阅读说明：本技术 聚丙烯酸锌/类辣椒素共聚物及其制备方法、防污涂料 (Zinc polyacrylate/capsaicinoid copolymer, preparation method thereof and antifouling paint ) 是由 沈小兵 许恒 管慧博 姚赞新 韩晓明 程江 解奎元 张驰 李盾 易俊松 于 2021-10-15 设计创作，主要内容包括：本发明涉及一种聚丙烯酸锌/类辣椒素共聚物及其制备方法、防污涂料。所述聚丙烯酸锌/类辣椒素共聚物的制备方法,包括如下步骤：将类辣椒素单体与丙烯酸类单体进行共聚反应,制备预聚物；将所述预聚物与锌盐进行交联反应,制备所述聚丙烯酸锌/类辣椒素共聚物；所述类辣椒素单体为N-苯基马来酰亚胺和/或8-甲基-N-[(4-羟基-3-甲氧基苯基)-甲基]-(反)-6-壬烯基酰胺。上述制备方法制备得到的聚丙烯酸锌/类辣椒素共聚物具有较长的防污寿命。(The invention relates to a zinc polyacrylate/capsaicinoid copolymer, a preparation method thereof and an antifouling paint. The preparation method of the zinc polyacrylate/capsaicinoid copolymer comprises the following steps: carrying out copolymerization reaction on a capsaicinoid monomer and an acrylic acid monomer to prepare a prepolymer; carrying out crosslinking reaction on the prepolymer and zinc salt to prepare the zinc polyacrylate/capsaicinoid copolymer; the capsaicinoid monomer is N-phenylmaleimide and/or 8-methyl-N- [ (4-hydroxy-3-methoxyphenyl) -methyl ] - (trans) -6-nonenylamide. The zinc polyacrylate/capsaicinoid copolymer prepared by the preparation method has longer antifouling life.)

1. The preparation method of the zinc polyacrylate/capsaicinoid copolymer is characterized by comprising the following steps:

carrying out copolymerization reaction on a capsaicinoid monomer and an acrylic acid monomer to prepare a prepolymer;

carrying out crosslinking reaction on the prepolymer and zinc salt to prepare the zinc polyacrylate/capsaicinoid copolymer;

the capsaicinoid monomer is N-phenylmaleimide and/or 8-methyl-N- [ (4-hydroxy-3-methoxyphenyl) -methyl ] - (trans) -6-nonenylamide.

2. The method for preparing zinc polyacrylate/capsaicinoid copolymer according to claim 1, wherein the acrylic monomer is one or more selected from acrylic acid, methyl acrylate, methyl methacrylate and hydroxyethyl methacrylate.

3. The method of claim 1, wherein the zinc salt is ZnCl₂。

4. The preparation method of the zinc polyacrylate/capsaicinoid copolymer according to any one of claims 1 to 3, wherein the copolymerization reaction comprises the following steps:

mixing the capsaicinoid monomer, the acrylic monomer, the dispersing agent and water, heating the obtained mixture to 60-70 ℃, and adding the initiator; then reacting for 3-4 h at the temperature of 80-90 ℃.

5. The method for preparing zinc polyacrylate/capsaicinoid copolymer according to claim 4, wherein the dispersant is sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate; and/or

The initiator is selected from one or more of ammonium persulfate, sodium persulfate, azobisisobutyronitrile and azobisisobutyramidine hydrochloride.

6. The method for preparing zinc polyacrylate/capsaicinoid copolymer according to any one of claims 1 to 3, wherein the molar ratio of the capsaicinoid monomer to the acrylic monomer is (0.1-1): 1.

7. The zinc polyacrylate/capsaicinoid copolymer prepared by the preparation method of any one of claims 1 to 6.

8. An emulsion comprising water and the zinc polyacrylate/capsaicinoid copolymer of claim 7.

9. The emulsion of claim 8, further comprising a co-solvent; the cosolvent is selected from one or two of acetone and butanone.

10. An antifouling paint characterized by comprising the zinc polyacrylate/capsaicinoid copolymer according to claim 7 or the emulsion according to claim 8 or 9 as a film-forming substrate.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a zinc polyacrylate/capsaicinoid copolymer, a preparation method thereof and an antifouling paint.

Background

The antifouling means of the ship are complex and various, and the technology is various. From the history of development of marine antifouling, adding antifouling agents to prepare antifouling paints is the most economically and technically feasible and effective means. The antifouling paint for ships can be divided into two categories, namely traditional antifouling paint and novel antifouling paint. The traditional antifouling paint, such as organotin self-polishing antifouling paint (TBT), has been forbidden in the global scope due to the problems of short antifouling aging, low antifouling efficiency, harm to marine life and marine ecology and the like, and the research and development of novel pollution-free antifouling paint capable of replacing TBT has gradually attracted attention of people. The tin-free self-polishing antifouling paint is the fastest developed one of environment-friendly antifouling paints and is also the main variety for replacing the organotin self-polishing antifouling paint at present. The film-forming matrix of the antifouling paint is a polymer with self-polishing characteristic and can be slowly hydrolyzed, the antifouling mechanism of the antifouling paint is similar to that of the organic tin self-polishing antifouling paint, and the polymer of non-tin metal salt (such as copper and zinc salt) is used for replacing the organic tin polymer.

Capsaicin, (trans) 8-methyl-N-vanillyl-6-nonenamide, which is an active ingredient of capsicum. Capsaicin, extracted from capsicum annuum, was first used in antifouling paints by watzer industries, usa, in 1995. Many scholars subsequently studied the antifouling properties of capsaicin. However, because the natural capsaicin is obtained in a small amount and is difficult to be applied in a large scale, people pay attention to the research on the capsaicinoid or the capsaicinoid structural unit.

If the method relates to a polyfunctional acrylamide compound containing a capsaicinoid functional structure, the capsaicin functional structure is formed in a structural unit of polyacrylic acid by a chemical synthesis method. Still another method relates to a dihydrocapsaicin-modified acrylic resin obtained by esterifying a phenolic hydroxyl group in a molecule of dihydrocapsaicin with acrylic acid.

However, in practical application, the tin-free self-polishing antifouling paint prepared from the modified acrylic resin has an excessively high dissolution rate in seawater and a short cycle life.

Disclosure of Invention

Based on the above, the invention provides the zinc polyacrylate/capsaicinoid copolymer with long antifouling cycle life, and the preparation method and the application thereof.

The first aspect of the invention provides a preparation method of a zinc polyacrylate/capsaicinoid copolymer, which comprises the following steps:

carrying out copolymerization reaction on a capsaicinoid monomer and an acrylic acid monomer to prepare a prepolymer;

carrying out crosslinking reaction on the prepolymer and zinc salt to prepare the zinc polyacrylate/capsaicinoid copolymer;

the capsaicinoid monomer is N-phenylmaleimide (N-PMI) and/or 8-methyl-N- [ (4-hydroxy-3-methoxyphenyl) -methyl ] - (trans) -6-nonenylamide [ (e) -8-methyl-N-vanillyl-6-nonenamide ].

In one embodiment, the acrylic monomer is selected from one or more of acrylic acid, methyl acrylate, methyl methacrylate, and hydroxyethyl methacrylate.

In one embodiment, the zinc salt is ZnCl₂。

In one embodiment, the copolymerization reaction comprises the steps of:

mixing the capsaicinoid monomer, the acrylic monomer, the dispersing agent and water, heating the obtained mixture to 60-70 ℃, and adding the initiator; then reacting for 3-4 h at the temperature of 80-90 ℃.

In one embodiment, the dispersant is sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate.

In one embodiment, the initiator is selected from one or more of ammonium persulfate, sodium persulfate, azobisisobutyronitrile, and azobisisobutyramidine hydrochloride.

In one embodiment, the molar ratio of the capsaicinoid monomer to the acrylic monomer is (0.1-1): 1.

In a second aspect of the invention, the zinc polyacrylate/capsaicinoid copolymer prepared by the preparation method is provided.

In a third aspect of the invention, there is provided an emulsion comprising water and the above zinc polyacrylate/capsaicinoid copolymer.

In one embodiment, the emulsion further comprises a co-solvent; the cosolvent is selected from one or two of acetone and butanone.

The fourth aspect of the invention provides an antifouling paint, wherein the zinc polyacrylate/capsaicinoid copolymer or the emulsion is used as a film forming matrix.

The preparation method adopts specific capsaicinoid monomers, specifically N-phenylmaleimide and/or 8-methyl-N- [ (4-hydroxy-3-methoxyphenyl) -methyl ] - (trans) -6-nonenylamide, to copolymerize with acrylic acid monomers, and then zinc salt is crosslinked to prepare the zinc polyacrylate/capsaicinoid copolymer, wherein polyacrylic acid has good water resistance, has carboxyl in the structure and can be crosslinked with zinc ions to form a zinc acrylate salt polymer, and the formed molecular network structure has slow release characteristics by matching with the specific capsaicinoid monomers, so that the dissolution speed of an antifouling coating formed after the copolymer is formed into a film in seawater can be effectively adjusted, and the antifouling coating has a long antifouling life. Meanwhile, the antifouling paint has obvious inhibition effect on the attachment and reproduction of marine organisms and good antifouling effect.

In addition, the antifouling paint using the zinc polyacrylate/capsaicinoid copolymer as the film forming matrix has the characteristic of high smoothness of a coating formed after coating.

In addition, the zinc polyacrylate/capsaicinoid copolymer can be used as a film-forming matrix of a tin-free self-polishing antifouling paint, has biosafety, environmental protection, no pollution to marine environment, no corrosion to metal and equipment, can be used for protecting antifouling coatings of ships and submarine pipelines, and has important application value in bionic antifouling paints.

Drawings

FIG. 1 is an infrared spectroscopic measurement of the AA/N-PMI prepolymer prepared in example 1;

FIG. 2 is an infrared spectroscopic test of the PAZ/N-PMI copolymer prepared in example 1.

Detailed Description

The zinc polyacrylate/capsaicinoid copolymer of the present invention, its preparation method and use are further described in detail with reference to the following examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

As used herein, the term "and/or", "and/or" includes any one of two or more of the associated listed items, as well as any and all combinations of the associated listed items, including any two of the associated listed items, any more of the associated listed items, or all combinations of the associated listed items.

As used herein, "one or more" refers to any one, any two, or any two or more of the listed items.

In the present invention, "first aspect", "second aspect", "third aspect", "fourth aspect" and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity indicating the technical feature indicated. Also, "first," "second," "third," "fourth," etc. are used for non-exhaustive enumeration of description purposes only and should not be construed as a closed limitation to the number.

In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.

In the present invention, the numerical range is defined to include both end points of the numerical range unless otherwise specified.

The percentage contents referred to in the present invention mean, unless otherwise specified, mass percentages for solid-liquid mixing and solid-solid phase mixing, and volume percentages for liquid-liquid phase mixing.

The percentage concentrations referred to in the present invention refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system to which the component is added.

The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.

The invention provides a preparation method of a zinc polyacrylate/capsaicinoid copolymer, which comprises the following steps:

carrying out copolymerization reaction on a capsaicinoid monomer and an acrylic acid monomer to prepare a prepolymer;

performing a crosslinking reaction on the prepolymer and zinc salt to prepare a zinc polyacrylate/capsaicinoid copolymer [ PAZ/CPC (capsaicin) ] (abbreviated as PAZ/CPC);

wherein the capsaicinoid monomer is N-phenylmaleimide (N-PMI) and/or 8-methyl-N- [ (4-hydroxy-3-methoxyphenyl) -methyl ] - (trans) -6-nonenylamide [ (e) -8-methyl-N-vanillyl-6-nonenamide ].

In some specific examples, the zinc polyacrylate/capsaicinoid copolymer described above is free of tin.

In some specific examples thereof, the acrylic monomer is selected from one or more of acrylic acid, methyl acrylate, methyl methacrylate, and hydroxyethyl methacrylate. Further, the acrylic monomer is acrylic acid.

In some specific examples, the zinc salt is ZnCl₂. It will be appreciated that the amount of zinc salt added determines the degree of crosslinking and can be determined according to the desired degree of crosslinking.

In some specific examples, the copolymerization reaction comprises the steps of:

mixing capsaicinoid monomer, acrylic monomer, dispersant and water, heating the obtained mixture to 60-70 ℃, and adding initiator; then reacting for 3-4 h at the temperature of 80-90 ℃.

In some specific examples, the copolymerization reaction is carried out under an inert gas atmosphere. Further, the inert gas is nitrogen.

In some specific examples, mixing the capsaicinoid monomer, the acrylic monomer, the dispersant, and the water means placing the capsaicinoid monomer, the acrylic monomer, and the dispersant in the water. If necessary, the dissolving mode can be at least one of stirring, ultrasonic and shaking.

In some specific examples, the temperature of the mixture is 60 ℃ to 70 ℃ when the initiator is added. Specifically, the temperature includes, but is not limited to: 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃ and 60 ℃.

In some specific examples, the temperature of the reaction is from 80 ℃ to 90 ℃. Specifically, the temperature of the reaction includes, but is not limited to: 80 deg.C, 81 deg.C, 82 deg.C, 83 deg.C, 84 deg.C, 85 deg.C, 86 deg.C, 87 deg.C, 88 deg.C, 89 deg.C, 90 deg.C.

In some specific examples, the reaction time is 3h to 4 h. Specifically, the time of the reaction includes, but is not limited to: 3h, 3.5h and 4 h.

In some specific examples, the dispersant is sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate. Further, the dispersant is sodium dodecyl sulfate.

In some specific examples, the amount of the dispersing agent is 5-15% of the mass of the capsaicinoid monomer. Specifically, such amounts of dispersant include, but are not limited to: 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%.

In some specific examples, the initiator is selected from one or more of ammonium persulfate, sodium persulfate, azobisisobutyronitrile, and azobisisobutyramidine hydrochloride. Further, the initiator is sodium persulfate.

In some specific examples, the initiator is used in an amount of 4% to 12% of the total mass of the capsaicinoid monomer and the acrylic monomer. Specifically, such amounts of initiator include, but are not limited to: 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%.

In some specific examples, the initiator is added slowly dropwise for 0.5-1 h.

In some specific examples, the molar ratio of the capsaicinoid monomer to the acrylic monomer is (0.1-1): 1. Furthermore, the molar ratio of the capsaicinoid monomer to the acrylic monomer is (0.1-0.5): 1. The molar ratio of capsaicinoid monomer to acrylic monomer includes, but is not limited to: 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1: 1.

In some specific examples, after the copolymerization reaction is finished, the method further comprises the step of purifying: and (3) dialyzing the reaction liquid obtained by the copolymerization reaction to remove the small molecular compounds and the initiator, and then evaporating to remove water to prepare the prepolymer.

In some specific examples, the dialysis membrane used in the dialysis treatment has a molecular weight cut-off of 13000-15000.

In some specific examples, after the crosslinking reaction is finished, the method further comprises a purification step: adding a solvent into the reaction liquid obtained by the crosslinking reaction to enable the reaction liquid to generate flocculation precipitation, and then centrifuging and drying the flocculation precipitation to prepare the zinc polyacrylate/capsaicinoid copolymer. Further, the solvent is a zinc polyacrylate/capsaicinoid copolymer insoluble solvent, such as acetone.

The invention also provides the zinc polyacrylate/capsaicinoid copolymer prepared by the preparation method.

Specifically, the zinc polyacrylate/capsaicinoid copolymer can be represented by the following structural characteristics:

m₁、n₁、m₂、n₂the value of (b) is determined by the charge ratio of the epoxy resin to the polyetherimide and the degree of polymerization.

The invention also provides an emulsion which comprises water and the zinc polyacrylate/capsaicinoid copolymer.

In some specific examples thereof, the emulsion further comprises a co-solvent; the cosolvent is selected from one or two of acetone and butanone. Furthermore, the amount of the cosolvent accounts for 5-10% of the volume of the water.

In some specific examples, the emulsion has a solids content of 40% to 70%.

The invention also provides an antifouling paint which takes the zinc polyacrylate/capsaicinoid copolymer or emulsion as a film forming matrix. The antifouling paint has long antifouling life and good antifouling effect.

In some specific examples, the mass percentage of the zinc polyacrylate/capsaicinoid copolymer in the antifouling paint is 10% to 20%. Taking 15% as an example, the antifouling paint is coated on the surface of steel or a culture cage, oyster and seaweed can not grow in seawater for 6 months, and only less than 5% of the surface is slightly attached by the algae and the oysters after one year. Whereas steel sheets coated with conventional antifouling paints had 100% of their surface covered with shells and seaweeds in seawater for 6 months.

The following are specific examples, and the raw materials used in the examples are all commercially available products unless otherwise specified.

Example 1

This example is a PAZ/N-PMI copolymer, which is prepared by the following steps:

(1) 1.73g N-PMI, 0.18g sodium dodecyl sulfate and 120mL water are taken, stirred vigorously for 5 minutes and then are subjected to ultrasonic oscillation to fully disperse the N-PMI in the water, so as to prepare a dispersed phase of the N-PMI; then, 7.20g of acrylic acid was dissolved in the dispersed phase of N-PMI, stirred uniformly, the reaction solution was placed in a three-necked flask, and the air in the three-necked flask was replaced by introducing nitrogen gas.

(2) 0.90g of sodium persulfate was dissolved in 30mL of water, and after the temperature of the reaction solution of the step (1) was raised to 65 ℃, an aqueous solution of sodium persulfate was slowly added dropwise (completion of addition for about 30 min).

(3) After the dropwise addition, the temperature is raised to 85 ℃, and the temperature is kept for 3 hours; after cooling, putting the solution into a dialysis bag with the molecular weight cutoff of 14000 for dialysis;

(4) removing water by using a rotary evaporator to obtain an AA/N-PMI prepolymer;

(5) dissolving the AA/N-PMI prepolymer in water, violently stirring, adding a little excessive zinc chloride to gelatinize the prepolymer, and then adding acetone to perform flocculation precipitation;

(6) and (3) centrifuging, drying and drying the flocculate to obtain the PAZ/N-PMI copolymer (solid resin).

The structural formula of the above Acrylic Acid (AA) is as follows:

the structural formula of N-phenylmaleimide (N-PMI) is as follows:

the structure of the PAZ/N-PMI copolymer prepared can be represented as follows:

and (3) structural identification: the AA/N-PMI prepolymer is subjected to infrared spectrum test, and the result is shown in figure 1 and is 2900-3000 cm^-1Has a broad and strong characteristic absorption peak of carboxylic acid at 1700cm^-1C-O stretching vibration peak is appeared nearby and is 1400-1500 cm^-1An absorption peak with the characteristics of a benzene ring is generated and is 1150-1250 cm^-1C-O stretching vibration peaks appear; the infrared spectrum test of the PAZ/N-PMI copolymer shows that the carboxylic acid is 2800-3300 cm^-1The characteristic absorption peak of (A) still exists, and is 1400-1500 cm^-1A smaller characteristic absorption peak of a benzene ring appears, and meanwhile, the absorption peak is 1450-1680 cm^-1Two absorption peaks of the carboxylate newly appear. It was confirmed that example 1 produced a PAZ/N-PMI copolymer.

Example 2

This example was carried out on the basis of example 1 using different ratios of Acrylic Acid (AA) to N-phenylmaleimide (N-PMI) for the preparation of PAZ/N-PMI copolymers.

The preparation method comprises the following steps:

(1) 2.5g N-PMI, 0.18g sodium dodecyl sulfate and 120mL water are taken, stirred vigorously for 5 minutes and then subjected to ultrasonic oscillation to fully disperse the N-PMI in the water, so as to prepare a dispersed phase of the N-PMI; then, 5.0g of acrylic acid was dissolved in the dispersed phase of N-PMI, stirred uniformly, the reaction solution was placed in a three-necked flask, and nitrogen gas was introduced to displace the air in the three-necked flask.

(2) 0.90g of sodium persulfate was dissolved in 3mL of water, and after the temperature of the reaction solution of the step (1) was raised to 65 ℃, an aqueous solution of sodium persulfate was slowly added dropwise.

(3) After the dropwise addition, the temperature is raised to 85 ℃, and the temperature is kept for 3 hours; after cooling, putting the solution into a dialysis bag with the molecular weight cutoff of 14000 for dialysis;

(4) removing water by using a rotary evaporator to obtain an AA/N-PMI prepolymer;

(5) dissolving the AA/N-PMI prepolymer in water, violently stirring, adding excessive zinc chloride to gelatinize the prepolymer, and then adding acetone to perform flocculation precipitation;

(6) and (3) centrifuging, drying and drying the flocculate to obtain the PAZ/N-PMI copolymer (solid resin).

Antifouling paints were prepared using the copolymers of examples 1-2 and tested for properties.

The preparation method of the antifouling paint comprises the following steps: and dissolving the copolymer in purified water (with 8% of acetone as cosolvent) to obtain a resin solution with a solid content of 60%.

The test results are given in table 2 below:

TABLE 2

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.