CN107652887B - Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent - Google Patents
Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent Download PDFInfo
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- CN107652887B CN107652887B CN201710809362.9A CN201710809362A CN107652887B CN 107652887 B CN107652887 B CN 107652887B CN 201710809362 A CN201710809362 A CN 201710809362A CN 107652887 B CN107652887 B CN 107652887B
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 51
- 239000011347 resin Substances 0.000 title claims abstract description 49
- 229920005989 resin Polymers 0.000 title claims abstract description 49
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000010703 silicon Substances 0.000 title claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 48
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000002519 antifouling agent Substances 0.000 title claims abstract description 25
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000001257 hydrogen Substances 0.000 claims abstract description 87
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 87
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 84
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 60
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 57
- 229920002545 silicone oil Polymers 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003921 oil Substances 0.000 claims abstract description 51
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010695 polyglycol Substances 0.000 claims abstract description 30
- 229920000151 polyglycol Polymers 0.000 claims abstract description 30
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 30
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 23
- 241000723346 Cinnamomum camphora Species 0.000 claims abstract description 22
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims abstract description 21
- 229960000846 camphor Drugs 0.000 claims abstract description 21
- 229930008380 camphor Natural products 0.000 claims abstract description 21
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims abstract description 20
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 18
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 16
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004090 dissolution Methods 0.000 claims abstract description 10
- 239000007858 starting material Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008096 xylene Substances 0.000 claims description 17
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 claims description 15
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 13
- 239000004952 Polyamide Substances 0.000 claims description 9
- 239000000049 pigment Substances 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 210000004556 brain Anatomy 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- -1 is stirred to react Substances 0.000 abstract description 15
- 238000010438 heat treatment Methods 0.000 abstract 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910021485 fumed silica Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 241000218652 Larix Species 0.000 description 4
- 235000005590 Larix decidua Nutrition 0.000 description 4
- YKPUWZUDDOIDPM-SOFGYWHQSA-N capsaicin Chemical compound COC1=CC(CNC(=O)CCCC\C=C\C(C)C)=CC=C1O YKPUWZUDDOIDPM-SOFGYWHQSA-N 0.000 description 4
- 229960002504 capsaicin Drugs 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PNTJBKYEZUZKFX-UHFFFAOYSA-N 3-chloro-2-octyl-3H-1,2-thiazole Chemical compound C(CCCCCCC)N1SC=CC1Cl PNTJBKYEZUZKFX-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000218195 Lauraceae Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- OGFYGJDCQZJOFN-UHFFFAOYSA-N [O].[Si].[Si] Chemical compound [O].[Si].[Si] OGFYGJDCQZJOFN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000010148 water-pollination Effects 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
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Paints Or Removers (AREA)
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Abstract
The invention discloses a kind of preparation methods of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, using allyl polyglycol ether or ethylene glycol monoallyl ether and containing hydrogen silicone oil as starting material, heating carries out hydrogen silicification reaction, then it is incorporated in the butyl rubber that dissolution is sufficiently swollen in dimethylbenzene, the reaction was continued is made silicon hydrogel resin；Keep reaction temperature constant, thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acid-β-lactone, the chloro- Kathon of 4,5- bis-, artificial camphor and cage modle polysilsesquioxane are added into gained silicon hydrogel resin, is stirred to react, component A is obtained, it is spare；Ethyl orthosilicate is uniformly mixed with di-n-butyltin dilaurate, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione and dimethylbenzene, obtains B component；Component A is uniformly mixed with B component according to 7~9:1 of mass ratio, solidifies 5~8 hours to get anti-fouling material.
Description
Technical field
The present invention relates to a kind of anti-fouling materials, and in particular to a kind of ring based on silicon hydrogel resin and natural anti-fouling agent
Border friendly anti-fouling material.Belong to technical field.
Background technique
Marine biofouling refers to marine microorganism, plant and animal in ship, marine facility adsorption, growth and numerous
The biofouling grown and formed, it to the mankind be engaged in Activities of Ocean bring it is many unfavorable.Brushing antifouling paint is as main antifouling
Means are worldwide widely used, wherein the most significant with tributyl tin (TBT) and cupric antifouling paint.However, applying
Anti-fouling agent in layer can be enriched with by food chain influences human health and ecological safety.In recent years, Marine Environmental Problems are compeled
Cutting concern promotes people constantly to study novel environmentally friendly antifouling paint.
Hydrogel is a kind of environmental-friendly new function high molecular material, it have crosslinking three-dimensional net structure,
It can be swollen and not dissolve in water, and large quantity of moisture can be kept.More and more results of study in relation to hydrogel show
Hydrogel is effective against the absorption of protein, is a kind of potential efficient and environmentally friendly novel sea antifouling paint.And currently,
Research about hydrogel is mostly also in theoretical research stage, although having, experimental results demonstrate hydrogels to have excellent antiplastering
Property and anti-fouling effect, but in the multifarious marine environment of complex biological, there are still certain defects, for example, after swelling
Mechanical property is poor, with the poor adhesion of coating surface, it is easy to aging the disadvantages of limit the development of hydrogel nonpolluting coating.
Summary of the invention
It is a kind of based on silicon hydrogel resin and day the purpose of the present invention is to overcome above-mentioned the deficiencies in the prior art, providing
The environmentally friendly anti-fouling material of right anti-fouling agent.
To achieve the above object, the present invention adopts the following technical solutions:
The preparation method of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, including it is following
Step:
(1) using allyl polyglycol ether or ethylene glycol monoallyl ether and containing hydrogen silicone oil as starting material, 70 are heated to
~90 DEG C of progress hydrogen silicification reactions, are then incorporated in the butyl rubber that dissolution is sufficiently swollen in dimethylbenzene, and the reaction was continued 50~70
Minute, silicon hydrogel resin is made；
(2) keep reaction temperature constant, be added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil,
3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, artificial camphor and the poly- sesquialter silicon of cage modle
Oxygen alkane is stirred to react 1~2 hour, obtains component A, spare；
(3) by ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione
It is uniformly mixed with dimethylbenzene, obtains B component；
(4) component A is uniformly mixed with B component according to 7~9:1 of mass ratio, solidifies 5~8 hours to get anti-fouling material；
Wherein, in component A, allyl polyglycol ether or ethylene glycol monoallyl ether, containing hydrogen silicone oil, dimethylbenzene, butyl
Rubber, thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, conjunction
It is 25~75:20~30:8~10:4~5:0.5~1.5:18~22:3 at the mass ratio of camphor and cage modle polysilsesquioxane
~5:4~6:4~6:0.4~0.6；In B component, ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxy silane
Alkane, cyclohexanone, acetylacetone,2,4-pentanedione and dimethylbenzene mass ratio be 20~21:0.008~0.012:2~2.2:2.1~2.3:5.7~
6:27~30.
Preferably, in step (1), the specific method of hydrogen silicification reaction is: by allyl polyglycol ether or ethylene glycol list
Allyl ether and Karstedt catalyst are configured to mixed liquor, are slowly added dropwise through 1 hour to 70~90 by constant pressure funnel
DEG C containing hydrogen silicone oil in, be added dropwise after the reaction was continued 3 hours, be down to room temperature.
Preferably, in step (1), the specific method of hydrogen silicification reaction is: by allyl polyglycol ether and Karstedt
Catalyst is configured to mixed liquor, is slowly added dropwise within 1 hour by constant pressure funnel into 70~90 DEG C of containing hydrogen silicone oil, is added dropwise
After the reaction was continued 2 hours, add vinyltriethoxysilane, the reaction was continued 2 hours, is down to room temperature；Vinyl three
The mass ratio of Ethoxysilane and containing hydrogen silicone oil is 9:25.
It is further preferred that the Karstedt catalyst is the xylene solution of mass concentration 2%, the dimethylbenzene is molten
The volume mass of liquid and containing hydrogen silicone oil ratio is 10~20 μm of L:25g.
It is further preferred that the hydrogen content of containing hydrogen silicone oil is 0.18% or >=0.6%.
Preferably, in step (2), allyl polyglycol ether or ethylene glycol monoallyl ether, containing hydrogen silicone oil, dimethylbenzene,
Butyl rubber, thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acid-β-lactone, the chloro- 2- n-octyl -4- isothiazoline -3- of 4,5- bis-
The mass ratio of ketone, artificial camphor and cage modle polysilsesquioxane is 25~75:25:9:4.5:0.5~1.5:20:4:5:5:0.5.
Preferably, iron oxide is also added into step (2) as pigment, the mass ratio with hydroxy silicon oil is 5~6:20.
Preferably, it is also added into larch extract, nanometer capsaicine and oyster shell powder in step (2), they and hydroxyl silicon
The mass ratio of oil is 3~4:1~2:4~5:20.
It is further preferred that the oyster shell powder is that oyster shell is cleaned, is dry, 50~80nm powder obtained by grinding.
Preferably, in step (2), the thixotropic agent is fumed silica and polyamide wax, they and hydroxy silicon oil
Mass ratio is 15:0.5~1.5:20.
Preferably, in step (2), the viscosity of hydroxy silicon oil is 5000cSt.
Preferably, in step (2), the cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, molecular formula
For (i-Bu)8Si8O12。
Preferably, in step (3), ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxysilane, hexamethylene
The mass ratio of ketone, acetylacetone,2,4-pentanedione and dimethylbenzene is 20.4:0.01:2.1:2.2:5.8:28.
Preferably, in step (4), component A is uniformly mixed with B component according to mass ratio 8:1.
Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is prepared by the above method
It obtains.
Beneficial effects of the present invention:
The present invention synthesized a kind of silicon hydrogel resin with self-reparing capability, and by answering with natural anti-fouling agent
It closes, is prepared into a kind of environmental-friendly novel sea antifouling paint.It is specific as follows:
1, the present invention uses allyl polyglycol ether or ethylene glycol monoallyl ether and containing hydrogen silicone oil, butyl rubber for original
Material carries out gradient hydrogen silicification reaction, improves the adhesive force and weatherability of resin using Karstedt catalyst.Resin leaching
After entering water, it will form the hydrophily flexible chain of pectination, be conducive to the promotion of resin anti-pollution.
2, the present invention uses traditional hydroxy silicon oil and ethyl orthosilicate, silicon oxygen silicon crosslinked action is made full use of, in silicone
In hydrogel resin system, a kind of resin network structure of three-dimensional space crosslinking is constructed.Meanwhile two laurels that B component introduces
Sour di-n-butyl tin catalyst can also be catalyzed the double-bond polymerization of butyl rubber system remaining, construct deeper cross-linked structure.
To it ensure that hydrogel resin immersion after, while there is extremely strong adhesive force, preferable water-retaining property and lasting stability.
3, it is additive using enclosed cage-type silsesquioxane (T8), reduces the surface energy of organic siliconresin, together
When assign silicon hydrogel resin certain self-reparing capability, after hydrogel resin inner surface is damaged, free T8 can be migrated
To damaged face, under the catalytic action of seawater alkaline matter, Si-O-Si enclosed construction is automatically opened, silicon occurs with damaged surface
Alcohol condensation reaction forms new Si-O-Si backbone, to repair to damaged surface.
It 4, is anti-fouling agent using natural products such as artificial camphor, 3- hydroxybutyric acid-β-lactones, and anti-fouling agent is in hydrogel
It in resin system, does not discharge substantially, to greatly reduce harm of the anti-fouling agent to the marine eco-environment.
5, present invention further introduces larch extract, nanometer capsaicine and oyster shell powder, they and artificial camphor and 3- hydroxyl
The natural anti-fouling agents such as base butenoic acid-β-lactone synergistic effect, improves anti-pollution.
Specific embodiment
Below with reference to embodiment, the present invention will be further elaborated, it should explanation, following the description merely to
It explains the present invention, its content is not defined.
The preparation route of embodiment 1 and embodiment 3~5 is as follows:
Wherein, x, y, z and n are >=1 integer.
Embodiment 1:
The preparation method of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, including it is following
Step:
(1) using allyl polyglycol ether and containing hydrogen silicone oil as starting material, 70 DEG C of progress hydrogen silicification reactions are heated to, so
It is incorporated in the butyl rubber that dissolution is sufficiently swollen in dimethylbenzene afterwards, the reaction was continued 50 minutes, and silicon hydrogel resin is made；
(2) keep reaction temperature constant, be added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil,
3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, artificial camphor and the poly- sesquialter silicon of cage modle
Oxygen alkane is stirred to react 1 hour, obtains component A, spare；
(3) by ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione
It is uniformly mixed with dimethylbenzene, obtains B component；
(4) component A is uniformly mixed with B component according to mass ratio 7:1, solidifies 5 hours to get anti-fouling material；
Wherein, in component A, allyl polyglycol ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon
Oil, 3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, artificial camphor and the poly- sesquialter of cage modle
The mass ratio of siloxanes is 25:20:8:4:0.5:18:3:4:4:0.4；In B component, ethyl orthosilicate and the positive fourth of tin dilaurate two
Ji Xi, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione and dimethylbenzene mass ratio be 20:0.008:2:2.1:5.7:27.
In step (1), the specific method of hydrogen silicification reaction is: allyl polyglycol ether and Karstedt catalyst are matched
It is set to mixed liquor, is slowly added dropwise within 1 hour by constant pressure funnel into 70 DEG C of containing hydrogen silicone oil, is continued after being added dropwise anti-
It answers 3 hours, is down to room temperature.
Karstedt catalyst is the xylene solution of mass concentration 2%, the body of the xylene solution and containing hydrogen silicone oil
Product mass ratio is 10 μm of L:25g.
The hydrogen content of containing hydrogen silicone oil is 0.18%.
Iron oxide is also added into step (2) as pigment, the mass ratio with hydroxy silicon oil is 5:20.
Thixotropic agent is fumed silica and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15:0.5:20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and molecular formula is (i-Bu)8Si8O12。
In step (4), component A is uniformly mixed with B component according to mass ratio 8:1.
Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is prepared by the above method
It obtains.
Embodiment 2:
The preparation method of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, including it is following
Step:
(1) using ethylene glycol monoallyl ether and containing hydrogen silicone oil as starting material, 90 DEG C of progress hydrogen silicification reactions are heated to, so
It is incorporated in the butyl rubber that dissolution is sufficiently swollen in dimethylbenzene afterwards, the reaction was continued 70 minutes, and silicon hydrogel resin is made；
(2) keep reaction temperature constant, be added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil,
3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, artificial camphor and the poly- sesquialter silicon of cage modle
Oxygen alkane is stirred to react 2 hours, obtains component A, spare；
(3) by ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione
It is uniformly mixed with dimethylbenzene, obtains B component；
(4) component A is uniformly mixed with B component according to mass ratio 9:1, solidifies 8 hours to get anti-fouling material；
Wherein, in component A, ethylene glycol monoallyl ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon
Oil, 3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, artificial camphor and the poly- sesquialter of cage modle
The mass ratio of siloxanes is 75:30:10:5:1.5:22:5:6:6:0.6；In B component, ethyl orthosilicate and tin dilaurate two are just
Butyl tin, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione and dimethylbenzene mass ratio be 21:0.012:2.2:2.3:6:
30。
In step (1), the specific method of hydrogen silicification reaction is: ethylene glycol monoallyl ether and Karstedt catalyst are matched
It is set to mixed liquor, is slowly added dropwise within 1 hour by constant pressure funnel into 70~90 DEG C of containing hydrogen silicone oil, is added dropwise subsequent
Continuous reaction 3 hours, is down to room temperature.
Karstedt catalyst is the xylene solution of mass concentration 2%, the body of the xylene solution and containing hydrogen silicone oil
Product mass ratio is 10~20 μm of L:25g.
The hydrogen content of containing hydrogen silicone oil is 0.18% or >=0.6%.
Iron oxide is also added into step (2) as pigment, the mass ratio with hydroxy silicon oil is 6:20.
Thixotropic agent is fumed silica and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15:1.5:20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and molecular formula is (i-Bu)8Si8O12。
In step (3), ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxysilane, cyclohexanone, acetyl
The mass ratio of acetone and dimethylbenzene is 20.4:0.01:2.1:2.2:5.8:28.
In step (4), component A is uniformly mixed with B component according to mass ratio 8:1.
Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is prepared by the above method
It obtains.
Embodiment 3:
The preparation method of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, including it is following
Step:
(1) using allyl polyglycol ether and containing hydrogen silicone oil as starting material, 80 DEG C of progress hydrogen silicification reactions are heated to, so
It is incorporated in the butyl rubber that dissolution is sufficiently swollen in dimethylbenzene afterwards, the reaction was continued 60 minutes, and silicon hydrogel resin is made；
(2) keep reaction temperature constant, be added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil,
3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, artificial camphor and the poly- sesquialter silicon of cage modle
Oxygen alkane is stirred to react 1 hour, obtains component A, spare；
(3) by ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione
It is uniformly mixed with dimethylbenzene, obtains B component；
(4) component A is uniformly mixed with B component according to mass ratio 8:1, solidifies 7 hours to get anti-fouling material；
Wherein, in component A, allyl polyglycol ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon
Oil, 3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, artificial camphor and the poly- sesquialter of cage modle
The mass ratio of siloxanes is 50:25:9:4.5:1:20:4:5:5:0.5；In B component, ethyl orthosilicate and the positive fourth of tin dilaurate two
Ji Xi, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione and dimethylbenzene mass ratio be 20.4:0.01:2.1:2.2:5.8:
28。
In step (1), the specific method of hydrogen silicification reaction is: allyl polyglycol ether and Karstedt catalyst are matched
It is set to mixed liquor, is slowly added dropwise within 1 hour by constant pressure funnel into 80 DEG C of containing hydrogen silicone oil, is continued after being added dropwise anti-
It answers 2 hours, adds vinyltriethoxysilane, the reaction was continued 2 hours, is down to room temperature；Vinyltriethoxysilane with
The mass ratio of containing hydrogen silicone oil is 9:25.
Karstedt catalyst is the xylene solution of mass concentration 2%, the body of the xylene solution and containing hydrogen silicone oil
Product mass ratio is 15 μm of L:25g.
Hydrogen content >=0.6% of containing hydrogen silicone oil.
Iron oxide is also added into step (2) as pigment, the mass ratio with hydroxy silicon oil is 5.5:20.
Thixotropic agent is fumed silica and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15:1:20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and molecular formula is (i-Bu)8Si8O12。
In step (4), component A is uniformly mixed with B component according to mass ratio 8:1.
Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is prepared by the above method
It obtains.
Embodiment 4:
The preparation method of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, including it is following
Step:
(1) using allyl polyglycol ether and containing hydrogen silicone oil as starting material, 80 DEG C of progress hydrogen silicification reactions are heated to, so
It is incorporated in the butyl rubber that dissolution is sufficiently swollen in dimethylbenzene afterwards, the reaction was continued 60 minutes, and silicon hydrogel resin is made；
(2) keep reaction temperature constant, be added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil,
3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, artificial camphor and the poly- sesquialter silicon of cage modle
Oxygen alkane is stirred to react 1 hour, obtains component A, spare；
(3) by ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione
It is uniformly mixed with dimethylbenzene, obtains B component；
(4) component A is uniformly mixed with B component according to mass ratio 8:1, solidifies 7 hours to get anti-fouling material；
Wherein, in component A, allyl polyglycol ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon
Oil, 3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, artificial camphor and the poly- sesquialter of cage modle
The mass ratio of siloxanes is 50:25:9:4.5:1:20:4:5:5:0.5；In B component, ethyl orthosilicate and the positive fourth of tin dilaurate two
Ji Xi, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione and dimethylbenzene mass ratio be 20.4:0.01:2.1:2.2:5.8:
28。
In step (1), the specific method of hydrogen silicification reaction is: allyl polyglycol ether and Karstedt catalyst are matched
It is set to mixed liquor, is slowly added dropwise within 1 hour by constant pressure funnel into 80 DEG C of containing hydrogen silicone oil, is continued after being added dropwise anti-
It answers 2 hours, adds vinyltriethoxysilane, the reaction was continued 2 hours, is down to room temperature；Vinyltriethoxysilane with
The mass ratio of containing hydrogen silicone oil is 9:25.
Karstedt catalyst is the xylene solution of mass concentration 2%, the body of the xylene solution and containing hydrogen silicone oil
Product mass ratio is 15 μm of L:25g.
Hydrogen content >=0.6% of containing hydrogen silicone oil.
Iron oxide is also added into step (2) as pigment, the mass ratio with hydroxy silicon oil is 5.5:20.
Larch extract, nanometer capsaicine and oyster shell powder, the quality of they and hydroxy silicon oil are also added into step (2)
Than for 3:1:4:20.Oyster shell powder is that oyster shell is cleaned, is dry, 50nm powder obtained by grinding.
Thixotropic agent is fumed silica and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15:1:20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and molecular formula is (i-Bu)8Si8O12。
In step (4), component A is uniformly mixed with B component according to mass ratio 8:1.
Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is prepared by the above method
It obtains.
Embodiment 5:
The preparation method of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, including it is following
Step:
(1) using allyl polyglycol ether and containing hydrogen silicone oil as starting material, 80 DEG C of progress hydrogen silicification reactions are heated to, so
It is incorporated in the butyl rubber that dissolution is sufficiently swollen in dimethylbenzene afterwards, the reaction was continued 60 minutes, and silicon hydrogel resin is made；
(2) keep reaction temperature constant, be added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil,
3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, artificial camphor and the poly- sesquialter silicon of cage modle
Oxygen alkane is stirred to react 1 hour, obtains component A, spare；
(3) by ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione
It is uniformly mixed with dimethylbenzene, obtains B component；
(4) component A is uniformly mixed with B component according to mass ratio 8:1, solidifies 7 hours to get anti-fouling material；
Wherein, in component A, allyl polyglycol ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon
Oil, 3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, artificial camphor and the poly- sesquialter of cage modle
The mass ratio of siloxanes is 50:25:9:4.5:1:20:4:5:5:0.5；In B component, ethyl orthosilicate and the positive fourth of tin dilaurate two
Ji Xi, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione and dimethylbenzene mass ratio be 20.4:0.01:2.1:2.2:5.8:
28。
In step (1), the specific method of hydrogen silicification reaction is: allyl polyglycol ether and Karstedt catalyst are matched
It is set to mixed liquor, is slowly added dropwise within 1 hour by constant pressure funnel into 80 DEG C of containing hydrogen silicone oil, is continued after being added dropwise anti-
It answers 2 hours, adds vinyltriethoxysilane, the reaction was continued 2 hours, is down to room temperature；Vinyltriethoxysilane with
The mass ratio of containing hydrogen silicone oil is 9:25.
Karstedt catalyst is the xylene solution of mass concentration 2%, the body of the xylene solution and containing hydrogen silicone oil
Product mass ratio is 15 μm of L:25g.
Hydrogen content >=0.6% of containing hydrogen silicone oil.
Iron oxide is also added into step (2) as pigment, the mass ratio with hydroxy silicon oil is 5.5:20.
Larch extract, nanometer capsaicine and oyster shell powder, the quality of they and hydroxy silicon oil are also added into step (2)
Than for 4:2:5:20.Oyster shell powder is that oyster shell is cleaned, is dry, 80nm powder obtained by grinding.
Thixotropic agent is fumed silica and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15:1:20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and molecular formula is (i-Bu)8Si8O12。
In step (4), component A is uniformly mixed with B component according to mass ratio 8:1.
Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is prepared by the above method
It obtains.
Comparative example 1
A kind of preparation method of anti-fouling material, comprising the following steps:
(1) using allyl polyglycol ether and containing hydrogen silicone oil as starting material, 80 DEG C of progress hydrogen silicification reactions are heated to, so
It is incorporated in the butyl rubber that dissolution is sufficiently swollen in dimethylbenzene afterwards, the reaction was continued 60 minutes, and silicon hydrogel resin is made；
(2) keep reaction temperature constant, be added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil,
4,5- bis- chloro- Kathons, artificial camphor and cage modle polysilsesquioxane are stirred to react 1 hour, obtain
It is spare to component A；
(3) by ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione
It is uniformly mixed with dimethylbenzene, obtains B component；
(4) component A is uniformly mixed with B component according to mass ratio 8:1, solidifies 7 hours to get anti-fouling material；
Wherein, in component A, allyl polyglycol ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon
Oil, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, artificial camphor and cage modle polysilsesquioxane mass ratio be 50:
25:9:4.5:1:20:5:5:0.5；In B component, ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxy silane
Alkane, cyclohexanone, acetylacetone,2,4-pentanedione and dimethylbenzene mass ratio be 20.4:0.01:2.1:2.2:5.8:28.
In step (1), the specific method of hydrogen silicification reaction is: allyl polyglycol ether and Karstedt catalyst are matched
It is set to mixed liquor, is slowly added dropwise within 1 hour by constant pressure funnel into 80 DEG C of containing hydrogen silicone oil, is continued after being added dropwise anti-
It answers 2 hours, adds vinyltriethoxysilane, the reaction was continued 2 hours, is down to room temperature；Vinyltriethoxysilane with
The mass ratio of containing hydrogen silicone oil is 9:25.
Karstedt catalyst is the xylene solution of mass concentration 2%, the body of the xylene solution and containing hydrogen silicone oil
Product mass ratio is 15 μm of L:25g.
Hydrogen content >=0.6% of containing hydrogen silicone oil.
Iron oxide is also added into step (2) as pigment, the mass ratio with hydroxy silicon oil is 5.5:20.
Thixotropic agent is fumed silica and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15:1:20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and molecular formula is (i-Bu)8Si8O12。
In step (4), component A is uniformly mixed with B component according to mass ratio 8:1.
A kind of anti-fouling material is prepared by the above method.
Comparative example 2
A kind of preparation method of anti-fouling material, comprising the following steps:
(1) using allyl polyglycol ether and containing hydrogen silicone oil as starting material, 80 DEG C of progress hydrogen silicification reactions are heated to, so
It is incorporated in the butyl rubber that dissolution is sufficiently swollen in dimethylbenzene afterwards, the reaction was continued 60 minutes, and silicon hydrogel resin is made；
(2) keep reaction temperature constant, be added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil,
3- hydroxybutyric acid-β-lactone, the chloro- Kathon of 4,5- bis- and cage modle polysilsesquioxane, stirring
Reaction 1 hour, obtains component A, spare；
(3) by ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione
It is uniformly mixed with dimethylbenzene, obtains B component；
(4) component A is uniformly mixed with B component according to mass ratio 8:1, solidifies 7 hours to get anti-fouling material；
Wherein, in component A, allyl polyglycol ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon
Oil, 3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and cage modle polysilsesquioxane
Mass ratio is 50:25:9:4.5:1:20:4:5:0.5；In B component, ethyl orthosilicate and di-n-butyltin dilaurate, methyl
Triethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione and dimethylbenzene mass ratio be 20.4:0.01:2.1:2.2:5.8:28.
In step (1), the specific method of hydrogen silicification reaction is: allyl polyglycol ether and Karstedt catalyst are matched
It is set to mixed liquor, is slowly added dropwise within 1 hour by constant pressure funnel into 80 DEG C of containing hydrogen silicone oil, is continued after being added dropwise anti-
It answers 2 hours, adds vinyltriethoxysilane, the reaction was continued 2 hours, is down to room temperature；Vinyltriethoxysilane with
The mass ratio of containing hydrogen silicone oil is 9:25.
Karstedt catalyst is the xylene solution of mass concentration 2%, the body of the xylene solution and containing hydrogen silicone oil
Product mass ratio is 15 μm of L:25g.
Hydrogen content >=0.6% of containing hydrogen silicone oil.
Iron oxide is also added into step (2) as pigment, the mass ratio with hydroxy silicon oil is 5.5:20.
Thixotropic agent is fumed silica and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15:1:20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and molecular formula is (i-Bu)8Si8O12。
In step (4), component A is uniformly mixed with B component according to mass ratio 8:1.
A kind of anti-fouling material is prepared by the above method.
Test example
1, the coating property that the anti-fouling material of Examples 1 to 5 or comparative example 1~2 is sprayed to tinplate is investigated, as a result
It is shown in Table 1.
1. coating property of table compares
As shown in Table 1, the paint film that is formed has good mechanical property and resistance to after the anti-fouling material spraying of Examples 1 to 5
Corrosive nature, wearability and adhesive force are also relatively good, and performance indexes is far superior to comparative example 1 and comparative example 2.
2, according to GB/T21805-2008, real extra large hanging plate test in 6 months has been carried out in Zhoushan spiral shell sea of gates domain, the results are shown in Table
2。
The real extra large hanging plate test result of table 2.
From table 2 it can be seen that comparative example 1 omits 3- hydroxybutyric acid-β-lactone, comparative example 2 omits artificial camphor, antifouling
Effect is obviously deteriorated, and the anti-fouling material of Examples 1 to 5 has obvious preferable anti-pollution.
Above-mentioned, although specific embodiments of the present invention have been described, not to the limit of the scope of the present invention
System, based on the technical solutions of the present invention, those skilled in the art do not need to make the creative labor can make it is each
Kind modification or deformation are still within protection scope of the present invention.
Claims (10)
1. the preparation method of the environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, feature exist
In, comprising the following steps:
(1) using allyl polyglycol ether or ethylene glycol monoallyl ether and containing hydrogen silicone oil as starting material, 70~90 are heated to
DEG C carry out hydrogen silicification reaction, be then incorporated in the butyl rubber that dissolution is sufficiently swollen in dimethylbenzene, the reaction was continued 50~70 minutes,
Silicon hydrogel resin is made；
(2) it keeps reaction temperature constant, thixotropic agent, hydroxy silicon oil, 3- hydroxyl is added into silicon hydrogel resin obtained by step (1)
Base butenoic acid-β-lactone, the chloro- Kathon of 4,5- bis-, artificial camphor and cage modle polysilsesquioxane,
It is stirred to react 1~2 hour, obtains component A, it is spare；
(3) by ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione and two
Toluene is uniformly mixed, and obtains B component；
(4) component A is uniformly mixed with B component according to 7~9:1 of mass ratio, solidifies 5~8 hours to get anti-fouling material；
Wherein, in component A, allyl polyglycol ether or ethylene glycol monoallyl ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber,
Thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acid-β-lactone, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, synthesis camphor tree
The mass ratio of brain and cage modle polysilsesquioxane is 25~75:20~30:8~10:4~5:0.5~1.5:18~22:3~5:4
~6:4~6:0.4~0.6；In B component, ethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxysilane, ring
The mass ratio of hexanone, acetylacetone,2,4-pentanedione and dimethylbenzene is 20~21:0.008~0.012:2~2.2:2.1~2.3:5.7~6:27
~30.
2. preparation method according to claim 1, which is characterized in that in step (1), the specific method of hydrogen silicification reaction
It is: allyl polyglycol ether or ethylene glycol monoallyl ether and Karstedt catalyst is configured to mixed liquor, pass through constant pressure
Dropping funel is slowly added dropwise into 70~90 DEG C of containing hydrogen silicone oil for 1 hour, and the reaction was continued 3 hours after being added dropwise, and is down to room
Temperature.
3. preparation method according to claim 1, which is characterized in that in step (1), the specific method of hydrogen silicification reaction
It is: allyl polyglycol ether and Karstedt catalyst is configured to mixed liquor, it is slow through 1 hour by constant pressure funnel
It is added dropwise in 70~90 DEG C of containing hydrogen silicone oil, the reaction was continued 2 hours after being added dropwise, vinyltriethoxysilane is added,
The reaction was continued 2 hours, is down to room temperature；The mass ratio of vinyltriethoxysilane and containing hydrogen silicone oil is 9:25.
4. preparation method according to claim 2 or 3, which is characterized in that the Karstedt catalyst is mass concentration
The volume mass ratio of 2% xylene solution, the xylene solution and containing hydrogen silicone oil is 10~20 μm of L:25g.
5. preparation method according to claim 1, which is characterized in that in component A, allyl polyglycol ether or ethylene glycol
Mono allyl ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acid-β-lactone, 4,5-
The mass ratio of two chloro- Kathons, artificial camphor and cage modle polysilsesquioxane is 25~75:25:
9:4.5:0.5~1.5:20:4:5:5:0.5.
6. preparation method according to claim 1, which is characterized in that iron oxide is also added into step (2) as pigment,
The mass ratio of itself and hydroxy silicon oil is 5~6:20.
7. preparation method according to claim 1, which is characterized in that in step (2), the thixotropic agent is gas phase titanium dioxide
Silicon and polyamide wax, the mass ratio of they and hydroxy silicon oil are 15:0.5~1.5:20.
8. preparation method according to claim 1, which is characterized in that in step (3), ethyl orthosilicate and tin dilaurate two
Normal-butyl tin, methyltriethoxysilane, cyclohexanone, acetylacetone,2,4-pentanedione and dimethylbenzene mass ratio be 20.4:0.01:2.1:2.2:
5.8:28.
9. preparation method according to claim 1, which is characterized in that in step (4), by component A and B component according to quality
It is uniformly mixed than 8:1.
10. the environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is by described in claim 1
Method be prepared.
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| CN102344747B (en) * | 2010-07-30 | 2013-12-04 | 雍飞 | Low surface energy organosilicon coating material composition, preparation method, updating method and application thereof |
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| CN105219206B (en) * | 2014-07-03 | 2017-11-21 | 浙江省海洋开发研究院 | The preparation method of silicone modified acrylic hydrogel antifouling paint |
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| WO2023031398A1 (en) * | 2021-09-06 | 2023-03-09 | SWISS KRONO Tec AG | Composition having antimicrobial properties, in particular biocidal properties, for surface coatings of wood boards |
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Denomination of invention: Environmentally friendly antifouling material based on silicone hydrogel resin and natural antifouling agent Granted publication date: 20190830 Pledgee: Industrial and Commercial Bank of China Limited Zhoushan Branch Pledgor: ZHEJIANG MARINE DEVELOPMENT Research Institute Registration number: Y2024330001953 |