Photosensitized monomers and photosensitized polymers for preventing biofouling and their preparation methods and applications

Abstract

The present invention relates to the technical field of antifouling coatings, and specifically to photosensitized monomers and photosensitized polymers for preventing biofouling, and their preparation methods and applications. The photosensitized monomers are prepared by reacting phthalocyanine photosensitizers with acrylic monomers, and the photosensitized polymers are polymerized by photosensitizing monomers and acrylic ester monomers. Solvents and additives are added to the polymerized photosensitized polymers to prepare antifouling coatings. The antifouling coatings are mainly used for surface coatings of ships, marine engineering buildings and marine equipment, and can effectively prevent the attachment and fouling of marine organisms. Compared with existing self-polishing antifouling coatings, the technology disclosed in the present invention does not add chemical poisons, has environmentally friendly characteristics, and can also play an antifouling role during ship stoppages and on the surfaces of stationary marine structures.

Description

Technical Field

[0001] The present invention relates to the technical field of antifouling coatings, and in particular to photosensitized monomers and photosensitized polymers for preventing biofouling, and preparation methods and applications thereof. Background Art

[0002] Marine biofouling refers to plants, animals and microorganisms attached and growing on the surface of structures in contact with the ocean water (hulls, docks, buoys, other marine engineering facilities, etc.), which have an adverse impact on human production and life activities. According to statistics, there are more than 200 major marine fouling organisms in my country, among which the most widely distributed ones include mollusks such as barnacles, ascidians, and bryozoans. For ships sailing in the ocean or moored at docks, the attachment of marine organisms increases the energy consumption of the ship and damages the hull structure. Spraying anti-fouling coatings is the main method to deal with the attachment of marine organisms.

[0003] At present, commercially used antifouling coatings are mainly divided into two types: low surface energy and self-polishing antifouling coatings. Low surface energy antifouling coatings mainly utilize the low surface energy effect of silane polymer coatings, and can also imitate the bionic low surface energy coatings of dolphin shark skin, but they face the problems of complex preparation and weak bonding with ship primers, and their application is limited. Antifouling coatings prepared by the self-polishing principle are the most widely used antifouling coatings on ships. Self-polishing antifouling coatings are usually based on polyacrylic acid and its derivatives and contain pesticides. Pesticides and self-polishing polymers can be dissolved at a certain rate under the action of seawater flow to kill microorganisms and attached organisms that contact the surface of the ship. The most effective organotin pesticides to date were banned by the International Maritime Organization as early as 2003, but it is currently difficult to find pesticides that can achieve the same killing efficiency of organotin in natural and synthetic chemicals. In addition, when moored at a dock or at too low a speed, self-polishing antifouling coatings will fail to a certain extent. Therefore, finding new antifouling methods and pesticides is still a hot topic in basic and applied research.

[0004] The process of marine biological attachment is generally considered to start with the adsorption of macromolecular organic matter such as proteins and polysaccharides on the surface of structures such as the bottom of the ship, which will form a layer of organic macromolecules, and then single-celled low-level microorganisms will attach and grow on this organic macromolecule layer, followed by more complex and higher-level microorganisms or organisms, until a typical fouling biological community represented by barnacles and ascidian is formed. Therefore, if the organic macromolecule layer and the attachment of low-level microorganisms that are initially formed can be destroyed, the subsequent attachment and growth of higher-level organisms such as barnacles will be effectively avoided. However, the anti-fouling pesticides added to the existing self-polishing anti-fouling coatings cannot have an effective effect on the initially adsorbed organic molecular layer.

[0005] The reactive oxygen species produced by the photosensitization effect have strong oxidizing properties and can oxidatively degrade organic macromolecules such as proteins and polysaccharides. At the same time, they have good cytotoxicity to lower microorganisms such as unicellular organisms and can effectively kill them. Patent application 202010430844.5 discloses a polyacrylic acid antifouling coating containing nano-titanium dioxide and nano-silicon dioxide; patent applications 201610903216.8 and 201911109110.0 also disclose a similar method for preparing photocatalytic marine antifouling coatings using nano-titanium dioxide, but nano-titanium dioxide requires ultraviolet light excitation to produce a good antifouling effect, and its nanoscale changes in the coating layer will also reduce the photocatalytic efficiency. In addition, titanium dioxide leaks into the ocean water and is difficult to degrade, which will bring environmental risks.

[0006] In addition to directly adding nano-photocatalysts, using monomers to introduce functional groups into polymers is also a common method. Patent 201310138388.7 discloses that phthalonitrile is connected to acrylic monomers by esterification. While acrylic acid is polymerized, phthalonitrile randomly forms phthalocyanine rings. The prepared polymer can be used as an electron acceptor and applied in solar cells; the literature in 2008 reported the use of diols to link copper phthalocyanine and acrylic acid to form polymers for dental filling materials (DOI: 10.1142 / S1088424608000212), and patent 201910069147.9 also discloses similar monomers obtained by linking diols to phthalonitrile and acrylic acid. The number of phthalocyanine molecules in these polymers is generally roughly controlled by the reaction conditions and randomly formed, and the quality control is difficult, and copper phthalocyanine has no application value as a photosensitizer.

[0007] Patent CN202110452630.2 discloses a gel anti-fouling coating formed by mixing a naphthalocyanine photosensitizer and sodium alginate. The prepared gel does not have the characteristics of a coating, is difficult to coat on substrates such as ships, and cannot form a true coating layer, limiting its technical application in the coating field. Summary of the invention

[0008] In order to solve the deficiencies in the prior art, the present invention provides photosensitized monomers and photosensitized polymers for preventing biofouling, and preparation methods and applications thereof.

[0009] To achieve the above object, the technical solution of the present invention is:

[0010] A photosensitizing monomer, the structural formula of the photosensitizing monomer is as follows:

[0011]

[0012] The synthetic route of the above-mentioned photosensitizing monomer is as follows:

[0013]

[0014] Wherein, M is one of Si, P, and Al. When M is Si or P, X is OH and Y is Cl. When M is Al, X and Y do not exist. R 1 H, CH 3 , C 2 H 5 、CH(CH 3 ) 2 One of the 2 CH 3 (CH 2 ) m -,m=3-10.

[0015] A method for preparing a photosensitized monomer comprises the following steps:

[0016] S1, dissolving acrylic acid monomer in toluene, and adding hydroquinone to the solution, wherein the mass of the hydroquinone is 0.1-0.5% of the mass of the acrylic acid monomer;

[0017] S2, dissolving a phthalocyanine photosensitizer in another portion of toluene, wherein the molar ratio of the phthalocyanine photosensitizer to the acrylic acid monomer is 1:0.8-1, and adding a molecular sieve catalyst HZSM to the phthalocyanine photosensitizer, wherein the mass of the molecular sieve catalyst HZSM is 0.5-1% of the mass of the phthalocyanine photosensitizer;

[0018] S3. The phthalocyanine photosensitizer solution is heated to reflux under the protection of argon, and then the acrylic acid monomer solution prepared in S1 is slowly added dropwise. After the addition is completed, the solution is refluxed for 2-6 hours. The product is separated and purified to obtain a photosensitizer monomer.

[0019] Furthermore, the acrylic acid monomer is one of acrylic acid, methacrylic acid, 2-ethylacrylic acid, and 2-isopropylacrylic acid.

[0020] A photosensitized polymer, the photosensitized polymer is prepared from the photosensitized monomer, and the structural formula of the photosensitized polymer is as follows:

[0021]

[0022] Wherein, M is one of Si, P, and Al. When M is Si or P, X is OH. When M is Al, X does not exist. R 1 H, CH 3 , C 2 H 5 、CH(CH 3 ) 2 One of the 2 CH 3 (CH 2 )m -,m=3-10;R 3 OCH 3 、OCH 2 CH 3 、OCH 2 CH 2 CH 3 One of the following; n is the degree of polymerization, n=5000-50000; a, b, c are the repetitions of each monomer fragment in the polymer chain, a, b, c are 0 or positive integers, and a+b+c=n; in the photosensitized polymer, the molar content of the photosensitized monomer is 0.1-10%.

[0023] A method for preparing a photosensitized polymer comprises the following steps: mixing a photosensitized monomer and an acrylate monomer and dissolving the mixture in an aqueous solution containing isopropyl alcohol and sodium dodecylbenzene sulfonate, wherein the molar ratio of the photosensitized monomer to the acrylate monomer is 1:9-999, subjecting the mixed solution to high-speed shear stirring for 1 hour, heating the mixture to 60°C to obtain an emulsion, slowly dripping a 1% ammonium persulfate aqueous solution within 60-120 minutes, reacting the mixture for 6-12 hours, and collecting a solid phase to obtain a photosensitized polymer.

[0024] Furthermore, the acrylic acid ester monomer has the following structural formula:

[0025]

[0026] Where R 1 H, CH 3 , C 2 H 5 、CH(CH 3 ) 2 One of the 3 OCH 3 ,OCH 2 CH 3 , OCH 2 CH 2 CH 3 One of them.

[0027] An application of a photosensitive polymer for surface coating of ships, offshore structures and marine equipment.

[0028] The beneficial effects achieved by the present invention are:

[0029] 1. Compared with antifouling coatings that use chemical or natural biocides as the main antifouling means, the present invention uses photosensitization technology, does not contain heavy metal pesticides, has a low manufacturing cost compared to natural pesticides, and the photosensitizer used can be photobleached in marine waters and has the advantage of being degradable.

[0030] 2. Compared with low surface energy antifouling coatings, the photosensitized polymer in the present invention makes full use of the environment near the waterline of the ship, which is in alternating contact with air and seawater under natural light, and can effectively exert the photosensitization effect, converting the destructive effects of dry-wet alternation and light on low surface energy antifouling coatings into favorable conditions for antifouling, and utilizing the strong oxidizing property of photosensitized active oxygen species to destroy the adsorption of proteins and polysaccharides, thereby preventing the initial adsorption layer of the marine fouling process and achieving the effect of cleaning the surface.

[0031] 3. Compared with the existing self-polishing antifouling coatings, the photosensitizer monomer hydrolyzed on the surface of the antifouling coating prepared by the photosensitized polymer in the present invention can exert phototoxicity alone, and does not require continuous dissolution and polishing of the antifouling coating. The antifouling coating has no requirements for the suspension period and ship speed. In June and July when marine algae reproduce most vigorously, due to strong sunlight, even under suspension conditions (such as fishing moratorium, etc.), the photosensitized coating can also exert good photosensitivity and inhibit the attachment of organic molecules and microorganisms. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 is the UV-visible spectrum of the antifouling coating of the present invention in DMF;

[0033] Figure 2 The active oxygen species produced by the antifouling coating of the present invention in seawater bleach the DPBF;

[0034] Figure 3 This is a picture of the ninhydrin colorimetric analysis of the experimental sample immersed in seawater for 7 days (the gray and thick lines are the colorimetric traces of protein macromolecules and ninhydrin). DETAILED DESCRIPTION

[0035] In order to better understand the purpose, structure and function of the present invention, the photosensitized monomer, photosensitized polymer, antifouling coating and preparation method and application thereof of the present invention are further described in detail below in conjunction with the accompanying drawings.

[0036] Example 1 Preparation of photosensitizing monomers and photosensitizing polymers

[0037] 0.8 mol of methacrylic acid was dissolved in 100 ml of toluene, 0.07 g of hydroquinone was added as an inhibitor, and 1 mol of tetrapentyloxydichlorosilicon phthalocyanine was dissolved in 1000 ml of toluene separately, 4.935 g of HZSM-5 molecular sieve (Guangxi Yamei Chemical) was added as a catalyst, and the mixed solution was heated to reflux under the protection of argon, and then methacrylic acid was added dropwise to the toluene solution of tetrapentyloxydichlorosilicon phthalocyanine, and the addition time was controlled to 1 hour. After the addition was completed, the reflux reaction was continued for 2 hours. The obtained product was washed and filtered with an alkaline solution, and then separated by column chromatography. The developing solvent was pyridine: toluene (volume ratio 1:2). The unreacted purple-red tetrapentyloxydichlorosilicon phthalocyanine was eluted first, and then the blue-purple photosensitized methacrylic acid with a strong polarity was eluted and separated. After the solvent was recovered, a solid was obtained. The structure of the obtained photosensitized monomer is as follows:

[0038]

[0039] Characterization: MALDI-TOF MS: theoretical value m / z: 986.45 (100.0%), 987.45 (60.6%), 988.46 (18.0%), 987.45 (5.1%), 988.45 (3.3%), measured value m / z: 986.46 (100.0%), 987.46 (65.8%), 988.45 (21.1%); elemental analysis: C56H62N8O7Si calculated value: C, 68.13; H, 6.33; N, 11.35; Si, 2.84, measured value C, 68.25; H 6.43; N 11.28; Si, 2.82.

[0040] 1 mol of the prepared photosensitizer monomer and 9 mol of methyl methacrylate were mixed and dissolved in 10 liters of an aqueous solution containing 1% isopropanol and 1% sodium dodecylbenzene sulfonate, stirred at high speed for 1 hour, and heated to 60°C to obtain an emulsion. 100 ml of a 1% ammonium persulfate aqueous solution was slowly added dropwise within 120 minutes, reacted for 8 hours, demulsified by centrifugation, the solid phase was collected, and the photosensitized polymer was obtained after washing.

[0041] Example 2 Preparation of photosensitized monomers and photosensitized polymers

[0042] 1.0 mol of 2-ethyl acrylic acid was dissolved in 100 ml of toluene, 0.3 g of hydroquinone was added as an inhibitor, and 1 mol of tetrabutoxy chloroaluminum phthalocyanine was dissolved in 1000 ml of toluene, 11.725 g of HZSM-5 molecular sieve (Guangxi Yamei Chemical) was added as a catalyst, and the mixed solution was heated to reflux under the protection of argon, and then 2-ethyl acrylic acid was added dropwise to the toluene solution of tetrabutoxy chloroaluminum phthalocyanine, and the addition time was controlled to 1 hour. After the addition was completed, the reflux reaction was continued for 6 hours. The obtained product was washed and filtered with an alkaline solution, and then separated by column chromatography. The developing solvent was pyridine: toluene (volume ratio 1:1). The unreacted blue-purple tetrabutoxy chloroaluminum phthalocyanine was eluted first, and then the polar dark blue photosensitized 2-ethyl acrylic acid was eluted and separated. After the solvent was recovered, a solid was obtained. The structure of the obtained photosensitized monomer is as follows:

[0043]

[0044] Characterization: MALDI-TOF MS: theoretical value m / z: 926.41 (100.0%), 927.41 (57.3%), 928.41 (16.1%), 927.40 (3.0%), 929.42 (2.7%), found value m / z: 926.43 (100.0%), 927.42 (60.8%), 928.41 (16.1%); elemental analysis: C53H55AlN8O6 calculated value: C, 68.67; H, 5.98; Al, 2.91; N, 12.09; O, 10.35, found value C, 68.61; H 6.03; N 12.18, Al 2.90.

[0045] 1 mol of the prepared photosensitizer monomer and 9 mol of ethyl 2-ethylacrylate were mixed and dissolved in 10 liters of an aqueous solution containing 1% isopropanol and 1% sodium dodecylbenzene sulfonate, stirred at high speed for 1 hour, and heated to 60°C to obtain an emulsion. 300 ml of a 1% ammonium persulfate aqueous solution was slowly added dropwise within 120 minutes, reacted for 12 hours, demulsified by centrifugation, the solid phase was collected, and the photosensitized polymer was obtained after washing.

[0046] Example 3 Preparation of photosensitizing monomers and photosensitizing polymers

[0047] 1.0 mol 2-isopropyl acrylic acid was dissolved in 100 ml toluene, 0.5 g hydroquinone was added as an inhibitor, 1 mol tetraoctyloxyphosphorus phthalocyanine was dissolved in 1000 ml toluene, 6.956 g HZSM-5 molecular sieve (Guangxi Yamei Chemical) was added as a catalyst, and the mixed solution was heated to reflux under the protection of argon, and then 2-isopropyl acrylic acid was added dropwise to the toluene solution of tetraoctyloxyphosphorus phthalocyanine, and the addition time was controlled to 1 hour. After the addition was completed, the reflux reaction was continued for 6 hours. The obtained product was washed and filtered with an alkaline solution, and then separated by column chromatography. The developing solvent was pyridine: toluene (volume ratio 3:1). The first thing to be eluted was the unreacted purple tetraoctyloxyphosphorus phthalocyanine, and then the blue-purple photosensitized 2-isopropyl acrylic acid with a strong polarity was eluted and separated. After the solvent was recovered, a solid was obtained. The structure of the obtained photosensitized monomer is as follows:

[0048]

[0049] Characterization: MALDI-TOF MS: theoretical value m / z: 1185.67 (100.0%), 1186.67 (75.7%), 1187.67 (28.3%), 1188.68 (6.1%), measured value m / z: 1185.65 (100.0%), 1186.66 (74.8%), 1187.66 (27.9%); elemental analysis: C70H90N8O7P calculated value: C, 70.86; H, 7.65; N, 9.44; O, 9.44, P, 2.61%, measured value C, 70.60; H 7.33; N 9.62; P, 2.70%.

[0050] 1 mol of the prepared photosensitizer monomer and 5 mol of 2-isopropyl acrylate were mixed and dissolved in 10 liters of an aqueous solution containing 1% isopropanol and 1% sodium dodecylbenzene sulfonate, stirred at high speed for 1 hour, and heated to 60°C to obtain an emulsion. 300 ml of a 1% ammonium persulfate aqueous solution was slowly dripped into the solution within 100 minutes, reacted for 8 hours, demulsified and centrifuged, the solid phase was collected, and the photosensitized polymer was obtained after washing.

[0051] Example 4 Photosensitization capability of antifouling coating

[0052] 1 kg of the photosensitized polymer prepared in Example 1 was added with 200 ml of propylene glycol monomethyl ether and 100 ml of n-butanol, 1 gram of polyamide wax, 100 g of zinc oxide, 50 g of zinc carbonate and 50 g of rosin, and the mixture was sand-milled at a temperature below 50° C. for 8 hours with 300 g of glass beads as abrasive until the slurry fineness was less than 60 μm, and the glass beads were filtered out to obtain a photosensitized antifouling coating. The coating was dissolved in DMF, and the UV-visible spectrum of the upper clear liquid showed a characteristic absorption of the phthalocyanine structure at 700 nm, indicating the stable presence of the phthalocyanine photosensitizer monomer in the coating (attached Figure 1 ).

[0053] The photosensitized antifouling coating prepared as above was added with 0.5% by mass of isocyanate as curing agent, and was coated on a 100×50mm low-carbon steel plate according to the method of national standard GB-T5370, and cured and dried to prepare a coating sample for testing, with a coating thickness of 80-120 microns. A single sample was placed in 500 ml of seawater, stirred to simulate ocean currents, and air was blown in using a micro air pump, and irradiated with a halogen lamp in the laboratory. DPBF / DMSO solution was added to the seawater as an active oxygen species scavenger, and the generation of active oxygen species under photosensitization conditions was tested using ultraviolet-visible spectrophotometry, and a blank was compared. The results showed that in the water sample placed in the photosensitized coating sample, the DPBF concentration gradually decreased over time. After 48 hours of illumination, the DPBF concentration decreased by 75%, while the DPBF concentration of the blank sample did not change substantially over time (see Appendix). Figure 2 ), indicating the generation of photosensitized reactive oxygen species.

[0054] Example 5 Coating preparation and anti-biomolecule attachment experiment

[0055] According to Example 4, a photosensitive antifouling coating sample was prepared, and multiple parallel samples were placed in the seawater in the tidal range area (Nanying Wharf, West Coast New District, Qingdao City), and a blank steel plate and a sample sprayed with commercial self-polishing antifouling paint were used as a comparison. After 7 days of the experiment, the sample was taken out, the surface was slowly washed with pure water, and vacuum dried at low temperature. Then, the nitrogen-containing organic molecules (proteins, polypeptides or amino acids) on the surface were detected by the ninhydrin colorimetric method. The results showed that (Attached Figure 3), no obvious protein color reaction was detected on the surface sprayed with photosensitized antifouling paint, while the blank steel plate and the sample surface sprayed with commercial self-polishing antifouling paint showed strong blue-purple traces, which showed that the photosensitized antifouling paint coating could significantly inhibit the adsorption of protein molecules on the sample surface; after the sample surface was sampled by ultrasonic and mechanical scraping methods, the total organic carbon test (TOC) method was used for detection. The results showed that the TOC content on the surface of the photosensitized coating sample was 98% lower than that on the blank sample, and the TOC content on the surface of the commercial antifouling paint sample was 70% lower than that on the blank sample surface, which showed that the organic molecules on the surface of the photosensitized coating sample were photocatalytically mineralized into inorganic matter, and the photosensitized coating could effectively prevent the adsorption of organic macromolecules such as protein in seawater on the steel plate surface.

[0056] Example 6 Coating preparation and anti-microbial algae fouling

[0057] According to Example 4, a photosensitive antifouling coating sample was prepared and placed in the seawater of the immersion area (Nanying Wharf, West Coast New District, Qingdao City). A blank steel plate and a sample sprayed with commercial self-polishing antifouling paint were used as comparisons. The experiment was carried out for 60 days. After being taken out, the algae attachment on the surface was evaluated with reference to GB-T5370. Under an optical microscope, it can be seen that no algae community adsorbed and grown on the sample coated with the photosensitive antifouling coating can be seen by the naked eye, while a large range of algae adsorbed and grown on the blank sample. The sample was dried and the attached matter on the surface was mechanically scraped and sampled, and then the total organic carbon (TOC) was analyzed. The results showed that the TOC on the surface of the sample coated with the photosensitive coating was reduced by 90% compared with the blank sample, and the surface coated with the commercial antifouling paint was reduced by 50% compared with the blank sample. This shows that the photosensitive coating can effectively inhibit the attachment and growth of unicellular algae on the sample surface in the experiment.

[0058] Example 7 Dissolution and degradation experiment of photosensitizer

[0059] The sample prepared according to the embodiment 4 was placed in a water tank containing 5 liters of seawater in the laboratory, and a small jet pump was used to simulate the seawater flow rate when the ship was running, so that the water flow directly impacted the coating on the panel. The experiment was carried out for 14 days under dark and light conditions. After the experiment, the phthalocyanine photosensitizer content in the dark and light water samples was tested by ultraviolet visible spectrophotometry. The results show that under the impact of high-speed water flow, the photosensitized coating dissolves at a rate of about 5 microns per day. Under dark conditions, about 150 mg of the coating dissolved from the sample into the water within 14 days; under light conditions, it was estimated by ultraviolet spectrum test that the residual antifouling paint was about 50 mg within 14 days, and the degradation rate was about 67%. This shows that under natural light, the photosensitized monomer in the photosensitized coating can be decomposed by its own photobleaching, so that the photosensitizer released into the seawater is degraded, which is conducive to reducing the impact of antifouling paint on the environment, especially for semi-enclosed dock waters where ships are docked.

[0060] Example 8

[0061] The photosensitized antifouling coatings prepared in Examples 2 and 3 were tested according to the methods of Examples 4-6. The results are shown in the following table:

[0062]

[0063] The DPBF bleaching rate of photosensitization ability is calculated as follows, where C 1 is the DPBF content in seawater with photosensitized coating, C 2 is the DPBF content in seawater without photosensitizer coating,

[0064]

[0065] The TOC removal rate is calculated as follows, where C 0 is the TOC content of the blank sample, C t TOC content of the sample coated with photosensitized antifouling paint,

[0066]

[0067] The photosensitizer degradation rate is calculated as follows, where C d is the photosensitizer concentration in seawater after 14 days in dark conditions, C l is the photosensitizer concentration in seawater after 14 days under light conditions,

[0068]

[0069] This shows that Examples 1-3 can all effectively exert photosensitized antifouling effects.

[0070] It is to be understood that the present invention is described by some embodiments, and it is known to those skilled in the art that various changes or equivalent substitutions may be made to these features and embodiments without departing from the spirit and scope of the present invention. In addition, under the teachings of the present invention, these features and embodiments may be modified to adapt to specific circumstances and materials without departing from the spirit and scope of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed herein, and all embodiments falling within the scope of the claims of this application are within the scope of protection of the present invention.

Claims

1. A photosensitizing monomer, characterized in that: The structural formula of the photosensitizing monomer is as follows: Its synthetic route is as follows: Wherein, M is one of Si, P, and Al. When M is Si or P, X is OH and Y is Cl. When M is Al, X and Y do not exist. R1 is one of H, CH3, C2H5, and CH(CH3)2. R2 is CH3(CH2). m -,m=3-10.

2. A method for preparing the photosensitizing monomer according to claim 1, characterized in that: The following steps are involved: S1, dissolving acrylic acid monomer in toluene, and adding hydroquinone to the solution, wherein the mass of the hydroquinone is 0.1-0.5% of the mass of the acrylic acid monomer; S2. Dissolve the phthalocyanine photosensitizer according to claim 1 in another portion of toluene, wherein the molar ratio of the phthalocyanine photosensitizer to the acrylic acid monomer is 1:0.8-1, and add a molecular sieve catalyst HZSM to the phthalocyanine photosensitizer, wherein the mass of the molecular sieve catalyst HZSM is 0.5-1% of the mass of the phthalocyanine photosensitizer; S3. The phthalocyanine photosensitizer solution is heated to reflux under the protection of argon, and then the acrylic acid monomer solution prepared in S1 is slowly added dropwise. After the addition is completed, the solution is refluxed for 2-6 hours. The product is separated and purified to obtain a photosensitizer monomer.

3. The method for preparing a photosensitizing monomer according to claim 2, characterized in that: The acrylic acid monomer is one of acrylic acid, methacrylic acid, 2-ethylacrylic acid, and 2-isopropylacrylic acid.

4. A photosensitized polymer, characterized in that The photosensitizer polymer is prepared from the photosensitizer monomer according to claim 1, and the structural formula of the photosensitizer polymer is as follows: Wherein, M is one of Si, P, and Al. When M is Si or P, X is OH. When M is Al, X does not exist. R1 is one of H, CH3, C2H5, and CH(CH3)2. R2 is CH3(CH2). m -, m = 3-10; R3 is one of OCH3, OCH2CH3, OCH2CH2CH3; n is the degree of polymerization, n = 5000-50000; a, b, c are the repetitions of each monomer fragment in the polymer chain, a, b, c are 0 or positive integers, and a+b+c=n; in the photosensitized polymer, the molar content of the photosensitized monomer is 0.1-10%.

5. A method for preparing a photosensitized polymer according to claim 4, characterized in that the steps include: The photosensitizer monomer and the acrylate monomer are mixed and dissolved in an aqueous solution containing isopropanol and sodium dodecylbenzene sulfonate, wherein the molar ratio of the photosensitizer monomer to the acrylate monomer is 1:9-999, the mixed solution is sheared and stirred at high speed for 1 hour, and the temperature is raised to 60° C. to obtain an emulsion, and a 1% ammonium persulfate aqueous solution is slowly dripped into it within 60-120 minutes, reacted for 6-12 hours, and the solid phase is collected to obtain a photosensitizer polymer.

6. The method for preparing a photosensitized polymer according to claim 5, characterized in that: The acrylic acid ester monomer structural formula is as follows: Wherein R1 is one of H, CH3, C2H5, CH(CH3)2; R3 is one of OCH3, OCH2CH3, OCH2CH2CH3.

7. An application of the photosensitized polymer according to claim 4, characterized in that: Used for surface coating of ships, offshore structures and marine equipment.

Images