CN111574658A - Structure of acrylic ester antifouling resin grafted with benzisothiazolinone formate monomer and preparation method thereof - Google Patents

Structure of acrylic ester antifouling resin grafted with benzisothiazolinone formate monomer and preparation method thereof Download PDF

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CN111574658A
CN111574658A CN202010055837.1A CN202010055837A CN111574658A CN 111574658 A CN111574658 A CN 111574658A CN 202010055837 A CN202010055837 A CN 202010055837A CN 111574658 A CN111574658 A CN 111574658A
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benzo
monomer
isothiazoline
isothiazolin
formate
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CN111574658B (en
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杨建新
董苗
王雪梅
王向辉
林强
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Hainan University
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance

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Abstract

The invention relates to an antifouling resin containing a benzo [ d ] isothiazoline-3-keto-formic acid alkenyl ester structure and a preparation method thereof, which are used in the field of marine antifouling materials. The antifouling resin containing the structure of the benzo [ d ] isothiazoline-3-keto-acid alkenyl ester monomer is obtained by carrying out copolymerization reaction on a mixed monomer consisting of the benzo [ d ] isothiazoline-3-keto-acid alkenyl ester functional monomer and one or more than two other alkenyl monomers in the presence of an initiator. The antifouling resin containing the benzo [ d ] isothiazoline-3-keto-formic acid alkenyl ester monomer structure provided by the invention is simple in preparation process, low in raw material price and suitable for industrial large-scale production. At the same time, it exhibits excellent algae inhibiting and sterilizing performance. The number average molecular weight of the synthesized resin polymer is 10000-.

Description

Structure of acrylic ester antifouling resin grafted with benzisothiazolinone formate monomer and preparation method thereof
Technical Field
The invention relates to the field of marine antifouling paint, in particular to a structure of a side chain grafted benzo [ d ] isothiazoline-3-ketone-2-formate functional monomer and a preparation method thereof. The copolymer structure contains benzo [ d ] isothiazoline-3-ketone active units, and can be used for marine antifouling anticorrosive coatings, industrial bactericidal coatings and the like.
Background
Since the use of organic tin antifouling paints has been prohibited globally from 2008.1, the resins used in the existing antifouling paints are mostly acrylic acid resins, chlorinated rubbers, epoxy resins, and the like, and these materials do not have an antifouling effect, and the inhibition of marine fouling needs to be realized by physically adding an antifouling agent such as cuprous oxide, zinc oxide, DDT, chlorothalonil, zinc pyrithione, 4, 5-dichloro-2-n-octyl-4-isothiazoline-3-one and the like, so that the application effect of the currently used antifouling paints is far lower than that of organic tin antifouling paints, mainly because these materials do not have an antifouling structure similar to butyl tin which is a side chain of organic tin resin, and the synergistic antifouling effect between the antifouling agent and the resin is reduced. Moreover, recent application results show that the effective components of some antifouling paints, such as cuprous oxide, cause different degrees of environmental damage due to long residual period and high cumulative toxicity, and massive enrichment of coastal sediments and organisms. Therefore, some european countries have started to ban the use of copper-based antifouling paints on small recreational ships in the offshore region, and the us stipulates that the use of cuprous oxide has been restricted since 2015. Therefore, the development of new efficient and environment-friendly antifouling paint is an important problem to be solved urgently at present.
1, 2-benzo [ d ] isothiazoline-3-ketone (BIT) is a novel industrial sterilization preservative with broad spectrum, high efficiency and low toxicity, has outstanding inhibition on the growth and the propagation of microorganisms such as bacteria, mildew, fungi, algae and the like, and is an ideal bactericide. In recent years, researches show that the compounds have good biological inhibitory activity and are widely applied to the fields of drug development and industry and agriculture. Because BIT has wide bactericidal and algae inhibiting activity, people apply BIT to marine antifouling paint and also obtain certain research results. From the structure, BIT belongs to a small molecular compound, so that the use mainly depends on physical addition and mixing, and the defects of poor water solubility, serious dialysis, short duration of drug effect and the like easily occur in the actual application process, so that the application range of the BIT is limited.
Domestic researchers also develop corresponding researches on functional antifouling functional resins. Chinese patent 201310021614.3 reports an epoxy resin antifouling paint containing a BIT structure, which is prepared by reacting an N-substituted acryloyloxymethyl BIT functional monomer with a plurality of double bond-containing monomers, and grafting the reaction product with bisphenol A epoxy resin to obtain an acrylic acid grafted epoxy resin containing the BIT structure.
Chinese patent 201510084390.X reports a method for preparing zinc acrylate resin with a modified BIT graft, which has an antifouling structure similar to tributyltin side chain. The marine bacteria growth inhibition experiment shows that the resin not only has an antibacterial function, but also can inhibit the attachment and growth of marine organisms. The resin has the hydrolysis self-polishing function, has the characteristic of delaying the release of the antifouling agent, and can effectively prolong the antifouling life of the coating. However, no relevant report is found in the method for obtaining the marine antifouling paint with the acrylic resin side chain grafted with the BIT active structural unit by reacting benzo [ d ] isothiazoline-3-ketone with allyl chloroformate and then copolymerizing the reaction product with acrylic ester.
Disclosure of Invention
In order to solve the problems, the invention provides a structure of acrylic antifouling resin grafted with benzo [ d ] isothiazoline-3-ketone-2-formate and a preparation method thereof. Performing copolymerization reaction on benzo [ d ] isothiazoline-3-ketone-2-allyl formate monomer and other double bond-containing functional monomers to obtain the acrylate antifouling resin grafted with the benzo [ d ] isothiazoline-3-ketone active structure. The structure connects BIT to the main chain of acrylic resin in a chemical bond mode, so that the BIT is not easy to diffuse and run off in the use process, and active substances such as benzo [ d ] isothiazolin-3-ketone and the like can be slowly and uniformly released through hydrolysis of a C-O-C bond. The using effect is improved, the using time is prolonged, and the defects of the micromolecule antifouling paint are overcome. The antifouling paint prepared by the resin has good antifouling performance and self-polishing performance, and has important significance for marine environment protection.
The invention aims to improve and enhance the antifouling performance of the marine antifouling paint and provides a preparation method of an acrylate resin green marine antifouling paint, which is environment-friendly and simple to prepare.
The invention provides a structure of acrylic ester marine antifouling paint grafted with benzo [ d ] isothiazoline-3-ketone-2-formate and a preparation method thereof.
The invention also provides a structure and a preparation method of the benzo [ d ] isothiazoline-3-ketone-2-allyl formate monomer.
The grafted acrylic resin prepared by the method provided by the invention is used for marine antifouling paint, has very good inhibition capacity on marine algae, fungi, large fouling organisms such as barnacles and mussels, has the characteristics of high efficiency, environmental protection, economy and the like, and has important significance on marine environmental protection.
The acrylate marine antifouling paint prepared by the method provided by the invention has the characteristics of simple structure, convenience in preparation, easiness in industrial production and the like.
Benzo [ d ] s according to the invention]The structural formula of the isothiazoline-3-ketone-2-alkenyl formate monomer compound I is shown in figure 1. Wherein R is1Selected from: h, CH3，CH2CH3，CH(CH3)2，C(CH3)3，OCH3，Cl，Br，F，SCH3，CN，COCH3，CONH2，CONHC6H5；R2Selected from: h, CH3，CH2CH3。
According to a preferred embodiment of the present invention, the benzo [ d ] isothiazolin-3-one monomer compound is: benzo [ d ] isothiazolin-3-one-2-allyl formate ester compound, characterized in that the compound is benzo [ d ] isothiazolin-3-one-2-allyl formate, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-methallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-ethyl allyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-isopropyl allyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-tert-butyl allyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-hydroxy allyl alcohol ester, Benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-methoxyallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-chloroallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-bromoallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-fluoroallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-methylthioallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-cyanoallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-acetylallyl alcohol ester, Benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-acetamidophenylalcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2- (N-phenyl) acetyl allylalcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-butenol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-pentenol ester.
The invention also relates to said benzo [ d]A preparation method of an isothiazoline-3-ketone-2-alkenyl formate monomer compound I. Benzo [ d ] depicted by FIG. 1]The synthesis method of the isothiazoline-3-ketone-2-allyl formate monomer compound I is obtained by reacting a compound II with a compound III in the presence of organic base, and the process is shown in figure 2. In the formula, R1Selected from: h, CH3，CH2CH3，CH(CH3)2，C(CH3)3，OCH3，Cl，Br，F，SCH3，CN，COCH3，CONH2，CONHC6H5；R2Selected from: h, CH3，CH2CH3。
The preparation process of the benzo [ d ] isothiazoline-3-ketone-2-carboxylic acid alkenyl ester monomer compound I is characterized by comprising the following steps: in an organic solvent, the ratio of benzo [ d ] isothiazoline-3-ketone (II) to alkenyl chloroformate (III) is 1: 1-1: 5, triethylamine is used as an acid-binding agent, the reaction temperature is 0-100 ℃, and the reaction time is 1-5 hours. Separating, washing and recrystallizing the generated product in absolute ethyl alcohol to obtain the acrylic acid enol ester compound with the benzo [ d ] isothiazoline-3-ketone monomer structure.
Said substituted chloromethyl acrylate compound is selected from: allyl chloroformate, 2-methylallyl chloroformate, 2-ethylallyl chloroformate, 2-isopropylallyl chloroformate, 2-tert-butylallyl chloroformate, 2-hydroxyallyl chloroformate, 2-methoxyallyl chloroformate, 2-chloroallyl chloroformate, 2-bromoallyl chloroformate, 2-fluoroallyl chloroformate, 2-methylthioallyl chloroformate, 2-cyanoallyl chloroformate, 2-acetylallyl chloroformate, 2-acetylaminoallyl chloroformate, 2- (N-phenyl) acetylallyl chloroformate, methyl ethyl chloroformate, ethyl propyl chloroformate, butyl chloroformate, propyl chloroformate, butyl 2-hydroxy allyl chloroformate, propyl, Chloroformic acid-2-butenol ester and chloroformic acid-2-pentenol ester.
The organic solvent is one or more selected from dichloromethane, chloroform, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, acetonitrile, dimethyl formamide, dimethyl sulfoxide, hexamethylphosphoric triamide, etc.
The grafted benzo [ d ] s according to the invention]The structural formula IV of the acrylate marine antifouling resin of the isothiazoline-3-ketone formate monomer is shown in figure 3. In the formula, R1Selected from: h, CH3，CH2CH3，CH(CH3)2，C(CH3)3，OCH3，Cl，Br，F，SCH3，CN，COCH3，CONH2，CONHC6H5；R2Selected from: h, CH3，CH2CH3。
The preparation method of the acrylate marine antifouling resin IV grafted with BIT-formate as shown in FIG. 3 is obtained by copolymerization of the compound I and other polymerizable unsaturated monomers in the presence of an initiator, and the reaction process is shown in FIG. 4.
The preparation process of the acrylate marine antifouling paint IV grafted with benzo [ d ] isothiazoline-3-ketoformate is characterized by comprising the following steps: adding a mixed solvent into a three-necked bottle provided with a stirrer, a thermometer and a condensing device, heating to 60-85 ℃, uniformly mixing an initiator, a benzo [ d ] isothiazoline-3-ketoformate monomer compound and an acrylate monomer according to a mass ratio, dropwise adding, controlling the dropwise adding speed, supplementing a small amount of initiator after 3h of dropwise adding, carrying out heat preservation reaction for 3-12 h, and cooling to room temperature to obtain yellow transparent resin, namely the antifouling resin with the grafted benzo [ d ] isothiazoline-3-ketoformate structure.
The benzo [ d ] isothiazoline-3-ketone formate monomer compound comprises: benzo [ d ] isothiazolin-3-one-2-allyl formate ester compound, characterized in that the compound is benzo [ d ] isothiazolin-3-one-2-allyl formate, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-methallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-ethyl allyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-isopropyl allyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-tert-butyl allyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-hydroxy allyl alcohol ester, Benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-methoxyallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-chloroallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-bromoallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-fluoroallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-methylthioallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-cyanoallyl alcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-acetylallyl alcohol ester, Benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-acetamidophenylalcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2- (N-phenyl) acetyl allylalcohol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-butenol ester, benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-pentenol ester; the other polymerizable unsaturated monomer comprises at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, butyl acrylate and butyl methacrylate; the initiator is azobisisobutyronitrile or benzoyl peroxide, or a mixture thereof; the mixed solvent is toluene, xylene, n-butanol or n-pentanol, or a mixture thereof.
The benzo [ d ] isothiazoline-3-ketoformate monomer accounts for 5 to 50 percent of the total weight of the mixed monomer; the acrylate monomer is at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, butyl acrylate and butyl methacrylate, and the dosage of the acrylate monomer accounts for 50 to 95 percent of the total weight of the mixed monomer; the solvent is toluene, xylene, n-butanol or n-pentanol, or a mixture thereof; the initiator is azobisisobutyronitrile or benzoyl peroxide or a mixture thereof. The resin prepared by the method is used as the base resin of the antifouling paint to prepare the antifouling paint, and the antifouling paint has good film forming performance and physical and mechanical properties, and has excellent self-polishing performance and marine antifouling performance.
The innovation points and advantages of the invention are as follows: the compound benzo [ d ] isothiazoline-3-ketone has the advantages of strong antibacterial ability and low toxicity, but can only be added physically in the practical application process, has poor water solubility, can cause serious dialysis, and is difficult to maintain the drug effect for a long time. The invention firstly carries out structural modification on the BIT molecule to obtain the BIT monomer structure containing alkenyl. The prepared BIT-monomer has good polymerizability, and the antifouling resin with higher molecular weight and grafted BIT active groups can be obtained through copolymerization, so that the antifouling agent is not easy to diffuse and run off in the use process, and the release rate can be controlled through hydrolysis of ester bonds, so that the antifouling agent is efficiently utilized. In the performance test process, the resin has good inhibition capacity on marine algae, fungi and typical fouling organisms (barnacles and mussels), the shallow sea hanging plate almost has no organism attachment after 30 days, and only a very small amount of organisms are attached after 60 days.
The preparation method provided by the invention has the advantages of simple synthetic route, low raw material price and easy realization of industrialization, and the prepared antifouling resin containing the BIT-alkenyl formate structure has wide development prospect in the field of marine antifouling paint.
The invention is described in more detail below by way of example. It is not intended to limit the present invention, and those skilled in the art can make various modifications or alterations without departing from the basic idea of the present invention.
Example 1
Preparation of benzo [ d ] isothiazolin-3-one-2-allyl formate monomer: in a 100 m1 three-necked flask equipped with a stirring device, a condenser tube and a thermometer, 1.51g (0.01 mol) of benzo [ d ] isothiazolin-3-one, 1.21 g (0.01 mol) of allyl chloroformate and a catalytic amount of triethylamine were charged in a 100 mL three-necked flask, 25mL of toluene was added, and after completion of dissolution, the reaction was stirred at room temperature for 2.0 hours and followed by TLC until completion. Cooling the reactant to room temperature, carrying out suction filtration, collecting filtrate, washing with water, neutralizing, drying, concentrating and evaporating to dryness, and separating and purifying residues to obtain light yellow solid with the yield of 84.5%.
Example 2
Preparation of benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-methylallyl alcohol ester monomer: in a 100 m1 three-necked flask equipped with a stirring device, a condenser tube and a thermometer, 1.51g (0.01 mol) of benzo [ d ] isothiazolin-3-one, 1.35 g (0.01 mol) of 2-methylallyl chloroformate and a catalytic amount of triethylamine were charged in a 100 mL three-necked flask, 25mL of toluene was added, and after completion of dissolution, the reaction was stirred at 50 ℃ for 2.0 hours and followed by TLC until completion. Cooling the reactant to room temperature, carrying out suction filtration, collecting filtrate, washing with water, neutralizing, drying, concentrating, evaporating to dryness, and separating and purifying residues to obtain a white solid with the yield of 83%.
Example 3
Preparation of benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-ethyl allyl alcohol ester monomer: in a 100 m1 three-necked flask equipped with a stirring device, a condenser tube and a thermometer, 1.51g (0.01 mol) of benzo [ d ] isothiazolin-3-one, 1.48 g (0.01 mol) of 2-ethylallyl chloroformate and a catalytic amount of triethylamine were charged in a 100 mL three-necked flask, 25mL of toluene was added, and after completion of dissolution, the reaction was stirred at 50 ℃ for 2.0 hours and followed by TLC until completion. And cooling the reactant to room temperature, carrying out suction filtration, collecting filtrate, washing with water, neutralizing, drying, concentrating and evaporating to dryness, and separating and purifying residues to obtain a white solid with the yield of 79.5%.
Example 4
Preparation of benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-isopropyl allyl alcohol ester monomer: in a 100 m1 three-necked flask equipped with a stirring device, a condenser tube and a thermometer, 1.51g (0.01 mol) of benzo [ d ] isothiazolin-3-one, 1.62g (0.01 mol) of 2-isopropylallyl chloroformate and a catalytic amount of triethylamine were charged in a 100 mL three-necked flask, 25mL of toluene was added, and after completion of dissolution, the reaction was stirred at 50 ℃ for 2.0 hours and followed by TLC until completion. Cooling the reactant to room temperature, carrying out suction filtration, collecting filtrate, washing with water, neutralizing, drying, concentrating, evaporating to dryness, and separating and purifying residues to obtain a white solid with the yield of 63%.
Example 5
Preparation of benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-tert-butyl allyl alcohol ester monomer: in a 100 m1 three-necked flask equipped with a stirring device, a condenser tube and a thermometer, 1.76g (0.01 mol) of benzo [ d ] isothiazolin-3-one, 1.35 g (0.01 mol) of 2-t-butylallyl chloroformate and a catalytic amount of triethylamine were charged in a 100 mL three-necked flask, 25mL of toluene was added, and after completion of dissolution, the reaction was refluxed for 2.0 hours, followed by TLC until completion. Cooling the reactant to room temperature, carrying out suction filtration, collecting filtrate, washing with water, neutralizing, drying, concentrating, evaporating to dryness, and separating and purifying residues to obtain white solid with the yield of 74.5%.
Example 6
Preparation of benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-hydroxy allyl alcohol ester monomer in a 100 m1 three-necked flask equipped with a stirring device, a condenser tube and a thermometer, 1.51g (0.01 mol) of benzo [ d ] isothiazolin-3-one, 1.36 g (0.01 mol) of 2-hydroxy allyl chloroformate and a catalytic amount of triethylamine were added to a 100 mL three-necked flask, 25mL of toluene was added, after complete dissolution, the reaction was stirred under reflux for 2.0 hours, and TLC followed up to completion. Cooling the reactant to room temperature, carrying out suction filtration, collecting filtrate, washing with water, neutralizing, drying, concentrating, evaporating to dryness, and separating and purifying residues to obtain a white solid with the yield of 78%.
Example 7
Preparation of benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-methoxy allyl alcohol ester monomer: in a 100 m1 three-necked flask equipped with a stirring device, a condenser tube and a thermometer, 1.51g (0.01 mol) of benzo [ d ] isothiazolin-3-one, 1.50 g (0.01 mol) of 2-methoxyallyl chloroformate and a catalytic amount of triethylamine were charged in a 100 mL three-necked flask, 25mL of dioxane was added, and after completion of dissolution, the reaction was stirred at 100 ℃ for 2.0 hours and followed by TLC until completion. Cooling the reactant to room temperature, carrying out suction filtration, collecting filtrate, washing with water, neutralizing, drying, concentrating, evaporating to dryness, and separating and purifying residues to obtain a white solid with the yield of 56%.
Example 8
Preparation of benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-chloroallyl alcohol ester monomer: in a 100 m1 three-necked flask equipped with a stirring device, a condenser tube and a thermometer, 1.51g (0.01 mol) of benzo [ d ] isothiazolin-3-one, 1.54 g (0.01 mol) of 2-chloroallyl chloroformate and a catalytic amount of triethylamine were charged in a 100 mL three-necked flask, 25mL of N, N' -Dimethylformamide (DMF) were added, and after completion of dissolution, the reaction was stirred at 100 ℃ for 3.0 hours and followed by TLC until completion. Cooling the reactant to room temperature, carrying out suction filtration, collecting filtrate, washing with water, neutralizing, drying, concentrating, evaporating to dryness, and separating and purifying residues to obtain a light yellow solid with the yield of 72%.
Example 9
Preparation of benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-acetyl allyl ester monomer: in a 100 m1 three-necked flask equipped with a stirring device, a condenser tube and a thermometer, 1.51g (0.01 mol) of benzo [ d ] isothiazolin-3-one, 1.76g (0.01 mol) of 2-acetylallylchloroformate and a catalytic amount of triethylamine were charged in a 100 mL three-necked flask, 25mL of N, N' -Dimethylformamide (DMF) were added, and after completion of dissolution, the reaction was stirred at 100 ℃ for 5.0 hours and followed by TLC until completion. And cooling the reactant to room temperature, carrying out suction filtration, collecting filtrate, extracting with dichloromethane, washing with water, neutralizing, drying, concentrating and evaporating to dryness, and separating and purifying residues to obtain a light yellow solid with the yield of 77.5%.
Example 10
Preparation of antifouling resin A-1 containing benzo [ d ] isothiazoline-3-ketone-2-allyl formate structure: 40 parts of dimethylbenzene and 10 parts of n-butyl alcohol are sequentially added into a 250 mL three-neck flask with a stirring and condensing device, and the temperature is raised to 85 ℃ in an oil bath. Fully dissolving 15 parts of benzo [ d ] isothiazoline-3-ketone-2-allyl formate monomer, 3 parts of AIBN, 42.5 parts of methyl methacrylate and 42.5 parts of butyl acrylate by using dimethylbenzene and n-butyl alcohol, adding the mixture into a cylindrical constant-pressure funnel, preparing for dropwise adding, keeping the temperature for 3 hours after the dropwise adding is finished, adding the rest 1.5 parts of AIBN, keeping the temperature for 3 to 5 hours, stopping heating after no monomer spot exists after TLC analysis, and cooling to room temperature to obtain the antifouling resin A-1 containing benzo [ d ] isothiazoline-3-ketone-2-allyl formate (a).
Example 11
Preparing antifouling resin A-2 containing benzo [ d ] isothiazoline-3-ketone-2-allyl formate structure: 40 parts of dimethylbenzene and 10 parts of n-butyl alcohol are sequentially added into a 250 mL three-neck flask with a stirring and condensing device, and the temperature is raised to 85 ℃ in an oil bath. 20 parts of benzo [ d ] isothiazoline-3-ketone-2-allyl formate monomer, 3 parts of AIBN, 40 parts of methyl methacrylate and 40 parts of butyl acrylate are fully dissolved by xylene and n-butyl alcohol and then added into a cylindrical constant-pressure funnel for preparation of dropwise addition, the dropwise addition time is 2 to 3 hours, after the dropwise addition is finished, the temperature is continuously kept for 3 hours, the rest 2 parts of AIBN is added, the temperature is continuously kept for 4 to 6 hours, no monomer spot exists after TLC analysis, the heating is stopped, and the temperature is reduced to the room temperature, so that the antifouling resin A-2 containing benzo [ d ] isothiazoline-3-ketone-2-allyl formate (a) is obtained.
Example 12
Preparation of antifouling resin B-1 containing benzo [ d ] isothiazoline-3-ketone-2-formic acid-2-methyl allyl alcohol ester structure: 40 parts of dimethylbenzene and 10 parts of n-butyl alcohol are sequentially added into a 250 mL three-neck flask with a stirring and condensing device, and the temperature is raised to 85 ℃ in an oil bath. Fully dissolving 15 parts of benzo [ d ] isothiazoline-3-ketone-2-formic acid-2-methyl allyl alcohol ester monomer, 3 parts of AIBN, 42.5 parts of methyl methacrylate and 42.5 parts of butyl acrylate by using dimethylbenzene and n-butyl alcohol, adding the mixture into a cylindrical constant-pressure funnel for dropwise addition, keeping the temperature for 3 hours after the dropwise addition is finished within 2-3 hours, adding the rest 1.5 parts of AIBN, keeping the temperature for 3-5 hours, stopping heating after no monomer spot exists after TLC analysis, and cooling to room temperature to obtain the antifouling resin B-1 containing benzo [ d ] isothiazoline-3-ketone-2-formic acid-2-methyl allyl alcohol ester (B).
Example 13
Preparation of antifouling resin B-2 containing benzo [ d ] isothiazolin-3-one-2-carboxylic acid-2-methylallyl alcohol ester: 40 parts of dimethylbenzene and 10 parts of n-butyl alcohol are sequentially added into a 250 mL three-neck flask with a stirring and condensing device, and the temperature is raised to 85 ℃ in an oil bath. 20 parts of benzo [ d ] isothiazoline-3-ketone-2-formic acid-2-methyl allyl alcohol ester monomer, 3 parts of AIBN, 40 parts of methyl methacrylate and 40 parts of butyl acrylate are fully dissolved by xylene and n-butyl alcohol and then added into a cylindrical constant pressure funnel for dropwise adding within 2-3 hours, after dropwise adding is finished, heat preservation is continuously carried out for 3 hours, the rest 2 parts of AIBN is added, heat preservation is continuously carried out for 4-6 hours, no monomer exists after TLC analysis, heating is stopped, and the temperature is reduced to room temperature, so that the antifouling resin B-2 containing benzo [ d ] isothiazoline-3-ketone-2-formic acid-2-methyl allyl alcohol ester (B) is obtained.
Example 14
Molecular weight (GPC) measurement of the antifouling resin polymers prepared in examples 10, 11, 12 and 13, the molecular weight and molecular weight distribution of the polymers were measured by gel permeation chromatography. The results of molecular weight test of antifouling resins A-1 and A-2 and B-1 and B-2 containing benzisothiazolinone formate structures are shown in the following table:
Figure 795656DEST_PATH_IMAGE001
the synthesized acrylic resin containing the benzisothiazolinone formate structure has the number average molecular weight (Mn) of 10056-11515 and the weight average molecular weight (Mw) of 10769-12702, which are not greatly different. While the Polymer Dispersibility Index (PDI) is between 1.05 and 1.12, indicating a relatively uniform molecular weight distribution.
Example 15
Bacteriostatic property test of the antifouling resins prepared in examples 10, 11, 12 and 13 the bacteriostatic property of the polymer was tested by absorbance method. In the antibacterial performance test of the antifouling resins A-1 and A-2 and B-1 and B-2 containing the benzisothiazolinone formate structure, the inhibition rates of the four resins on staphylococcus aureus, vibrio coralliilyticus and vibrio parahaemolyticus in 12 hours are respectively tested as follows:
Figure 516487DEST_PATH_IMAGE002
the results show that the samples coated with antifouling resin containing benzisothiazolinone formate structure had significantly smaller numbers of bacterial species in the well plates compared to the blank samples, which indicates that the antifouling resin containing benzisothiazolinone formate structure prepared in examples 10, 11, 12 and 13 had excellent ability to inhibit the growth of marine bacteria.
Example 16
The antifouling resins prepared in examples 10, 11, 12 and 13 were subjected to an algae inhibition test, and the polymers were subjected to an absorbance test. In the algae inhibition performance test of antifouling resins A-1 and A-2 containing benzisothiazolinone formate structures and B-1 and B-2, the inhibition rates of four resins on dinoflagellates such as chlorella, coccobanchum and the like and 7d of chaetoceros tenella are respectively tested as follows:
Figure 416310DEST_PATH_IMAGE003
the results show that the color of the algae liquid is much lighter in the plastic cups of the sample plates containing the antifouling resin with the benzisothiazolinone formate structure compared with the blank samples, and the antifouling resin with the benzisothiazolinone formate structure prepared in the examples 10, 11, 12 and 13 has good capability of inhibiting the growth of marine algae.
Example 17
Antifouling properties of the antifouling resins prepared in examples 11 and 13 were measured, and the antifouling properties of the prepared antifouling paints were evaluated with reference to the national standard "antifouling paint sample plate shallow sea immersion test method". The marine antifouling property test of the antifouling resins A-2 and B-2 containing the benzisothiazolinone formate structure is shown in figure 5.
The major marine fouling organisms in the ocean are barnacles, mussels, limestans, oysters and various seaweeds. After a test of 30 days on the shallow sea hanging plate, the blank sample plate has obvious barnacle, mussel, lima and other organisms, and the sample plate coated with the antifouling resin containing the benzisothiazolinone formate structure has no obvious marine animal and plant attachment; after the shallow sea hanging plate is tested for 60 days, the blank sample plate is full of organisms such as barnacles, mussels and the like, but the sample plate coated with the antifouling resin containing the benzisothiazolinone formate structure only has a very small amount of marine animals and plants attached, which shows that the antifouling resin containing the benzisothiazolinone formate structure prepared in examples 11 and 13 has very good antifouling performance.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and variations, additions and substitutions which are within the spirit and scope of the present invention by those skilled in the art are included.
Drawings
FIG. 1 is a schematic structural diagram of a benzo [ d ] isothiazolin-3-one-2-carboxylate monomer compound.
FIG. 2 is a schematic view showing a method for preparing a benzo [ d ] isothiazolin-3-one-2-carboxylate monomer compound.
FIG. 3 is a schematic structural diagram of an acrylate marine antifouling paint grafted with benzo [ d ] isothiazoline-3-ketone-2-formate monomer.
FIG. 4 is a schematic diagram of a preparation method of an acrylate marine antifouling paint grafted with benzo [ d ] isothiazoline-3-ketone-2-formate.
FIG. 5 is a schematic diagram of marine antifouling property tests of antifouling resins A-2 and B-2 with a grafted benzisothiazolinone formate structure.

Claims (6)

1. A benzo [ d ] isothiazolin-3-one-2-formate monomer is characterized in that the structure of the monomer is shown as the formula (I):
Figure RE-77629DEST_PATH_IMAGE001
in the formula, R1Selected from: h, CH3，CH2CH3，CH(CH3)2，C(CH3)3，OCH3，Cl，Br，F，SCH3，CN，COCH3，CONH2，CONHC6H5；R2Selected from: h, CH3，CH2CH3。
2. The method for preparing benzo [ d ] isothiazolin-3-one-2-carboxylate monomer according to claim 1, wherein: carrying out condensation reaction on benzo [ d ] isothiazoline-3-ketone (II) and vinyl chloroformate (III) to obtain a benzo [ d ] isothiazoline-3-ketone-2-formate monomer structure (formula I).
Figure RE-645008DEST_PATH_IMAGE002
3. The method for preparing benzo [ d ] isothiazolin-3-one-2-formate monomer (I) according to claim 2, wherein the ratio of benzo [ d ] isothiazolin-3-one to alkenyl chloroformate is 1:1.0 to 1:3.5, triethylamine is used as an acid-binding agent, the reaction temperature is 0 to 120 ℃, and the reaction time is 1 to 5 hours; separating, washing and recrystallizing the generated product in absolute ethyl alcohol to obtain the benzo [ d ] isothiazoline-3-ketone formate monomer compound I.
4. An acrylate marine antifouling resin grafted with benzo [ d ] isothiazoline-3-ketone-2-formate monomer is characterized in that the structure of the resin is shown as the formula (IV):
Figure RE-382020DEST_PATH_IMAGE003
in the formula, R1Selected from: h, CH3，CH2CH3，CH(CH3)2，C(CH3)3，OCH3，Cl，Br，F，SCH3，CN，COCH3，CONH2，CONHC6H5；R2Selected from: h, CH3，CH2CH3。
5. The method for preparing the acrylic ester marine antifouling resin grafted with benzo [ d ] isothiazolin-3-one-2-formate monomer according to claim 4 is characterized in that: 2.5-20 parts of benzo [ d ] isothiazoline-3-ketone-2-formic ether monomer, 20-40 parts of acrylate unsaturated monomer, 40-60 parts of organic solvent and 0.1-1.0 part of initiator; uniformly mixing the monomers according to the mass ratio, dropwise adding the mixture into an organic reaction solvent, reacting at 60-120 ℃ for 6-12 h, and cooling to room temperature to obtain a yellow transparent solution, thus obtaining the acrylic ester marine antifouling resin copolymer grafted with benzo [ d ] isothiazoline-3-ketone-2-formate monomer. Wherein, the acrylic ester unsaturated monomer comprises but is not limited to one or the combination of several of methyl methacrylate, butyl acrylate, propyl methacrylate, tert-butyl acrylate, isobutyl acrylate, 2-ethylhexyl methacrylate and vinyl versatate; the initiator is azobisisobutyronitrile or benzoyl peroxide, or a mixture thereof; the organic solvent can be one or more of dichloromethane, chloroform, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, such as acetonitrile, dimethylformamide, dimethyl sulfoxide, and hexamethylphosphoric triamide.
6. The acrylate resin grafted with benzo [ d ] isothiazolin-3-one formate monomer according to claim 4 is used for preparing a novel marine antifouling paint, wherein the benzisothiazolin-3-one compound is a substance for inhibiting marine biological activity, and the marine antifouling paint with the structural system can be coated on the surfaces of marine ships and solid buildings independently or mixed with other paints, has an outstanding effect on inhibiting the growth of large marine fouling organisms such as seaweeds, barnacles and oysters, and has the characteristics of easy degradation, low residue, safety and environmental protection.
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