CN117210130A - Cross-linked amphiphilic acrylate marine antifouling coating and preparation method and application thereof - Google Patents

Abstract

The invention discloses a cross-linked amphiphilic acrylate marine antifouling coating and its preparation method and application. In the preparation method of the cross-linked amphiphilic acrylate antifouling coating, first, a free radical polymerization method is used. Prepare amphiphilic acrylate polymer; then use amino-terminated polydimethylsiloxane to undergo a ring-opening reaction with the epoxy group in the amphiphilic acrylate polymer to prepare a coating, and obtain a cross-linked polymer with a general structure Synthetic amphiphilic acrylate polymer. The polymer can be further dried and solidified on the substrate by spin coating to obtain an antifouling coating. The antifouling coating is a high-performance, environmentally friendly, static marine antifouling coating. The cross-linked design improves mechanical strength to meet practical applications in complex marine environments.

Description

Cross-linked amphiphilic acrylate marine antifouling coating and its preparation method and application

Technical field

The invention relates to the field of marine antifouling coatings, and in particular to a cross-linked amphiphilic acrylate marine antifouling coating and its preparation method and application.

Background technique

The problem of biological fouling is a common problem in marine facilities. Microorganisms, animals and plants in the ocean will adhere to the surface of the equipment to form macroscopic fouling, causing adverse effects such as weight gain on ships and biological invasion, thus limiting the development of the marine industry. Applying antifouling coatings is the simplest and most efficient way to solve biological fouling. Traditional antifouling coatings kill fouling organisms on the surface by releasing biocides or toxic metals. However, studies have shown that releasing toxic substances into seawater Significantly solves the problem of fouling and adhesion, but it will cause deformity in biological accumulation and violate environmentally friendly strategies. Marine biofilm is a key step in the adhesion process of fouling organisms and provides strong conditions for the subsequent propagation and attachment of fouling. Therefore, suppressing biofilm formation from the source is an effective strategy. Traditional acrylic paint is a self-polishing type. When soaked in seawater, the side chains are hydrolyzed and peeled off layer by layer, removing the fouling organisms attached to the surface. However, it will destroy the internal and surface structure of the coating, resulting in a decrease in mechanical properties. The inventor, Humanities, introduced functional groups to design a cross-linked structure to reduce such problems.

Chinese patent document CN103694421B (Patent No. 201310642570.6) discloses a self-crosslinking low surface energy antifouling coating resin and its preparation method. Polysiloxane acrylate, methacrylate and KH-570 are polymerized by solution polymerization. . The polymer can self-crosslink through moisture, which can improve the mechanical properties of the coating; the side chain contains polysiloxane chains to provide the coating with fouling release properties.

Chinese patent document CN115584153B (Patent No. 202211292892.8) discloses a modified silicone marine antifouling coating based on an ion network and its preparation method. The strong cross-linked structure based on polysiloxane improves the strength and toughness of the coating. , the introduction of imidazolium salt and benzenetetracarboxylic acid gives the coating good elasticity and high energy dissipation. The dual network coating formed by the combination of the two not only has excellent marine antifouling capabilities, but also has strong adhesion to various substrates.

The present invention starts from different inventive concepts and aims to design a marine antifouling coating with high tensile strength and efficient antifouling.

Contents of the invention

In view of this, the purpose of the present invention is to propose a cross-linked amphiphilic acrylate marine antifouling coating and its preparation method and application, and design and prepare a marine antifouling coating with high tensile strength and efficient antifouling. dirt coating.

The technical solutions adopted are:

A cross-linked amphiphilic acrylate marine antifouling coating of the present invention, the structural formula of the antifouling coating is as follows:

In the above formula, r1, r2, r3, r4, and r5 are the number of repeating units of random copolymerization, all of which are natural numbers >1; the repeating monomer of r1 is glycidyl methacrylate; the repeating monomer of r2 is methyl Methyl acrylate; the repeating monomer of r3 is polyethylene glycol methyl ether methacrylate, where n is a natural number between 26 and 30; the repeating monomer of r4 is hydroxyethyl acrylate; the repeating monomer of r5 is Isobornyl acrylate; the wavy line in the above structural formula represents the remaining structure of amino-terminated polydimethylsiloxane without bis-NH ₂ functional group, where m is the number of repeating units of siloxane, m=10-25 of natural numbers.

The preparation method of the above-mentioned cross-linked amphiphilic acrylate marine antifouling coating of the present invention includes the following steps:

S1. Preparation of amphiphilic acrylate polymer:

Add xylene and N-N-dimethylformamide into a round-bottomed flask equipped with a thermometer, magnetic stirrer and condenser, and add nitrogen; preheat to 85-90°C, combine xylene, N-N-dimethylformamide Formamide, glycidyl methacrylate, methyl methacrylate, polyethylene glycol methyl ether methacrylate, hydroxyethyl acrylate, isobornyl acrylate, and initiator are mixed evenly, and the above mixed liquid is added dropwise at a uniform speed ; After the dropwise addition is completed, dropwise add the mixed solution of benzoyl peroxide and xylene, and keep it warm after the dropwise addition is completed to obtain the amphiphilic acrylate polymer;

S2. Preparation of cross-linked amphiphilic acrylate marine antifouling coating:

Put amphiphilic acrylate polymer and xylene solvent into a container and stir evenly; add amino-terminated polydimethylsiloxane to the above mixed solution, fully react in a nitrogen environment, and obtain a cross-linked type after the reaction is completed Amphiphilic acrylic antifouling coating.

Further, the preparation method of the cross-linked amphiphilic acrylate marine antifouling coating includes the following steps:

S1. Preparation of amphiphilic acrylate polymer:

Add 15-25 parts by mass of xylene and 5-10 parts by mass of N-N-dimethylformamide into a round-bottomed flask equipped with a thermometer, magnetic stirrer and condenser tube, and add nitrogen; preheat to 85-90°C , 4-7 parts by mass of xylene, 9-11 parts by mass of N-N-dimethylformamide, 10-14 parts by mass of glycidyl methacrylate, 20-23 parts by mass of methyl methacrylate, 4-7 parts by mass 10-14 parts by mass of polyethylene glycol methyl ether methacrylate, 10-14 parts by mass of hydroxyethyl acrylate, 8-11 parts by mass of isobornyl acrylate, 0.4-1 parts by mass of initiator and mix evenly, and dropwise add the above mixed liquid at a constant speed ; After the dropwise addition is completed, add dropwise a mixed solution of 0.1-0.3 parts by mass of benzoyl peroxide and 4-7 parts by mass of xylene, and keep it warm for 1-2h after the dropwise addition is completed to obtain an amphiphilic acrylate polymer;

S2. Preparation of cross-linked amphiphilic acrylate marine antifouling coating:

Weigh 8-11 parts by mass of amphiphilic acrylate polymer and 4-6 parts by mass of xylene solvent in a container and stir evenly; add 0.1-2 parts by mass of amino-terminated polydimethylsiloxane to the above mixed solution , fully react in a nitrogen environment, and after the reaction is completed, a cross-linked amphiphilic acrylate antifouling coating is obtained.

Further, in S1, the initiator is one or both of azobisisobutyronitrile and azobisisovaleronitrile.

Further, in S1, use a constant pressure dropping funnel to drop the above mixed liquid at a constant speed for 3 hours.

Further, in S2, the reaction was carried out in a nitrogen atmosphere at 60°C for 4 hours.

Further, the preparation method of the cross-linked amphiphilic acrylate marine antifouling coating also includes S3. The coating prepared in S2 is applied on the surface of the substrate by spin coating and is heated and solidified.

Further, in S3, the spin coating speed was set to 1500-2000 rpm.

Furthermore, in S3, the curing temperature is 80°C.

The present invention relates to the application of the above-mentioned cross-linked amphiphilic acrylate marine antifouling coating on the surface of ships.

In the above technical solution,

The invention provides a marine antifouling coating that chemically reacts to form a cross-linked structure, thereby improving the tensile strength of the coating. The high tensile strength of the coating comes from the ring-opening reaction of amino-terminated polydimethylsiloxane and amphiphilic acrylate. The abundant epoxy groups on the amphiphilic acrylate side chain interact with the amino-terminated polydimethylsiloxane. The amino groups on both ends of the methylsiloxane react to form a cross-linked network. Amphiphilic acrylates are prepared by introducing borneol (isobornyl acrylate) and polyethylene glycol (polyethylene glycol methyl ether methacrylate) antifouling monomers into acrylic esters using a free radical polymerization method to impart resistance to the coating. The ability of marine fouling organisms to adhere.

In the preparation method of the cross-linked amphiphilic acrylate antifouling coating, the amphiphilic acrylate polymer is first prepared through free radical polymerization; then amino-terminated polydimethylsiloxane and amphiphilic acrylic are used The epoxy group in the ester polymer undergoes a ring-opening reaction to prepare the coating, and a cross-linked amphiphilic acrylate polymer with a general structure is obtained. The polymer can be further dried and solidified on the substrate by spin coating to obtain an antifouling coating. The antifouling coating is a high-performance, environmentally friendly, static marine antifouling coating. The cross-linked design improves mechanical strength to meet practical applications in complex marine environments.

To sum up, the beneficial effects of the present invention are:

1. The preparation process is simple and controllable, and the cross-linked structure of the coating exists stably under seawater conditions.

2. The ring-opening reaction between the amino functional groups at both ends of amino-terminated polydimethylsiloxane and the amphiphilic acrylate rich in epoxy functional groups in the side chain improves the tensile strength of the coating.

3. The free radical polymerization method introduces borneol and polyethylene glycol side chains to construct an amphiphilic polymer to resist the adhesion of bacteria and diatoms in the ocean.

Description of the drawings

Figure 1 is a stress-strain curve diagram of the cross-linked amphiphilic acrylate marine antifouling coating of Examples 1-4;

Figure 2 is a diagram showing the experimental results of the cross-linked amphiphilic acrylate marine antifouling coatings inhibiting Dimycoides algae in Examples 1-4 and Comparative Example 1;

Figure 3 is a graph showing the experimental results of the cross-linked amphiphilic acrylate marine antifouling coatings inhibiting Nitzschia microphylla in Examples 1-4 and Comparative Example 1;

Figure 4 is a graph showing the experimental results of the cross-linked amphiphilic acrylate marine antifouling coatings inhibiting Escherichia coli in Examples 1-4 and Comparative Example 1;

Figure 5 is a graph showing the experimental results of the cross-linked amphiphilic acrylate marine antifouling coatings inhibiting Staphylococcus aureus in Examples 1-4 and Comparative Example 1;

Figure 6 is a graph showing the experimental results of the cross-linked amphiphilic acrylate marine antifouling coating in Examples 1-4 and Comparative Example 1 for inhibiting Pseudoalteromonas Xiamenensis.

Detailed ways

The present invention will be described in detail below through specific examples. However, the purpose and purpose of these exemplary embodiments are only to illustrate the present invention, and do not constitute any form of limitation on the actual protection scope of the present invention, let alone limit the scope of the present invention. The scope of protection is limited to this.

Example 1

The preparation method of a cross-linked amphiphilic acrylate marine antifouling coating in this embodiment includes the following steps:

Step 1: Preparation of amphiphilic acrylate polymer:

Xylene (20g) and N-N-dimethylformamide (10g) were added to a three-neck flask. The entire device was equipped with a thermometer, a magnetic stirrer and a condenser tube and was filled with nitrogen in advance. The three-neck flask is heated to 85-90°C, and then xylene (5g), N-N-dimethylformamide (10g), glycidyl methacrylate (12g), methyl methacrylate (21g), poly Ethylene glycol methyl ether methacrylate (6g), hydroxyethyl acrylate (12g), isobornyl acrylate (9g), 0.5g initiator (azobisisobutyronitrile and azobisisovaleronitrile) mixed Evenly, use a constant pressure dropping funnel to drop the above mixed liquid at a constant speed for 3 hours. After the dropwise addition is completed, continue to dropwise add a mixed solution of 0.1g benzoyl peroxide and 5g xylene. After the dropwise addition is completed, keep it warm for 1-2 hours to obtain an amphiphilic acrylate polymer, recorded as A;

Step 2: Preparation of cross-linked amphiphilic acrylate marine antifouling coating:

Weigh 10g of amphiphilic acrylate polymer and 5g of xylene in a three-neck flask and stir evenly, add 1g of amino-terminated polydimethylsiloxane to the above solution, and react for 4 hours at 60°C in a nitrogen atmosphere. After the reaction, a cross-linked amphiphilic acrylate antifouling coating is obtained, marked as B;

Step 3: Use spin coating method B to spin-coat on the substrate to obtain coating C at 80°C.

Conduct the following experiments to test the performance of the coating:

Coating tensile property test: Prepare the sample into a dumbbell shape, use a universal testing machine to test the mechanical properties of the material, and test three parallel samples for each sample. Figure 1 is the stress-strain curve of the cross-linked amphiphilic acrylate marine antifouling coating;

The tensile strength and elongation at break of the material were calculated to be 3.15MPa and 113%.

Laboratory diatom inhibition experiment: The coating size is made into 2.5cm × 3.5cm, and a blank glass piece is selected as a control sample. The sample and blank are soaked in two model algae species (Bibliophora and Nitzschia microphylla), respectively. Soak in the algae solution for 2 days and 7 days. After taking out the sample, rinse the unattached diatoms on the surface with deionized water. Photograph the algae adhesion on the coating under an optical microscope. 5 randomly selected areas of each coating are photographed. Calculate the number of diatom cells on the sample and blank glass slides using the formula:

Among them, D is the inhibition rate of diatom attachment, C _B is the average number of diatom cells on the surface of the blank glass sheet, and C is the average number of diatom cells on the surface of the sample. Figures 2 and 3 show the experimental results of the cross-linked amphiphilic acrylate marine antifouling coating for inhibiting the algae and Nitzschia microphylla;

The calculated inhibition rates of Bibidium algae attachment and inhibition rate of Nitzschia micronensis attachment were 92.36% and 94.93% respectively.

Laboratory antibacterial experiment: Make the sample coating size into 2.5cm Co-cultivate (E. coli, Staphylococcus aureus), the incubation time is 12h and 24h respectively, dilute to the same multiple with nutrient solution, use the plate coating method to spread a certain amount of bacterial liquid on the solid culture medium (each sample is parallel Coating 3 times), incubate at 37°C for 12h and 24h respectively, take out the plate, and use the colony counting method to calculate the number of colonies on the sample and blank glass slide respectively, using the formula:

Where S is the inhibition rate of bacterial adhesion, N _B is the average number of bacterial adhesion on the surface of the blank glass slide, and N is the average number of bacterial adhesion on the sample surface. Figures 4, 5 and 6 show the experimental results of the cross-linked amphiphilic acrylate marine antifouling coating against Escherichia coli, Staphylococcus aureus and Pseudoalteromonas Xiamen;

The calculated antibacterial rates of Escherichia coli and Staphylococcus aureus were 96.6% and 80.5% respectively.

Pseudoalteromonas Xiamen (MCCC 1A06494) was selected as the model strain. The samples and blank glass slides were incubated with the bacterial solution at 28-30°C for 48 hours. They were diluted with nutrient solution to the same multiple and then spread using the plate coating method. Spread the bacterial solution on the solid culture medium (each sample is coated 3 times in parallel), incubate at 28-30°C for 48 hours, take out the plate, and use the colony counting method to count the number of colonies on the sample and blank glass slide respectively, and compare with the above inhibition The formula for calculating the bacterial attachment rate is the same, and the calculated bacteriostatic rate of Pseudoalteromonas Xiamen is 96.83%.

Comparative example 1

Referring to Example 1, the difference from Example 1 is that in the preparation process of a cross-linked amphiphilic acrylate marine antifouling coating, the amount of amino-terminated polydimethylsiloxane added is 0g, and the other methods remain unchanged, as shown in Example 1.

The test was carried out according to the test method of Example 1, as shown in Figures 2 to 6. The results are: this comparative example did not obtain tensile strength test data because a qualified test sample could not be obtained after curing; 89.69%, the inhibition rate of Nitzschia minor was 84.33%; the inhibition rate of Escherichia coli was 79.56%, the inhibition rate of Staphylococcus aureus was 42.76%, and the inhibition rate of Pseudoalteromonas Xiamen was 91.99%.

Example 2

Referring to Example 1, the difference from Example 1 is that in the preparation process of a cross-linked amphiphilic acrylate marine antifouling coating, the amount of amino-terminated polydimethylsiloxane added is 0.25g, and the other methods remain unchanged, as shown in Example 1.

The test was carried out according to the test method of Example 1, as shown in Figures 1 to 6. The results are: the inhibition rate of Bibilodium is 89.73%, the inhibition rate of Nitzschia minor is 86.7%; the inhibition rate of Escherichia coli is 88.06%. The inhibition rate of Staphylococcus aureus is 61.46%, and the inhibition rate of Pseudoalteromonas Xiamen is 95.21%; the tensile strength and elongation at break are 1.34MPa and 198% respectively.

Example 3

Referring to Example 1, the difference from Example 1 is that in the preparation process of a cross-linked amphiphilic acrylate marine antifouling coating, the amount of amino-terminated polydimethylsiloxane added is 0.5g, and the other methods remain unchanged, as shown in Example 1.

The test was carried out according to the test method of Example 1, as shown in Figures 1 to 6. The results are: the inhibition rate of Bibilodium is 89.76%, the inhibition rate of Nitzschia minor is 87.7%; the inhibition rate of Escherichia coli is 94.1%. The inhibition rate of Staphylococcus aureus is 67.4%, and the inhibition rate of Pseudoalteromonas Xiamen is 95.51%; the tensile strength and elongation at break are 1.70MPa and 161% respectively.

Example 4

Referring to Example 1, the difference from Example 1 is that in the preparation process of a cross-linked amphiphilic acrylate marine antifouling coating, the amount of amino-terminated polydimethylsiloxane added is 0.75g, and the other methods remain unchanged, as shown in Example 1.

The test was carried out according to the test method of Example 1, as shown in Figures 1 to 6. The results are: the inhibition rate of Bibigoella is 90.66%, the inhibition rate of Nitzschia minor is 90.23%; the inhibition rate of Escherichia coli is 95.2%. The inhibition rate of Staphylococcus aureus was 74.8%, and the inhibition rate of Pseudoalteromonas Xiamen was 96.05%; the tensile strength and elongation at break were 2.02MPa and 128% respectively.

The series of detailed descriptions listed above are only specific descriptions of feasible embodiments of the present invention. They are not intended to limit the protection scope of the present invention. Any equivalent embodiments or embodiments that do not deviate from the technical spirit of the present invention are not intended to limit the protection scope of the present invention. All changes should be included in the protection scope of the present invention.

Claims (10)

1. The cross-linked amphiphilic acrylate marine antifouling coating is characterized by comprising the following structural formula:

in the above formula, r1, r2, r3, r4 and r5 are random copolymerized repeating unit numbers, and are natural numbers more than 1; the monomer with r1 repeated is glycidyl methacrylate; r2 is methyl methacrylate; r3 is polyethylene glycol methyl ether methacrylate, wherein n is a natural number between 26 and 30; r4 is hydroxyethyl acrylate as a monomer; the monomer with r5 repeated is isobornyl acrylate; the wavy line in the above structure represents that the material does not have double-NH ₂ The remaining structure of the amino-terminated polydimethylsiloxane of the functional group, where m is the number of repeating units of the siloxane and m = natural number from 10 to 25.

2. A method for preparing the crosslinked amphiphilic acrylate marine antifouling coating of claim 1, comprising the steps of:

s1, preparing an amphiphilic acrylic ester polymer:

adding dimethylbenzene and N-N-dimethylformamide into a round bottom flask with a thermometer, a magnetic stirrer and a condenser, and introducing nitrogen; preheating to 85-90 ℃, uniformly mixing dimethylbenzene, N-N-dimethylformamide, glycidyl methacrylate, methyl methacrylate, polyethylene glycol methyl ether methacrylate, hydroxyethyl acrylate and isobornyl acrylate as an initiator, and dripping the mixed liquid at a uniform speed; after the dripping is completed, the mixed solution of benzoyl peroxide and dimethylbenzene is dripped, and the temperature is kept after the dripping is completed so as to obtain the amphiphilic acrylic ester polymer;

s2, preparing a crosslinked amphiphilic acrylic ester marine antifouling coating:

taking an amphiphilic acrylic polymer and a dimethylbenzene solvent in a container and uniformly stirring; adding amino-terminated polydimethylsiloxane into the mixed solution, fully reacting in a nitrogen environment, and obtaining the crosslinked amphiphilic acrylic ester antifouling coating after the reaction is finished.

3. The method for preparing the crosslinked amphiphilic acrylate marine antifouling coating according to claim 2, comprising the following steps:

s1, preparing an amphiphilic acrylic ester polymer:

15-25 parts by mass of xylene and 5-10 parts by mass of N-N-dimethylformamide are added to a round-bottomed flask equipped with a thermometer, a magnetic stirrer and a condenser, and nitrogen is introduced; preheating to 85-90 ℃, uniformly mixing 4-7 parts by mass of dimethylbenzene, 9-11 parts by mass of N-N-dimethylformamide, 10-14 parts by mass of glycidyl methacrylate, 20-23 parts by mass of methyl methacrylate, 4-7 parts by mass of polyethylene glycol methyl ether methacrylate, 10-14 parts by mass of hydroxyethyl acrylate and 8-11 parts by mass of isobornyl acrylate, and dropwise adding the mixed liquid at a uniform speed, wherein the initiator is 0.4-1 part by mass; after the dripping is completed, 0.1 to 0.3 mass part of benzoyl peroxide and 4 to 7 mass parts of dimethylbenzene mixed solution are dripped, and the temperature is kept for 1 to 2 hours after the dripping is completed so as to obtain the amphiphilic acrylic ester polymer;

s2, preparing a crosslinked amphiphilic acrylic ester marine antifouling coating:

weighing 8-11 parts by mass of amphiphilic acrylate polymer and 4-6 parts by mass of xylene solvent in a container, and uniformly stirring; adding 0.1-2 parts by mass of amino-terminated polydimethylsiloxane into the mixed solution, fully reacting in a nitrogen environment, and obtaining the crosslinked amphiphilic acrylic ester antifouling coating after the reaction is finished.

4. The method for preparing a crosslinked amphiphilic acrylate marine antifouling coating according to claim 3, wherein in S1, the initiator is one or two of azobisisobutyronitrile and azobisisovaleronitrile.

5. The method for preparing a crosslinked amphiphilic acrylate marine antifouling coating according to claim 3, wherein in S1, the mixed liquid is dropped into the coating at a constant speed by a constant pressure dropping funnel for 3 hours.

6. The method for preparing a crosslinked amphiphilic acrylate marine antifouling coating according to claim 3, wherein in S2, the reaction is performed for 4 hours at 60 ℃ in a nitrogen atmosphere.

7. The method for preparing the crosslinked amphiphilic acrylate marine antifouling coating according to claim 3, further comprising the steps of S3, coating the coating prepared by S2 on the surface of a substrate by adopting a spin coating mode, and heating and curing.

8. The method for producing a crosslinked amphiphilic acrylate marine antifouling coating according to claim 7, wherein in S3, the spin coating speed is set to 1500-2000rmp.

9. The method for preparing a crosslinked amphiphilic acrylate marine antifouling coating according to claim 7, wherein in S3, the curing temperature is 80 ℃.

10. Use of the crosslinked amphiphilic acrylate marine antifouling coating of claim 1 on a marine vessel surface.