CN115044290B - Gel microsphere hybrid paint phenol-based marine antifouling coating material and preparation method thereof - Google Patents

Gel microsphere hybrid paint phenol-based marine antifouling coating material and preparation method thereof Download PDF

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CN115044290B
CN115044290B CN202210602338.9A CN202210602338A CN115044290B CN 115044290 B CN115044290 B CN 115044290B CN 202210602338 A CN202210602338 A CN 202210602338A CN 115044290 B CN115044290 B CN 115044290B
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gel
urushiol
antifouling coating
coating material
microspheres
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CN115044290A (en
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林凤采
徐艳莲
郑笑笑
林棋
陈基棚
郑国才
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Minjiang University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable

Abstract

The invention discloses a phenolic marine antifouling coating material of a gel microsphere hybrid paint and a preparation method thereof, and relates to the technical field of biomass coatings. Firstly, dissolving natural macromolecules in a solvent, adding an antibacterial agent to obtain a dispersion liquid, then mixing and emulsifying the dispersion liquid and an oil phase, and freeze-drying to obtain dry gel microspheres; and finally, dispersing the dry gel microspheres in a solvent to obtain a gel microsphere suspension, and performing reflux reaction on the gel microsphere suspension, the urushiol, the diisocyanate and the biodegradable polymer to obtain the gel microsphere hybrid urushiol-based marine antifouling coating material. The environment-friendly antifouling coating is constructed by combining the urushiol, the natural polymer gel microspheres, the natural antibacterial agent and the biodegradable polymer, the preparation process is simple, the traditional complex petroleum-based polymer chemical modification and synthesis processes are avoided, and the prepared hydrogel microsphere hybrid urushiol-based antifouling coating has excellent performance.

Description

Gel microsphere hybrid paint phenol-based marine antifouling coating material and preparation method thereof
Technical Field
The invention relates to the technical field of biomass coatings, in particular to a phenolic marine antifouling coating material of a gel microsphere hybrid paint and a preparation method thereof.
Background
Marine biofouling is a major problem in marine engineering and marine equipment, not only can accelerate corrosion of marine equipment such as ships and warships and seriously threaten safe operation, but also can increase frictional resistance between the surface and water flow, thereby causing energy loss and increasing greenhouse gas emission. At present, petroleum-based high-molecular resin antifouling paint for assisting toxic biocides is generally adopted at home and abroad to solve the problem of biofouling, however, the safety of an ocean ecosphere is seriously threatened by non-fatal chronic influence of self-consumption products of a coating in an antifouling process on non-target organisms.
The bionic anti-fouling coating is a non-toxic anti-fouling technology emerging in recent years, and is based on the design concept of bionics, and any feasible aspect of a simulated organism is endowed with special surface performance to achieve the goal of fouling protection, for example: micro-nano structure for preventing biological adhesion, mucus or bioactive substances secreted on the body surface, exfoliation and desquamation of epidermis and the like. The body surfaces of fishes and frogs can continuously secrete mucin and form a thin hydrogel layer on the body surfaces, so that the adhesion of fouling organisms can be inhibited, and the smooth and clean body surfaces can be kept for a long time. These self-cleaning features of fish and frog body surfaces provide a referable solution to our marine antifouling problem. The hydrogel has a three-dimensional network structure capable of absorbing a large amount of water, and has the specific water absorption and retention property, smooth flexibility and biocompatibility similar to mucus layers secreted by the dolphin body surface. The gel coating material swells in a water body environment after absorbing water, a mucus layer which is similar to a dolphin body surface and has lower surface energy is formed, attachment of fouling organisms is not facilitated, and under the flushing of water flow, the flexible gel coating forms an unstable dynamic surface, so that microorganisms are difficult to identify and attach, and a small amount of attached fouling organisms are thrown away. Therefore, the hydrogel is an ideal material for constructing the dolphin skin-like antifouling coating. However, the application of the gel coating as a coating in the field of actual marine antifouling is limited by the problems of poor adhesion of the gel coating to the surface of a substrate and poor mechanical properties.
Disclosure of Invention
The invention aims to provide a phenolic marine antifouling coating material of a gel microsphere hybrid paint and a preparation method thereof, which are used for solving the problems in the prior art, so that the coating material has excellent antifouling performance and the characteristic of environmental friendliness.
In order to achieve the purpose, the invention provides the following scheme:
one of the purposes of the invention is to provide a preparation method of a gel microsphere hybrid paint phenolic marine antifouling coating material, which comprises the following steps:
(1) Dissolving natural polymer in a solvent, adding an antibacterial agent, and fully stirring and dissolving to obtain a dispersion liquid;
(2) Adding the dispersion liquid into the oil phase solution under the stirring state, stirring and emulsifying to obtain an emulsion, adjusting the pH of the emulsion or adding a cross-linking agent to obtain natural polymer gel microspheres from the obtained emulsion through a sol-gel conversion method, and filtering, washing and freeze-drying to obtain dry gel microspheres;
(3) Preparing an antifouling coating material by adopting an in-situ polymerization method: dispersing the dry gel microspheres in a solvent to obtain a gel microsphere suspension; under a protective atmosphere, adding urushiol, diisocyanate and biodegradable macromolecules into the gel microsphere suspension, and performing reflux reaction to obtain the gel microsphere hybrid urushiol-based marine antifouling coating material.
In the step (1), the solvent is deionized water, a NaOH/urea solution system (the mass ratio of NaOH to urea is 7.
In the step (2), the stirring is high-speed stirring, and the rotating speed is 300-2000r/min; stirring and emulsifying for 60-300min.
Adjusting the pH value of the emulsion to be neutral in the step (2); the addition amount of the cross-linking agent is 0.1-3% of the emulsion by mass, and the cross-linking agent is epichlorohydrin, calcium chloride solution (mass solubility is 1-3%) or glutaraldehyde (mass solubility is 3%).
The solvent in the step (3) is an organic solvent, and comprises chloroform, 1,4 dioxane, N dimethylformamide, toluene, acetone, xylene or dichloromethane.
Further, the natural polymer is a natural polymer containing hydroxyl or amino, and specifically is one or more of cellulose, sodium alginate, sodium carboxymethylcellulose, guar gum, chitosan or agar; the mass concentration of the natural polymer in the solvent is 1-10%.
Further, the antibacterial agent is a natural antibacterial agent, and comprises natural polyphenols or terpenoids; specifically, the antibacterial agent comprises capsaicin, curcumin, rosin, tannic acid, tannin extract, anthocyanin or eugenol.
The load capacity of the antibacterial agent in the dry gel microspheres is 1-30wt%.
The mass ratio of the dry gel microspheres to the solvent is 0-100.
In the step (3), the mass ratio of the urushiol to the dry gel microspheres is 60-60, and is not 0; the mass ratio of the biodegradable polymer to the dry gel microspheres is 60-60, and is not 0; the mass ratio of the diisocyanate to the dry gel microspheres is 50-50 and is not 0.
Further, in the step (2), the oil phase is one or a mixture of several of liquid paraffin, dimethyl silicone oil, petroleum ether or vegetable oil.
Further, the diisocyanate in the step (3) includes 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, hexamethylene diisocyanate or trans-cyclohexane diisocyanate.
Further, the biodegradable polymer in the step (3) is a polyol having a molecular weight of 1X 10 2 ～1×10 5 。
Further, the biodegradable polymer in the step (3) is polyethylene glycol adipate ((C) 6 H 10 O 4. C 2 H 6 O 2 ) n ) Bishydroxy terminated polycaprolactone (HO- [ CO (CH)) 2 ) 5 CO] n -OH), polylactide (CH) 3 (CH 2 ) 15 O(C 6 H 8 O 4 ) n H) Polyethylene glycol (HO (CH) 2 CH 2 O) n H) Poly (caprolactone-lactide) ([ OCO (CH)) 2 ) 5 OCOCHCH 3 )] n OH), poly (caprolactone-ethylene glycol) (HO (CH) 2 ) 5 OC) n O(CH 2 O) n (CO(CH 2 ) 5 O) n H) Or dihydroxypolylactic acid (HO (OCHCH) 3 CO) n OH)。
Further, the reflux reaction temperature in the step (3) is 50-150 ℃, and the reaction time is 3-24h.
The invention also aims to provide the gel microsphere hybrid paint phenol-based marine antifouling coating material prepared by the preparation method.
The invention also aims to provide the application of the phenolic marine antifouling coating material of the gel microsphere hybrid paint in the antifouling field.
Urushiol is a main film forming substance in raw lacquer, accounts for 50% -80% of the raw lacquer content, and is mainly a catechol derivative in a chemical structure, and a side chain on a benzene ring is a C15-C17 straight-chain alkane structure. The abundant hydroxyl and unsaturated double bonds in the urushiol structure make it have very high chemical activity and molecular modifiability. The urushiol polymer has the specificity in the aspect of physical and chemical properties, has the advantages that the synthesized high-molecular coating derived from fossil resources cannot replace, and has the characteristics of natural reproducibility, environmental friendliness, strong adhesion, corrosion resistance, wear resistance, durability and the like.
The hydrogel microspheres are a functional gel material with the diameter generally in micron order and the shape of a sphere, can be used as a microstructure unit, a microreactor, a micro separator and the like, and have important application in the fields of catalysis, drug sustained-release materials, adsorption separation and the like. Compared with petroleum-based polymer microspheres and inorganic microspheres, the hydrogel microspheres based on natural polymers have great advantages in material properties and performance, and thus are of great interest. Meanwhile, the three-dimensional network structure in the gel microsphere has rich load space to combine with other heterogeneous multifunctional components, so that the gel microsphere has more diversified functions.
The micro-scale hydrogel spheres loaded with the natural antibacterial agent are combined in a urushiol-based polymer coating structure in a covalent bond mode, so that the technical problems of poor mechanical property and poor binding force with the coating of the existing hydrogel coating can be solved, the dissolution and release rate of the gel in the composite coating is expected to be regulated and controlled by controlling factors such as the content, the particle size and the like of gel microspheres, and theoretical and technical bases are provided for constructing a novel bio-based environment-friendly marine coating. The method is simple and convenient to operate, all the raw materials are natural polymers, the method is green and environment-friendly, the safety is high, and a new technical guide can be provided for preparing the biomass-based advanced antifouling paint with excellent performance.
The invention makes the coating have self-cleaning capability by simulating the metabolism renewal capability of dolphin skin mucus layer. The natural polymer gel microspheres with rich hydroxyl structures and high swelling property on the surfaces and the biodegradable polymer are used as regulation units, and the gel microspheres are introduced into a urushiol-based polyurethane polymer network structure through an in-situ polymerization method to construct a novel green and nontoxic antifouling coating material. The hydrogel microspheres loaded with the antibacterial agent are introduced into a urushiol-based polymer structure, and the urushiol-based polyurethane with good adhesiveness can effectively solve the problem of fixing the hydrogel microspheres on a ship body. The swelling-dissolving of the gel microspheres on the surface of the coating layer forms a soft hydrogel layer which simulates a low-surface-energy mucus layer secreted by the surface of the dolphin and resists attachment of fouling organisms, and meanwhile, natural antibacterial agents (such as capsaicin, curcumin, tannic acid, anthocyanin, rosin and eugenol) in the gel microspheres are released along with the swelling and dissolving of the hydrogel microspheres and diffuse into seawater so as to play a role in preventing attachment of the marine organisms. The degradable polymer is introduced into the urushiol-based polyurethane matrix, so that the degradability of raw urushiol-based polyester in seawater can be regulated and controlled, and the degradable urushiol-based elastic polyurethane antifouling paint is constructed. The upper surface of the polyurethane coating contacted with seawater is firstly degraded and dropped off to remove adhered fouling organisms, and a new antifouling coating surface is exposed, so that the flexible hydrogel layer on the upper surface of the coating is continuously updated, the clean surface structure is maintained, and the bionic coating is endowed with the static sea antifouling performance.
The invention discloses the following technical effects:
compared with the existing petroleum-based high-molecular marine antifouling coating technology with a large amount of toxic biocides, the urushiol in the invention is derived from natural plants, is rich in resources and nontoxic, is combined with natural high-molecular gel microspheres, natural antibacterial agents and biodegradable polymers to construct an environment-friendly antifouling coating, is simple in preparation process, avoids the traditional complex petroleum-based high-molecular chemical modification and synthesis processes, and is excellent in performance of the prepared hydrogel microsphere hybrid urushiol-based antifouling coating.
The method has the advantages of simple process, environmental protection, rich raw material resources and high safety, and can become a new technology for constructing the marine antifouling paint with excellent performance, low carbon, long effect and environmental friendliness.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is the results of shallow sea immersion test of phenolic based bionic anti-fouling coating material samples of gel microsphere hybrid paints prepared in examples 1-4; wherein: a1, b1, c1 and d1 are respectively a graph of the adhesion condition of the surface fouling organisms when the shallow sea is soaked for 0 day in the examples 1 to 4, and a2, b2, c2 and d2 are respectively a graph of the adhesion condition of the surface fouling organisms after the shallow sea is soaked for 120 days in the examples 1 to 4;
FIG. 2 is a graph showing the effect of cellulose gel microspheres loaded with different natural antimicrobial agents on the antimicrobial properties of a urushiol-based coating; wherein: (ii) eugenol, (b) capsaicin, (c) curcumin, (d) tannic acid, (e) rosin, (f) tannin extract, (g) anthocyanin, (h) blank (no natural antibacterial agent);
FIG. 3 is a self-cleaning process of the surface of a phenolic bionic coating of a gel microsphere hybrid paint with different addition amounts of dyed oil stains; wherein: 0 wt.%, (b) 5 wt.%, (c) 10 wt.%, (d) 15 wt.%, (e) 20 wt.%, (f) 25 wt.%, (g) 30 wt.%.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
(1) Dissolving sodium alginate 2.0g in deionized water 97.5g, adding natural antibacterial agent tannin 0.5g, and stirring for 120min to obtain uniform solution.
(2) Slowly dropping the sodium alginate/tannin mixed solution in the step (1) into 500mL of liquid paraffin/petroleum ether (mass ratio is 7. And finally, filtering, washing and freeze-drying at (-48 ℃) to obtain the dry sodium alginate gel microspheres containing the tannic acid (the loading amount of the natural antibacterial agent in the dry sodium alginate gel microspheres is 20 wt%).
(3) Preparing the sodium alginate gel microsphere hybrid paint phenol-based marine antifouling coating material by adopting an in-situ polymerization method: dispersing 10.0g of the dry sodium alginate gel microspheres prepared in the step (2) in 100mL of chloroform in a nitrogen atmosphereNext, 10.0g of urushiol, 20.0g of 1, 6-hexamethylene diisocyanate, and 10.0g of bishydroxy-terminated polycaprolactone (HO- [ CO (CH)) 2 ) 5 CO] n -OH, molecular weight: 5000 Adding the sodium alginate gel microsphere chloroform suspension, and performing reflux reaction at 90 ℃ for 360min to obtain the sodium alginate gel microsphere hybrid urushiol-based antifouling paint.
Example 2
(1) Dissolving 3.0g guar gum in 96.0g deionized water, adding 1.0g natural antibacterial agent- -curcumin, and stirring for 90min to obtain a uniform solution.
(2) Slowly dripping the guar gum/curcumin mixed solution in the step (1) into 500mL of liquid paraffin/petroleum ether (mass ratio is 5). And finally, filtering, washing and freeze-drying at (-48 ℃) to obtain the dry guar gum gel microspheres containing the curcumin (the loading capacity of the natural antibacterial agent in the dry guar gum gel microspheres is 25 wt%).
(3) Preparing the guar gum microsphere hybrid paint phenolic-based marine antifouling coating material by adopting an in-situ polymerization method: and (3) dispersing 5.0g of the dry guar gel microspheres prepared in the step (2) in 100mL of dichloromethane, adding 10.0g of urushiol, 25.0g of trimethyl-1, 6-hexamethylene diisocyanate and 15.0g of polyethylene glycol (molecular weight 2000) into the guar gel microsphere dichloromethane suspension in a nitrogen atmosphere, and carrying out reflux reaction at 80 ℃ for 400min to obtain the guar gel microsphere hybrid urushiol-based antifouling paint.
Example 3
(1) Dissolving agar 1.8g in deionized water 98.0g, adding capsaicin as natural antibacterial agent 0.2g, and stirring for 85min to obtain a uniform solution.
(2) Slowly dripping the agar/capsaicin mixed solution in the step (1) into 500mL of soybean oil/petroleum ether (mass ratio is 5). Finally, filtering, washing and freeze-drying (-48 ℃) to obtain the dry agar gel microspheres containing capsaicin (the loading amount of the natural antibacterial agent in the dry agar gel microspheres is 10 wt%).
(3) Preparing the agar gel microsphere hybrid paint phenolic marine antifouling coating material by adopting an in-situ polymerization method: 5.0g of the dry agar gel microspheres prepared in step (2) was dispersed in 100mL of N, N-dimethylformamide, and 10.0g of urushiol, 25.0g of hexamethylene diisocyanate, and 15.0g of polylactide (CH) were added under a nitrogen atmosphere 3 (CH 2 ) 15 O(C 6 H 8 O 4 ) n H, molecular weight: 4000 Adding the agar gel microsphere N, N dimethyl formamide suspension, and carrying out reflux reaction at 80 ℃ for 360min to obtain the agar gel microsphere hybrid urushiol-based antifouling paint.
Example 4
(1) Dissolving 2.85g of bamboo pulp cellulose in a 97g NaOH/urea solution system (the mass ratio of NaOH to urea is 7.
(2) And (2) slowly dripping the cellulose/eugenol mixed solution in the step (1) into 500mL of dimethyl silicone oil/petroleum ether (mass ratio is 7). And finally, filtering, washing and freeze-drying at (-48 ℃) to obtain the dry cellulose gel microspheres containing the eugenol (the loading amount of the natural antibacterial agent in the dry cellulose gel microspheres is 5 wt%).
(3) Preparing a cellulose gel microsphere hybrid paint phenolic marine antifouling coating material by adopting an in-situ polymerization method: 15.0g of the dry cellulose gel microspheres prepared in step (2) were dispersed in 100mL of 1,4 dioxane, and 15.0g of urushiol, 30.0g of isophorone diisocyanate, and 15.0g of dihydroxy polylactic acid (HO (OCHCH) were added under a nitrogen atmosphere 3 CO) n OH, molecular weight: 8000 Adding the cellulose gel microsphere 1,4 dioxane suspension, and carrying out reflux reaction at 100 ℃ for 300min to obtain the cellulose gel microsphere hybrid urushiol-based antifouling paint.
The results of the performance tests of the phenolic-based bionic antifouling coating material of the gel microsphere hybrid paint prepared in the examples 1 to 4 are shown in table 1:
TABLE 1
Figure BDA0003670130630000111
Note: 1 the hardness of the paint film is measured by a GB/T6739-2006 color paint and varnish pencil method; 2 determination of paint film glossiness at 20 ℃ of ISO 13803-2014 colored paint and varnish; 3 GB/T6742-2007 paint and varnish bending tests (cylindrical axis); 4 GB/T1732-2020 paint film impact resistance determination method; 5 GB/T9286-2021 colored paint and varnish lattice test; 6 GB/T21866-2008 antibacterial coating (paint film) antibacterial property testing method and antibacterial effect.
The gel microsphere hybrid paint phenolic bionic antifouling coating material samples prepared in the embodiments 1 to 4 are subjected to a shallow sea immersion test according to a GB/T5370-2007 antifouling paint sample plate shallow sea immersion test method, and the test results of the adhesion condition of fouling organisms on the surfaces of the samples are shown in FIG. 1. In FIG. 1: a1, b1, c1 and d1 are graphs of the surface fouling organism adhesion condition of the shallow sea of examples 1-4 after being soaked for 0 day, and a2, b2, c2 and d2 are graphs of the surface fouling organism adhesion condition of the shallow sea of examples 1-4 after being soaked for 120 days.
The results show that: after being soaked in shallow sea for 120 days, the steel plates coated with the steel plates of examples 1-4 on the surface have only a small amount of marine organisms attached to the surface, have no large-scale marine organisms attached to the surface, and show good long-acting antifouling performance.
The invention further examines the influence of the cellulose gel microspheres loaded with different natural antibacterial agents (the cellulose gel microspheres prepared in example 4) on the antibacterial performance of the urushiol-based coating. As shown in fig. 2, the influence of the cellulose gel microspheres loaded with 5% of rosin, tannin, capsaicin, curcumin, eugenol, tannin extract and anthocyanin on the antibacterial performance (escherichia coli) of the urushiol-based antifouling coating is respectively examined, and the cellulose gel microspheres without natural antibacterial agents are used as a control.
The result shows that different natural antibacterial agents can improve the antibacterial performance of the coating, and the antibacterial performance of the coating is eugenol, capsaicin, curcumin, tannin, rosin, tannin extract and anthocyanin. Thus, preferred natural antimicrobial agents are eugenol, capsaicin, curcumin, tannic acid, rosin.
In FIG. 2: the composition comprises (a) eugenol, (b) capsaicin, (c) curcumin, (d) tannin, (e) rosin, (f) tannin, (g) anthocyanin and (h) blank (without natural antibacterial agent).
The invention further inspects the influence of different gel microsphere contents on the self-cleaning performance of the urushiol-based coating. Taking the cellulose gel microspheres prepared in example 4 as an example, as shown in fig. 3, the influence of the addition of 5wt% eugenol-loaded cellulose gel microspheres of 0wt%,5wt%,10wt%,15wt%,20wt%,25wt% and 30wt% on the self-cleaning performance of the urushiol-based coating is respectively examined, and the results show that the self-cleaning performance of the coating can be improved by the addition of different cellulose gel microspheres, and when the addition of the cellulose gel microspheres is between 20 and 30wt%, the dyed oil droplets are integrally and rapidly removed from the surface of the coating, no trace of any oil stain is left, and good self-cleaning performance is shown. Therefore, the preferable addition amount of the cellulose gel microspheres is 20 to 30wt%.
In FIG. 3, the gel microspheres are added in amounts of (a) 0wt%, (b) 5wt%, (c) 10wt%, (d) 15wt%, (e) 20wt%, (f) 25wt%, (g) 30wt%, respectively.
The invention further inspects the influence of different urushiol contents on the adhesion performance of the coating. The effects of urushiol addition amounts of 10wt%,20wt%,30wt%,40wt%,50wt%, and 60wt% on the coating adhesion were examined, respectively, and the results showed that the coating adhesion and mechanical properties increased with the increase in the urushiol content within a certain range, and that the coating adhesion was rated 2 to 3 when the urushiol addition amount was 40 to 60wt%, pencil hardness was in the range of 4H,3H,2H, HB, B, and 2B, glossiness was 95 to 100, bending property (cylindrical axis diameter) was 4 to 6mm, and impact resistance (height) was 20 to 25cm. Therefore, the preferred amount of urushiol added is 40 to 60% by weight.
The invention further inspects the influence of different biodegradable high molecular contents on the degradation performance of the coating. Terminated by dihydroxy polycaprolactone (HO- [ CO (CH) 2 ) 5 CO] n -OH, molecular weight: 6000 For example, the influence of the addition of 10wt%,20wt%,30wt%,40wt%,50wt%,60wt% of dihydroxy-terminated polycaprolactone on the degradation performance of the coating was examined, and the results showed that the degradation performance of the coating increased with the increase of urushiol content, and the degradation rate of the coating was 13.7-28.3 μ g/(cm) when the addition of dihydroxy-terminated polycaprolactone was between 20-40wt% 2 D) meets the requirements for self-renewing coatings. In order to prevent the coating from degrading too fast, the preferred amount of dihydroxy terminated polycaprolactone added is 20-40wt%.
According to the invention, urushiol is used as a main component, active hydroxyl groups loaded with natural antibacterial agent gel microspheres and urushiol structures react with diisocyanate to form an environment-friendly coating with excellent performance, and the structure of polyurethane and the degradability of the polyurethane in seawater are effectively regulated and controlled by introducing biodegradable macromolecules. The soft hydrogel layer formed by swelling-dissolving out of the gel microspheres on the surface of the coating simulates a low-surface-energy mucus layer secreted by the surface of a dolphin, has the characteristic of difficult adhesion and easy detachment of microorganisms, and forms an unstable surface which is difficult to identify and attach fouling organisms under the action of dynamic water flow scouring shearing force on the gel hydration layer with bionic flexible characteristics, so that the coating has high-efficiency self-cleaning characteristic. Meanwhile, the antibacterial agent of the hydrogel microspheres is slowly released along with the swelling and dissolution of the hydrogel microspheres, biodegradable macromolecules on the surface of the coating are gradually degraded into small molecules in seawater, and a new antifouling coating in the coating is exposed, the repeated self-updating process is similar to the self-updating effect of a mucous layer on the skin of marine organisms such as dolphin and the like, and the clean surface structure of the coating is maintained in the continuous self-updating process, so that the coating not only has good controllable release performance of the antifouling agent, but also has the long-acting antifouling and sea-cleaning antifouling performance, and the application requirements of the actual marine antifouling engineering are met.
Compared with the existing petroleum-based high-molecular marine antifouling coating technology with a large amount of toxic biocides, the urushiol in the invention is derived from natural plants, is rich in resources and nontoxic, and meanwhile, the technology combines natural high-molecular gel microspheres, natural antibacterial agents and biodegradable polymers to construct an environment-friendly antifouling coating, so that the preparation process is simple, the traditional complex petroleum-based high-molecular chemical modification and synthesis process is avoided, and the prepared hydrogel microsphere hybrid urushiol-based antifouling coating has excellent performance. The method has the advantages of simple process, environmental protection, rich raw material resources and high safety, and can become a new technology for constructing the marine antifouling paint with excellent performance, low carbon, long effect and environmental friendliness.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (6)

1. A preparation method of a gel microsphere hybrid paint phenol-based marine antifouling coating material is characterized by comprising the following steps:
(1) Dissolving natural polymer in a solvent, and then adding an antibacterial agent to obtain a dispersion liquid;
(2) Adding the dispersion into the oil phase solution under stirring, stirring and emulsifying, adjusting the pH of the emulsion or adding a cross-linking agent, obtaining natural polymer gel microspheres by a sol-gel conversion method, and filtering, washing and freeze-drying to obtain dry gel microspheres;
(3) Dispersing the dry gel microspheres in a solvent to obtain a gel microsphere suspension; under a protective atmosphere, adding urushiol, diisocyanate and biodegradable macromolecules into the gel microsphere suspension, and performing reflux reaction to obtain the gel microsphere hybrid urushiol-based marine antifouling coating material;
the natural polymer is one or more of cellulose, sodium alginate, sodium carboxymethylcellulose, guar gum, chitosan or agar; the mass concentration of the natural polymer in the solvent is 1-10%;
the antibacterial agent comprises capsaicin, curcumin, rosin, tannic acid, tannin extract, anthocyanin or eugenol;
biodegradation in the step (3)The molecular weight of the polymer is 1X 10 2 ～1×10 5 ；
In the step (3), the biodegradable polymer is polyethylene glycol adipate, dihydroxy terminated polycaprolactone, polylactide, polyethylene glycol, poly (caprolactone-lactide), poly (caprolactone-ethylene glycol) or dihydroxy polylactic acid.
2. The preparation method according to claim 1, wherein the oil phase solution in step (2) is one or more of liquid paraffin, dimethicone, petroleum ether, and vegetable oil.
3. The method according to claim 1, wherein the diisocyanate in the step (3) comprises 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, hexamethylene diisocyanate or trans cyclohexane diisocyanate.
4. The method according to claim 1, wherein the reflux reaction temperature in the step (3) is 50 to 150 ℃ and the reaction time is 3 to 24 hours.
5. The gel microsphere hybrid paint phenolic-based marine antifouling coating material prepared by the preparation method of any one of claims 1 to 4.
6. The application of the phenolic marine antifouling coating material of the gel microsphere hybrid paint in the antifouling field.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1644452A2 (en) * 2003-07-03 2006-04-12 McDaniel, Steven C. Antifungal and antibacterial coating compositions
WO2010089598A1 (en) * 2009-02-05 2010-08-12 Danisco A/S Composition
CN105111407A (en) * 2015-09-15 2015-12-02 湖南科技大学 Method for preparing biodegradable ocean antifouling polyurethane hybrid materials and product thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0515297A (en) * 2004-09-14 2008-07-15 Microtek Lab Inc microencapsulated biocide, coating composition, and coating material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1644452A2 (en) * 2003-07-03 2006-04-12 McDaniel, Steven C. Antifungal and antibacterial coating compositions
WO2010089598A1 (en) * 2009-02-05 2010-08-12 Danisco A/S Composition
CN105111407A (en) * 2015-09-15 2015-12-02 湖南科技大学 Method for preparing biodegradable ocean antifouling polyurethane hybrid materials and product thereof

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