, epoxy intermediate paint) on the basis of maintaining excellent antifouling effect, and is obviously improved compared with the comparative example. This shows that the organic silicon marine antifouling paint with hydrogen bond complexing effect has excellent antifouling performance and good adhesion and binding force.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (7)
1. The organic silicon marine antifouling paint with the hydrogen bond complexing effect is characterized by comprising, by weight, 10-30 parts of (1) a component A; (2) 5-10 parts of a component B; (3) 1-3 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:
80-120 parts of organic silicon hydrophobic resin
Pigment and filler 0-40 parts
0-2 parts of auxiliary agent
10-20 parts of metal oxide cluster with sub-nano structure
50-80 parts of a first solvent;
the component B comprises the following components in parts by weight:
20-50 parts of monomer with hydroxyl group and unsaturated double bond group
20-50 parts of silane monomer with (methyl) acryloyloxy group
1-2 parts of initiator
40-100 parts of a second solvent;
the component C comprises the following components in parts by weight
5-10 parts of a crosslinking catalyst
And 15-30 parts of a third solvent.
2. The coating of claim 1 wherein the silicone hydrophobic resin is one of an α, ω -dihydroxypolysiloxane, an α, ω -dihydroxypolydimethylsiloxane, and an α, ω -dihydroxypolymethylsiloxane resin.
3. The coating of claim 1, wherein the metal oxide clusters having a sub-nanostructure are one of 1 nm silicotungstic acid, 1 nm phosphotungstic acid.
4. The coating of claim 1, wherein the monomer having a hydroxyl group and an unsaturated double bond group is one of phenylacrylic acid, 4-hydroxy butyl acrylate, hydroxy ethyl acrylate, dihydroxy ethyl methacrylate, undecylenic alcohol.
5. The coating of claim 1, wherein the silane monomer having a (meth) acryloyloxy group is one of gamma-methacryloxypropyl triisopropoxysilane, gamma-methacryloxypropyl methyldimethoxysilane, and 3-methacryloxypropyl trimethyloxysilane.
6. The method of preparing a coating according to any one of claims 1-5, wherein the B component is prepared by the steps of:
(1) In a light-shielding environment, mixing a monomer with a hydroxyl group and an unsaturated double bond group, a silane monomer with (methyl) acryloyloxy group and 50% by weight of a second solvent for 10-30 min under 100-300 rpm by mechanical stirring;
(2) Mixing an initiator and 50% by weight of a second solvent at 100-200 rpm for 10-20 min by mechanical stirring;
(3) And (3) placing the two mixtures in the step (1) and the step (2) in a reaction kettle, keeping a nitrogen protection state, and reacting for 4-7 h at 45-65 ℃.
7. The coating prepared from the marine antifouling paint according to any of claims 1-5, wherein the coating is prepared by uniformly mixing the component a and the component B, standing for at least 30min, then adding the component C, uniformly mixing, applying by brush coating, spray coating or roller coating, and curing by crosslinking.
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| CN117363212A (en) * | 2023-11-01 | 2024-01-09 | 常熟理工学院 | Organic silicon marine antifouling paint based on affinity synergistic effect |
| CN117363135A (en) * | 2023-11-01 | 2024-01-09 | 常熟理工学院 | Hydrogen-bonding modified organic silicon marine antifouling paint |
| CN117363212B (en) * | 2023-11-01 | 2024-05-17 | 常熟理工学院 | Organic silicon marine antifouling paint based on affinity synergistic effect |
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| CN114874699A (en) * | 2022-06-16 | 2022-08-09 | 常熟理工学院 | Bionic modified organic silicon marine antifouling paint and preparation method thereof |
| CN115093789A (en) * | 2022-06-16 | 2022-09-23 | 常熟理工学院 | Modified organic silicon marine antifouling paint and preparation method thereof |
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| EP2607413A1 (en) * | 2011-12-22 | 2013-06-26 | Shin-Etsu Chemical Co., Ltd. | Plastic Substrate for Automotive Glazing and Its Repairing Method |
| WO2017154264A1 (en) * | 2016-03-09 | 2017-09-14 | 株式会社Ｌｉｘｉｌ | Coating material, coating material set, and member for use in wet area |
| CN114015320A (en) * | 2021-11-26 | 2022-02-08 | 常熟理工学院 | Low-surface-energy organic silicon marine antifouling paint |
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| CN117363135A (en) * | 2023-11-01 | 2024-01-09 | 常熟理工学院 | Hydrogen-bonding modified organic silicon marine antifouling paint |
| CN117363212B (en) * | 2023-11-01 | 2024-05-17 | 常熟理工学院 | Organic silicon marine antifouling paint based on affinity synergistic effect |
| CN117363135B (en) * | 2023-11-01 | 2024-05-17 | 常熟理工学院 | Hydrogen-bonding modified organic silicon marine antifouling paint |
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