阅读说明：本技术 一种接枝苯并异噻唑啉酮甲酸酯单体的丙烯酸酯类防污树脂的结构及其制备方法 (Structure of acrylic ester antifouling resin grafted with benzisothiazolinone formate monomer and preparation method thereof ) 是由 杨建新 董苗 王雪梅 王向辉 林强 于 2020-01-17 设计创作，主要内容包括：本发明涉及一种含苯并[d]异噻唑啉-3-酮甲酸烯基酯结构的防污树脂及其制备方法,用于海洋防污材料领域。采用苯并[d]异噻唑啉-3-酮甲酸烯基酯功能单体、其它一种或两种以上烯基单体组成的混合单体,在引发剂存在下进行共聚反应,得到黄色透明的含苯并[d]异噻唑啉-3-酮甲酸烯基酯单体结构的防污树脂。本发明提供的含苯并[d]异噻唑啉-3-酮甲酸烯基酯单体结构的防污树脂,制备工艺简单,原料价格低廉,适合工业上的大规模生产。同时,它表现出优异的抑藻和杀菌性能。所合成的树脂聚合物的数均分子量在10000-20000之间,通过共价键的水解可以控制活性物质的释放速率,使涂料达到长期防污效果,具有很好的实际应用价值和广阔的发展前景。(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-.)

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):

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).

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):

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.