Preparation method of a self-renewing bionic marine antifouling coating

Abstract

The present invention discloses a preparation method of a self-renewing bionic marine antifouling coating. First, an amphiphilic block prepolymer with terminal dihydroxy groups containing poly(dimethylaminoethyl methacrylate) is synthesized by a method of continuous feeding living radical polymerization. Then, the tertiary amine in the dihydroxy prepolymer reacts with haloacetate to generate a prepolymer with cationic groups in the side chains. The dihydroxy cationic prepolymer, dihydroxy polycaprolactone, dihydroxy silicone oil and diisocyanate are condensed to generate a film-forming substance for the marine antifouling coating with a quaternary ammonium salt structure in the side chains. This film-forming substance is directly used as the marine antifouling coating. Under the action of seawater, the side chains undergo hydrolysis to generate super-hydrophilic zwitterions for the antifouling structure, and the main chain of the coating resin gradually hydrolyzes to regenerate the amphiphilic silicone oil with a self-lubricating effect, imitating the lubricating substances continuously secreted by the surface of living marine organisms, so as to achieve the goal of environmentally friendly antifouling.

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 materials. Background Art

[0002] The attachment of marine fouling organisms will increase the self-weight of marine ships and equipment, etc., increase the energy consumption of the transportation industry and the maintenance cost of the equipment; the acidic substances generated by them accelerate the corrosion rate of marine engineering metals, resulting in a significant reduction in lifespan; it is estimated that the economic loss caused by the attachment of fouling organisms globally exceeds 450 billion US dollars annually.

[0003] Applying an antifouling coating is considered to be a protection measure with low cost and significant effect. However, the coating of the mainstream copper antifouling agent belongs to a low-toxic antifouling paint. With the increasing global attention to environmental protection, the development of non-toxic antifouling paints has become the trend of the development of marine paints. However, the existing non-toxic antifouling paints are mainly fouling-release fluorosilicon low-surface-energy materials. The representative product is the intersleek series of IP Company. However, this type of paint requires a ship to have a sailing rate of more than 50%, a speed of more than 10 knots to reduce biological fouling by using the scouring force of seawater, and requires manual cleaning regularly within 15 - 30 days. If the ship remains stationary for more than 2 weeks, the coating will lose its antifouling effect. Therefore, its antifouling effect is still restricted by various factors. As is well known, marine living organisms can exhibit antifouling characteristics because they continuously secrete various lubricating substances on their body surfaces. Therefore, it is of great significance to imitate living marine organisms and continuously secrete substances with antifouling characteristics as an antifouling coating.

[0004] From the perspective of bionics, the present invention designs an amphiphilic structural unit with a main chain that can be slowly degraded and side groups with antifouling characteristics, simulating living marine organisms to continuously secrete self-lubricating antifouling substances, so as to achieve the purpose of antifouling. The characteristics of the present invention are: first, a one-pot continuous reaction is adopted to reduce costs; second, the side groups contain a cationic sterilization structure, which is converted into an anti-adsorption zwitterionic pair structure through hydrolysis to achieve functional conversion; third, the main chain is copolymerized with a degradable component and an organosilicon component to fully adjust the degradation rate of the coating, and then achieve a longer service life; fourth, after the main chain is continuously self-renewed and hydrolyzed at the molecular level, the organosilicon component at the coating interface gradually forms an amphiphilic liquid silicone oil, a self-lubricating antifouling substance secreted by bionic marine organisms, which can alleviate the problem of insufficient stationary antifouling of the intersleek coating; fifth, the coating is environmentally friendly and does not produce marine microplastics. Summary of the Invention

[0005] A preparation method of a self-renewing bionic marine antifouling coating. By using halopropylene glycol as an atom transfer radical initiator, a terminal dihydroxy amphiphilic block copolymer is prepared. After the block copolymer undergoes a cationization reaction, its hydrophilic antifouling characteristics are further enhanced. Further, the dihydroxy groups at one end of the cationic polymer are copolymerized with dihydroxy silicone oil, dihydroxy polycaprolactone and diisocyanate to obtain a film-forming polymer for the bionic coating. The creativity of this coating lies in: 1. It is found that chloropropylene glycol can be used as an active radical initiator to realize the low-cost preparation of the key intermediate of the dihydroxy amphiphilic polymer; 2. For the above amphiphilic block copolymer intermediate, its hydrophilic segment adopts a random copolymerization method. After cationization of the tertiary amine group, the interaction of net charges can be reduced, its stretching property is improved, and the risk that the terminal hydroxy group of the hydrophobic segment polymer is buried inside the core-shell structure is solved, which is beneficial to the next polymerization reaction with dihydroxy polyester, dihydroxy silicone oil and diisocyanate to produce a new functional marine antifouling resin containing antifouling side groups. 3. The main chain is degradable, and the coating can achieve self-renewal at the molecular level, rather than the hydrolysis of the side groups of the existing marine antifouling coating acrylic resin, and the degree of polymerization of the main chain macromolecule remains unchanged; 4. This film-forming resin is obtained by a one-pot continuous polymerization method, and the preparation process is reasonably designed. The obtained resin solution can be directly used without purification treatment, which is beneficial to reducing the industrial production cost.

[0006] To achieve the above, the present invention provides the following technical solutions:

[0007] A preparation method of a self-renewing bionic marine antifouling coating. The preparation reaction of the coating resin is as follows in Formula 1:

[0008]

[0009] In Formula 1 of the present invention: The structure of the halopropylene glycol is as shown in Formula 2 or 3 below, where X is chlorine or bromine.

[0010]

[0011] In the catalyst CuX of the present invention, X is chlorine or bromine;

[0012] The ligand of the present invention is one or a mixture of three of 2,2'-bipyridine, pentamethyldiethylenetriamine or hexamethyltriethylenetetramine;

[0013] In the intermediate polymer a of the present invention, the number of repeating units m1 is an integer between 10 and 100, m2 + m3 is an integer between 10 and 100, and m3 is an integer between 1 and 100;

[0014] In the intermediate polymer a of the present invention, the group *—R 1 is a saturated alkyl group with 6 to 16 carbon atoms;

[0015] The group *—R in the intermediate polymer a of the present invention 2 The group is *—(CH2CH2O) y CH3 or *—(CH2CH2O) y CH2CH3, where y is an integer between 2 and 10;

[0016] The solvent of the present invention is one or a mixture of xylene, ethyl acetate, methyl ethyl ketone, and cyclohexanone;

[0017] The group *—R in the intermediate polymer b of the present invention 3 is *—CH3, *—CH2CH3, *—OC6H5 or *—OC7H7;

[0018] The HO—PCL—OH of the present invention is dihydroxy polycaprolactone;

[0019] 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;

[0020] 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;

[0021]

[0022] The repeating units n1, n2, and n3 in the main chain of the polymer c of the present invention are respectively integers from 10 to 100;

[0023] The specific preparation process of the self-renewing bionic marine antifouling coating of the present invention is as follows: 10 - 100 mmol of halopropylene glycol is used as an initiator for atom transfer radical polymerization (ATRP), 10 - 100 mmol of CuX is used as a catalyst, 10 - 200 mmol of a ligand, and 100 - 10000 mmol of CH2=C(CH3)CO2R 1 are added to a three-necked flask. Under nitrogen protection, after stirring the polymerization reaction at 30 - 80 °C for 2 - 10 h, under a nitrogen atmosphere, CH2=C(CH3)CO2R 2 and a mixture of CH2=C(CH3)CO2(CH2)2N(CH3)2 are added, and the living polymerization reaction is continued by stirring at 60 - 90 °C for 8 - 24 h to generate an intermediate polymer a; a solvent is added to the polymer a, and ClCH2CO2R with an equimolar amount to CH2=C(CH3)CO2(CH2)2N(CH3)2 is added 3, after reacting at 60 - 100 °C for 0.5 - 10 h, intermediate polymer b is obtained; 10 - 100 mmol of dihydroxy polycaprolactone, 30 - 300 mmol of diisocyanate and 10 - 100 mmol of dihydroxy silicone oil are added to the polymer b solution, and the reaction is carried out at 60 - 100 °C for 3 - 10 h to obtain a solution of the degradable bionic marine antifouling coating polymer c, and this solution can be directly used for brushing.

[0024] The molecular weight of the dihydroxy polycaprolactone HO—PCL—OH used in the present invention is between 1000 and 5000.

[0025] The amount of the solvent used in the present invention is 4.5 - 10 times the mass of intermediate polymer a. Detailed implementation mode

[0026] Example 1:

[0027] 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) 11 CH3 are added to a three-necked flask. Under nitrogen protection, an ATRP polymerization reaction is carried out at 35 °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 is added, and the polymerization reaction is continued with stirring at 60 °C for 24 h to generate intermediate polymer a1; 200 g of the solvent xylene is added to polymer a1, and 50 mmol of ClCH2CO2C2H5 is added. After reacting at 60 °C for 5 h, intermediate polymer b1 is obtained; a certain proportion of 10 mmol of dihydroxy polycaprolactone with a molecular weight of 1000, 29.7 mmol of OCN—(CH2)6—NCO and 10 mmol of HO(CH2)3-(Si(CH3)2O) 10 -Si(CH3)2(CH2)3OH are added to the polymer b1 solution, and the reaction is carried out at 60 °C for 10 h to obtain the degradable bionic marine antifouling coating c1.

[0028] Example 2:

[0029] 10 mmol of 2-chloropropanediol, 10 mmol of CuBr, 20 mmol of pentamethyldiethylenetriamine and 100 mmol (31.00 g) of CH2=C(CH3)CO2(CH2) 15CH3 was added to a three-necked flask. Under nitrogen protection, after stirring the polymerization reaction at 50 °C for 6 h, 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 by stirring at 90 °C for 15 h to form intermediate polymer a2; 150 g of ethyl acetate and 200 g of methyl ethyl ketone mixture were added to polymer a2 as a solvent, and 40 mmol 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, 59.4 mmol of diphenylmethane diisocyanate, and 30 mmol of dihydroxy silicone oil HO(CH2)3-(Si(CH3)2O)8-Si(CH3)2(CH2)3OH were added to the polymer b2 solution, and the reaction was carried out at 80 °C for 6 h to obtain the degradable bionic marine antifouling coating c2.

[0030] Example 3:

[0031] 10 mmol of 2-bromopropanediol, 10 mmol of CuCl, 10 mmol of hexamethyltriethylenetetramine, and 1000 mmol (170.00 g) of CH2=CH(CH3)CO2(CH2)5CH3 were added to a three-necked flask. Under nitrogen protection, after stirring the polymerization reaction at 80 °C for 4 h, under a nitrogen atmosphere, a mixture of 500 mmol (94.00 g) of CH2=CH(CH3)CO2(CH2CH2O)2CH3 and 300 mmol (47.10) 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; 2000 g of cyclohexanone solvent was added to polymer a3, and 300 mmol of ClCH2CO2C2H5 was added simultaneously. After reacting at 60 °C for 10 h, intermediate polymer b3 was obtained; 100 mmol of dihydroxy polycaprolactone with a molecular weight of 5000, 208 mmol of m-phenylene diisocyanate, and 100 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 the degradable bionic marine antifouling coating c3.

[0032] Example 4:

[0033] 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) 11CH3 was added to a three-necked flask. Under nitrogen protection, after stirring the polymerization reaction 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, and the reaction was carried out at 60 °C for 5 h to obtain intermediate polymer b4; 30 mmol of dihydroxy polycaprolactone with a molecular weight of 3000, 118.7 mmol of OCNCH2CH2O(CH2CH2O) 10 CH2CH2NCO and 80 mmol of dihydroxy silicone oil HO(CH2)3-(Si(CH3)2O)8Si(CH3)2(CH2)3OH were added, and the reaction was carried out at 100 °C for 10 h to obtain a degradable bionic marine antifouling coating c4.

[0034] The preparation method of a copper ion slow-release functional marine antifouling coating resin provided by the present invention is 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 examples 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 present invention's rights.

Claims

1. A method for preparing a self-renewing bionic marine antifouling coating, characterized in that: The preparation reaction of polymer c 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 in the intermediate polymer a is an integer between 10 and 100, m2+m3 is an integer between 10 and 100, and m3 is an integer between 1 and 100; Group *—R in the intermediate polymer a 1 is a saturated alkyl group having 6 to 16 carbon atoms; Group *—R in the intermediate polymer a 2 The group is *—(CH2CH2O) y CH3 or *—(CH2CH2O) y CH2CH3, wherein y is an integer between 2 and 10; The solvent is one of xylene, ethyl acetate, butanone and cyclohexanone or a mixture thereof; Group *—R in the intermediate polymer b 3 is *—CH3, *—CH2CH3, *—OC6H5 or *—OC7H7; HO—PCL—OH is dihydroxy polycaprolactone; HO(CH2)3-(Si(CH3)2O) m4 -Si(CH3)2(CH2)3OH is dihydroxy silicone oil, in which m4 is an integer between 10 and 50; OCN-R 4 —NCO is a diisocyanate, where the group *—R 4 —* is one or a mixture of the following formulas 4 to 13, *—CH2CH2O(CH2CH2O)m5CH2CH2-* 13, Wherein, m5 in Formula 13 is an integer between 0 and 10; The repeating units n1, n2 and n3 in the main chain of polymer c are integers of 10 to 100; The specific preparation process of the self-renewing bionic marine antifouling coating is as follows: 10-100 mmol of halogenated propylene glycol as an atom transfer radical method (ATRP) initiator, 10-100 mmol of CuX as a catalyst, 10-200 mmol of ligand and 100-10000 mmol of CH2=C(CH3)CO2R 1 Add to the three-necked bottle, under nitrogen protection, stir the polymerization reaction at 30-80℃ for 2-10h, then add CH2=C(CH3)CO2R 2 and CH2=C(CH3)CO2(CH2)2N(CH3)2, and continue the active polymerization reaction at 60-90℃ with stirring for 8-24h to generate intermediate polymer a; add solvent to polymer a, and add ClCH2CO2R in an amount equal in mole to CH2=C(CH3)CO2(CH2)2N(CH3)2 3 , react at 60-100° C. for 0.5-10 hours to obtain an intermediate polymer b solution; add 10-100 mmol of dihydroxy polycaprolactone, 30-300 mmol of diisocyanate and 10-100 mmol of dihydroxy silicone oil to the polymer b solution, and react at 60-100° C. for 3-10 hours to obtain a polymer c solution, which is a self-renewing bionic marine antifouling coating.

2. The method for preparing a self-renewing bionic marine antifouling coating according to claim 1, characterized in that: The molecular weight of the used dihydroxy polycaprolactone HO-PCL-OH is between 1000 and 5000.

3. The method for preparing a self-renewing bionic marine antifouling coating 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.

Images