Preparation method of complex-coated copper self-renewing marine antifouling coating resin composite

Abstract

The invention discloses a preparation method of a complex-coated copper self-renewing marine antifouling coating resin composite. First, an amphiphilic block prepolymer with terminal dihydroxy groups containing poly(dimethylaminoethyl methacrylate) is synthesized by a continuous feeding living radical polymerization method. Then, the dihydroxy prepolymer, dihydroxy polycaprolactone, dihydroxy silicone oil and diisocyanate are condensed to obtain a marine antifouling coating film-forming matrix with a tertiary amine block polymer on the side chain and a biodegradable main chain. A physical mixture of the coating resin and antifouling agent components such as Cu2O is used to obtain a marine antifouling coating. Its advantages are that under the action of seawater, the tertiary amine structure of the coating resin complexes with copper ions, which can effectively regulate the release of the copper antifouling agent. The main chain at the coating interface degrades for self-renewal, and a multiple-coupled dynamic antifouling mechanism such as the gradual formation of lubricating substances such as silicone oil is formed, thereby obtaining a good antifouling effect.

Description

Technical Field

[0001] The present invention belongs to the field of polymer material synthesis, and particularly relates to a preparation method of marine antifouling coatings. Background Art

[0002] Marine corrosion and fouling organism attachment cause losses accounting for about 10% of the marine economy. For example, in ship shipping, it not only increases the energy consumption of the transportation industry and the maintenance cost of equipment, but the acidic substances generated accelerate the corrosion rate of marine engineering metals, resulting in a significant reduction in lifespan. It is statistically shown that the economic losses caused by the attachment of fouling organisms globally exceed 450 billion US dollars annually.

[0003] Applying antifouling coatings is considered to be a protection measure with low cost and significant effect. However, the coatings of existing mainstream copper antifouling agents belong to polyacrylic resin materials, and their main chains are extremely difficult to degrade under natural conditions. Hundreds of thousands of tons of marine coating resins enter the ocean every year, forming marine microplastics. With the global emphasis on environmental protection, developing environmentally friendly marine coating resins with degradable main chains has become the development trend of marine coatings. However, existing copper-based marine coating resins contain some acrylic structures, which increase the hydrophilicity of the coatings to facilitate the release of copper antifouling agents in the coatings and play an antifouling role. However, the hydrophilic components in the resins are not conducive to the adhesion of the coatings. Therefore, the core problems in developing coatings with degradable main chains are as follows: one is how to ensure good compatibility between copper antifouling agents and coating resins; the other is that to ensure the adhesion of the coatings, the coating resins generally need to have strong hydrophobicity. However, the problem is that hydrophobicity often leads to insufficient release of copper antifouling agents, directly affecting the antifouling effect. Therefore, how to ensure the controlled release of copper antifouling agents is the key problem to be solved.

[0004] Organic tertiary amine compounds have been proven to be able to effectively complex copper compounds in seawater (see, Chemical Journal of Chinese Universities 2018, 39, 1602 - 1610, Progress in Organic Coatings, 2022, 170, 107003).

[0005] To solve the above problems, the present invention designs an amphiphilic structural unit resin with a slowly degradable main chain and complexing and coating properties of side groups, which forms a marine antifouling coating composite with a copper antifouling agent. The side groups of the resin have an amphiphilic structure. The hydrophilic segment has a complexing functional tertiary amine structure, which is tightly combined with the copper antifouling agent through a charge transfer effect. The hydrophobic segment structure in the side groups is beneficial to forming a stable hydrophobic complexing and coating copper structure, improving its compatibility with the overall antifouling coating resin, and at the same time ensuring the adhesion ability of the coating resin. Under the action of seawater, the main chain of the coating resin gradually degrades, and the amphiphilic structure of the complexing and coating copper gradually turns over in sequence as the coating hydrolyzes, enabling the copper antifouling agent to contact seawater. The divalent copper ions formed are enriched on the coating surface under the action of hydrophilic tertiary amine complexing, realizing the controllable release of copper ions and improving its antifouling efficiency. Summary of the Invention

[0006] A preparation method of a complexing and coating copper self-renewing marine antifouling coating resin composite. By using halopropylene glycol as an atom transfer radical initiator, a block functional copolymer with terminal dihydroxy groups containing a tertiary amine segment is prepared. This terminal dihydroxy block copolymer is copolymerized with dihydroxy silicone oil, dihydroxy polycaprolactone and diisocyanate to obtain a coating film-forming polymer. The tertiary amine units in this coating film-forming polymer form a composite structure with cuprous oxide antifouling agent through complexing and coating, improving the dispersion of the copper antifouling agent in the coating. The creativity of this marine composite antifouling coating lies in: 1. Chloropropylene glycol can be used as an active radical initiator to realize the preparation of a key intermediate of a dihydroxy amphiphilic block polymer; 2. The above amphiphilic block copolymer intermediate, with its strict AB segment structure, can achieve perfect complexing and coating of copper inorganic substances, laying the foundation for subsequent controllable release of copper; 3. Under the catalytic action of the tertiary amine group, it is beneficial for the next step of polycondensation reaction with dihydroxy polyester, dihydroxy silicone oil and diisocyanate to generate a side group complexing copper type functional marine antifouling resin; 4. The main chain is degradable, and the coating can achieve self-renewal at the molecular level, rather than the hydrolysis of the existing marine antifouling coating acrylic silicone ester with a difficult-to-degrade main chain; 5. This film-forming resin is obtained by a one-pot continuous polymerization method, with a reasonable preparation process design. The obtained resin solution can be directly used without purification treatment, which is beneficial for industrial production.

[0007] To achieve the above content, the present invention provides the following technical solutions:

[0008] A preparation method of a complexing and coating copper self-renewing marine antifouling coating resin composite. The preparation reaction of the coating resin is as follows

[0009] Formula 1:

[0010]

[0011] In the above formula (1) of the present invention: the structure of the halogenated propylene glycol is as shown in formula (2) or (3) below, where X is chlorine or bromine.

[0012]

[0013] In the catalyst CuX of the present invention, X is chlorine or bromine.

[0014] The ligand of the present invention is one or a mixture of three of 2,2'-bipyridine, pentamethyldiethylenetriamine or hexamethyltriethylenetetramine.

[0015] In the intermediate polymer a of the present invention, the number of repeating units m1 is an integer between 10 and 100, and m2 and m3 are respectively integers between 5 and 100.

[0016] In the intermediate polymer a of the present invention, the group *—R 1 is a saturated alkyl group with 6 to 16 carbon atoms.

[0017] In the intermediate polymer a of the present invention, the group *—R 2 The group is *—(CH2CH2O) y CH3 or *—(CH2CH2O) y CH2CH3, where y is an integer between 2 and 10.

[0018] The solvent of the present invention is one or a mixture of xylene, ethyl acetate, methyl ethyl ketone and cyclohexanone.

[0019] In the intermediate polymer b of the present invention, the group *—R 3 is *—CH3, *—CH2CH3, *—OC6H5 or *—OC7H7.

[0020] The HO—PCL—OH of the present invention is dihydroxy polycaprolactone.

[0021] The molecular formula of the dihydroxy silicone oil of the present invention is HO(CH2)3-(Si(CH3)2O) m4 -Si(CH3)2(CH2)3OH, where m4 is an integer between 10 and 50.

[0022] The OCN—R 4 —NCO in the present invention is a diisocyanate, where the group *—R 4 —* is one or a mixture of several of the following formulas (4) to (13), where in formula (13), m5 is an integer between 0 and 10.

[0023]

[0024] In the main chain of the polymer c of the present invention, the repeating units n1, n2 and n3 are respectively integers between 10 and 100.

[0025] The specific preparation process of the self-renewable marine antifouling coating resin described in the present invention is as follows: Add 10 - 100 mmol of a halogenated propanediol ATRP initiator, 10 - 100 mmol of a CuX catalyst, 10 - 200 mmol of a ligand, and 100 - 10000 mmol of CH2=C(CH3)CO2R1 into a three-neck flask. Under nitrogen protection, stir and carry out a polymerization reaction at 30 - 80 °C for 2 - 10 h. Then, under a nitrogen atmosphere, add 100 - 10000 mmol of CH2=C(CH3)CO2(CH2)2N(CH3)2 and continue to carry out an ATRP polymerization reaction at 60 - 90 °C for 5 - 24 h to generate an intermediate polymer a. After adding a solvent to polymer a, simultaneously add 10 - 100 mmol of a dihydroxy polycaprolactone, 30 - 300 mmol of a diisocyanate, and 10 - 100 mmol of a dihydroxy silicone oil, and react at 60 - 100 °C for 3 - 10 h to obtain a solution of a self-renewable and degradable marine antifouling coating polymer resin b;

[0026] The preparation of the complex-coated copper self-renewable marine antifouling coating resin composite described in the present invention is as follows: Take 100 g of the above polymer resin solution b, add 2 - 30 g of cuprous oxide powder, and stir at a speed of 300 - 2000 revolutions per minute for 10 - 60 minutes to obtain a marine antifouling coating resin composite coated with cuprous oxide;

[0027] The molecular weight of the dihydroxy polycaprolactone HO—PCL—OH used in the present invention is between 1000 and 5000, and the particle size of the Cu2O powder used is between 1 nanometer and 50 micrometers;

[0028] The amount of the solvent used in the present invention is 4.5 - 10 times the mass of the intermediate polymer a. Specific embodiments

[0029] Example 1:

[0030] Add 10 mmol of 1-chloropropanediol, 10 mmol of CuCl, 20 mmol of 2,2’-bipyridine, and 100 mmol (25.40 g) of CH2=C(CH3)CO2(CH2) 11CH3 was added to a three-necked flask. Under nitrogen protection, an ATRP polymerization reaction was carried out at 30 °C for 10 h. Then, under a nitrogen atmosphere, a mixture of 50 mmol (9.40 g) of CH2=C(CH3)CO2(CH2CH2O)2CH3 and 50 mmol (7.85 g) of CH2=C(CH3)CO2(CH2)2N(CH3)2 was added, and the polymerization reaction was continued with stirring at 60 °C for 24 h to form intermediate polymer a1. 200 g of the solvent xylene was added to polymer a1, and 50 mmol of ClCH2CO2C2H5 was added. After reacting at 60 °C for 5 h, intermediate polymer b1 was obtained. A certain proportion of 10 mmol of dihydroxy polycaprolactone with a molecular weight of 1000, 30.3 mmol of OCN—(CH2)6—NCO, and 10 mmol of HO(CH2)3-(Si(CH3)2O) 10 -Si(CH3)2(CH2)3OH was added to the solution of polymer b1, and the reaction was carried out at 60 °C for 10 h to obtain a solution of the degradable bionic marine antifouling coating polymer c1.

[0031] Example 2:

[0032] 10 mmol of 2-propylene glycol, 10 mmol of CuBr, 20 mmol of pentamethyldiethylenetriamine, and 100 mmol (31.00 g) of CH2=C(CH3)CO2(CH2) 15 CH3 were added to a three-necked flask. Under nitrogen protection, the polymerization reaction was carried out with stirring at 40 °C for 6 h. Then, under a nitrogen atmosphere, a mixture of 60 mmol (16.56 g) of CH2=C(CH3)CO2(CH2CH2O)4CH3 and 40 mmol (6.28 g) of CH2=C(CH3)CO2(CH2)2N(CH3)2 was added, and the polymerization reaction was continued with stirring at 90 °C for 15 h to form intermediate polymer a2. A mixture of 150 g of ethyl acetate and 200 g of butanone was used as the solvent and added to polymer a2, and 40 mmol (4 g) of ClCH2CO2CH3 was added. After reacting at 100 °C for 0.5 h, intermediate polymer b2 was obtained. 20 mmol of dihydroxy polycaprolactone with a molecular weight of 2000, 60.5 mmol of diphenylmethane diisocyanate, and 31.2 mmol of dihydroxy silicone oil HO(CH2)3-(Si(CH3)2O)8-Si(CH3)2(CH2)3OH were added to the solution of polymer b2, and the reaction was carried out at 80 °C for 6 h to obtain a solution of the degradable bionic marine antifouling coating polymer c2.

[0033] Example 3:

[0034] 100 mmol of 2-bromopropanediol, 100 mmol of CuCl, 100 mmol of hexamethyltriethylenetetramine and 10000 mmol (1700.00 g) of CH2=CH(CH3)CO2(CH2)5CH3 were added to a three-necked flask. Under nitrogen protection, after stirring and polymerizing at 80 °C for 4 h, under a nitrogen atmosphere, a mixture of 5000 mmol (940.00 g) of CH2=CH(CH3)CO2(CH2CH2O)2CH3 and 3000 mmol (471.0) of CH2=C(CH3)CO2(CH2)2N(CH3)2 was added, and the polymerization reaction was continued by stirring at 90 °C for 12 h to form intermediate polymer a3; 20000 g of cyclohexanone solvent was added to polymer a3, and at the same time 3000 mmol of ClCH2CO2C2H5 was added. After reacting at 60 °C for 10 h, intermediate polymer b3 was obtained; 80 mmol of dihydroxy polycaprolactone with a molecular weight of 5000, 232 mmol of m-phenylene diisocyanate and 50 mmol of dihydroxy silicone oil HO(CH2)3-(Si(CH3)2O)8Si(CH3)2(CH2)3OH were added to the polymer b solution, and the reaction was carried out at 100 °C for 10 h to obtain a solution of the degradable bionic marine antifouling coating polymer c3.

[0035] Example 4:

[0036] 10 mmol of 1-chloropropanediol, 10 mmol of CuCl, 20 mmol of pentamethyldiethylenetriamine and 400 mmol (101.60 g) of CH2=CH(CH3)CO2(CH2) 11 CH3 were added to a three-necked flask. Under nitrogen protection, after stirring and polymerizing at 35 °C for 5 h, under a nitrogen atmosphere, a mixture of 200 mmol (55.2 g) of CH2=C(CH3)CO2(CH2CH2O)4CH3 and 200 mmol (31.4 g) of CH2=C(CH3)CO2(CH2)2N(CH3)2 was added, and the polymerization reaction was continued by stirring at 80 °C for 18 h to form intermediate polymer a4; 1800 g of xylene solvent and 200 mmol (24.00 g) of ClCH2CO2C2H5 were added to polymer a4. After reacting at 60 °C for 5 h, intermediate polymer b4 was obtained; 70 mmol of dihydroxy polycaprolactone with a molecular weight of 3000, 178 mmol of OCNCH2CH2O(CH2CH2O) 10 CH2CH2NCO and 100 mmol of dihydroxy silicone oil HO(CH2)3-(Si(CH3)2O)8Si(CH3)2(CH2)3OH were added to the polymer b4 solution, and the reaction was carried out at 100 °C for 10 h to obtain a solution of the degradable bionic marine antifouling coating polymer c4.

[0037] The preparation method of a copper ion slow-release functional marine antifouling coating resin provided by the present invention has been introduced in detail above. Specific examples are used in this article to elaborate on the principle and implementation manner of the present invention. The description of the above embodiments is only used to help understand the method and its core idea of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also belong to the scope of the protection of the rights of the present invention.

Claims

1. A method for preparing a complex-coated copper self-renewal marine antifouling coating resin composite, characterized in that: Step 1: Preparation of marine antifouling coating resin is as follows: In the above formula 1: The structure of the halogenated propylene glycol is the following formula 2 or 3, wherein X is chlorine or bromine, In the catalyst CuX, X is chlorine or bromine; The ligand is one of 2,2'-bipyridine, pentamethyldiethylenetriamine or hexamethyltriethylenetetramine, or a mixture of the three; The number of repeating units m1 and m2 in the intermediate polymer a is an integer between 10 and 100; Group *—R in the intermediate polymer a 1 is a saturated alkyl group having 6 to 18 carbon atoms; The solvent is one of xylene, butanone and cyclohexanone or a mixture thereof; HO—PCL—OH is dihydroxy polycaprolactone; HO(CH2)3-(Si(CH3)2O) m3 -Si(CH3)2(CH2)3OH is a dihydroxy silicone oil, in which m3 is an integer between 10 and 50; OCN-R 2 —NCO is a diisocyanate, where the group *—R 2 —* is one or a mixture of the following formulas 4 to 12, The repeating units n1, n2 and n3 in the main chain of polymer b are integers of 10 to 100; The specific preparation process of self-renewing marine antifouling coating resin is as follows: 10-100 mmol of halogenated propylene glycol ATRP initiator, 10-100 mmol of CuX catalyst, 10-200 mmol of ligand and 100-10000 mmol of CH2=C(CH3)CO2R 1 Add the mixture to a three-necked flask, stir and polymerize at 30-80° C. for 2-10 hours under nitrogen protection, then add 100-10000 mmol of CH2=C(CH3)CO2(CH2)2N(CH3)2 under nitrogen atmosphere, and continue ATRP polymerization at 60-90° C. for 5-24 hours to generate an intermediate polymer a; add a solvent to the polymer a, and then simultaneously add 10-100 mmol of dihydroxy polycaprolactone, 30-300 mmol of diisocyanate, and 10-100 mmol of dihydroxy silicone oil, and react at 60-100° C. for 3-10 hours to obtain a solution of a self-renewing degradable marine antifouling coating polymer resin b; Step 2: Preparation of the complex-coated copper self-renewal marine antifouling coating resin composite is as follows: Take 100 grams of the polymer resin solution b, add 2 to 30 grams of cuprous oxide powder, and stir at a speed of 300 to 2000 rpm for 10 to 60 minutes to obtain a marine antifouling coating resin composite coated with cuprous oxide.

2. A method for preparing a copper-coated self-renewing marine antifouling coating resin composite according to claim 1, characterized in that: The molecular weight of the used dihydroxy polycaprolactone HO-PCL-OH is between 1000 and 5000, and the particle size of the used Cu2O powder is between 1 nanometer and 50 micrometers.

3. A method for preparing a self-renewing marine antifouling coating resin composite of complex copper according to claim 1, characterized in that: The amount of the solvent used is 4.5 to 10 times the mass of the intermediate polymer a.

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