CN117210130A - Cross-linked amphiphilic acrylate marine antifouling coating and preparation method and application thereof - Google Patents
Cross-linked amphiphilic acrylate marine antifouling coating and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 claims description 6
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- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
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- 238000005303 weighing Methods 0.000 claims description 3
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- Paints Or Removers (AREA)
Abstract
The invention discloses a crosslinked amphiphilic acrylic ester marine antifouling coating and a preparation method and application thereof, wherein in the preparation method of the crosslinked amphiphilic acrylic ester antifouling coating, an amphiphilic acrylic ester polymer is prepared by a free radical polymerization method; and then, performing ring-opening reaction on amino-terminated polydimethylsiloxane and epoxy groups in the amphiphilic acrylate polymer to prepare a coating, so as to obtain the crosslinked amphiphilic acrylate polymer with the general structure. The polymer can be further dried and solidified on the substrate by a spin coating method to obtain the antifouling coating. The antifouling coating is a high-performance environment-friendly static marine antifouling coating, and the mechanical strength is improved by the cross-linking design, so that the practical application in a complex marine environment is satisfied.
Description
Technical Field
The invention relates to the field of marine antifouling coatings, in particular to a crosslinked amphiphilic acrylic ester marine antifouling coating, and a preparation method and application thereof.
Background
The fouling organism problem is a common problem of marine facilities, and microorganisms, animals and plants in the ocean can adhere to the surfaces of equipment to form macroscopic dirt, so that adverse effects such as ship weight gain and biological invasion are caused, and the development of the marine industry is limited. The application of antifouling paint is the simplest and most efficient way to solve biofouling, traditional antifouling paint kills fouling organisms on the surface by releasing biocides or toxic metals, but researches show that releasing toxic substances into seawater can cause deformity in organisms and violate an environment-friendly strategy although the problem of fouling adhesion is obviously solved. Marine biofilm is a critical step in the process of attachment of fouling organisms, providing powerful conditions for the proliferation and attachment of subsequent fouling, and thus, the control of biofilm formation from the source is an effective strategy. The traditional acrylic coating belongs to the self-polishing type, and side chains are hydrolyzed and peeled off layer by layer under seawater soaking to remove fouling organisms attached to the surface. However, the internal and surface structures of the coating layer are destroyed, resulting in a decrease in mechanical properties, and the inventors have found that the introduction of functional groups to design a crosslinked structure can reduce such problems.
Chinese patent document CN103694421B (patent No. 201310642570.6) discloses a self-crosslinking type low surface energy antifouling paint resin and a preparation method thereof, in which polysiloxane acrylate, methacrylate and KH-570 are polymerized by a solution polymerization method. The polymer can be self-crosslinked by moisture, so that the mechanical property of the coating can be improved; the side chains contain polysiloxane chains to provide fouling release properties to the coating.
Chinese patent document CN115584153B (patent No. 202211292892.8) discloses a modified silicone marine antifouling coating based on an ion network and a preparation method thereof, the strength and toughness of the coating are improved based on a strong cross-linking structure of polysiloxane, and imidazole salt and benzene tetracarboxylic acid are introduced to endow the coating with good elasticity and high energy dissipation. The double-network coating formed by combining the two has excellent marine antifouling capacity and strong adhesive force to various base materials.
The invention starts from different inventive concepts and aims at designing a marine antifouling coating with high tensile strength and high antifouling efficiency.
Disclosure of Invention
In view of the above, the invention aims to provide a cross-linked amphiphilic acrylic ester marine antifouling coating, and a preparation method and application thereof, and designs and prepares the marine antifouling coating with high tensile strength and high antifouling efficiency.
The adopted technical scheme is as follows:
the invention relates to a crosslinked amphiphilic acrylic ester marine antifouling coating, which has 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.
The preparation method of the crosslinked amphiphilic acrylate marine antifouling coating comprises the following steps:
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 ester 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.
Further, the preparation method of the crosslinked amphiphilic acrylate marine antifouling coating comprises 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.
Further, in S1, the initiator is one or both of azobisisobutyronitrile and azobisisovaleronitrile.
Further, in S1, the above mixed liquid was dropped with a constant pressure dropping funnel at a constant speed for 3 hours.
Further, in S2, the reaction was carried out under a nitrogen atmosphere at 60℃for 4 hours.
Further, the preparation method of the crosslinked amphiphilic acrylic ester marine antifouling coating further comprises the steps of S3, coating the coating prepared in the step S2 on the surface of a substrate in a spin coating mode, and heating and curing.
Further, in S3, the spin coating speed is set to 1500-2000rmp.
Further, in S3, the curing temperature is 80 ℃.
The application of the crosslinked amphiphilic acrylate marine antifouling coating on the surface of a ship is disclosed.
In the technical proposal described above, the method comprises the steps of,
the invention provides a marine antifouling coating which is formed into a crosslinked structure through chemical reaction so as to improve the tensile strength of the coating. The high tensile strength of the coating is derived from the ring-opening reaction of the amino-terminated polydimethylsiloxane and the amphiphilic acrylic ester, and the abundant epoxy groups on the side chains of the amphiphilic acrylic ester react with the amino groups at the two ends of the amino-terminated polydimethylsiloxane to form a crosslinked network. The amphipathic acrylic ester is prepared by introducing borneol (isobornyl acrylate) and polyethylene glycol (polyethylene glycol methyl ether methacrylate) antifouling monomers into acrylic ester by a free radical polymerization method, so that the coating has the capability of resisting marine fouling organism adhesion.
In the preparation method of the crosslinked amphiphilic acrylate antifouling coating, firstly, preparing an amphiphilic acrylate polymer by a free radical polymerization method; and then, performing ring-opening reaction on amino-terminated polydimethylsiloxane and epoxy groups in the amphiphilic acrylate polymer to prepare a coating, so as to obtain the crosslinked amphiphilic acrylate polymer with the general structure. The polymer can be further dried and solidified on the substrate by a spin coating method to obtain the antifouling coating. The antifouling coating is a high-performance environment-friendly static marine antifouling coating, and the mechanical strength is improved by the cross-linking design, so that the practical application in a complex marine environment is satisfied.
In summary, the invention has the following beneficial effects:
1. the preparation process is simple and controllable, and the crosslinked structure of the coating exists stably under the seawater condition.
2. The ring-opening reaction of the amino functional groups at the two ends of the amino-terminated polydimethylsiloxane and the amphiphilic acrylic ester with the side chain rich in epoxy functional groups improves the tensile strength of the coating.
3. And introducing borneol and polyethylene glycol side chains by a free radical polymerization method to construct an amphiphilic polymer for resisting adhesion of bacteria and diatom in the ocean.
Drawings
FIG. 1 is a stress-strain plot of the crosslinked amphiphilic acrylate marine antifouling coatings of examples 1-4;
FIG. 2 is a graph of experimental results of inhibition of Phaeophyta by the crosslinked amphiphilic acrylate marine antifouling coatings of examples 1-4 and comparative example 1;
FIG. 3 is a graph of experimental results of the inhibition of the marine antifouling coatings of the crosslinked amphiphilic acrylates of examples 1-4 and comparative example 1 against Nicotiana microphylla;
FIG. 4 is a graph of experimental results of inhibition of E.coli by the crosslinked amphiphilic acrylate marine antifouling coatings of examples 1-4 and comparative example 1;
FIG. 5 is a graph of experimental results of inhibition of Staphylococcus aureus by the crosslinked amphiphilic acrylate marine antifouling coatings of examples 1-4 and comparative example 1;
FIG. 6 is a graph showing the results of experiments on the inhibition of Pseudomonas mansoni by the crosslinked amphiphilic acrylate marine antifouling coatings of examples 1-4 and comparative example 1.
Detailed Description
The present invention will be described in detail by way of specific examples, but the purpose and purpose of these exemplary embodiments are merely to illustrate the present invention, and are not intended to limit the actual scope of the present invention in any way.
Example 1
The preparation method of the crosslinked amphiphilic acrylate marine antifouling coating comprises the following steps:
step one: preparation of amphiphilic acrylate polymer:
xylene (20 g) and N-N-dimethylformamide (10 g) were charged into a three-necked flask, and the whole apparatus was equipped with a thermometer, a magnetic stirrer and a condenser tube and purged with nitrogen. The three-necked flask was heated to 85-90℃and then xylene (5 g), N-N-dimethylformamide (10 g), glycidyl methacrylate (12 g), methyl methacrylate (21 g), polyethylene glycol methyl ether methacrylate (6 g), hydroxyethyl acrylate (12 g), isobornyl acrylate (9 g), 0.5g of an initiator (azobisisobutyronitrile and azobisisovaleronitrile) were uniformly mixed, and the above mixed liquid was added dropwise at a constant speed for 3 hours using a constant pressure dropping funnel. After the dripping is finished, continuously dripping 0.1g of mixed solution of benzoyl peroxide and 5g of dimethylbenzene, and preserving heat for 1-2h after the dripping is finished to obtain an amphiphilic acrylic ester polymer, which is marked as A;
step two: preparing a crosslinked amphiphilic acrylic ester marine antifouling coating:
weighing 10g of amphiphilic acrylate polymer and 5g of dimethylbenzene, uniformly stirring in a three-necked flask, adding 1g of amino-terminated polydimethylsiloxane into the solution, reacting for 4 hours at 60 ℃ in a nitrogen environment, and obtaining a crosslinked amphiphilic acrylate antifouling coating after the reaction is finished, which is marked as B;
step three: spin coating is carried out on the base material by adopting a spin coating mode B, and the coating C is obtained at 80 ℃.
The following experiments were performed to test the properties of the coatings:
coating tensile property test: samples were prepared into dumbbell shapes, and the mechanical properties of the materials were tested using a universal tester, three parallel samples per sample. FIG. 1 is a stress-strain graph of a crosslinked amphiphilic acrylate marine antifouling coating;
the tensile strength and elongation at break of the material were calculated to be 3.15MPa and 113%.
Laboratory inhibition diatom experiments: the coating size is made to be 2.5cm multiplied by 3.5cm, a blank glass sheet is selected as a control sample, the sample and the blank are soaked in two model algae species (double-eyebrow algae and small-crescent diamond algae) respectively, the samples are soaked in algae liquid for 2 days and 7 days, the diatom with unattached surface is washed by deionized water after the samples are taken out, the algae attachment condition on the coating is photographed under an optical microscope respectively, 5 regions are randomly selected for photographing of each coating, and the cell number of the diatom on the sample and the blank glass sheet is calculated by the formula:
wherein D is the inhibition of diatom attachment rate, C B The average value of the number of diatom cells on the surface of the blank glass sheet is given, and C is the average value of the number of diatom cells on the surface of the sample. Fig. 2 and 3 are graphs of experimental results of inhibition of the cross-linked amphiphilic acrylate marine antifouling coating against bindweed and crescendo not;
the calculated inhibition ratio of the attachment of the double-eyebrow alga and the inhibition ratio of the attachment of the small crescent diamond alga are 92.36 percent and 94.93 percent respectively.
Laboratory antibacterial experiments: preparing a sample coating with the size of 2.5cm multiplied by 3.5cm, preparing a blank glass sheet with the size of 2.5cm multiplied by 3.5cm as a control sample, co-culturing the sample, the blank glass sheet and bacterial liquid at 37 ℃ (escherichia coli and staphylococcus aureus) for 12h and 24h respectively, diluting the bacterial liquid to the same multiple, coating a certain amount of bacterial liquid on a solid culture medium (each sample is coated for 3 times in parallel) by adopting a flat plate coating method, culturing for 12h and 24h respectively under the condition of 37 ℃, taking out a flat plate, and calculating the colony numbers on the sample and the blank glass sheet respectively by adopting a colony counting method, wherein the colony numbers are calculated by the following formula:
wherein S is the inhibition of bacterial attachment, N B The average value of the number of bacterial adhesion on the surface of the blank glass sheet, and N is the average value of the number of bacterial adhesion on the surface of the sample. FIGS. 4, 5 and 6 are graphs showing experimental results of inhibition of E.coli, staphylococcus aureus and Pseudomonas mansion on cross-linked amphiphilic acrylate marine antifouling coatings;
the calculated coliform bacteria inhibition rate and the calculated staphylococcus aureus bacteria inhibition rate are 96.6 percent and 80.5 percent respectively.
The method comprises the steps of selecting pseudoalteromonas mansion (MCCC 1A 06494) as a model strain, co-culturing a sample and a blank glass sheet with bacterial liquid for 48 hours at 28-30 ℃, diluting the sample and the blank glass sheet to the same multiple with the nutrient liquid, coating the bacterial liquid on a solid culture medium (each sample is coated for 3 times in parallel) by adopting a flat plate coating method, culturing the sample for 48 hours at 28-30 ℃, taking out the flat plate, respectively calculating the colony numbers on the sample and the blank glass sheet by adopting a colony counting method, and calculating the bacterial inhibition rate of the pseudoalteromonas mansion as 96.83% according to the same calculation formula of the bacterial inhibition rate.
Comparative example 1
Referring to example 1, unlike example 1, a crosslinked amphiphilic acrylate marine antifouling coating of this comparative example was prepared with an amino-terminated polydimethylsiloxane addition of 0g, with the remainder unchanged as shown in example 1.
The test was performed according to the test method of example 1, see fig. 2-6, and the results were: tensile strength test data were not obtained for this comparative example because no acceptable test samples could be obtained after curing; the inhibition rate of the double-eyebrow algae is 89.69 percent, and the inhibition rate of the small-crescent diamond algae is 84.33 percent; the inhibition rate of the escherichia coli is 79.56%, the inhibition rate of the staphylococcus aureus is 42.76%, and the inhibition rate of the pseudomonas mansion is 91.99%.
Example 2
Referring to example 1, unlike example 1, a crosslinked amphiphilic acrylate marine antifouling coating of this example was prepared with an amino-terminated polydimethylsiloxane addition of 0.25g, with the remainder unchanged as shown in example 1.
The test was performed according to the test method of example 1, see fig. 1-6, and the results were: the inhibition rate of the double-eyebrow algae is 89.73 percent, and the inhibition rate of the small crescent diamond algae is 86.7 percent; the inhibition rate of the escherichia coli is 88.06%, the inhibition rate of the staphylococcus aureus is 61.46%, and the inhibition rate of the pseudomonas mansion is 95.21%; the tensile strength and elongation at break were 1.34MPa and 198%, respectively.
Example 3
Referring to example 1, unlike example 1, a crosslinked amphiphilic acrylate marine antifouling coating of this example was prepared with an amino-terminated polydimethylsiloxane addition of 0.5g, with the remainder unchanged as shown in example 1.
The test was performed according to the test method of example 1, see fig. 1-6, and the results were: the inhibition rate of the double-eyebrow algae is 89.76 percent, and the inhibition rate of the small-crescent diamond algae is 87.7 percent; the inhibition rate of the escherichia coli is 94.1 percent, the inhibition rate of staphylococcus aureus is 67.4 percent, and the inhibition rate of the pseudomonas mansion is 95.51 percent; the tensile strength and elongation at break were 1.70MPa and 161%, respectively.
Example 4
Referring to example 1, unlike example 1, a crosslinked amphiphilic acrylate marine antifouling coating of this example was prepared with an amino-terminated polydimethylsiloxane addition of 0.75g, with the remainder unchanged as shown in example 1.
The test was performed according to the test method of example 1, see fig. 1-6, and the results were: the inhibition rate of the double-eyebrow algae is 90.66 percent, and the inhibition rate of the small crescent diamond algae is 90.23 percent; the inhibition rate of the escherichia coli is 95.2%, the inhibition rate of staphylococcus aureus is 74.8%, and the inhibition rate of the pseudomonas mansion is 96.05%; the tensile strength and elongation at break were 2.02MPa and 128%, respectively.
The above list of detailed descriptions is only specific to practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and all equivalent embodiments or modifications that do not depart from the spirit of the present invention should be included in the 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.
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