CN115895321A - Antifouling intrinsic coating and preparation method and application thereof - Google Patents
Antifouling intrinsic coating and preparation method and application thereof Download PDFInfo
- Publication number
- CN115895321A CN115895321A CN202111156760.8A CN202111156760A CN115895321A CN 115895321 A CN115895321 A CN 115895321A CN 202111156760 A CN202111156760 A CN 202111156760A CN 115895321 A CN115895321 A CN 115895321A
- Authority
- CN
- China
- Prior art keywords
- antifouling
- intrinsic
- paint
- vinyl
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 139
- 238000000576 coating method Methods 0.000 title claims abstract description 70
- 239000011248 coating agent Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 13
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 61
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- 229920005989 resin Polymers 0.000 claims abstract description 33
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
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- 238000006243 chemical reaction Methods 0.000 claims description 61
- 125000000524 functional group Chemical group 0.000 claims description 30
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- 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 description 26
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- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
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- 239000002131 composite material Substances 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 9
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- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
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- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 6
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- 229920000642 polymer Polymers 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 3
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- 230000000977 initiatory effect Effects 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
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- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 7
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- 238000011160 research Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
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- 239000006228 supernatant Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to an antifouling intrinsic coating and a preparation method and application thereof. Compared with the prior art, the antifouling intrinsic coating is obtained by carrying out free radical copolymerization on different vinyl monomers to prepare the matrix resin of the antifouling intrinsic coating and carrying out chemical bond bonding on the matrix resin and 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile. And different auxiliary additives such as an antioxidant, an anti-ultraviolet agent and the like can be added according to the requirements of different application fields to directly become the antifouling intrinsic oil-soluble paint and the spray paint, or to be used as the antifouling intrinsic functional auxiliary agent of the conventional oil-soluble paint and the spray paint. The antifouling intrinsic emulsion paint for the inner and outer walls or the antifouling intrinsic functional auxiliary agent for the conventional emulsion paint can be prepared by concentration and emulsification. The invention has the characteristics of non-dissolution and safety, and becomes a coating and a spray coating which can resist bacteria, super bacteria, mould, fungus and mites for a long time and have the function of preventing fresh water and marine organisms from adhering.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to an antifouling intrinsic coating as well as a preparation method and application thereof.
Background
The currently used anti-bioadhesion coating, antibacterial coating, mildew-proof coating, antifouling coating, etc. basically take effect by depending on the dissolution and release of various active substances (exerting antibacterial, mildew-proof or antifouling performances) to the outside, so that the following problems occur: 1. the environment is polluted; 2. the safety of human beings is greatly threatened; 3. long-lasting property is hardly ensured, etc. For example, the paint for inner and outer walls can become mildewed and black quickly when meeting moisture. For example, the antifouling paint for marine equipment is effective only by releasing added antifouling active substances such as cuprous oxide and organic tin from the paint, so that the antifouling paint causes very serious pollution to marine environment, destroys marine ecological environment, further causes great threat to human health of mariculture products, and has short service life. Thus, annual losses of $ 1500 billion worldwide are reported due to the adhesion of marine organisms.
To avoid such losses, and to improve the human hygiene environment, a great deal of research is also being focused in this field:
for example, CN201810831756.9 discloses a technology of using 0-10% of nano silver and 0-5% of nano zinc oxide as an antibacterial and mildewproof active ingredient to prepare an aqueous inorganic mildew-proof coating without VOC. CN201811226547.8 discloses a technology for preparing a nano heat-insulating antibacterial coating by adopting 15-25 parts of nano silver oxide as an effective component.
For another example, in the field of antifouling for preventing marine organism adhesion, CN108816704A, CN108816706A, CN108855836A, CN108906544a discloses a technology for ship and propeller surface coatings. In the field, the most applied method is to add metal, metal oxide and organic metal compound into the paint, so as to dissolve out the metal in the water, poison algae and shellfish and achieve the purpose of preventing fouling. The technology disclosed in this aspect is: CN105482702A, CN105860842A, CN107446500A, CN106349777A, CN106221330A, CN107936723A, CN108329789A, CN108977077A, CN108795287A. However, such techniques have problems in that: its toxicity is very damaging to the environment.
Chinese patent CN 110408278A discloses an intrinsic functional coating and preparation and application thereof, wherein a non-leachable intrinsic harmful microorganism resistant functional coating is obtained by copolymerizing different resin monomers to prepare a matrix resin and then carrying out chemical bond bonding with guanidine oligomers. According to the requirements of different application fields, different auxiliary additives such as an antioxidant, an anti-ultraviolet agent and the like can be added to directly become the intrinsic oil-soluble paint or the intrinsic functional auxiliary agent of the oil-soluble paint; or the intrinsic functional auxiliary agent of the general internal and external wall intrinsic emulsion coating or the emulsion coating can be prepared by concentration and emulsification.
In the patent, guanidine oligomers are mainly used for playing the functions of antibiosis, mould prevention and dirt prevention, and the functional groups of the guanidine oligomers cannot be dissolved out of the coating by utilizing the chemical reaction between the coating matrix resin and the guanidine oligomers, so that the long-acting property of the guanidine oligomers is kept. Only the polarity of the guanidine oligomer is very large, and the guanidine oligomer is bonded into the matrix resin of the coating, so that the hydrophilicity of the surface of the coating is increased, and the capability of preventing biological adhesion is reduced to a certain extent.
Chinese patent CN110964407A discloses an anticorrosion antifouling integrated paint for coating repair and a preparation method thereof, ECONEA is used as an antifouling auxiliary agent, but in the patent, ECONEA is physically mixed with matrix resin.
Chinese patent CN112955513A discloses a solvent-free marine antifouling paint and a preparation method thereof, wherein the main antifouling agent disclosed in the patent can be selected from 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (Econea), and Econea in the patent is also physically mixed with matrix resin.
Chinese patent CN109153840B discloses a polymer-containing composition and an antifouling coating composition, and discloses that an antifouling agent can be selected from 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (Econea), and that an excellent antifouling effect can be exhibited for a long period of time by always exposing the antifouling agent to the surface of a coating film. In this patent, ECONEA is also physically mixed with the matrix resin.
The technique disclosed in the above 3 inventions employs Econea having a small surface tension and a good effect of preventing the adhesion of living organisms, but the fluorine-containing nonpolar Econea in the matrix resin is easily released. As a result, the environment may be polluted and the service life is shortened.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an antifouling intrinsic coating as well as a preparation method and application thereof.
The antifouling intrinsic paint is a functional paint which is safe, non-dissolving, intrinsic to prevent biological adhesion and resistant to harmful microorganisms.
The antifouling intrinsic coating provided by the invention has application value in the fields of daily necessities, chemical products, medical and health materials, buildings, aquaculture net cages, ships, marine equipment and the like.
The purpose of the invention can be realized by the following technical scheme:
the invention provides an antifouling intrinsic paint, which is a polymer paint with an antifouling function and has a chemical structure shown in a formula (1):
wherein:
R 1 is the residue after initiation of the free radical initiator;
h. l and m are each independently selected from any natural number from 0 to 100, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 … … 95, 96, 97, 98, 99, 100;
k is any natural number from 1 to 30, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.... 28, 29, 30;
p is any natural number from 1 to 60, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 … …, 56, 57, 58, 59, 60;
b is one or any two or more than two structures of functional groups shown in the formula (2) and is compounded together according to any mass ratio:
when h is not 0, Y is one or any two or more than two of functional groups shown in the formula (3) and is compounded together according to any mass ratio:
in some embodiments of the invention, the free radical initiator is selected from one or more of an inorganic peroxide initiator, an organic peroxide initiator, an azo-type initiator, or a redox initiator.
In some embodiments of the invention, the inorganic peroxide initiator is selected from one or more of potassium persulfate, sodium persulfate, or ammonium persulfate.
In some embodiments of the invention, the organic peroxide initiator has the general formula: R-O-O-R ', wherein R, R ' are independently selected from H, alkyl, acyl or carbonate, and R, R ' may be the same or different.
In some embodiments of the present invention, the azo-type initiator is selected from one or both of azobisisobutyronitrile or azobisisoheptonitrile.
In some embodiments of the invention, the redox initiator is selected from one or both of cumene hydroperoxide-ferrous salt or organic peroxide-tertiary aromatic amine system.
The invention also provides a preparation method of the antifouling intrinsic paint, which comprises two steps of synthesizing the vinyl copolymer and bonding reaction with the functional group:
1) Synthesis of vinyl copolymer: adding a vinyl monomer for forming a structure shown in a formula (1) and a vinyl monomer capable of forming a structure B into a polymerization reactor, adding a solvent and an initiator, and reacting to obtain a matrix resin solution of the antifouling intrinsic coating; wherein the vinyl monomers used to form the structure of formula (1) include, but are not limited to: methyl methacrylate, butyl acrylate, styrene, acrylic acid, vinyl acetate, vinyl chloride, butadiene, and isoprene; the vinyl monomer capable of forming structure B means a vinyl monomer containing an epoxy group, or an acid anhydride, or an isocyanate.
2) Bonding reaction of functional groups: dissolving 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (Econea) in a solvent to prepare an Econea solution, adding the Econea solution into the matrix resin solution of the antifouling intrinsic coating obtained in the step 1), and continuing to react to obtain the antifouling intrinsic coating.
In some embodiments of the present invention, the amount of the solvent added in the synthesis step of the vinyl copolymer is 0.4 to 9 times the total mass of the vinyl monomer.
In some embodiments of the present invention, the initiator is added in an amount of 0.02 to 5% of the total mass of the vinyl monomers in the step of synthesizing the vinyl copolymer.
In some embodiments of the present invention, in the vinyl copolymer synthesis step, the reactor temperature is controlled within the range of 40 ℃ to 170 ℃, the mixture is fully and uniformly stirred, the reaction is carried out for 2 to 10 hours in the inert gas atmosphere, and then the mixture is cooled to room temperature, so as to obtain the matrix resin solution of the antifouling intrinsic coating.
In some embodiments of the present invention, in the step of the functional group bonding reaction, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (Econea) is used in an amount of 0.3% to 15% by mass based on the total mass of the vinyl monomers.
In some embodiments of the present invention, the percentage concentration of the Econea solution in the step of the bonding reaction of the functional group is 3% to 40%.
In some embodiments of the present invention, the Econea solution is gradually added to the base resin solution of the antifouling intrinsic paint under stirring of the reactor in the functional group bonding reaction step.
In some embodiments of the present invention, in the step of bonding reaction of functional groups, the conditions for continuing the reaction are: controlling the temperature within the range of 40-110 ℃ and continuing the reaction for 2-8 hours.
In some embodiments of the present invention, in the step of bonding reaction of the functional groups, after the reaction is finished, the temperature is reduced to room temperature, so as to obtain the antifouling intrinsic paint.
In some embodiments of the present invention, in the step of functional group bonding reaction, after the reaction is finished, cooling to room temperature, adding the antioxidant or the anti-ultraviolet agent, and stirring uniformly to obtain the anti-fouling paint which takes the anti-fouling intrinsic paint as a core raw material and contains the antioxidant or the anti-ultraviolet agent.
The principle of the preparation method is as follows: the basic performance of the coating resin is obtained by copolymerizing different vinyl monomers shown in a formula (1) and vinyl monomers containing epoxy groups, acid anhydrides or isocyanates which have the structure shown in a formula (2) after reacting with secondary amines. Then carrying out chemical bonding reaction with 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (Econea) to finally obtain the solution of the antifouling intrinsic coating. The bonding structure ensures that the functional group Econea can not be dissolved out of the coating, the environment is not polluted, meanwhile, the coating has the functions of preventing biological adhesion, resisting bacteria, preventing mildew and the like, can not be reduced due to loss, and ensures long-acting property.
The invention also provides another preparation method of the antifouling intrinsic paint, which comprises two steps of bonding reaction of functional groups and synthesis reaction of a vinyl copolymer:
1) Bonding reaction of functional groups: dissolving 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (Econea) in a solvent to prepare an Econea solution, adding the Econea solution into a reaction kettle with a stirrer, selecting a vinyl monomer containing an epoxy group, an anhydride or an isocyanate and having a structure shown in a formula (2) after reacting with secondary amine, and adding the vinyl monomer into the reactor of the Econea solution; adding a polymerization inhibitor, and reacting to obtain a functional group bonding type vinyl monomer; these functional group-bonded vinyl monomers have a structure represented by formula (4).
2) Synthesis of vinyl copolymer: and adding the obtained functional group bonding type vinyl monomer and other vinyl monomers for forming the structure shown in the formula (1) into a polymerization reactor, adding a solvent and an initiator, fully and uniformly stirring, and carrying out polymerization reaction to obtain the antifouling intrinsic coating. Other vinyl monomers among them that are used to form the structure of formula (1) include but are not limited to methyl methacrylate, butyl acrylate, styrene, acrylic acid, vinyl acetate, vinyl chloride, butadiene, and isoprene.
In some embodiments of the present invention, the percentage concentration of the Econea solution in the step of the bonding reaction of the functional group is 3% to 40%.
In some embodiments of the present invention, in the functional group bonding reaction step, a vinyl monomer containing an epoxy group, or an acid anhydride, or an isocyanate is gradually added to the reactor of the Econea solution with uniform stirring.
In some embodiments of the present invention, in the step of bonding the functional groups, the molar ratio of the vinyl monomer containing an epoxy group, or an acid anhydride, or an isocyanate to 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (Econea) is 0.8 to 1.2.
In some embodiments of the present invention, in the step of bonding reaction of functional groups, the polymerization inhibitor is added in an amount of 0.4% of the total mass of Econea and vinyl monomers.
In some embodiments of the present invention, in the step of bonding reaction of functional groups, the reaction conditions are: controlling the temperature within the range of 40-110 ℃ and reacting for 2-8 hours.
In some embodiments of the present invention, the amount of the solvent added in the synthesis step of the vinyl copolymer is 0.4 to 9 times the total mass of all vinyl monomers.
In some embodiments of the present invention, in the step of synthesizing the vinyl copolymer, the initiator is added in an amount of 0.02 to 5% of the total mass of all vinyl monomers.
In some embodiments of the present invention, in the step of synthesizing the vinyl copolymer, the polymerization reaction conditions are: controlling the temperature of the reactor within the range of 40-170 ℃, carrying out polymerization reaction for 2-10h under the inert gas atmosphere, and then cooling to room temperature.
In some embodiments of the present invention, in the step of synthesizing the vinyl copolymer, after the reaction is finished, cooling to room temperature, adding the antioxidant or the anti-ultraviolet agent, and fully and uniformly stirring to obtain the anti-fouling paint which takes the anti-fouling intrinsic paint as a core raw material and contains the antioxidant or the anti-ultraviolet agent.
In some embodiments of the invention, the solvent is selected from one or more of ethanol, butanol, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, chloroform, dichloroethane, benzene, toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, isopropanol, isobutanol, ethylene glycol, dioxane, acetic acid, nitrobenzene, nitromethane, acetonitrile, banana water, or rosin water.
The invention also provides an antifouling paint which comprises one or two of an antioxidant or an uvioresistant agent besides the antifouling intrinsic paint.
In some embodiments of the invention, the antioxidant is selected from one or more of commercially available antioxidant 168, antioxidant 1076, antioxidant bht, antioxidant B215, antioxidant 245, antioxidant 1010, dioctadecyl thiodipropionate, benzisoxyoctyl phosphite, tetrakis [ methyl- β - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid octadecyl ester, 2,2' -methylenebis (4-methyl-6-tert-butyl) phenol, 4'4-thiobis (6-tert-butyl-o-cresol), 4,4' -thiobis (3-methyl-6-tert-butyl) phenol, or 4234 ' -dihydroxy-zxft-butyl-5 ' -biphenyl 5364.
In some embodiments of the invention, the anti-ultraviolet agent is selected from one or more of UV-531, UV-9, UV-326, UV-327, UV-328, UV-329, phenyl o-hydroxybenzoate, o-nitroaniline, or p-cresol.
The invention also provides the use of an antifouling intrinsic paint or an antifouling paint. The antifouling intrinsic paint or the antifouling paint can be directly used as the intrinsic oil-soluble paint or the spray paint, or can be used as the antifouling intrinsic functional auxiliary agent of the conventional oil-soluble paint or the spray paint for composite use;
or the antifouling intrinsic paint or the antifouling paint is concentrated and emulsified to prepare the antifouling intrinsic emulsion paint or is used as the antifouling intrinsic functional auxiliary agent of the conventional emulsion paint for composite use.
The antifouling paint contains an antifouling intrinsic paint and one or two of an antioxidant and an anti-ultraviolet agent.
In some embodiments of the present invention, the concentration and emulsification process is: the oil-in-water type surfactant is added to the antifouling type intrinsic paint or antifouling paint, followed by concentration under reduced pressure to remove the solvent, and then water is added for emulsification.
In some embodiments of the invention, after removal of the solvent and emulsification with water, the solids content is 40-85wt%.
In the invention, in the chemical structure shown in the formula (1), the statistical average values of h, l, m and k,
not only the proportion of each reaction raw material is given, but also the glass transition temperature, T, of the synthetic coating is determined g (expressed in absolute temperature) as shown in the following calculation formula:
wherein k is h 、k l 、k m Three different monomer homopolymer p-copolymer T of h, l and m respectively g The influence factor of (2) is obtained by experiments. W h 、T gh The molecular weight of the monomer h and the glass transition temperature of its homopolymer, respectively.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
according to the invention, different vinyl monomers are copolymerized by free radicals to prepare the matrix resin of the antifouling intrinsic coating, and then the matrix resin is chemically bonded with 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile to obtain the antifouling intrinsic coating which is safe, non-leachable, resistant to harmful microorganisms and capable of preventing bioadhesion.
According to the invention, econea with good anti-biological adhesion effect is fixed on the molecular chain of the matrix resin through chemical bonding reaction, so that the Econea cannot be dissociated out of the coating, thus not only maintaining efficient antifouling effect for a long time, but also avoiding environmental pollution.
The obtained antifouling intrinsic paint can be added with different auxiliary additives such as an antioxidant, an anti-ultraviolet agent and the like according to the requirements of different application fields, and can be directly used as an antifouling intrinsic oil-soluble paint and a spray paint or used as an antifouling intrinsic functional auxiliary agent of a conventional oil-soluble paint and a spray paint. The antifouling intrinsic emulsion paint for the inner and outer walls or the antifouling intrinsic functional auxiliary agent for the conventional emulsion paint can be prepared by concentration and emulsification. No matter which application mode, the coating has the characteristics of non-dissolution and safety, and becomes a coating and a spray coating which have the functions of resisting bacteria, super bacteria, mould, fungi and mites and preventing adhesion of fresh water and marine organisms for a long time.
Drawings
FIG. 1 is an infrared spectrum of a vinyl paint base resin with Econea and an antifouling intrinsic paint;
FIG. 2 is a molecular weight distribution of a base resin (EA) of a solution type vinyl-based paint;
FIG. 3 is a comparison of the antifouling performance of a vinyl paint base resin with Econea and an antifouling make-coat.
Detailed Description
The invention provides an antifouling intrinsic paint, which is a polymer paint with an antifouling function and has a chemical structure shown in a formula (1):
wherein:
R 1 is the residue following initiation by a free radical initiator;
h. l and m are each independently selected from any natural number from 0 to 100, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 … … 95, 96, 97, 98, 99, 100;
k is any natural number from 1 to 30, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.... 28, 29, 30;
p is any natural number from 1 to 60, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 … …, 56, 57, 58, 59, 60;
b is one or any two or more than two structures of functional groups shown in formula (2) and is compounded together according to any mass ratio:
when h is not 0, Y is one or any two or more than two of functional groups shown in the formula (3) and is compounded together according to any mass ratio:
in some embodiments of the invention, the free radical initiator is selected from one or more of an inorganic peroxide initiator, an organic peroxide initiator, an azo-type initiator, or a redox initiator.
In some embodiments of the invention, the inorganic peroxide initiator is selected from one or more of potassium persulfate, sodium persulfate, or ammonium persulfate.
In some embodiments of the invention, the organic peroxide initiator has the general formula: R-O-O-R ', wherein R, R ' are independently selected from H, alkyl, acyl or carbonate, and R, R ' may be the same or different.
In some embodiments of the present invention, the azo initiator is selected from one or both of azobisisobutyronitrile or azobisisoheptonitrile.
In some embodiments of the invention, the redox initiator is selected from one or both of cumene hydroperoxide-ferrous salt or organic peroxide-tertiary aromatic amine systems.
The invention also provides a preparation method of the antifouling intrinsic paint, which comprises two steps of synthesizing the vinyl copolymer and bonding reaction with the functional group:
1) In the vinyl copolymer synthesis step, the vinyl monomer shown in the formula (1) and the determined molar weight thereof are added into a polymerization reactor, and a solvent or a composite solvent thereof which is 0.4-9 times of the total amount of the monomer and an initiator or a composite initiator thereof which is 0.02-5% of the total amount of the monomer are added.
2) Controlling the temperature of the reactor within the range of 40-170 ℃, fully and uniformly stirring, reacting for 2-10h under the inert gas atmosphere, and then cooling to room temperature to obtain the matrix resin solution of the antifouling intrinsic coating.
3) In the step of functional group bonding reaction, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (Econea) accounting for 0.3-15% of the total mass of vinyl monomers is weighed and dissolved in a solvent to prepare a uniform solution with the concentration of 3-40%.
4) Gradually adding the Econea solution into the copolymer matrix resin solution of the vinyl coating under the stirring of a reactor, controlling the temperature within the range of 40-110 ℃, and continuously reacting for 2-8 hours. And cooling to room temperature, adding an antioxidant or an anti-ultraviolet agent, and fully and uniformly stirring to obtain the antifouling intrinsic coating.
The invention also provides another preparation method of the antifouling intrinsic paint, which comprises the bonding reaction of functional groups, the synthesis of a vinyl copolymer and two steps:
1) In the step of functional group bonding reaction, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (Econea) is dissolved in a solvent to prepare a 3-40% uniform solution, and the solution is added into a reaction kettle with a stirrer.
2) Selecting a vinyl monomer containing an epoxy group, or an acid anhydride, or isocyanate, which has a structure shown in formula (2) after reacting with secondary amine, and gradually adding the vinyl monomer into a reactor of the Econea solution under uniform stirring. The molar ratio of the two is 0.8-1.2. Firstly adding a polymerization inhibitor accounting for 0.4 percent of the total amount of Econea and vinyl monomers into a reaction kettle, and then controlling the temperature within the range of 40-110 ℃ to react for 2-8 hours to obtain the functional group bonding type vinyl monomers.
3) In the synthesis step of the vinyl copolymer, the obtained functional group bonding type vinyl monomer, other vinyl monomers shown in the formula (1) and the determined molar weight are added into a polymerization reactor, a solvent or a composite solvent thereof which is 0.4-9 times of the total weight of the monomers and an initiator or a composite initiator thereof which is 0.02-5% of the total weight of the monomers are added, and the mixture is fully and uniformly stirred. Controlling the temperature of the reactor within the range of 40-170 ℃, carrying out polymerization reaction for 2-10h under the inert gas atmosphere, and then cooling to room temperature. And adding an antioxidant or an anti-ultraviolet agent, and fully and uniformly stirring to obtain the antifouling intrinsic coating.
The functional group-bonded vinyl monomer has a structure represented by formula (4):
the invention also provides the application of the antifouling intrinsic paint, and the antifouling intrinsic paint can be directly used as the intrinsic oil-soluble paint and the spray paint or used as the antifouling intrinsic functional auxiliary agent of the conventional oil-soluble paint and the spray paint for composite use; or the antifouling intrinsic paint is concentrated and emulsified to prepare the antifouling intrinsic emulsion paint or is used as the antifouling intrinsic functional auxiliary agent of the conventional emulsion paint for composite use.
The concentration and emulsification process comprises the following steps: the oil-in-water type surfactant is added to the intrinsic functional coating material, followed by concentration under reduced pressure to remove the solvent, and then water is added for emulsification. The final solids content is 40-85wt%.
The invention is described in detail below with reference to the figures and specific embodiments. The following examples are given in detail of the embodiments and specific procedures of the present invention, but the scope of the present invention is not limited to the following examples.
The following detection methods were used in the examples:
the antifouling intrinsic paint containing the chemical structural formula shown in the formula (1) or the paint added with the antifouling intrinsic paint mother liquor is prepared by concentrating and drying, taking 5-10g of the antifouling intrinsic paint, accurately weighing the antifouling intrinsic paint, crushing the antifouling intrinsic paint, putting the crushed antifouling intrinsic paint into a Soxhlet extractor, extracting the crushed antifouling intrinsic paint for more than 5 hours by adopting ethanol at the temperature of about 78 ℃, taking out the crushed antifouling intrinsic paint, drying and accurately weighing the mass of the antifouling intrinsic paint. The dissolution rate can be determined. The calculation formula is as follows:
dissolution rate = (C) 1 -C 2 )/C 1 ×100％
Wherein, C 1 And C 2 The weights are accurately weighed before and after extraction, respectively.
The invention is further illustrated by the following examples and comparative examples:
comparative example 1:
styrene (St), butyl Acrylate (BA), methyl Methacrylate (MMA) and Glycidyl Methacrylate (GMA) are taken as mixed monomers, wherein the mole numbers of the monomers marked as h, l, m and k in the formula (1) are respectively as follows: 0. 0.078, 0.35 and 0.035. The mixed monomer was poured into a three-necked flask placed in a water bath together with Azobisisobutyronitrile (AIBN) 0.25g and ethyl acetate 145 mL. After nitrogen is introduced into the flask for protection, the temperature of a hot water bath is increased to 60-70 ℃, the reaction is maintained for 4-6h, and the temperature is reduced by cooling, so that the base resin (EA) of the solution type vinyl coating is obtained, wherein the infrared spectrum of the base resin (EA) is shown in figure 1, the molecular weight distribution is shown in a double-detection GPC curve in figure 2, the number average molecular weight is 90700, and the molecular weight distribution index is 1.5.
Selecting a 316 stainless steel sheet with the thickness of 0.5mm, cleaning for 10min at the temperature of 40 ℃ by using a detergent, then washing for 3 times by using clean water, drying by using hot air at the temperature of 105 ℃, and cooling to room temperature for later use. The solution type vinyl paint obtained above was uniformly coated on a stainless steel sheet using a spin coater, spin-coated again after being substantially dried in a fume hood, and then dried again until the coating layer reached a thickness of about 0.3mm for testing, and the results are shown in table 1. It can be seen that the resulting solution-type coating does not have any antibacterial properties. The biological adhesion pollution condition after the biological adhesion pollution is hung in river water for 1 day, 7 days and 60 days is shown as A (1), (2) and (3) in figure 3.
Example 1:
first, 5g of Econea was added to a 500ml flask, and the IR spectrum was shown by the Econea curve in FIG. 1. Further, 200ml of ethyl acetate was added thereto, and the mixture was sufficiently stirred to obtain an Econea ethyl acetate solution.
The first step is exactly the same as comparative example 1, only the mass of each monomer is increased by a factor of 5 compared to comparative example. Styrene (St), butyl Acrylate (BA), methyl Methacrylate (MMA) and Glycidyl Methacrylate (GMA) are taken as mixed monomers, wherein the mole numbers of the monomers marked as h, l, m and k in the formula (1) are respectively: 0. 0.39, 1.75, and 0.175. This mixed monomer was poured into a three-necked flask placed in a water bath together with Azobisisobutyronitrile (AIBN) 1.25g and ethyl acetate 725 mL. And after introducing nitrogen into the flask for protection, heating the water bath to 60-70 ℃, maintaining the reaction for 4-6h, and cooling to obtain the base resin (EA) of the solution type vinyl coating. Then, 1/5 of the total amount was taken out therefrom and added to the above flask in which Econea was dissolved. Controlling the temperature within the range of 40-110 ℃, continuing to react for 2-8h, carrying out the second step of bonding reaction, then cooling to room temperature, taking out a small amount of ethanol as a precipitator, precipitating the polymer, removing the supernatant, and drying the obtained solid coating, wherein the infrared spectrum of the obtained solid coating is shown as EA-Econea curve in figure 1. And adding all the products of the bonding reaction in the second step into the flask of the polymerization reaction in the first step, fully and uniformly stirring the products and other 4/5 materials, adding 0.51g of UV-327 uvioresistant agent, and fully and uniformly stirring the materials again to obtain the antifouling intrinsic paint.
Similar to comparative example 1, a sheet of 0.5mm 316 stainless steel was selected, washed once with a detergent at 40 ℃ and then 3 times with clean water, dried with hot air at 105 ℃ and then cooled to room temperature for use. The antifouling type intrinsic paint obtained above was uniformly coated on a stainless steel sheet using a spin coater, and after being substantially dried in a fume hood, spin-coated again, and then dried again until the coating layer reached about 0.3mm thickness, for testing, and the results are shown in table 1. The obtained antifouling intrinsic paint has extremely excellent antibacterial and antifouling functions. The biological adhesion pollution prevention conditions after the biological adhesion pollution is hung in river water for 1 day, 7 days and 60 days are shown in B (1), (2) and (3) in figure 3.
Example 2:
in the first step of bonding reaction, 0.75g of Econea was first added to a 50ml flask, and 5ml of ethyl acetate was then added thereto, followed by thorough stirring to obtain an Econea ethyl acetate solution. Then adding 0.28g of Allyl Glycidyl Ether (AGE) and 0.004g of B215 antioxidant, controlling the temperature within the range of 70-110 ℃ while stirring, reacting for 2-8h, and then cooling to room temperature to obtain the vinyl monomer of the bonding functional group.
In a second step, similar to comparative example 1, styrene (St), butyl Acrylate (BA), methyl Methacrylate (MMA) are used as mixed monomers, wherein the mole numbers of the monomers marked as h, l and m in formula (1) are respectively: 0.15, 0.078, 0.2, and all the functional vinyl monomers obtained in the first bonding reaction were charged into a pressure resistant reactor together with 0.5g of dicumyl peroxide (DCP) and 145mL of ethyl acetate. And (3) introducing nitrogen into the reaction kettle for protection, heating to 140-170 ℃, maintaining the reaction for 4-6h, cooling to room temperature, adding 0.1g of UV-327 uvioresistant agent, and fully and uniformly stirring again to obtain the antifouling intrinsic coating.
Similarly to comparative example 1, a sheet of 0.5mm 316 stainless steel was selected, washed once with a detergent at 40 ℃ and then 3 times with clean water, then dried with hot air at 105 ℃ and cooled to room temperature for use. The antifouling intrinsic paint obtained above was uniformly coated on a stainless steel sheet using a spin coater, spin-coated again after being substantially dried in a fume hood, and then dried again until the coating layer reached a thickness of about 0.3mm for testing, and the results are shown in table 1. The obtained antifouling intrinsic paint has extremely excellent antibacterial and antifouling functions.
Example 3:
in the first step of the bonding reaction, 0.75g of Econea was first placed in a 50ml flask, and 5ml of ethyl acetate was added thereto, followed by sufficient stirring to obtain an ethyl acetate solution of Econea. Then adding 0.24g of Maleic Anhydride (MAH), controlling the temperature within the range of 70-110 ℃ while stirring, reacting for 2-8h, and then cooling to room temperature to obtain the vinyl monomer with bonded functional groups.
In a second step, similarly to comparative example 1, styrene (St), butyl Acrylate (BA), methyl Methacrylate (MMA) are used as mixed monomers, wherein the mole numbers of the monomers marked as h, l and m in formula (1) are respectively: 0.15, 0.078, 0.2, and the whole of the functional vinyl monomer obtained in the first bonding reaction were poured into a flask together with 0.11g of Benzoyl Peroxide (BPO) and 145mL of ethyl acetate. And introducing nitrogen into the flask for protection, heating to 40-100 ℃, maintaining the reaction for 4-6h, cooling to room temperature, adding 0.1g of UV-327 uvioresistant agent, and fully and uniformly stirring again to obtain the antifouling intrinsic coating.
Similarly to comparative example 1, a sheet of 0.5mm 316 stainless steel was selected, washed once with a detergent at 40 ℃ and then 3 times with clean water, then dried with hot air at 105 ℃ and cooled to room temperature for use. The antifouling intrinsic paint obtained above was uniformly coated on a stainless steel sheet using a spin coater, spin-coated again after being substantially dried in a fume hood, and then dried again until the coating layer reached a thickness of about 0.3mm for testing, and the results are shown in table 1. The obtained antifouling intrinsic paint has extremely excellent antibacterial and antifouling functions.
Example 4:
in the first step of the bonding reaction, 5g of Econea was first placed in a 500ml flask, and 200ml of ethyl acetate was added thereto, followed by sufficient stirring to obtain an Econea ethyl acetate solution. Adding 2.3g of Isocyano Ethyl Methacrylate (IEM) and 0.015g of B215 antioxidant, stirring while controlling the temperature within the range of 60-90 ℃, reacting for 2-8h, and then cooling to room temperature to obtain the vinyl monomer with the bonded functional group.
In a second step, similarly to comparative example 1, styrene (St), butyl Acrylate (BA), methyl Methacrylate (MMA) are used as mixed monomers, wherein the mole numbers of the monomers marked as h, l and m in formula (1) are respectively: 0.15, 0.078 and 0.2, and all the functional vinyl monomers obtained in the first bonding reaction were poured into a flask together with Azobisisobutyronitrile (AIBN) 0.25g and ethyl acetate 145 mL. And introducing nitrogen into the flask for protection, heating to 50-90 ℃, maintaining the reaction for 4-6h, cooling to room temperature, adding 0.1g of UV-327 uvioresistant agent, and fully and uniformly stirring again to obtain the mother liquor of the antifouling intrinsic coating. Selecting a Basf M20S acrylate type isocyanate spray coating and the mother liquor of the prepared antifouling intrinsic coating, wherein the mass ratio of the two is 8:1, uniformly mixing to obtain the antifouling intrinsic paint.
Similarly to comparative example 1, a sheet of 0.5mm 316 stainless steel was selected, washed once with a detergent at 40 ℃ and then 3 times with clean water, then dried with hot air at 105 ℃ and cooled to room temperature for use. The antifouling intrinsic paint obtained above was uniformly coated on a stainless steel sheet using a spin coater, spin-coated again after being substantially dried in a fume hood, and then dried again until the coating layer reached a thickness of about 0.3mm for testing, and the results are shown in table 1. The resulting antifouling intrinsic paint was seen to have excellent antimicrobial and antifouling properties.
Comparative example 2:
similar to comparative example 1, st, BA, MMA and GMA are used as mixed monomers, wherein the mole numbers of several monomers marked as h, l, m and k are respectively: 0.193, 0.176, 0.024, and 0.020. This mixed monomer was poured into a three-necked flask placed in a water bath together with Azobisisobutyronitrile (AIBN) 0.25g and ethyl acetate 145 mL. After nitrogen is introduced into the flask for protection, the temperature of hot water bath is heated to 60-70 ℃, the reaction is maintained for 4-6h, the cooling is carried out, the matrix resin of the solution type vinyl coating is obtained, 0.1g of UV-327 uvioresistant agent is added into the system, and the matrix resin of the solution type coating is obtained after full stirring. 1g of isopropanol, 2g of OP-10, 10g of titanium dioxide and 30g of light CaCO are added respectively 3 After uniform mixing, the mixture was concentrated under reduced pressure to remove the solvent until the solid content became about 95% by weight. Then adding the concentrated coating into 100g of water in a high-speed emulsifier, and emulsifying at high speed to form stable emulsion, thus obtaining the universal interior wall emulsion coating.
Selecting 50 x 50cm 2 The surfaces of the three splints are cleaned and then are reserved at room temperature. The universal interior wall emulsion paint obtained above was uniformly coated on the three plywood sheets to a thickness of 0.1mm or less, and was fully dried in a fume hood for testing, and the results are shown in table 1. It can be seen that the obtained emulsion type coating does not have any antibacterial and antifouling functions.
Example 5:
first, 5g of Econea was added to a 50ml flask, and the IR spectrum was shown by the Econea curve in FIG. 2. Further, 20ml of ethyl acetate was added thereto, and the mixture was sufficiently stirred to obtain an ethyl acetate solution of Econea.
In the first step, st, BA, MMA and GMA are used as mixed monomers, wherein the mole numbers of the monomers marked as h, l, m and k are respectively as follows: 0.193, 0.176, 0.024, and 0.020. The mixed monomer was poured into a three-necked flask placed in a water bath together with Azobisisobutyronitrile (AIBN) 0.25g and ethyl acetate 145 mL. After nitrogen is introduced into the flask for protection, the temperature of a hot water bath is heated to 60-70 ℃, the reaction is maintained for 4-6h, and the temperature is cooled to obtain the matrix resin of the solution type vinyl coating. And 0.1g of UV-327 uvioresistant agent is added into the system, and the solution type paint matrix resin is obtained after full stirring.
In the second step of bonding reaction, the Econea ethyl acetate solution is introduced into the base resin of the polymerized solution type coating, the mixture is mixed and stirred, the temperature is increased to 40-110 ℃ for reaction, the reaction is continued for 2-8h, and then the temperature is reduced to room temperature, thus obtaining the solution of the intrinsic functional coating. Then respectively adding 1g of isopropanol, 2g of OP-10, 10g of titanium dioxide and 30g of light CaCO 3 After uniform mixing, the mixture was concentrated under reduced pressure to remove the solvent until the solid content became about 95% by weight. Then adding the concentrated coating into 100g of water in a high-speed emulsifier, and emulsifying at high speed to form stable emulsion, thus obtaining the antifouling intrinsic mother coating. Selecting German Dou Fangdi jazz interior wall paint and the mother liquor of the prepared antifouling intrinsic paint, wherein the mass ratio of the two is 8:1, uniformly mixing to obtain the antifouling intrinsic paint.
Similar to comparative example 2, 50X 50cm was used 2 The surfaces of the three splints are cleaned and then are reserved at room temperature. The intrinsic functional interior wall latex paint obtained above was uniformly coated on the three plywood plates to a thickness of 0.1mm or less, and was fully dried in a fume hood for testing, see table 1. It can be seen that the obtained intrinsic functional interior wall emulsion coating has very excellent antibacterial, mildew-proof and antifouling functions, which are very similar to those of example 1.
TABLE 1
Note: determination of antifouling performance: hanging the board in river water at 25-32 deg.c for 60 days. Expressed as the percentage of the contaminated area to the area of the board.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. An antifouling intrinsic paint, which is a polymer paint with an antifouling function and has a chemical structure shown in a formula (1):
wherein:
R 1 is the residue after initiation of the free radical initiator;
h. l and m are respectively and independently selected from any natural number from 0 to 100;
k is any natural number from 1 to 30;
p is any natural number from 1 to 60;
b is one or more than two composite structures of functional groups shown in formula (2):
when h is not 0, Y is one or a composite structure of two or more of the functional groups represented by the formula (3):
2. an antifouling intrinsic paint according to claim 1, wherein the free radical initiator is selected from one or more of inorganic peroxide initiator, organic peroxide initiator, azo initiator or redox initiator;
the inorganic peroxide initiator is selected from one or more of potassium persulfate, sodium persulfate or ammonium persulfate;
the organic peroxide initiator has the general formula: R-O-O-R ', wherein R, R ' are independently selected from H, alkyl, acyl or carbonate, and R, R ' may be the same or different;
the azo initiator is selected from one or two of azobisisobutyronitrile or azobisisoheptonitrile;
the redox initiator is selected from one or two of cumene hydroperoxide-ferrous salt or organic peroxide-tertiary arylamine systems.
3. The method for preparing an antifouling intrinsic paint according to claim 1 or 2, comprising two steps of synthesizing a vinyl copolymer and bonding with a functional group:
1) Synthesis of vinyl copolymer: adding a vinyl monomer for forming the structure shown in the formula (1) and a vinyl monomer for forming the structure B into a polymerization reactor, adding a solvent and an initiator, and reacting to obtain a matrix resin solution of the antifouling intrinsic coating; wherein the vinyl monomers used to form the structure of formula (1) include, but are not limited to: methyl methacrylate, butyl acrylate, styrene, acrylic acid, vinyl acetate, vinyl chloride, butadiene isoprene;
2) Bonding reaction of functional groups: dissolving 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (Econea) in a solvent to prepare an Econea solution, adding the Econea solution into a matrix resin solution of the antifouling intrinsic coating, and continuously reacting to obtain the antifouling intrinsic coating.
4. The method for preparing the antifouling intrinsic paint according to claim 1 or 2, characterized by comprising two steps of bonding reaction of functional groups and synthesis reaction of vinyl copolymer:
1) Bonding reaction of functional groups: dissolving 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile in a solvent to prepare an Econea solution, adding the Econea solution into a reaction kettle with a stirrer, selecting a vinyl monomer containing an epoxy group, or anhydride or isocyanate, which has a structure shown in a formula (2) after reacting with secondary amine, and adding the vinyl monomer into the reactor of the Econea solution; adding a polymerization inhibitor, and reacting to obtain a functional group bonding type vinyl monomer; these functional group-bonded vinyl monomers have a structure represented by formula (4);
2) Synthesis of vinyl copolymer: adding the obtained functional group bonding type vinyl monomer and other vinyl monomers for forming the structure shown in the formula (1) into a polymerization reactor, adding a solvent and an initiator, fully and uniformly stirring, and carrying out polymerization reaction to obtain the antifouling intrinsic paint; wherein other vinyl monomers useful in forming the structure of formula (1) include, but are not limited to: methyl methacrylate, butyl acrylate, styrene, acrylic acid, vinyl acetate, vinyl chloride, butadiene, and isoprene;
5. the method for preparing an antifouling intrinsic paint as claimed in claim 3 or 4, wherein in the vinyl copolymer synthesizing step, the solvent is added in an amount of 0.4-9 times the total mass of the vinyl monomers;
in the step of synthesizing the vinyl copolymer, the amount of the added initiator is 0.02 to 5 percent of the total mass of the vinyl monomer;
in the vinyl copolymer synthesis step, the temperature of a reactor is controlled within the range of 40-170 ℃, the mixture is fully and uniformly stirred, the reaction is carried out for 2-10h under the inert gas atmosphere, and then the mixture is cooled to room temperature.
6. The method for preparing an antifouling intrinsic paint according to claim 3 or 4, wherein in the step of the functional group bonding reaction, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (Econea) is used in an amount of 0.3-15% by mass based on the total mass of the vinyl monomers;
in the step of bonding reaction of functional groups, the percentage concentration of Econea solution is 3-40%;
in the step of bonding reaction of functional groups, the reaction conditions are as follows: controlling the temperature within the range of 40-110 ℃ and reacting for 2-8 hours.
7. The method for preparing the antifouling intrinsic paint according to the claim 3 or 4, wherein the reaction in the step 2) is finished, the temperature is reduced to room temperature, then the antioxidant or the uvioresistant agent is added, and the mixture is fully and uniformly stirred to obtain the antifouling paint which takes the antifouling intrinsic paint as the core raw material and contains the antioxidant or the uvioresistant agent.
8. An antifouling paint characterized by comprising one or both of an antioxidant and an ultraviolet screening agent in addition to the intrinsic antifouling paint according to claim 1 or 2.
9. The use of the intrinsic antifouling paint according to claim 1 or 2 or the intrinsic antifouling paint according to claim 8, wherein the intrinsic antifouling paint according to claim 1 or 2 or the intrinsic antifouling paint according to claim 8 is used as an intrinsic oil-soluble paint or spray paint, or is used as an intrinsic antifouling functional auxiliary agent for a conventional oil-soluble paint or spray paint;
or the antifouling intrinsic paint according to claim 1 or 2 or the antifouling paint according to claim 8 is concentrated and emulsified to prepare the antifouling intrinsic emulsion paint or used as an antifouling intrinsic functional auxiliary agent of a conventional emulsion paint in combination.
10. The use according to claim 9, wherein the concentration and emulsification process comprises: adding an oil-in-water type surfactant to the intrinsic paint of antifouling type according to claim 1 or 2 or the antifouling paint according to claim 8, followed by concentration under reduced pressure to remove the solvent, and adding water for emulsification;
after removal of the solvent and emulsification with water, the solids content is 40-85wt%.
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