Antifouling and antibacterial coating material as well as preparation method and application thereof

Abstract

The invention relates to the field of new materials, and discloses an antifouling and antibacterial coating material as well as a preparation method and application thereof, and the antifouling and antibacterial coating material comprises glycidyl methacrylate, a methacrylate betaine monomer and a methacrylate quaternary ammonium salt monomer. Compared with a release type antifouling and antibacterial coating, the antifouling and antibacterial coating material adopts a bionic technology, uses sulphobetaine as a functional group, is good in biocompatibility, does not contain toxic or heavy metal antibacterial agents, can ensure that the material is non-toxic for a long time, realizes eco-friendly long-acting antifouling and antibacterial effects, can be combined with a large number of water molecules, and has the advantages of being environmentally friendly and free of pollution. The coating contains quaternary ammonium salt monomers, forms a hydration layer on the surface, keeps certain biological inertness, reduces protein adsorption, contains the quaternary ammonium salt monomers, has excellent inhibition and killing effects on various bacterial infections, overcomes the problem that the coating is easy to fall off, and realizes firm bonding of the surface of the pipeline.

Description

Technical Field

[0001] The present invention relates to the field of new materials, and in particular to an antifouling and antibacterial coating material and a preparation method and application thereof. Background Art

[0002] Marine biofouling caused by the attachment, growth and reproduction of marine organisms is a major problem faced by marine engineering equipment and facilities during their service. As an important tool for mass transfer and transportation, various pipelines, especially polymer and composite pipelines, have the advantages of high mechanical strength, good stability, chemical corrosion resistance and good electrical insulation performance. They are widely used in the fields of shipbuilding and marine engineering (such as desulfurization, ballast, cooling, spraying and fire fighting, etc.). However, during the service of the pipeline, the attachment and growth of marine organisms will make the pipe wall thicker or even block the pipeline, resulting in obstruction of mass transfer, reduced efficiency, increased energy consumption, and affecting the normal operation of the equipment. Replacing pipelines and cleaning internal and external pollution will cause frequent downtime and increase operating costs. Therefore, anti-fouling and antibacterial properties of pipelines are of great significance to the normal operation of marine engineering equipment and facilities.

[0003] In order to reduce the attachment and growth of marine microorganisms and bacteria, mechanical cleaning and antifouling material coating are usually used. Pipeline antifouling includes physical and chemical methods. Physical methods include ultrasonic cleaning, magnetic field cleaning, ultraviolet irradiation and embedded cleaning. They are environmentally friendly and pollution-free and only require general maintenance after installation, but they require the design of supporting equipment. Due to space constraints, it is difficult to design ideal physical antifouling equipment for in-service marine facilities, so their application is limited. Chemical antifouling methods use oxidizing or non-oxidizing compounds to prevent fouling. Oxidizing compounds include sodium hypochlorite, chlorine dioxide and ozone, which achieve antifouling purposes by destroying important structures of microbial cells. Non-oxidizing compounds include isothiazolinone, aldehyde bactericides, quaternary ammonium salts, and fatty amine antifouling agents, which achieve antifouling purposes by attacking specific targets in cells (such as cytoplasmic components). Chemical antifouling is the mainstream method for pipeline antifouling today due to its easy operation and good antifouling effect. It will remain one of the important methods for pipeline antifouling for some time to come. However, for the purpose of protecting the environment, the dosage of toxic agents is limited, making it difficult to achieve the expected effect.

[0004] In order to solve the problem of anti-fouling and anti-bacterial of pipelines, anti-fouling and anti-bacterial coating treatment on the pipeline surface has become an effective and major means.

[0005] The development of environmentally friendly marine antifouling and antibacterial materials has given polymer surface coatings new connotations, including hydrophilic, non-toxic and biomimetic directions: (1) Hydrophilic direction, introducing hydrophilic components such as hydrophilic polymers and zwitterions into the coating, mainly reducing the attachment of macroscopic organisms by inhibiting the formation of conditional membranes and biofilms, but the introduction of too many hydrophilic groups will lead to a serious deterioration of the underwater mechanical properties of the coating, and too few hydrophilic groups will not be able to effectively inhibit the formation of conditional membranes and biofilms; (2) Non-toxic direction, including the application of natural antifouling agents and synthetic non-toxic antifouling agents, but these antifouling agents are released quickly in seawater, easily degraded, and have a short antifouling life; (3) Bionic micro-nanostructure surface antifouling, but this type of antifouling surface is not easy to prepare on a large scale, and is easy to wear and difficult to regenerate. Therefore, the environmentally friendly marine antifouling materials reported so far face difficulties in practical application. Summary of the invention

[0006] In order to meet the actual needs of marine antifouling and antibacterial, the present invention proposes an antifouling and antibacterial coating material with adsorption inhibition, good bioaffinity, firm structure and bactericidal function, as well as a preparation method and application thereof.

[0007] To achieve the above-mentioned purpose, the present invention provides the following technical solution: an antifouling and antibacterial coating material, comprising glycidyl methacrylate, methacrylate betaine monomer and methacrylate quaternary ammonium salt monomer, the antifouling and antibacterial coating material is composed of glycidyl methacrylate, methacrylate betaine monomer and methacrylate quaternary ammonium salt monomer and is obtained by free radical polymerization.

[0008] Preferably, the methacrylate betaine monomer is methacryloyloxyethyl sulfobetaine, and the methacrylate quaternary ammonium salt monomer is methacryloyloxyethyl trimethylammonium chloride.

[0009] Preferably, the molar ratio of glycidyl methacrylate, methacryloyloxyethyl sulfobetaine, and methacryloyloxyethyl trimethylammonium chloride is (0.1-0.3): (0.7-0.9): (0.01-0.1).

[0010] A method for preparing an antifouling and antibacterial coating material comprises the following steps: S1: dissolving glycidyl methacrylate, methacryloyloxyethyl sulfobetaine, methacryloyloxyethyl trimethylammonium chloride monomers and initiator azobisisobutyronitrile in a methanol / water mixed solvent, deoxygenating and reacting at 50-70°C for 3-5h under nitrogen protection; S2: After the reaction is completed, methanol is used for precipitation and washing, and then dried to obtain a white crystalline powder, which is the antifouling and antibacterial polymer.

[0011] Preferably, the volume ratio of methanol to water in the methanol / water mixed solvent in S1 is (1-3):1.

[0012] The invention discloses an application of an antifouling and antibacterial coating material, wherein the antifouling and antibacterial coating material is used to prevent biological fouling, inhibit bacterial adhesion and growth, and is an antifouling and antibacterial coating for preventing fouling and antibacterial effects on the surface of a pipeline.

[0013] Compared with the prior art, the beneficial effects of the present invention are: the antifouling and antibacterial coating material, 1. The antifouling and antibacterial coating material can achieve the purpose of antifouling and antibacterial. Compared with the release-type antifouling and antibacterial coating, this coating adopts bionic technology and uses sulfobetaine as the functional group. It has good biocompatibility and does not contain toxic or heavy metal antibacterial agents. It can ensure that the material is non-toxic for a long time and achieve eco-friendly and long-term antifouling and antibacterial properties. 2. The antifouling and antibacterial coating material can achieve the purpose of reducing the adsorption of proteins. Due to the presence of quaternary ammonium groups and sulfonate groups in the sulfobetaine group, the coating maintains equal amounts of positive and negative charges in the same molecule, can bind a large number of water molecules, form a hydration layer on the surface, and maintain a certain degree of biological inertness, thereby reducing the adsorption of proteins; 3. The antifouling and antibacterial coating material can achieve the purpose of antibacterial. The coating contains quaternary ammonium salt monomers, which have excellent inhibitory and killing effects on various bacterial infections; 4. The antifouling and antibacterial coating material can achieve the purpose of increasing the connection strength. The coating overcomes the problem of easy shedding of the coating. The present invention uses epoxy group copolymerization so that the coating can be cured later to enhance the connection strength between the coating and the substrate surface, thereby achieving firm bonding to the pipeline surface. DETAILED DESCRIPTION

[0014] An antifouling and antibacterial coating material comprises glycidyl methacrylate, methacrylate betaine monomers and methacrylate quaternary ammonium salt monomers. The antifouling and antibacterial coating material is composed of glycidyl methacrylate, methacrylate betaine monomers and methacrylate quaternary ammonium salt monomers and is obtained by free radical polymerization. The preparation steps include: mixing glycidyl methacrylate, methacryloyloxyethyl sulfobetaine, and methacryloyloxyethyl trimethylammonium chloride monomers in a molar ratio of (0.1-0.3): (0.7-0.9): (0.01-0.1) under deoxygenation and nitrogen protection, using azobisisobutyronitrile as an initiator, and reacting in a methanol / water mixed solvent at a temperature of 50-70°C for 3-5 hours. After the reaction is completed, methanol is used for precipitation and washing, and a white crystalline powder is obtained after drying, which is the antifouling and antibacterial polymer.

[0015] Example 1: 20 mmol of glycidyl methacrylate was dissolved in 50 mL of methanol, 80 mmol of methacryloyloxyethyl sulfobetaine and 3 mmol of quaternary ammonium salt of methacrylate were mixed and dissolved in 50 mL of deionized water, mixed and stirred for 15 min, then purged with nitrogen for 30 min, and then 1 mmol of initiator azobisisobutyronitrile and 5 mmol of chain transfer agent trimercaptopropionic acid were added, and then stirred appropriately to fully dissolve, and the solution was placed in a 60°C oil bath and stirred for 3 h. After the reaction was completed, a cold water bath was placed for more than 3 h to precipitate, and the precipitate was purified three times with methanol and dried to obtain a white crystalline powder.

[0016] The obtained white crystalline powder was dissolved in deionized water to form a 10wt.% polymer aqueous solution, and 1% triethylamine was added to the aqueous solution by volume, and the mixture was stirred evenly. The substrate was fully infiltrated with the mixed solution by dip coating. After 10 minutes, the glass fiber reinforced epoxy resin GRE sheet immersed in the mixed solution was taken out and dried naturally. The dried sample surface coating can be used for antifouling and antibacterial performance testing.

[0017] Example 2: 20 mmol of glycidyl methacrylate was dissolved in 50 mL of methanol, 80 mmol of methacryloyloxyethyl sulfobetaine and 5 mmol of quaternary ammonium salt of methacrylate were mixed and dissolved in 50 mL of deionized water, mixed and stirred for 15 min, then purged with nitrogen for 30 min, and then 1 mmol of initiator azobisisobutyronitrile and 5 mmol of chain transfer agent trimercaptopropionic acid were added, and then stirred appropriately to fully dissolve, and the solution was placed in a 60°C oil bath and stirred for 3 h. After the reaction was completed, a cold water bath was placed for more than 3 h to precipitate, and the precipitate was purified three times with methanol and dried to obtain a white crystalline powder.

[0018] The preparation method of the polymer coating is the same as that of Example 1.

[0019] Example 3: 20 mmol of glycidyl methacrylate was dissolved in 50 mL of methanol, 80 mmol of methacryloyloxyethyl sulfobetaine and 10 mmol of quaternary ammonium salt of methacrylate were mixed and dissolved in 50 mL of deionized water, mixed and stirred for 15 min, then purged with nitrogen for 30 min, and then 1 mmol of initiator azobisisobutyronitrile and 5 mmol of chain transfer agent trimercaptopropionic acid were added, and then stirred appropriately to fully dissolve, and the solution was placed in a 60°C oil bath and stirred for 3 h. After the reaction was completed, a cold water bath was placed for more than 3 h to precipitate, and the precipitate was purified three times with methanol and dried to obtain a white crystalline powder.

[0020] The preparation method of the polymer coating is the same as that of Example 1.

[0021] Example 4: 20 mmol of glycidyl methacrylate was dissolved in 25 mL of methanol, 80 mmol of methacryloyloxyethyl sulfobetaine and 10 mmol of quaternary ammonium salt of methacrylate were mixed and dissolved in 75 mL of deionized water, mixed and stirred for 15 min, then purged with nitrogen for 30 min, and then 1 mmol of initiator azobisisobutyronitrile and 5 mmol of chain transfer agent trimercaptopropionic acid were added, and then stirred appropriately to fully dissolve, and the solution was placed in a 60°C oil bath and stirred for 3 h. After the reaction was completed, a cold water bath was placed for more than 3 h to precipitate, and the precipitate was purified three times with methanol and dried to obtain a white crystalline powder.

[0022] The preparation method of the polymer coating is the same as that of Example 1.

[0023] Example 5: 20 mmol of glycidyl methacrylate was dissolved in 25 mL of methanol, 80 mmol of methacryloyloxyethyl sulfobetaine and 10 mmol of quaternary ammonium salt of methacrylate were mixed and dissolved in 75 mL of deionized water, mixed and stirred for 15 min, then purged with nitrogen for 30 min, and then 1 mmol of initiator azobisisobutyronitrile and 5 mmol of chain transfer agent trimercaptopropionic acid were added, and then stirred appropriately to fully dissolve, and the solution was placed in a 70°C oil bath and stirred for 3 h. After the reaction was completed, a cold water bath was placed for more than 3 h to precipitate, and the precipitate was purified three times with methanol and dried to obtain a white crystalline powder.

[0024] The preparation method of the polymer coating is the same as that of Example 1.

[0025] Example 6: 20 mmol of glycidyl methacrylate was dissolved in 33 mL of methanol, 80 mmol of methacryloyloxyethyl sulfobetaine and 10 mmol of quaternary ammonium salt of methacrylate were mixed and dissolved in 67 mL of deionized water, mixed and stirred for 15 min, then purged with nitrogen for 30 min, then 1 mmol of initiator azobisisobutyronitrile and 5 mmol of chain transfer agent trimercaptopropionic acid were added, and then stirred appropriately to fully dissolve, and the solution was placed in a 50°C oil bath and stirred for 5 h. After the reaction was completed, a cold water bath was placed for more than 3 h to precipitate, and the precipitate was purified three times with methanol and dried to obtain a white crystalline powder.

[0026] The preparation method of the polymer coating is the same as that of Example 1.

[0027] Comparative Example 1: Dissolve 20mmol of glycidyl methacrylate and 80mmol of methacryloyloxyethyl sulfobetaine in 50mL of methanol and 50mL of deionized water, respectively, mix and stir for 15min, then purge with nitrogen for 30min, then add 1mmol of initiator azobisisobutyronitrile and 5mmol of chain transfer agent trimercaptopropionic acid, stir appropriately to fully dissolve, place the solution in a 60℃ oil bath and stir for 3h. After the reaction is completed, cool the solution in a water bath for more than 3h to precipitate, purify the precipitate with methanol three times, and dry to obtain a white crystalline powder.

[0028] The preparation method of the polymer coating is the same as that of Example 1.

[0029] The coating samples obtained in Examples 1-6 and Comparative Example 1 were subjected to antifouling and antibacterial experiments. Bovine serum albumin was used to test the anti-protein adhesion performance of the coating, and Gram-positive bacteria Staphylococcus aureus and Gram-negative bacteria Escherichia coli were used to test the antibacterial effect of the coating.

[0030] In summary, the antifouling and antibacterial coating material achieves the purpose of antifouling and antibacterial, reducing protein adsorption, inhibiting bacteria and increasing connection strength, and meets people's usage needs.

[0031] Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. An antifouling and antibacterial coating material, characterized in that: The antifouling and antibacterial coating material comprises glycidyl methacrylate, methacrylate betaine monomer and methacrylate quaternary ammonium salt monomer. The antifouling and antibacterial coating material is composed of glycidyl methacrylate, methacrylate betaine monomer and methacrylate quaternary ammonium salt monomer and is obtained through free radical polymerization.

2. The antifouling and antibacterial coating material according to claim 1, characterized in that: The methacrylate betaine monomer is methacryloyloxyethyl sulfobetaine, and the methacrylate quaternary ammonium salt monomer is methacryloyloxyethyl trimethylammonium chloride.

3. The antifouling and antibacterial coating material according to claim 1, characterized in that: The molar ratio of glycidyl methacrylate, methacryloyloxyethyl sulfobetaine and methacryloyloxyethyl trimethylammonium chloride is (0.1-0.3): (0.7-0.9): (0.01-0.1).

4. A method for preparing an antifouling and antibacterial coating material, characterized in that: The following steps are involved: S1: dissolving glycidyl methacrylate, methacryloyloxyethyl sulfobetaine, methacryloyloxyethyl trimethylammonium chloride monomers and initiator azobisisobutyronitrile in a methanol / water mixed solvent, deoxygenating and reacting at 50-70°C for 3-5h under nitrogen protection; S2: After the reaction is completed, methanol is used for precipitation and washing, and then dried to obtain a white crystalline powder, which is the antifouling and antibacterial polymer.

5. The method for preparing the antifouling and antibacterial coating material according to claim 4, characterized in that: The volume ratio of methanol to water in the methanol / water mixed solvent in S1 is (1-3):

1.

6. An application of an antifouling and antibacterial coating material, characterized in that: The antifouling and antibacterial coating material is used to prevent biological fouling, inhibit bacterial adhesion and growth, and is used as an antifouling and antibacterial coating for preventing fouling and antibacterial effects on the surface of pipelines.