CN117659259A - Vanillin ester acrylate self-polishing antifouling resin and preparation method and application thereof - Google Patents
Vanillin ester acrylate self-polishing antifouling resin and preparation method and application thereof Download PDFInfo
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 74
- 229920005989 resin Polymers 0.000 title claims abstract description 65
- 239000011347 resin Substances 0.000 title claims abstract description 65
- 238000005498 polishing Methods 0.000 title claims abstract description 64
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 55
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 150000002148 esters Chemical class 0.000 title claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 23
- 238000002360 preparation method Methods 0.000 title abstract description 8
- CPOQZWDLPWEJET-UHFFFAOYSA-N (4-formyl-2-methoxyphenyl) 2-methylprop-2-enoate Chemical compound COC1=CC(C=O)=CC=C1OC(=O)C(C)=C CPOQZWDLPWEJET-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 29
- -1 methyl-acrylic acid vanillin ester Chemical class 0.000 claims abstract description 20
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 15
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 150000001299 aldehydes Chemical class 0.000 claims abstract 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 99
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 28
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000003973 paint Substances 0.000 claims description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 230000000977 initiatory effect Effects 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000013535 sea water Substances 0.000 abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 125000004185 ester group Chemical group 0.000 abstract description 4
- 239000013543 active substance Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 4
- 239000003999 initiator Substances 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 241000195493 Cryptophyta Species 0.000 description 13
- 239000011521 glass Substances 0.000 description 13
- 230000005764 inhibitory process Effects 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
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- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 230000004580 weight loss Effects 0.000 description 7
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 6
- 229920005610 lignin Polymers 0.000 description 6
- 229910003460 diamond Inorganic materials 0.000 description 5
- 239000010432 diamond Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 3
- 239000005770 Eugenol Substances 0.000 description 3
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 229960002217 eugenol Drugs 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- URFLCXSTNZSALZ-UHFFFAOYSA-N [F].C(C(=C)C)(=O)O Chemical compound [F].C(C(=C)C)(=O)O URFLCXSTNZSALZ-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000002390 cell membrane structure Anatomy 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- XPLSDXJBKRIVFZ-UHFFFAOYSA-L copper;prop-2-enoate Chemical compound [Cu+2].[O-]C(=O)C=C.[O-]C(=O)C=C XPLSDXJBKRIVFZ-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
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- 150000003254 radicals Chemical class 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
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- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a vanillyl aldehyde ester acrylic acid self-polishing antifouling resin and a preparation method and application thereof, wherein the preparation method of the vanillyl aldehyde ester acrylic acid self-polishing antifouling resin is mainly synthesized by taking azodiisobutyronitrile and benzoyl peroxide as initiators through free radical polymerization reaction in a protective gas environment. Among them, vanillin methacrylate monomers are preferably prepared by substitution reaction of vanillin with methacryloyl chloride. The side chain phenolic ester group of the methyl-acrylic acid vanillin ester in the vanillin ester-based acrylic acid self-polishing anti-fouling resin can hydrolyze in seawater to realize self-polishing, and simultaneously release the vanillin which is an anti-fouling active substance from the surface of the material, so that the vanillin ester-based acrylic acid self-polishing anti-fouling resin is an environment-friendly self-polishing anti-fouling resin with resistance to small-scale and large-scale fouling organisms.
Description
Technical Field
The invention relates to the technical field of marine antifouling paint, in particular to vanillin ester acrylate self-polishing antifouling resin, and a preparation method and application thereof.
Background
The attachment of a large number of microorganisms, animals and plants in the ocean to the surface of a ship brings about a number of adverse effects, which increase the roughness of the surface of the ship and the overall weight, affect the sailing of the ship and increase the consumption of fuel, and thus bring about adverse effects on the environment. The conventional acrylate self-polishing antifouling paint is characterized in that organic tin with higher toxicity is used for pursuing good antifouling effect, and irreversible damage is brought to marine environment. Nowadays, organotin self-polishing antifouling paints have been disabled and replaced with low-toxicity self-polishing antifouling paints of zinc acrylate, copper acrylate and the like. However, this can also cause some damage to the marine environment. Therefore, there is a need to develop an acrylic self-polishing antifouling resin which is completely non-toxic and has better antifouling properties.
Chinese patent document CN115197360a discloses a method for preparing eugenol ester methacrylate fluorine self-polishing antifouling resin, which introduces eugenol into an acrylic ester self-polishing antifouling resin system. The natural non-toxic eugenol with antibacterial effect is released by hydrolysis under the weak alkaline environment of seawater, and the acrylic self-polishing resin without heavy metal ions is obtained.
Chinese patent CN107033273a discloses a base resin composition for use in an environment-friendly marine antifouling paint, which comprises a difunctional zinc acrylate monomer and other unsaturated monomers capable of radical initiated polymerization, and is prepared by copolymerization. The self-polishing resin has good adhesion to a substrate, a certain self-polishing rate, a good antifouling effect in a marine environment and good practical application and development prospects.
The invention starts from different invention conception, firstly, vanillin is introduced into acrylic ester self-polishing resin, although partial monomers are similar to each other in selection, various properties of vanillin methacrylate such as hydrophilicity and hydrophobicity, an antibacterial mechanism and anti-algae capability are different, and the inventor is still required to perform optimization and improvement on various aspects of synthesis process, monomer proportion, solvent selection and the like, so that the self-polishing anti-fouling resin different from the prior art can be prepared.
Disclosure of Invention
Therefore, the invention aims to provide the vanillin ester acrylate self-polishing antifouling resin, and the preparation method and the application thereof, wherein the vanillin ester acrylate self-polishing antifouling resin can be hydrolyzed in seawater quickly, has a good self-polishing antifouling effect in a static state, and is an environment-friendly self-polishing antifouling resin with resistance to small-scale and large-scale fouling organisms.
The adopted technical scheme is as follows:
the invention relates to vanillin ester acrylate self-polishing antifouling resin, which has the following structural formula:
wherein a, b, c, d, e is the number of repeating units of random copolymerization, and the monomer of a repeating is methyl methacrylate; b repeating monomer is butyl acrylate; c repeating the monomer which is 2-methoxyethyl acrylate; d repeating monomer is hexafluorobutyl methacrylate; e repeating monomer is vanillin methacrylate; co represents random copolymerization of monomers.
The preparation method of the vanillin ester acrylate self-polishing antifouling resin comprises the following steps of:
s1, mixing and dissolving 30-60 parts of methyl methacrylate, 25-35 parts of butyl acrylate, 5-30 parts of vanillin methacrylate, 10-20 parts of hexafluorobutyl methacrylate, 2-5 parts of 2-methoxyethyl acrylate and 0.5-2 parts of azobisisobutyronitrile into not more than 20 parts of N, N-dimethylformamide solution;
s2, adding 75 parts of N, N-dimethylformamide into a four-neck flask, heating to 80-95 ℃, slowly dropwise adding the mixed solution in a protective atmosphere, continuously dropwise adding, slowly adding an N, N-dimethylformamide solution containing 0.1-1 part of benzoyl peroxide after dropwise adding is completed for secondary initiation, ensuring that the total parts of N, N-dimethylformamide are identical to the parts of monomers, continuously dropwise adding, and continuously stirring at the same temperature to ensure full reaction, thereby finally obtaining the N, N-dimethylformamide solution of the vanillin ester acrylate self-polishing antifouling resin.
Further, in S1, the vanillin methacrylate is obtained by a preparation method comprising the following steps, in parts by weight:
s11, dissolving 1 part of vanillin and 1.2-1.5 parts of acid-binding agent triethylamine in 4-10 parts of dichloromethane;
s12, slowly dripping 1.05-1.1 parts of methacryloyl chloride into the solution at a low temperature of 0-5 ℃, continuously stirring, and fully reacting at room temperature after dripping;
s13, adding 0.1-0.2 part of deionized water to react unreacted methacryloyl chloride to generate methacrylic acid, reacting methacrylic acid with triethylamine to generate salt precipitate, adding 0.12-0.2 part of anhydrous magnesium sulfate to remove water, filtering to remove ammonium salt and magnesium sulfate hydrate, taking filtrate, and vacuum drying to remove dichloromethane and triethylamine to obtain the vanillyl methacrylate monomer.
Further, in S12, the mixture was stirred at room temperature after completion of the dropwise addition and reacted sufficiently for 24 hours.
Further, in S2, the protective atmosphere is one or more of nitrogen, argon and helium.
Further, in S2, the mixed solution is slowly added dropwise in a protective atmosphere, and the dropping speed is 50-150g/h.
Further, in S1, the N, N-dimethylformamide solution is 5-15 parts.
Further, in S2, the dropwise addition was continued for 30 minutes, after which stirring was continued for 3 hours while maintaining the same temperature to ensure the reaction was sufficient.
The invention relates to application of the vanillin ester acrylate self-polishing antifouling resin in preparing marine antifouling paint.
Further, the phenolic ester group contained in the vanillin methacrylate self-polishing antifouling resin can be hydrolyzed in the ocean to realize self-polishing, and the hydrolysis reaction formula of the vanillin methacrylate self-polishing antifouling resin is as follows:
in the technical proposal described above, the method comprises the steps of,
(1) Vanillin costs less. The source of vanillin can be obtained by lignin degradation. For example, CN107857696a discloses a method for preparing high-purity vanillin by catalytic oxidation of lignin, which comprises mixing lignin with -base supported oxide catalyst, adding phenol, stirring, dissolving, degrading lignin under the reaction condition of oxygen pressure of 1-3MPa to obtain a decomposition product mainly containing vanillin, and separating the product to obtain vanillin. The vanillin obtained by degrading lignin can effectively solve the problem that lignin is difficult to utilize, and has better application prospect.
(2) The vanillin methacrylate is taken as a functional monomer, and can be hydrolyzed more quickly when contacting with seawater, so that the vanillin methacrylate becomes more hydrophilic, and falls off from the surface of the coating, and the purpose of antifouling is realized by forming an unstable surface.
(3) The addition of hexafluorobutyl methacrylate ensures the hydrophobicity of the resin so that it does not hydrolyze too rapidly.
(4) The glass transition temperature of the resin is regulated by methyl methacrylate and butyl acrylate, so that the coating has certain flexibility.
(5) The N, N-dimethylformamide is used as a solvent, so that the compatibility with resin is good, the solid content of the resin is controlled to be about 50%, the moderate viscosity can be ensured, the resin can be stored for a long time, and the application of coating is facilitated.
In order to solve the adverse effects of marine biofouling on activities such as marine resource development and ship navigation, vanillin is creatively introduced into an acrylic ester self-polishing system, and is successfully prepared into vanillin ester-based acrylic ester antifouling resin with other acrylic ester monomers in a free radical polymerization mode, phenolic ester groups of side chains are hydrolyzed in a seawater environment, vanillin is released, and the adhesion of small fouling organisms is resisted. Meanwhile, the surface becomes brittle, and the resin falls off under the scouring of seawater to resist the adhesion of large fouling organisms, so that the environment-friendly self-polishing anti-fouling resin with the resistance to both small-scale and large-scale fouling organisms can be finally constructed.
In summary, compared with the prior art, the invention has the following beneficial effects:
1. the invention introduces the methyl acrylic acid vanillin ester antifouling monomer with environmental protection and lower cost into the field of acrylic acid ester self-polishing antifouling paint for the first time, and has a certain application prospect;
2. the hydrolysis of the vanillin methacrylate in a weak alkaline environment is utilized, vanillin is released to destroy the cell membrane structure of bacteria to realize sterilization and self-polishing, and the self-polishing speed and the service life of the resin can be controlled by controlling the content of hexafluorobutyl methacrylate and vanillin methacrylate;
3. the resin can be hydrolyzed in seawater quickly, and the self-polishing antifouling effect is good under static state;
4. the polymer resin has good compatibility with a solvent, can be stored for a long time without deterioration or solidification, and is convenient for the application of the subsequent marine antifouling paint or the compounding of the marine antifouling paint.
5. The coating of marine antifouling paint is self-polished by hydrolysis of the side chain phenolic ester group of vanillin methacrylate in seawater, while releasing the antifouling active substance vanillin from the material surface.
Detailed Description
The present invention will be described in detail by way of specific examples, but the purpose and purpose of these exemplary embodiments are merely to illustrate the present invention, and are not intended to limit the actual scope of the present invention in any way.
Unless otherwise indicated, the parts in the examples below are parts by weight.
Example 1
The vanillin ester acrylate self-polishing antifouling resin of the embodiment is prepared by the following steps:
1. synthesis of vanillin methacrylate
(1) 1 part of vanillin and 1.5 parts of triethylamine as an acid-binding agent are dissolved in 8 parts of dichloromethane;
(2) Slowly dropwise adding 1.05 parts of methacryloyl chloride into the solution at the temperature of 0 ℃, continuously stirring the solution, and stirring the solution at room temperature for reaction for 24 hours after the dropwise adding is finished;
(3) Adding 0.1 part of deionized water to react unreacted methacryloyl chloride to generate methacrylic acid, reacting methacrylic acid with triethylamine to generate salt precipitate, adding 0.12 part of anhydrous magnesium sulfate to remove water, filtering to remove ammonium salt and magnesium sulfate hydrate, taking filtrate, and vacuum drying to remove dichloromethane and triethylamine to obtain the vanillin methacrylate monomer.
2. Synthesis of vanillin ester based methacrylic acid self-polishing antifouling resin
(1) 41.51g of methyl methacrylate, 22.49g of butyl acrylate, 9g of hexafluorobutyl methacrylate, 2g of 2-methoxyethyl acrylate, 25g of vanillin methacrylate and 1g of azobisisobutyronitrile were dissolved in 10g of N, N-dimethylformamide solution.
(2) 85g of N, N-dimethylformamide was added to a 1L four-necked flask and heated to 90℃and the above-mentioned mixed solution was added dropwise under a nitrogen atmosphere, the dropwise addition was continued with stirring at 400rpm for 3 hours. After completion of the dropwise addition, a solution of 3g of benzoyl peroxide in N, N-dimethylformamide (5 g) was added dropwise over 30 minutes for secondary initiation. Stirring was then continued for 3 hours at 90 ℃ to ensure adequate reaction. Finally, the N, N-dimethylformamide solution of the vanillin ester methacrylic acid self-polishing antifouling resin is obtained, and can be directly used for preparing marine antifouling paint. This resin solution was designated VMP-25.
The following experiments were performed:
1. laboratory static inhibition diatom experiments: uniformly smearing the sample of the embodiment 1 on a glass sheet with the size of 2.5cm multiplied by 3.5cm, selecting a blank glass sheet as a blank control, soaking the sample sheet and the blank glass sheet in two model algae species (double-eyebrow algae and small-crescent diamond algae) for 1 day and 3 days respectively, taking out the sample, removing unattached algae, photographing the algae attachment condition on the coating under an optical microscope respectively, photographing 5 areas randomly selected for each coating, calculating the average diatom cell number on the blank glass sheet and the sample of the embodiment 1, and calculating by the following formula (1):
wherein K is the inhibition of diatom attachment, N B The average value of the number of diatom cells on the surface of the blank glass sheet is given, and N is the average value of the number of diatom cells on the surface of the sample.
The calculated inhibition ratio of the attachment of the double-eyebrow alga and the inhibition ratio of the attachment of the diamond-shaped alga of the small crescent are 92.95 percent and 95.30 percent respectively.
2. Laboratory static self-polishing test: the mass of a glass sheet with the size of 2.5cm multiplied by 3.5cm is weighed, the sample of the example 1 is uniformly smeared on the glass sheet, the mass is weighed after being completely solidified, the glass sheet is taken out and dried after being soaked in artificial seawater for 30 days, the glass sheet is weighed, the coating weight loss rate is calculated, and the glass sheet is calculated by the following formula (2):
wherein M is the coating weight loss rate, M0 is the mass of the blank glass sheet, M1 is the total mass of the coating and the glass sheet after the sample is completely cured, and M2 is the total mass of the coating and the glass sheet after the sample is completely soaked for 30 days and dried.
The calculated weight loss ratio was 8.68%.
Example 2
The vanillin ester acrylate self-polishing antifouling resin of the embodiment is prepared by the following steps:
1. synthesis of vanillin methacrylate
(1) 1 part of vanillin and 1.5 parts of triethylamine as an acid-binding agent are dissolved in 8 parts of dichloromethane;
(2) Slowly dropwise adding 1.05 parts of methacryloyl chloride into the solution at the temperature of 0 ℃, continuously stirring the solution, and stirring the solution at room temperature for reaction for 24 hours after the dropwise adding is finished;
(3) Adding 0.1 part of deionized water to react unreacted methacryloyl chloride to generate methacrylic acid, reacting methacrylic acid with triethylamine to generate salt precipitate, adding 0.12 part of anhydrous magnesium sulfate to remove water, filtering to remove ammonium salt and magnesium sulfate hydrate, taking filtrate, and vacuum drying to remove dichloromethane and triethylamine to obtain the vanillin methacrylate monomer.
2. Synthesis of vanillin ester based methacrylic acid self-polishing antifouling resin
(1) 44.76g of methyl methacrylate, 24.24g of butyl acrylate, 9g of hexafluorobutyl methacrylate, 2g of 2-methoxyethyl acrylate, 20g of vanillin methacrylate and 1g of azobisisobutyronitrile were dissolved in 10g of N, N-dimethylformamide solution.
(2) 85g of N, N-dimethylformamide was added to a 1L four-necked flask and heated to 90℃and the above-mentioned mixed solution was added dropwise under a nitrogen atmosphere, the dropwise addition was continued with stirring at 400rpm for 3 hours. After completion of the dropwise addition, a solution of 3g of benzoyl peroxide in N, N-dimethylformamide (5 g) was added dropwise over 30 minutes for secondary initiation. Stirring was then continued for 3 hours at 90 ℃ to ensure adequate reaction. Finally, the N, N-dimethylformamide solution of the vanillin ester methacrylic acid self-polishing antifouling resin is obtained, and can be directly used for preparing antifouling paint. This resin solution was designated VMP-20.
The test was performed according to the test method of example 1, with the following results: the inhibition rate of the double-eyebrow algae is 83.41 percent, and the inhibition rate of the small crescent diamond algae is 93.59 percent; the weight loss rate was 7.92%.
Example 3
The vanillin ester acrylate self-polishing antifouling resin of the embodiment is prepared by the following steps:
1. synthesis of vanillin methacrylate
(1) 1 part of vanillin and 1.5 parts of triethylamine as an acid-binding agent are dissolved in 8 parts of dichloromethane;
(2) Slowly dropwise adding 1.05 parts of methacryloyl chloride into the solution at the temperature of 0 ℃, continuously stirring the solution, and stirring the solution at room temperature for reaction for 24 hours after the dropwise adding is finished;
(3) Adding 0.1 part of deionized water to react unreacted methacryloyl chloride to generate methacrylic acid, reacting methacrylic acid with triethylamine to generate salt precipitate, adding 0.12 part of anhydrous magnesium sulfate to remove water, filtering to remove ammonium salt and magnesium sulfate hydrate, taking filtrate, and vacuum drying to remove dichloromethane and triethylamine to obtain the vanillin methacrylate monomer.
2. Synthesis of vanillin ester based methacrylic acid self-polishing antifouling resin
(1) 48g of methyl methacrylate, 26g of butyl acrylate, 9g of hexafluorobutyl methacrylate, 2g of 2-methoxyethyl acrylate, 15g of vanillin methacrylate and 1g of azobisisobutyronitrile were dissolved in 10g of N, N-dimethylformamide solution.
(2) 85g of N, N-dimethylformamide was added to a 1L four-necked flask and heated to 90℃and the above-mentioned mixed solution was added dropwise under a nitrogen atmosphere, the dropwise addition was continued with stirring at 400rpm for 3 hours. After completion of the dropwise addition, a solution of 3g of benzoyl peroxide in N, N-dimethylformamide (5 g) was added dropwise over 30 minutes for secondary initiation. Stirring was then continued for 3 hours at 90 ℃ to ensure adequate reaction. Finally, the N, N-dimethylformamide solution of the vanillin ester methacrylic acid self-polishing antifouling resin is obtained, and can be directly used for preparing antifouling paint. This resin solution was designated VMP-15.
The test was performed according to the test method of example 1, with the following results: the inhibition rate of the double-eyebrow algae is 78.18 percent, and the inhibition rate of the small crescent diamond algae is 89.74 percent; the weight loss rate was 6.86%.
Example 4
The vanillin ester acrylate self-polishing antifouling resin of the embodiment is prepared by the following steps:
1. synthesis of vanillin methacrylate
(1) 1 part of vanillin and 1.5 parts of triethylamine as an acid-binding agent are dissolved in 8 parts of dichloromethane;
(2) Slowly dropwise adding 1.05 parts of methacryloyl chloride into the solution at the temperature of 0 ℃, continuously stirring the solution, and stirring the solution at room temperature for reaction for 24 hours after the dropwise adding is finished;
(3) Adding 0.1 part of deionized water to react unreacted methacryloyl chloride to generate methacrylic acid, reacting methacrylic acid with triethylamine to generate salt precipitate, adding 0.12 part of anhydrous magnesium sulfate to remove water, filtering to remove ammonium salt and magnesium sulfate hydrate, taking filtrate, and vacuum drying to remove dichloromethane and triethylamine to obtain the vanillin methacrylate monomer.
2. Synthesis of vanillin ester based methacrylic acid self-polishing antifouling resin
(1) 51.24g of methyl methacrylate, 27.76g of butyl acrylate, 9g of hexafluorobutyl methacrylate, 2g of 2-methoxyethyl acrylate, 10g of vanillin methacrylate and 1g of azobisisobutyronitrile were dissolved in 10g of N, N-dimethylformamide solution.
(2) 85g of N, N-dimethylformamide was added to a 1L four-necked flask and heated to 90℃and the above-mentioned mixed solution was added dropwise under a nitrogen atmosphere, the dropwise addition was continued with stirring at 400rpm for 3 hours. After completion of the dropwise addition, a solution of 3g of benzoyl peroxide in N, N-dimethylformamide (5 g) was added dropwise over 30 minutes for secondary initiation. Stirring was then continued for 3 hours at 90 ℃ to ensure adequate reaction. Finally, the N, N-dimethylformamide solution of the vanillin ester methacrylic acid self-polishing antifouling resin is obtained, and can be directly used for preparing antifouling paint. This resin solution was designated VMP-10.
The test was performed according to the test method of example 1, with the following results: the inhibition rate of the double-eyebrow algae is 74.32 percent, and the inhibition rate of the small crescent diamond algae is 82.48 percent; the weight loss rate was 6.26%.
Example 5
The vanillin ester acrylate self-polishing antifouling resin of the embodiment is prepared by the following steps:
1. synthesis of vanillin methacrylate
(1) 1 part of vanillin and 1.5 parts of triethylamine as an acid-binding agent are dissolved in 8 parts of dichloromethane;
(2) Slowly dropwise adding 1.05 parts of methacryloyl chloride into the solution at the temperature of 0 ℃, continuously stirring the solution, and stirring the solution at room temperature for reaction for 24 hours after the dropwise adding is finished;
(3) Adding 0.1 part of deionized water to react unreacted methacryloyl chloride to generate methacrylic acid, reacting methacrylic acid with triethylamine to generate salt precipitate, adding 0.12 part of anhydrous magnesium sulfate to remove water, filtering to remove ammonium salt and magnesium sulfate hydrate, taking filtrate, and vacuum drying to remove dichloromethane and triethylamine to obtain the vanillin methacrylate monomer.
2. Synthesis of vanillin ester based methacrylic acid self-polishing antifouling resin
(1) 54.49g of methyl methacrylate, 29.51g of butyl acrylate, 9g of hexafluorobutyl methacrylate, 2g of 2-methoxyethyl acrylate, 5g of vanillin methacrylate and 1g of azobisisobutyronitrile were dissolved in 10g of N, N-dimethylformamide solution.
(2) 85g of N, N-dimethylformamide was added to a 1L four-necked flask and heated to 90℃and the above-mentioned mixed solution was added dropwise under a nitrogen atmosphere, the dropwise addition was continued with stirring at 400rpm for 3 hours. After completion of the dropwise addition, a solution of 3g of benzoyl peroxide in N, N-dimethylformamide (5 g) was added dropwise over 30 minutes for secondary initiation. Stirring was then continued for 3 hours at 90 ℃ to ensure adequate reaction. Finally, the N, N-dimethylformamide solution of the vanillin ester methacrylic acid self-polishing antifouling resin is obtained, and can be directly used for preparing antifouling paint. This resin solution was designated VMP-5.
The test was performed according to the test method of example 1, with the following results: the inhibition rate of the double-eyebrow algae is 67.95 percent, and the inhibition rate of the small-crescent diamond algae is 76.88 percent; the weight loss rate was 5.41%.
The above list of detailed descriptions is only specific to practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and all equivalent embodiments or modifications that do not depart from the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A vanillin ester acrylate self-polishing antifouling resin is characterized by having the following structural formula:
wherein a, b, c, d, e is the number of repeating units of random copolymerization, and the monomer of a repeating is methyl methacrylate; b repeating monomer is butyl acrylate; c repeating the monomer which is 2-methoxyethyl acrylate; d repeating monomer is hexafluorobutyl methacrylate; e repeating monomer is vanillin methacrylate; co represents random copolymerization of monomers.
2. A method for preparing the vanillin ester acrylate self-polishing antifouling resin according to claim 1, which comprises the following steps in parts by weight:
s1, mixing and dissolving 30-60 parts of methyl methacrylate, 25-35 parts of butyl acrylate, 5-30 parts of vanillin methacrylate, 10-20 parts of hexafluorobutyl methacrylate, 2-5 parts of 2-methoxyethyl acrylate and 0.5-2 parts of azobisisobutyronitrile into not more than 20 parts of N, N-dimethylformamide solution;
s2, adding 75 parts of N, N-dimethylformamide into a four-neck flask, heating to 80-95 ℃, slowly dropwise adding the mixed solution in a protective atmosphere, continuously dropwise adding, slowly adding an N, N-dimethylformamide solution containing 0.1-1 part of benzoyl peroxide after dropwise adding is completed for secondary initiation, ensuring that the total parts of N, N-dimethylformamide are identical to the parts of monomers, continuously dropwise adding, and continuously stirring at the same temperature to ensure full reaction, thereby finally obtaining the N, N-dimethylformamide solution of the vanillin ester acrylate self-polishing antifouling resin.
3. The method for preparing a vanillin ester based acrylate self-polishing anti-fouling resin according to claim 2, wherein in S1, said vanillin methacrylate is prepared by the following steps, in parts by weight:
s11, dissolving 1 part of vanillin and 1.2-1.5 parts of acid-binding agent triethylamine in 4-10 parts of dichloromethane;
s12, slowly dripping 1.05-1.1 parts of methacryloyl chloride into the solution at a low temperature of 0-5 ℃, continuously stirring, and fully reacting at room temperature after dripping;
s13, adding 0.1-0.2 part of deionized water to react unreacted methacryloyl chloride to generate methacrylic acid, reacting methacrylic acid with triethylamine to generate salt precipitate, adding 0.12-0.2 part of anhydrous magnesium sulfate to remove water, filtering to remove ammonium salt and magnesium sulfate hydrate, taking filtrate, and vacuum drying to remove dichloromethane and triethylamine to obtain the vanillyl methacrylate monomer.
4. The method for producing a vanillyl ester acrylate self-polishing antifouling resin according to claim 3, wherein in S12, the reaction is carried out for 24 hours with stirring at room temperature after completion of the dropping.
5. The method for preparing a vanillyl aldehyde ester acrylate self-polishing antifouling resin according to claim 2, wherein in S2, the protective atmosphere is one or more of nitrogen, argon and helium.
6. The method for producing a vanillyl ester acrylate self-polishing antifouling resin according to claim 2, wherein in S2, the above-mentioned mixed solution is slowly dropped in a protective atmosphere at a dropping speed of 50-150g/h.
7. The method for producing a vanillyl ester acrylate self-polishing antifouling resin according to claim 2, wherein in S1, the N, N-dimethylformamide solution is 5 to 15 parts.
8. The method for preparing a vanillyl aldehyde ester acrylate self-polishing antifouling resin according to claim 2, wherein in S2, dropwise addition is continued for 30 minutes, and then stirring is continued for 3 hours at the same temperature to ensure sufficient reaction.
9. Use of the vanillin ester based acrylate self-polishing anti-fouling resin of claim 1 for preparing marine anti-fouling paint.
10. Use according to claim 9, wherein the vanillin-based acrylate self-polishing anti-fouling resin has a hydrolysis reaction formula:
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