A zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure, its preparation method and application

Abstract

The present invention discloses a zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure, its preparation method and application. The resin is copolymerized from a zinc bisacrylate monomer and a 2-oxo-1,2-benzisothiazol-3-one monomer. The finally prepared zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure has a good self-polishing antifouling effect and is suitable for large-scale antifouling applications in dynamic waters and static waters.

Description

Technical Field

[0001] The present invention relates to the field of marine antifouling resin coatings, and particularly to a zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure, and also provides a corresponding preparation method and application. Background Art

[0002] Marine underwater facilities and ships sailing in the ocean inevitably face the problem of attachment of marine fouling organisms (animals, plants, and microorganisms). This not only greatly accelerates the corrosion of the facilities and ships, thereby shortening their service life, but also significantly increases the energy consumption for sailing ships. To prevent the attachment of marine organisms on the surface of underwater facilities, the most common method is to coat a layer of antifouling paint on the surface of the underwater facilities. Due to its advantages such as economy, effectiveness, and easy operation, it has developed the fastest and been the most widely used in recent years. The antifouling agents popular in the mid-19th century were mainly copper oxides, arsenic oxides, and mercury oxides, which have long been phased out due to their excessive toxicity; the highly effective tributyltin (TBT) used since the mid-20th century has been explicitly prohibited by the International Maritime Organization (IMO) since January 1, 2008 due to its harm to the marine ecological environment and even human health. Therefore, the development of environmentally friendly functional marine antifouling resins with low toxicity or no toxicity has become a research hotspot.

[0003] In the past few decades, researchers have developed a variety of antifouling strategies: micro / nanostructured surface coatings, natural antifouling agent-releasing coatings, low surface energy coatings, dynamic surface coatings, and zwitterionic coatings, etc. According to the results of in-sea test experiments of relevant research, it can be seen that using natural antifouling agent-releasing coatings is an effective antifouling strategy. Natural antifouling agents have the characteristics of environmental friendliness, diverse categories, degradability, high efficiency, and broad spectrum, and have become a type of antifouling agent widely studied by researchers. However, the production of natural antifouling agents is small, the extraction process is cumbersome, and large-scale production is difficult. Therefore, synthetic antifouling agents with degradable performance are needed as an alternative solution. Thus, synthesizing hybrid compounds with the same performance as natural antifouling agents has become an alternative method being applied to marine antifouling.

[0004] The zinc bisacrylate resin draws on the structural characteristics of polished organotin resins. By replacing the environmentally harmful tin ions with environmentally friendly zinc ions, a zinc bisacrylate resin with properties similar to those of organotin acrylate resins is synthesized. The zinc-containing acrylic copolymer undergoes ion exchange with sodium ions in seawater to achieve the antifouling purpose. Many achievements have been made in the development of environmentally friendly resins and antifouling agents with zinc bisacrylate self-polishing coatings. However, the main problems currently faced in this direction are the short antifouling period of the coatings and the unclear antifouling effect in static waters. Therefore, new self-polishing antifouling coatings will develop in the directions of environmental friendliness, simple process, excellent antifouling performance, and dual antifouling in dynamic and static waters. Summary of the Invention

[0005] 1. Problems to be Solved

[0006] Based on the above, in the process of using zinc acrylate resin, there is a problem of poor antifouling effect. One of the purposes of the present invention is to provide a zinc diacrylate resin grafted with 1,2-benzisothiazol-3-one structure. The zinc diacrylate resin grafted with 1,2-benzisothiazol-3-one structure has BIT monomer and heterocyclic structure. As an antifouling agent, it has stable, efficient and environmentally friendly antifouling effect.

[0007] Based on one of the purposes of the present invention, the present invention also provides a preparation method of the zinc diacrylate resin grafted with 1,2-benzisothiazol-3-one structure.

[0008] 2. Technical Solutions

[0009] To solve the above problems, the technical solutions adopted by the present invention are as follows:

[0010] According to one of the purposes of the present invention, there is provided a zinc diacrylate resin grafted with 1,2-benzisothiazol-3-one structure, and the resin has a structure shown in formula (Ⅰ-1):

[0011]

[0012] In the formula,

[0013] R 1 is selected from one of -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 ;

[0014] R 2 is selected from one of -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 ;

[0015] R3 Selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 ; and one of the following

[0016] R 4 Selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 ; and one of the following

[0017] wherein L, M, and N respectively correspond to the addition ratio of monomers of benz[d]isothiazol-3-one compounds, zinc acrylate monomers, methyl methacrylate monomers, and butyl acrylate monomers.

[0018] The zinc diacrylate resin grafted with a 1,2-benz[d]isothiazol-3-one structure according to any embodiment of the first aspect of the first object of the present invention, the resin has a structure shown in formula (I-2):

[0019]

[0020] In the formula

[0021] R 1 Selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 ; and one of the following

[0022] R 2 Selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2, -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 ; one of the following:

[0023] R 3 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 ; one of the following:

[0024] R 4 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 ; one of the following:

[0025] The zinc bisacrylate resin grafted with 1,2 - benzisothiazolin - 3 - one structure according to any embodiment of the first aspect of the first object of the present invention is polymerized from benzisothiazolin - 3 - one compound monomers, zinc acrylate monomers, methyl methacrylate monomers and butyl acrylate monomers.

[0026] The zinc bisacrylate resin grafted with 1,2 - benzisothiazolin - 3 - one structure according to any embodiment of the first aspect of the first object of the present invention, the benzisothiazolin - 3 - one compound monomer has the structure shown in formula (Ⅱ):

[0027]

[0028] wherein, R 1 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3, one of -CN;

[0029] R 1 preferably selected from -H, -CH 3 one of them.

[0030] The zinc acrylate monomer has the structure shown in formula (Ⅲ):

[0031]

[0032] wherein, R 2 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 one of them;

[0033] R 3 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 one of them;

[0034] Preferably, R 2 is selected from -H, -CH 3 one of them;

[0035] R 3 is selected from -H, -CH 3 one of them.

[0036] The second object of the present invention is to provide a preparation method of a zinc diacrylate resin grafted with 1,2-benzisothiazol-3-one structure, and the method includes:

[0037] In an organic solvent, a benzisothiazol-3-one compound monomer, a zinc acrylate monomer, a methyl methacrylate monomer and a butyl acrylate monomer are copolymerized under the action of an initiator;

[0038] The preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure according to any embodiment of the first aspect of the second object of the present invention, calculated by mass ratio, the dosage ratio of the benzisothiazol-3-one compound monomer, zinc acrylate monomer, methyl methacrylate monomer and butyl acrylate monomer is (1-20):(1-20):(3-20):(3-20).

[0039] Preferably, the dosage ratio of the benzisothiazol-3-one compound monomer, zinc acrylate monomer, methyl methacrylate monomer and butyl acrylate monomer is (2-9):(2-9):(3-10):(3-10);

[0040] More preferably, the dosage ratio of the benzisothiazol-3-one compound monomer, zinc acrylate monomer, methyl methacrylate monomer and butyl acrylate monomer is (3-6):(3-6):(4-7):(4-7).

[0041] The preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure according to any embodiment of the first aspect of the second object of the present invention, calculated by mass ratio, the amount of the organic solvent is 3-7 times the amount of the benzisothiazol-3-one compound monomer; preferably 4-6 times, and most preferably 5 times.

[0042] The preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure according to any embodiment of the first aspect of the second object of the present invention includes the following steps:

[0043] (A) Prepare a mixed solution of a benzisothiazol-3-one compound monomer, a zinc acrylate monomer, a methyl methacrylate monomer, a butyl acrylate monomer and an initiator;

[0044] Prepare an organic solvent

[0045] (B) Mix the mixed solution with the organic solvent in a dropwise manner;

[0046] (C) After mixing is completed, carry out heat preservation treatment, and add an initiator during this period.

[0047] In the preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure according to any embodiment of the first aspect of the second object of the present invention, in step (B), the dropping temperature is 60-90 °C; the dropping rate is 1-4 s / d; preferably the dropping rate is 2-3 s / d.

[0048] According to the preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure in any embodiment of the first aspect of the second object of the present invention, in step (C), the heat preservation temperature is 60-90 °C; the total heat preservation time is 6-12 h.

[0049] According to the preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure in any embodiment of the first aspect of the second object of the present invention, in step (C), after step (B) ends, heat preservation treatment is started. When the heat preservation time reaches 2-3 h, the remaining initiator is added, and then heat preservation continues for 3-9 h.

[0050] According to the preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure in any embodiment of the first aspect of the second object of the present invention, calculated by mass ratio, the usage amount of the initiator in step (A) accounts for 30 wt%-70 wt% of the total amount of the initiator; preferably, the usage amount of the initiator in step (A) accounts for 40 wt%-60 wt% of the total amount of the initiator;

[0051] The usage amount of the initiator in step (C) accounts for 30 wt%-70 wt% of the total amount of the initiator; preferably, the usage amount of the initiator in step (C) accounts for 40 wt%-60 wt% of the total amount of the initiator;

[0052] According to the preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure in any embodiment of the first aspect of the second object of the present invention, the initiator includes any one or two of azobisisobutyronitrile and benzoyl peroxide.

[0053] According to the preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure in any embodiment of the first aspect of the second object of the present invention, the organic solvent is one or a mixture of two or more of dichloromethane, chloroform, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide (HMPA), alcohol (such as methanol, ethanol, n-butanol, etc.);

[0054] Preferably, the organic solvent is xylene and n-butanol.

[0055] Based on the first object of the present invention and any of the technical solutions thereof, or based on the second object of the present invention and any of the technical solutions thereof, the third object of the present invention is to provide an application of a zinc bisacrylate resin grafted with a 1,2-benzisothiazol-3-one structure, and apply the zinc bisacrylate resin grafted with a 1,2-benzisothiazol-3-one structure to anti-fouling. For example, apply the zinc bisacrylate resin grafted with a 1,2-benzisothiazol-3-one structure to the preparation of marine anti-fouling coatings.

[0056] Based on the first object of the present invention and any of the technical solutions thereof, or based on the second object of the present invention and any of the technical solutions thereof, the third object of the present invention is to provide a marine anti-fouling coating, and the marine anti-fouling coating contains the zinc bisacrylate resin grafted with a 1,2-benzisothiazol-3-one structure.

[0057] Beneficial effects

[0058] (1) The zinc bisacrylate resin grafted with a 1,2-benzisothiazol-3-one structure provided by the present invention grafts both bifunctional zinc acrylate and benzisothiazol-3-one onto the acrylic resin, and prepares a multifunctional marine anti-fouling coating with self-polishing performance and high-efficiency sterilization performance, which is suitable for both dynamic waters and static waters, has low cost and simple process, and makes up for the deficiencies of single-type anti-fouling coatings;

[0059] The results of the actual sea hanging panel test show that the zinc bisacrylate resin grafted with a 1,2-benzisothiazol-3-one structure has good algae growth inhibition, anti-biofouling performance and excellent long-term and high-efficiency marine anti-fouling effect.

[0060] (2) The preparation method of the zinc bisacrylate resin grafted with a 1,2-benzisothiazol-3-one structure provided by the present invention only needs to carry out a free radical copolymerization reaction by heating at 70-100 °C to prepare the corresponding zinc bisacrylate resin grafted with a 1,2-benzisothiazol-3-one structure. The method is mild and simple, can achieve large-scale batch production under economic conditions, and has good market prospects in the field of marine anti-fouling coatings.

[0061] (3) Apply the zinc bisacrylate resin grafted with a 1,2-benzisothiazol-3-one structure provided by the present invention to anti-fouling coatings or compositions, and coat the anti-fouling coatings alone or mixed with other components on the surfaces of marine ships and solid buildings, which can effectively inhibit the growth of marine organisms, especially the growth of algal marine organisms;

[0062] During its application process, the antifouling effect of the marine antifouling agent is less affected by seasonal climate and environmental temperature changes, and it has good antifouling effects at different temperatures, having broad development prospects and application values. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] Figure 1 Acrylate antifouling resin grafted with benzisothiazolinone formate monomer;

[0064] Figure 2 Schematic diagram of the morphology of resin plates coated with different resins for in-sea panel test. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0065] The present disclosure can be more easily understood by referring to the following description in conjunction with the accompanying drawings and examples, all of which form a part of the present disclosure. It should be understood that the present disclosure is not limited to the specific products, methods, conditions or parameters described and / or illustrated herein. Further, the terms used herein are for the purpose of describing specific embodiments by way of example only and are not intended to be limiting, unless otherwise specified.

[0066] It should also be understood that, for the sake of clarity, certain features of the present disclosure may be described herein in the context of separate embodiments, but may also be provided in combination with each other in a single embodiment. That is, unless clearly incompatible or specifically excluded, each separate embodiment is considered combinable with any other embodiment, and such combination is considered to represent another different embodiment. Conversely, for the sake of brevity, the various features of the present disclosure described in the context of a single embodiment may also be provided separately or in any sub-combination. Finally, although a particular embodiment may be described as part of a series of steps or part of a more general structure, each step or sub-structure itself may also be considered an independent embodiment.

[0067] Unless otherwise specified, it should be understood that each individual element in a list and each combination of individual elements in the list will be interpreted as a different embodiment. For example, a list of embodiments represented as "A, B or C" should be interpreted as including the embodiments "A", "B", "C", "A or B", "A or C", "B or C" or "A, B or C".

[0068] In the present disclosure, the singular forms of the articles "a", "an" and "the" also include the corresponding plural referents, and the reference to a particular numerical value includes at least that particular value, unless the context clearly indicates otherwise. Thus, for example, the reference to "a substance" is a reference to at least one of such substance and its equivalents.

[0069] Terms including ordinal numbers such as "first" and "second" may be used to explain various components or fluids, but these components and fluids are not limited by these terms. Thus, without departing from the teachings of the present disclosure, these terms are only used to distinguish one component / fluid from another component / fluid.

[0070] When describing items by using associative terms such as "…… and / or ……" etc., the description should be understood to include any one of the associated listed items and all combinations of one or more thereof.

[0071] Generally, the use of the term "about" indicates an approximation that may vary according to the desired characteristics obtained through the disclosed subject matter, and will be interpreted in a context-dependent manner based on functionality. Thus, those of ordinary skill in the art will be able to interpret a certain degree of difference on a case-by-case basis. In some cases, the number of significant digits used when expressing a particular value may be a representative technique for determining the difference allowed by the term "about". In other cases, the gradient in a series of values may be used to determine the range of difference allowed by the term "about". Further, all ranges in the present disclosure are inclusive and combinable, and the mention of values described in the range includes each value within that range.

[0072] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which this invention belongs; the terms used herein and / or include any and all combinations of one or more of the associated listed items.

[0073] Regarding the existing zinc acrylate resin in antifouling coatings, the main problems currently faced include short antifouling period effect, unclear antifouling effect in static waters, etc. The present invention provides a zinc bisacrylate resin grafted with a 1,2-benzisothiazol-3-one structure. The idea is to graft a benzisothiazolone compound (abbreviated as BIT compound) with a zinc bisacrylate monomer, hoping to combine the low toxicity, high stability, high-efficiency broad-spectrum algicidal property, antibacterial activity, etc. of the benzisothiazolone compound (abbreviated as BIT compound) with the advantages of the zinc acrylate resin to form a new idea suitable for marine antifouling. Especially Figure 1 Represented by, the BIT compound with an ester group is the initial focus of the new idea design. Because of the presence of the ester group, it is easier for the heterocycle in the structure of this type of BIT compound to release, form a hydrogen bond with the base in the protein in the bacterial body, thereby destroying the structure of intracellular DNA and making it lose the replication ability, thus playing a role in killing bacteria and exerting its high-efficiency bactericidal and algicidal properties.

[0074] However, a major obstacle encountered during the research was that the preparation cycle of this type of BIT compound with an ester group was as long as several days, and the steps were complex, which was contrary to the current development direction of new self-polishing antifouling coatings that require simple processes. Based on this, subsequent researchers found that grafting the BIT compound shown in formula (II) used in the present invention with a zinc diacrylate monomer, the finally prepared resin had an antifouling effect comparable to that of the resin prepared using the BIT compound with an ester group, which was the initial focus of attention, and greatly simplified the preparation process and cycle. Further research found that the reason was that the product purity of this type of BIT compound with an ester group in the product prepared by its process was not ideal. On this basis, graft polymerization with zinc acrylate monomer, methyl methacrylate monomer, and butyl acrylate monomer as raw materials would also indirectly affect the purity of the obtained product and its antifouling effect during actual use.

[0075] Under this background, the present invention provides a zinc diacrylate resin grafted with a 1,2-benzisothiazol-3-one structure, and the zinc diacrylate resin grafted with a 1,2-benzisothiazol-3-one structure has a structure shown in formula (I):

[0076]

[0077] In the formula,

[0078] R 1 is selected from one of -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 ;

[0079] R 2 is selected from one of -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 ;

[0080] R 3 is selected from -H, -CH 3 , -CH 2 CH3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 one of the following;

[0081] R 4 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 one of the following.

[0082] Among them, L, M, and N respectively correspond to the addition ratio of the monomers of benzod[d]isothiazolin-3-one compound, zinc acrylate monomer, methyl methacrylate monomer, and butyl acrylate monomer.

[0083] Furthermore, the zinc diacrylate resin grafted with 1,2-benzod[d]isothiazolin-3-one structure as described above is copolymerized from four monomers: the monomer of benzod[d]isothiazolin-3-one compound, the zinc acrylate monomer with bifunctional groups, methyl methacrylate monomer, and butyl acrylate monomer are polymerized; among them,

[0084] the monomer of the benzod[d]isothiazolin-3-one compound has the structure shown in formula (Ⅱ):

[0085]

[0086] Among them, R 1 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN one of the following;

[0087] the zinc acrylate monomer has the structure shown in formula (Ⅲ):

[0088]

[0089] Among them, R2 Selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 ; one selected from the group consisting of

[0090] R 3 Selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 ; one selected from the group consisting of

[0091] The preparation method of the above-mentioned zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure includes:

[0092] (A) Prepare a mixed solution: First dissolve the benzisothiazol-3-one compound monomer in DMF, and dissolve the bifunctional zinc acrylate monomer in dichloromethane; then mix the above two with methyl methacrylate monomer, butyl acrylate monomer and initiator;

[0093] Prepare an organic solvent

[0094] (B) Drop the above mixed solution into the organic solvent at a temperature of 60-90 °C. After the dropping is completed, carry out heat preservation treatment to finally obtain a transparent viscous liquid, which is the co-grafted zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure;

[0095] The dropping rate is 0.5-10 s / d, preferably 3-5 s / d;

[0096] The total time from the start of dropping to the end of treatment is 6-12 h;

[0097] After the dropping is completed, start heat preservation treatment. After heat preservation for 2-3 h, add the remaining initiator, and then continue heat preservation for 3-9 h. The total heat preservation treatment time is 6-12 h.

[0098] Schematically, the initiator can be selected from, for example, azobisisobutyronitrile or benzoyl peroxide, or a mixture of azobisisobutyronitrile or benzoyl peroxide.

[0099] Schematically, the organic solvent can be selected from any one or a mixture of any two or more of, for example, dichloromethane, chloroform, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide (HMPA), alcohols (such as methanol, ethanol, n-butanol, etc.); preferably a mixture of xylene and n-butanol, and the two are mixed in a mass ratio of (3 - 5):1, preferably in a mass ratio of (3.5 - 4.5):1, and more preferably in a mass ratio of 4:1.

[0100] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, specific embodiments will be listed below to explain the present invention in more detail. Obviously, the described embodiments are part of rather than all of the embodiments of the present application. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present application without creative efforts fall within the scope of protection of the present application.

[0101] Example 1

[0102] Prepare the monomer of benzothiazole - 3 - one compound: 2 - acryloylbenzothiazole - 3 - one monomer A;

[0103] In a three - necked flask equipped with a stirring device, add 30 mL of toluene, and control the temperature below 10 °C using an ice - water bath. Sequentially add 4.53 g of benzothiazole - 3 - one and 3.03 g of triethylamine. After mixing 8.15 g of acryloyl chloride and 20 mL of toluene, add the mixture dropwise to the three - necked flask, control the dropping rate to keep the temperature at 0 - 10 °C. After the dropping is complete, react for another 0.5 h and then naturally warm up to room temperature, and continue stirring and reacting for 4 h. Transfer the reaction solution to a separatory funnel for washing and extraction, pour out the toluene layer and dry it with anhydrous magnesium sulfate for 12 h. After drying, filter to remove anhydrous magnesium sulfate, and concentrate the filtrate by vacuum distillation to remove the solvent, thus obtaining 2 - acryloylbenzothiazole - 3 - one.

[0104] Example 2

[0105] Prepare the monomer of benzothiazole - 3 - one compound: 2 - methacryloylbenzothiazole - 3 - one monomer B;

[0106] In a three-necked flask equipped with a stirring device, add 30 mL of toluene, and control the temperature below 10 °C using an ice-water bath. Sequentially add 5.00 g of benz[d]isothiazol-3-one and 3.33 g of triethylamine. After mixing 7.65 g of methacrylic anhydride and 20 mL of toluene, add it dropwise to the three-necked flask, controlling the dropping rate to maintain the temperature at 0 - 10 °C. After the dropping is complete, react for another 0.5 h and then naturally warm up to room temperature, and continue stirring and reacting for 4 h. Transfer the reaction solution to a separatory funnel for washing and extraction. Pour out the toluene layer and dry it with anhydrous magnesium sulfate for 12 h. After drying, filter to remove anhydrous magnesium sulfate, and concentrate the filtrate by vacuum distillation to remove the solvent, thus obtaining 2-methacryloylbenz[d]isothiazol-3-one.

[0107] Example 3

[0108] Preparation of (bifunctional) zinc acrylate monomer: acryloyloxymethacryloyloxy zinc monomer 1;

[0109] Sequentially add 10 g of freshly prepared zinc hydroxide solid and 70 mL of xylene to a three-necked flask, and ultrasonically stir and disperse for 30 min. Take 7.2 g of acrylic acid, mix it with 30 mL of xylene, and transfer it to a constant-pressure funnel. Under the condition of 70 °C, slowly add it dropwise to the three-necked flask. After the dropping is complete, maintain the temperature and continue stirring for 0.5 h. Then take 10.34 g of methacrylic acid, mix it with 30 mL of xylene, and add it dropwise to the flask in the same operation as above. After the dropping is complete, turn off the heating and react for 1 h. After the reaction is complete, filter the reaction solution and wash it several times with xylene. Dry the filter cake at 50 °C to obtain a white powder. Dissolve the obtained white powder in dichloromethane, filter off the undissolved impurities, and concentrate the filtrate to remove the solvent to obtain acryloyloxymethacryloyloxy zinc monomer.

[0110] Example 4

[0111] Preparation of (bifunctional) zinc acrylate monomer: bisacryloyloxy zinc monomer 2;

[0112] Sequentially add 10 g of freshly prepared zinc hydroxide solid and 70 mL of xylene to a three-necked flask, and ultrasonically stir and disperse for 30 min. Take 14.4 g of acrylic acid, mix it with 60 mL of xylene, and transfer it to a constant-pressure funnel. Under the condition of 70 °C, slowly add it dropwise to the three-necked flask. After the dropping is complete, turn off the heating and react for 1 h. After the reaction is complete, filter the reaction solution and wash it several times with xylene. Dry the filter cake at 50 °C to obtain a white powder. Dissolve the obtained white powder in dichloromethane, filter off the undissolved impurities, and concentrate the filtrate to remove the solvent to obtain bisacryloyloxy zinc monomer.

[0113] Example 5

[0114] Preparation of (bifunctional) zinc acrylate monomer: bismethacryloyloxy zinc monomer 3;

[0115] Add 10 g of freshly prepared zinc hydroxide solid and 70 mL of xylene to a three-necked flask in sequence, and ultrasonically stir and disperse for 30 min. Mix 17.2 g of methacrylic acid with 60 mL of xylene and transfer it to a constant-pressure funnel. Under the condition of 70 °C, slowly add it dropwise to the three-necked flask. After the addition is completed, turn off the heating and react for another 1 h. After the reaction is completed, filter the reaction solution and wash it several times with xylene. Dry the filter cake at 50 °C to obtain a white powder. Dissolve the obtained white powder in dichloromethane, filter off the undissolved impurities, and concentrate the filtrate to remove the solvent to obtain the dimethacryloyloxy zinc monomer.

[0116] Example 6

[0117] Prepare a zinc acrylate resin grafted with 1,2-benzisothiazol-3-one structure: Zinc acrylate self-polishing antifouling resin A-1 containing benzisothiazol-3-one monomer.

[0118] In a 100 mL three-necked flask equipped with a stirring device, add 40 parts of xylene and 10 parts of n-butanol in sequence, and heat up to 85 °C. Add 10 parts of 2-acryloylbenzisothiazol-3-one monomer (first dissolved in DMF), 10 parts of acryloyloxymethacryloyloxy zinc monomer (first dissolved in dichloromethane), 3 parts of AIBN, 20 parts of methyl methacrylate, and 10 parts of butyl acrylate to a constant-pressure funnel, and slowly add it dropwise to the flask. The addition is completed in 2 - 3 hours, continue to keep warm for 3 hours, then add the remaining 1 part of AIBN, continue to keep warm for 8 hours, and cool to room temperature to obtain zinc acrylate self-polishing antifouling resin A-1 containing benzisothiazol-3-one monomer.

[0119] Example 7

[0120] Prepare a zinc acrylate resin grafted with 1,2-benzisothiazol-3-one structure: Zinc acrylate self-polishing antifouling resin A-2 containing benzisothiazol-3-one monomer;

[0121] In a 100 mL three-necked flask equipped with a stirring device, add 40 parts of xylene and 10 parts of n-butanol in sequence, and heat up to 85 °C. Add 10 parts of 2-acryloylbenzisothiazol-3-one monomer (first dissolved in DMF), 10 parts of dimethacryloyloxy zinc monomer (first dissolved in dichloromethane), 3 parts of AIBN, 20 parts of methyl methacrylate, and 10 parts of butyl acrylate to a constant-pressure funnel, and slowly add it dropwise to the flask. The addition is completed in 2 - 3 hours, continue to keep warm for 3 hours, then add the remaining 1 part of AIBN, continue to keep warm for 8 hours, and cool to room temperature to obtain zinc acrylate self-polishing antifouling resin A-2 containing benzisothiazol-3-one monomer.

[0122] Example 8

[0123] Preparation of zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure: Zinc acrylate self-polishing antifouling resin A-3 containing benzisothiazol-3-one monomer;

[0124] In a 100 mL three-necked flask equipped with a stirring device, 40 parts of xylene and 10 parts of n-butanol were added in sequence, and the temperature was raised to 85 °C. 10 parts of 2-acryloylbenzisothiazol-3-one monomer (first dissolved in DMF), 10 parts of zinc dimethacryloxy monomer (first dissolved in dichloromethane), 3 parts of AIBN, 20 parts of methyl methacrylate, and 10 parts of butyl acrylate were added to the constant pressure funnel and slowly dropped into the flask. The dropping was completed in 2 - 3 hours, and the temperature was kept for 3 hours. Then, the remaining 1 part of AIBN was added, and the temperature was kept for another 8 hours. After cooling to room temperature, zinc acrylate self-polishing antifouling resin A-3 containing benzisothiazol-3-one monomer was obtained.

[0125] Example 9

[0126] Preparation of zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure: Zinc acrylate self-polishing antifouling resin B-1 containing benzisothiazol-3-one monomer;

[0127] In a 100 mL three-necked flask equipped with a stirring device, 40 parts of xylene and 10 parts of n-butanol were added in sequence, and the temperature was raised to 85 °C. 10 parts of 2-methacryloylbenzisothiazol-3-one monomer (first dissolved in DMF), 10 parts of acryloxymethacryloxy zinc monomer (first dissolved in dichloromethane), 3 parts of AIBN, 20 parts of methyl methacrylate, and 10 parts of butyl acrylate were added to the constant pressure funnel and slowly dropped into the flask. The dropping was completed in 2 - 3 hours, and the temperature was kept for 3 hours. Then, the remaining 1 part of AIBN was added, and the temperature was kept for another 8 hours. After cooling to room temperature, zinc acrylate self-polishing antifouling resin B-1 containing benzisothiazol-3-one monomer was obtained.

[0128] Example 10

[0129] Preparation of zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure: Zinc acrylate self-polishing antifouling resin B-2 containing benzisothiazol-3-one monomer;

[0130] In a 100 mL three-necked flask equipped with a stirring device, 40 parts of xylene and 10 parts of n-butanol were added in sequence, and the temperature was raised to 85 °C. 10 parts of 2-methacryloylbenzothiazole-3-one monomer (first dissolved in DMF), 10 parts of bisacryloyloxy zinc monomer (first dissolved in dichloromethane), 3 parts of AIBN, 20 parts of methyl methacrylate, and 10 parts of butyl acrylate were added to a constant pressure funnel and slowly dropped into the flask. The dropping was completed in 2 - 3 hours, and the mixture was kept warm for another 3 hours. Then, the remaining 1 part of AIBN was added, and it was kept warm for 8 hours. After cooling to room temperature, a zinc acrylate self-polishing antifouling resin B-2 containing benzothiazole-3-one monomer was obtained.

[0131] Example 11

[0132] Preparation of a zinc diacrylate resin grafted with a 1,2-benzothiazole-3-one structure: zinc acrylate self-polishing antifouling resin B-3 containing benzothiazole-3-one monomer;

[0133] In a 100 mL three-necked flask equipped with a stirring device, 40 parts of xylene and 10 parts of n-butanol were added in sequence, and the temperature was raised to 85 °C. 10 parts of 2-methacryloylbenzothiazole-3-one monomer (first dissolved in DMF), 10 parts of bis-methacryloyloxy zinc monomer (first dissolved in dichloromethane), 3 parts of AIBN, 20 parts of methyl methacrylate, and 10 parts of butyl acrylate were added to a constant pressure funnel and slowly dropped into the flask. The dropping was completed in 2 - 3 hours, and the mixture was kept warm for another 3 hours. Then, the remaining 1 part of AIBN was added, and it was kept warm for 8 hours. After cooling to room temperature, a zinc acrylate self-polishing antifouling resin B-3 containing benzothiazole-3-one monomer was obtained.

[0134] Example 13

[0135] Preparation of a zinc diacrylate resin grafted with a 1,2-benzothiazole-3-one structure: zinc acrylate self-polishing antifouling resin B-3 containing benzothiazole-3-one monomer;

[0136] In a 100 mL three-necked flask equipped with a stirring device, 40 parts of xylene and 10 parts of n-butanol were added in sequence, and the temperature was raised to 85 °C. 20 parts of 2-methacryloylbenzothiazole-3-one monomer (first dissolved in DMF), 20 parts of bis-methacryloyloxy zinc monomer (first dissolved in dichloromethane), 1 part of AIBN, 10 parts of methyl methacrylate, and 20 parts of butyl acrylate were added to a constant pressure funnel and slowly dropped into the flask. The dropping was completed in 2 - 3 hours, and the mixture was kept warm for another 3 hours. Then, the remaining 3 parts of AIBN were added, and it was kept warm for 8 hours. After cooling to room temperature, a zinc acrylate self-polishing antifouling resin B-3 containing benzothiazole-3-one monomer was obtained.

[0137] Example 13

[0138] To describe the resin properties of the present invention, taking the antifouling resins prepared in Examples 6-11 of the present invention as examples, its main performance characterizations include: antibacterial performance, algal inhibition performance test, antifouling performance, and antifouling agent release amount test.

[0139] The test groups include:

[0140] (1) Experimental group: Resins A-1 - A-3, Resins B-1 - B-3;

[0141] The above resins were respectively coated on different glass plates to form the target resin plates of the experimental group;

[0142] (2) Blank group: Blank resin plate: A glass plate without coating resin was used as the blank group;

[0143] 【1】Antibacterial performance test, and its performance test method is as follows:

[0144] The specific information of its performance test is as follows: The antibacterial performance was tested using common Escherichia coli and Staphylococcus aureus. The obtained bacterial strains were added to tryptone soy broth TSB medium (0.1 g / mL), placed on a shaker for activation for 12 hours, and then the above steps were repeated for secondary activation to obtain the antibacterial test bacterial solution used. It should be noted that if the bacteria are only activated once, the activity is insufficient and they cannot grow and reproduce rapidly, which will affect the antibacterial performance test. Then the resin was coated on a 6-well plate, and the corresponding bacterial solution was added thereto. After culturing in a constant temperature incubator at 37 °C for 12 h and 24 h, 60 μL of the bacterial solution was aspirated into a 96-well plate, and the absorbance of the bacterial solution was measured at 600 nm. The inhibition rate of each resin against the two bacteria was calculated based on the absorbance of the bacterial solution.

[0145] It was found through testing that, compared with the blank group, for the resin plates of the experimental group coated with Resins A-1 - A-3 and B-1 - B-3 prepared by the present invention, at 12 h, the inhibition rates against Escherichia coli and Staphylococcus aureus could both reach 100%; at 24 h, the inhibition rates against Escherichia coli and Staphylococcus aureus could also both reach 100%.

[0146] The above shows that the zinc acrylate self-polishing antifouling resin containing 1,2-benzisothiazol-3(2H)-one monomer prepared by the present invention has good ability to inhibit bacterial growth.

[0147] 【2】Algal inhibition performance test: The algal inhibition performance was tested by the absorbance method;

[0148] (1) The algal inhibition performance was tested using Chlorella vulgaris and Chaetoceros curvisetus, and the operation process description:

[0149] First, dilute the cultured algal solution with boiled seawater to an absorbance of about 0.05 Abs. At this time, the algae are in the rapid growth stage of the S growth curve. Then, take 200 mL of the algal solution and add it to a plastic cup. Place a resin plate in it and ensure that the room temperature is around 25°C. Measure the absorbance of the algal solution on the 7th day, and calculate the inhibition rate of the corresponding resin according to the absorbance of the algal solution, as shown in the following table. It should be noted that the suitable growth temperature of Chlorella is between 25 - 30°C, and the suitable growth temperature of Chaetoceros curvisetus is between 20 - 25°C. If the temperature is too low, it will affect the growth of algae and cause a large deviation in the test of algal inhibition performance. Therefore, the temperature is ensured to be between 25 - 30°C in this test.

[0150] Table 1 Algal inhibition rate of each resin plate on the 7th day

[0151] Name Chlorella Chaetoceros curvisetus Blank 0 0 Resin A-1 89.65％ 90.23％ Resin A-2 92.18％ 93.65％ Resin A-3 90.43％ 92.10％ Resin B-1 88.94％ 89.38％ Resin B-2 91.52％ 92.47％ Resin B-3 92.87％ 93.89％

[0152] As shown in Table 1, it can be seen from the table of the algal inhibition rate of each resin plate on the 7th day that

[0153] Compared with the blank group, the resin plate coated with the resin prepared by the present invention has good inhibitory effects on both Chlorella and Chaetoceros curvisetus;

[0154] The above shows that the zinc acrylate self-polishing antifouling resin containing 1,2-benzisothiazol-3(2H)-one monomer prepared by the present invention has good ability to inhibit the growth of marine algae; even in the case of relatively high temperature, it still has a good algal inhibition rate.

[0155] 【3】Antifouling performance test: Refer to the national standard "Test Method for Submerged Exposure of Antifouling Paint Panels in Shallow Sea" to evaluate the antifouling performance of the prepared antifouling coatings.

[0156] (1) The performance test method is as follows: The antifouling performance test refers to the national standard "Test Method for Submerged Exposure of Antifouling Paint Panels in Shallow Sea", and real-sea panel hanging is carried out in the shallow sea of Haikou Bay, Haikou City, Hainan Province. The total panel hanging time is 60 days. During this period, there are mainly algae, barnacles, oysters, etc. growing in the sea. Take pictures once every 30 days after panel hanging, and evaluate the antifouling performance of the resin of the present invention according to the biological attachment situation on the panel. Finally, the biological coverage rates of each resin plate are shown in Table 2.

[0157] Table 2 Biological coverage rates of each resin plate in real-sea panel hanging

[0158]

[0159] According to Figure 2 the pictures of the sea panel hanging, it can be seen that after 30 days of panel hanging, there are obvious seaweeds and a small amount of barnacles on the blank panel, while there is no obvious attachment of marine animals and plants on the plate coated with the zinc acrylate self-polishing antifouling resin containing 1,2-benzisothiazol-3(2H)-one monomer prepared by the present invention, showing good performance in inhibiting algal growth.

[0160] After 60 days of hanging the board, the blank sample boards were covered with organisms such as barnacles, mussels and a large amount of seaweed, and there was also a lot of green algae accumulation on the PBH-0 resin board. However, on the resin board coated with the zinc acrylate self-polishing antifouling resin containing 1,2-benzisothiazol-3(2H)-one monomer prepared by the present invention, there was still almost no attachment of organisms, especially large fouling organisms. This again shows that the resin of the zinc acrylate self-polishing antifouling resin containing 1,2-benzisothiazol-3(2H)-one monomer prepared by the present invention has good antifouling performance.

[0161] 【4】Antifouling agent release amount test: Refer to the national standard "Test Method for Submerged Exposure of Antifouling Paint Panels in Shallow Sea" to evaluate the antifouling performance of the prepared antifouling coatings.

[0162] (1) The performance test method is as follows:

[0163] Using resin boards with the same mass of each resin added physically as a control, after natural air drying, they were placed in the same volume of filtered seawater, and the total content of BIT in the solution was measured every 5 days. The antifouling agent release rate is shown in Table 3 below.

[0164] Table 3 Antifouling agent release amount (mg / cm 2 )

[0165]

[0166]

[0167] It can be seen from Table 3 of the antifouling agent release amount of each resin board every 5 days that the release amount is in the range of 0.03 - 0.06 mg / (cm 2 ·d), and with the increase of the immersion time, the mass loss rate does not decrease, but is slow and stable all the time, indicating that the antifouling agent in the resin can be released slowly and steadily for a long time, so that the antifouling can be carried out effectively for a long time.

[0168] The above description is not a limitation of the present invention, and the present invention is not limited to the above examples. Those of ordinary skill in the art within the scope of the essence of the present invention, making structural changes, adding or replacing substituents, all belong to the protection scope of the present invention.

Claims

1. Preparation method of a zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure, characterized in that, in an organic solvent, a benzisothiazol-3-one compound monomer, a zinc acrylate monomer, a methyl methacrylate monomer and a butyl acrylate monomer are copolymerized under the action of an initiator; calculated by mass ratio, the dosage ratio of the benzisothiazol-3-one compound monomer, the zinc acrylate monomer, the methyl methacrylate monomer and the butyl acrylate monomer is (1-20):(1-20):(3-20):(3-20); wherein, the benzisothiazol-3-one compound monomer has the structure shown in formula (Ⅱ): Formula (Ⅱ) Among them, R 1 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ), 2 , -C(CH 3 ), 3 , -F, -Cl, -Br, -SCH 3 , -CN; the zinc acrylate monomer has the structure shown in formula (Ⅲ): Formula (Ⅲ) wherein, R 2 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 ; and R 3 Selected from -H, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -F, -Cl, -Br, -SCH 3 , -CN, -COCH 3 and one of them.

2. The preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure according to claim 1, characterized in that, The said R 1 is selected from -H, -CH 3 and one of the following; The R 2 is selected from -H, -CH 3 ; and one of them R 3 Selected from -H, -CH 3 One of them.

3. The preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure according to claim 2, characterized in that, comprises the following steps: (A)Prepare a mixed solution of a benzisothiazol-3-one compound monomer, a zinc acrylate monomer, a methyl methacrylate monomer, a butyl acrylate monomer and an initiator; Prepare an organic solvent (B)Mix the mixed solution with the organic solvent in a dropping manner; (C)After mixing is completed, enter the heat preservation treatment, and add an initiator during this period.

4. The preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure according to claim 3, characterized in that, in step (B), the dropping temperature is 60-90 °C; the dropping speed is 1-4 d / s; and / or, in step (C), the heat preservation temperature is 60-90 °C; the total heat preservation time is 6-12 h; and / or, in step (C), after heat preservation treatment for 2-3 h, add the remaining initiator and continue the heat preservation treatment; and / or, calculated by mass ratio, the usage amount of the initiator in step (A) accounts for 30wt%-70wt% of the total amount of the initiator; the total usage amount of the initiator in step (C) accounts for 30wt%-70wt% of the total amount of the initiator.

5. The preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure according to claim 3, characterized in that, the dropping speed is 2-3 d / s.

6. The preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure according to claim 3, characterized in that, the initiator includes any one or two of azobisisobutyronitrile and benzoyl peroxide.

7. The preparation method of the zinc bisacrylate resin grafted with 1,2-benzisothiazol-3-one structure according to claim 3, characterized in that, The organic solvent is any one or a mixture of two or more of dichloromethane, chloroform, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, methanol, ethanol, and n-butanol.

8. A zinc bisacrylate resin grafted with a 1,2-benzisothiazol-3-one structure Characterized in that It is prepared by the method according to any one of claims 1 to 7.

9. Use of the zinc bisacrylate resin grafted with a 1,2-benzisothiazol-3-one structure prepared by the method according to any one of claims 1 to 7 Characterized in that It is used for marine antifouling.

10. An antifouling paint or antifouling composition Characterized in that It contains the zinc bisacrylate resin grafted with a 1,2-benzisothiazol-3-one structure prepared by the method according to any one of claims 1 to 7.

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