Zeolite imidazole framework material modified antibacterial epoxy resin coating and preparation method thereof

Abstract

The invention discloses a zeolite imidazole framework material modified antibacterial epoxy resin coating and a preparation method, the modified antibacterial epoxy resin coating comprises a component A and a component B, the formula ratio of the component A to the component B is 4: 1, the component A comprises the following components in parts by weight: 25-30 parts of zeolite imidazole framework material modified antibacterial epoxy resin, 2-5 parts of a reactive diluent, 0.5-0.8 part of a wetting dispersant and 0.1-0.3 part of a defoaming agent, and the component B comprises the following components in parts by weight: 0.5-0.8 part of a defoaming agent; the paint comprises the following components in parts by weight: 0.5-1 part of an adhesion promoter, 0.5-1 part of an anti-settling agent, 5-10 parts of a pigment, 45-55 parts of a filler, 1.5-2 parts of an anti-sagging agent and 1-1.5 parts of a leveling agent. And the component B comprises the following components in parts by weight: 20-30 parts of a polyamide curing agent. The zeolite imidazole framework material (ZIF-8) is adopted to modify the antibacterial epoxy resin, so that the tensile strength, bending strength, elasticity modulus, toughness and impact toughness of the composite material can be better improved.

Description

Technical Field

[0001] The invention relates to the field of coatings, in particular to a zeolite imidazole skeleton material modified antibacterial epoxy resin coating and a preparation method thereof. Background Art

[0002] As a traditional heavy-duty anti-corrosion product, epoxy coatings are widely used in ships, bridges, factory buildings, nuclear power and other environments. They are exposed to environmental hazards, which can cause various damages and consumption to the coating film. Among them, the generation of microorganisms on the coating surface is a more serious problem. Microorganisms such as bacteria attach to the surface of epoxy paint films, and the enzymes they secrete can decompose the organisms in the paint, damage the integrity of the paint film, reduce the protective ability of the coating, endanger the performance of the material itself, and cause unnecessary losses and waste, thereby endangering the safety performance and service life of the protected objects or equipment.

[0003] During use, the existing antibacterial coatings have low tensile strength, bending strength, elastic modulus, toughness and impact toughness as composite materials, and the antibacterial species of the antibacterial coatings are single and the antibacterial ability decreases rapidly. Therefore, the present invention proposes a zeolite imidazole framework material modified epoxy antibacterial coating and a preparation method thereof, wherein ZIF-8 is a typical imidazole zeolite metal-organic framework material (MOF), and its active groups can interact with the polymer in the coating to form covalent bonds or non-covalent bonds, so that its compatibility with organic polymers is better than that of traditional nanofillers to solve the above problems. Summary of the invention

[0004] The purpose of the present invention is to provide a zeolite imidazole framework material modified antibacterial epoxy resin coating and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0005] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a zeolite imidazole skeleton material modified antibacterial epoxy resin coating, the modified antibacterial epoxy resin coating comprises component A and component B, the formula ratio of component A and component B is 4:1, component A is calculated by weight: 25 to 30 parts of zeolite imidazole skeleton material modified antibacterial epoxy resin, 2 to 5 parts of active diluent, 0.5 to 0.8 parts of wetting dispersant, 0.1 to 0.3 parts of defoaming agent, 0.5 to 1 parts of adhesion promoter, 0.5 to 1 parts of anti-settling agent, 5 to 10 parts of pigment, 45 to 55 parts of filler, 1.5 to 2 parts of anti-sagging agent, and 1 to 1.5 parts of leveling agent; component B is calculated by weight: 20 to 30 parts of polyamide curing agent.

[0006] Preferably, the preparation process of the antibacterial epoxy resin modified by zeolite imidazole framework material includes: first, adding 15 grams of DMG modified zeolite imidazole framework material solution to 5 grams of xylene solution, then adding 20 grams of epoxy resin E-51 and 14 grams of epoxy resin E44 in sequence, ultrasonically dispersing, stirring at a speed of 800 r / min for 30 minutes, and obtaining the antibacterial epoxy resin modified by zeolite imidazole framework material.

[0007] Preferably, the preparation process of the DMG modified zeolite imidazole framework material comprises: slowly dripping hydrochloric acid into 1,6-hexanediamine at a rate of 25 drops / minute, and standing for 20 minutes to generate a 1,6-hexanediamine dihydrochloride solution, transferring it into a 500ml three-mouth reactor, maintaining a rotation speed of 200r / min, slowly dripping dicyandiamide, and then mixing and stirring evenly at room temperature, dripping 1-butanol, heating to 60 degrees, maintaining a rotation speed of 400r / min, continuously stirring for 1 hour, and standing for 24 hours to obtain DMG containing guanidine group to obtain dimethylolpropionamide; then mixing DMG with a dispersion of the zeolite imidazole framework material in a mixing ratio of 2:1, placing it in a reactor, and adding a diluent, the diluent is 7 parts of xylene and 3 parts of n-butanol, and continuously stirring for 60 minutes at a rotation speed of 400r / min, and standing for 4 hours to obtain a DMG modified zeolite imidazole framework material.

[0008] Preferably, the dispersion of zeolite imidazole framework material is prepared by the following process: completely dispersing zeolite imidazole framework material nanoparticles in an ethanol solution, maintaining a rotation speed of 200 r / min, stirring for 40 minutes, adding a long carbon chain silane coupling agent, the silane coupling agent used is at least one of 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane, the mass ratio is 1:3, stirring at room temperature for 2 to 4 hours to obtain a hydrophobic treatment to obtain zeolite imidazole framework material ZIF-8; then centrifugally washing the zeolite imidazole framework material ZIF-8, using ethanol as a centrifugal washing liquid, centrifugally washing 2 to 4 times at a rotation speed of 5000 to 8000 r / min, the mass ratio of ethanol to zeolite imidazole framework material ZIF-8 is 1:6, and a dispersion of zeolite imidazole framework material ZIF-8 is obtained.

[0009] Preferably, the zeolite imidazole framework material nanoparticles are prepared by dissolving 0.312g Zn(NO3)2.6H2O and 0.185g 2-methylimidazole in 150ml N,N-dimethylformamide respectively. After complete dissolution, the two solutions are mixed, stirred continuously for 1 hour at room temperature at a speed of 200r / min and allowed to stand for 24 hours; then centrifuged at a speed of 5000r / min for 5mins, the precipitate is taken out and washed with methanol 3 times, and the product is placed in an oven at 80 degrees and dried for 12 hours to constant weight to obtain zeolite imidazole framework material nanoparticles.

[0010] Preferably, the present invention also provides a method for preparing the above-mentioned zeolite imidazole framework material modified antibacterial epoxy resin coating, comprising the steps of:

[0011] Step 1: Weigh the zeolite imidazole framework material modified antibacterial epoxy resin, active diluent, wetting dispersant, pigment and filler according to the ratio of component A, place them in a multifunctional dispersing stirring kettle, and stir at a stirring speed of 200 r / min for 30 minutes;

[0012] Step 2: Slowly add anti-settling agent, defoaming agent, anti-sagging agent and leveling agent during stirring, maintain medium stirring speed of 400r / min, stir for 60 minutes, then add adhesion promoter, stir at 200r / min for 30 minutes;

[0013] Step 3: Add component B and stir to obtain a modified antibacterial epoxy resin coating.

[0014] Compared with the prior art, the present invention has the following beneficial effects:

[0015] 1. The present invention adopts zeolite imidazole framework material (ZIF-8) to modify antibacterial epoxy resin, which can better improve the tensile strength, flexural strength, elastic modulus, toughness and impact toughness of the composite material. Metal ions (or oxide clusters) connected by organic ligands are introduced as new hybrid materials. ZIF-8 is a typical imidazole zeolite MOF. Its active groups can interact with the polymer in the coating, making its compatibility with organic polymers better than traditional nanofillers.

[0016] 2. The DMG (dimethylolpropionamide containing guanidine) introduced in the present invention has a relatively broad spectrum of antibacterial properties and stability, which solves the problem that the antibacterial varieties of antibacterial coatings on the market are single and the antibacterial ability decreases rapidly. The present invention is recommended for use in special antibacterial environments such as the interior of bridge steel structures, inclined cable parts, port machinery corridors, and the interior of steel structure facilities with medical antibacterial grade requirements, which greatly enhances the applicability of the original products. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] The invention provides a technical solution: a zeolite imidazole skeleton material modified antibacterial epoxy resin coating and a preparation method thereof, comprising: the modified antibacterial epoxy resin coating comprising component A and component B, wherein the formula ratio of component A to component B is 4:1, and component A comprises, by weight: 25 to 30 parts of zeolite imidazole skeleton material modified antibacterial epoxy resin, 2 to 5 parts of active diluent, 0.5 to 0.8 parts of wetting dispersant, 0.1 to 0.3 parts of defoaming agent, 0.5 to 1 parts of adhesion promoter, 0.5 to 1 parts of anti-settling agent, 5 to 10 parts of pigment, 45 to 55 parts of filler, 1.5 to 2 parts of anti-sagging agent and 1 to 1.5 parts of leveling agent; and component B comprises, by weight: 20 to 30 parts of polyamide curing agent.

[0019] In this embodiment, the preparation process of the zeolite imidazole framework material modified antibacterial epoxy resin includes: first, adding 15 grams of DMG modified zeolite imidazole framework material solution to 5 grams of xylene solution, and then adding 20 grams of epoxy resin E-51 and 14 grams of epoxy resin E44 in sequence, ultrasonically dispersing, and stirring at a speed of 800 r / min for 30 minutes to obtain the zeolite imidazole framework material modified antibacterial epoxy resin.

[0020] In this embodiment, the preparation process of the DMG modified zeolite imidazole framework material includes: slowly dripping hydrochloric acid into 1,6-hexanediamine at a rate of 25 drops / minute, and standing for 20 minutes to generate a 1,6-hexanediamine dihydrochloride solution, transferring it to a 500ml three-mouth reactor, maintaining a speed of 200r / min, slowly dripping dicyandiamide, and then mixing and stirring evenly at room temperature, dripping 1-butanol, heating to 60 degrees, maintaining a speed of 400r / min, stirring continuously for 1 hour, standing for 24 hours, and obtaining DMG containing guanidine to obtain dimethylolpropionamide; then mixing DMG with a dispersion of the zeolite imidazole framework material in a mixing ratio of 2:1, placing it in a reactor, and adding a diluent, the diluent is 7 parts of xylene and 3 parts of n-butanol, and stirring continuously for 60 minutes at a speed of 400r / min, and standing for 4 hours to obtain a DMG modified zeolite imidazole framework material.

[0021] In this embodiment, the dispersion of zeolite imidazole framework material is prepared by the following process: completely dispersing zeolite imidazole framework material nanoparticles in an ethanol solution, maintaining a rotation speed of 200 r / min, stirring for 40 minutes, adding a long carbon chain silane coupling agent, the silane coupling agent used is at least one of 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane, the mass ratio is 1:3, stirring at room temperature for 2 to 4 hours to obtain a hydrophobic treatment to obtain zeolite imidazole framework material ZIF-8; then the zeolite imidazole framework material ZIF-8 is centrifuged and washed, using ethanol as a centrifugal washing liquid, and centrifuged and washed 2 to 4 times at a rotation speed of 5000 to 8000 r / min, the mass ratio of ethanol to zeolite imidazole framework material ZIF-8 is 1:6, and a dispersion of zeolite imidazole framework material ZIF-8 is obtained.

[0022] In this embodiment, zeolite imidazole framework material nanoparticles are prepared by dissolving 0.312g Zn(NO3)2.6H2O and 0.185g 2-methylimidazole in 150ml N,N-dimethylformamide respectively. After complete dissolution, the two solutions are mixed, stirred continuously for 1 hour at 200r / min and room temperature and allowed to stand for 24 hours; then centrifuged at 5000r / min for 5mins, the precipitate is taken out and washed 3 times with methanol, and the product is placed in an oven at 80 degrees and dried for 12 hours to constant weight to obtain zeolite imidazole framework material nanoparticles.

[0023] In this embodiment, the present invention also provides a method for preparing the above-mentioned zeolite imidazole framework material modified antibacterial epoxy resin coating, comprising the steps of:

[0024] Step 1: Weigh the zeolite imidazole framework material modified antibacterial epoxy resin, active diluent, wetting dispersant, pigment and filler according to the ratio of component A, place them in a multifunctional dispersing stirring kettle, and stir at a stirring speed of 200 r / min for 30 minutes;

[0025] Step 2: Slowly add anti-settling agent, defoaming agent, anti-sagging agent and leveling agent during stirring, maintain medium stirring speed of 400r / min, stir for 60 minutes, then add adhesion promoter, stir at 200r / min for 30 minutes;

[0026] Step 3: Add component B and stir to obtain a modified antibacterial epoxy resin coating.

[0027] Embodiment 1:

[0028] The modified antibacterial epoxy resin coating includes component A and component B, wherein component A includes 25.5 parts of epoxy resin, 2 parts of active diluent, 14 parts of pigment, 54.4 parts of filler, 0.5 parts of anti-settling agent, 0.1 parts of defoaming agent, 1.5 parts of anti-sagging agent, 1 part of leveling agent, and 1 part of adhesion promoter by weight; component B includes 25 parts of polyamide curing agent by weight.

[0029] Embodiment 2:

[0030] The modified antibacterial epoxy resin coating includes component A and component B, wherein component A includes 28.2 parts of epoxy resin, 2.5 parts of active diluent, 14 parts of pigment, 50.7 parts of filler, 0.75 parts of anti-settling agent, 0.1 parts of defoaming agent, 1.75 parts of anti-sagging agent, 1.5 parts of leveling agent, and 0.5 parts of adhesion promoter by weight; component B includes 25 parts of polyamide curing agent by weight.

[0031] Embodiment 3:

[0032] The modified antibacterial epoxy resin coating includes component A and component B, wherein component A includes 26.7 parts of epoxy resin, 4 parts of active diluent, 15 parts of pigment, 49.3 parts of filler, 0.8 parts of anti-settling agent, 0.2 parts of defoaming agent, 2 parts of anti-sagging agent, 1.5 parts of leveling agent, and 0.5 parts of adhesion promoter by weight; component B includes 25 parts of polyamide curing agent by weight.

[0033] Raw material name Example 1 Example 2 Example 3 Component A Epoxy resin 25.5 28.2 26.7 Active diluent 2 2.5 4 pigment 14 14 15 filler 54.4 50.7 49.3 Anti-settling agent 0.5 0.75 0.8 Defoaming agent 0.1 0.1 0.2 Anti-sagging agent 1.5 1.75 2 Leveling agent 1 1.5 1.5 Adhesion promoter 1 0.5 0.5 Component B Polyamide curing agent 25 25 25

[0034] The test results are shown in the following table:

[0035] characteristic Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 2 Antiviral ○ ◎ ○ × ○ ○ Antimicrobial ○ ◎ ◎ × ◎ ○ Water resistance ◎ ◎ ◎ ◎ ◎ ◎ Adhesion ◎ ◎ ◎ ◎ ◎ ◎ Rust resistance ○ ◎ ◎ ◎ ◎ ◎

[0036] In the above experiment, Comparative Example 1 is our company's conventional epoxy primer, and Comparative Examples 2 and 3 are commercially available antibacterial coatings. The experimental results show that the antiviral and antibacterial properties of Examples 1, 2, and 3 are better than conventional antiseptic products and better than the antibacterial epoxy products currently available on the market.

[0037] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A zeolite imidazole framework material modified antibacterial epoxy resin coating, characterized in that: The modified antibacterial epoxy resin coating comprises component A and component B, wherein the formula ratio of component A to component B is 4:1, and component A comprises, by weight, 25 to 30 parts of antibacterial epoxy resin modified with zeolite imidazole skeleton material, 2 to 5 parts of active diluent, 0.5 to 0.8 parts of wetting dispersant, 0.1 to 0.3 parts of defoaming agent, 0.5 to 1 parts of adhesion promoter, 0.5 to 1 parts of anti-settling agent, 5 to 10 parts of pigment, 45 to 55 parts of filler, 1.5 to 2 parts of anti-sagging agent and 1 to 1.5 parts of leveling agent; and component B comprises, by weight, 20 to 30 parts of polyamide curing agent.

2. The zeolite imidazole framework material modified antibacterial epoxy resin coating according to claim 1, characterized in that: The preparation process of the zeolite imidazole skeleton material modified antibacterial epoxy resin comprises: firstly, adding 15 grams of DMG modified zeolite imidazole skeleton material solution to 5 grams of xylene solution, then adding 20 grams of epoxy resin E-51 and 14 grams of epoxy resin E44 in sequence, ultrasonically dispersing, stirring at a speed of 800 r / min for 30 minutes, and obtaining the zeolite imidazole skeleton material modified antibacterial epoxy resin.

3. The zeolite imidazole framework material modified antibacterial epoxy resin coating according to claim 2, characterized in that: The preparation process of the DMG modified zeolite imidazole framework material comprises: slowly dripping hydrochloric acid into 1,6-hexanediamine at a speed of 25 drops / minute, and standing for 20 minutes to generate a 1,6-hexanediamine dihydrochloride solution, transferring it into a 500ml three-mouth reactor, maintaining a rotation speed of 200r / min, slowly dripping dicyandiamide, and then mixing and stirring evenly at room temperature, dripping 1-butanol, heating to 60 degrees, maintaining a rotation speed of 400r / min, continuously stirring for 1 hour, and standing for 24 hours to obtain DMG containing guanidine groups to obtain dihydroxymethylpropionamide; then mixing DMG with a dispersion of the zeolite imidazole framework material at a mixing ratio of 2:1, placing it in a reactor, and adding a diluent, the diluent being 7 parts of xylene and 3 parts of n-butanol, and continuously stirring for 60 minutes at a rotation speed of 400r / min, and standing for 4 hours to obtain the DMG modified zeolite imidazole framework material.

4. The zeolite imidazole framework material modified antibacterial epoxy resin coating according to claim 3, characterized in that: The dispersion of the zeolite imidazole framework material is prepared by the following process: completely dispersing zeolite imidazole framework material nanoparticles in an ethanol solution, maintaining a rotation speed of 200 r / min, stirring for 40 minutes, adding a long carbon chain silane coupling agent, the silane coupling agent used is at least one of 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane, the mass ratio is 1:3, stirring at room temperature for 2 to 4 hours to obtain a hydrophobic treatment to obtain the zeolite imidazole framework material ZIF-8; then centrifugally washing the zeolite imidazole framework material ZIF-8, using ethanol as a centrifugal washing liquid, centrifugally washing 2 to 4 times at a rotation speed of 5000 to 8000 r / min, the mass ratio of ethanol to the zeolite imidazole framework material ZIF-8 is 1:6, and a dispersion of the zeolite imidazole framework material ZIF-8 is obtained.

5. The zeolite imidazole framework material modified antibacterial epoxy resin coating according to claim 4, characterized in that: The zeolite imidazole framework material nanoparticles are prepared by dissolving 0.312g Zn(NO3)2.6H2O and 0.185g 2-methylimidazole in 150ml N,N-dimethylformamide respectively. After complete dissolution, the two solutions are mixed, stirred continuously for 1 hour at a speed of 200r / min and room temperature and allowed to stand for 24 hours; then centrifuged at a speed of 5000r / min for 5mins, the precipitate is taken out and washed with methanol for 3 times, and the product is placed in an oven at 80 degrees to dry for 12 hours to constant weight to obtain zeolite imidazole framework material nanoparticles.

6. A method for preparing a zeolite imidazole framework material modified antibacterial epoxy resin coating according to any one of claims 1 to 5, characterized in that: Includes steps: Step 1: Weigh the zeolite imidazole framework material modified antibacterial epoxy resin, active diluent, wetting dispersant, pigment and filler according to the ratio of component A, place them in a multifunctional dispersing stirring kettle, and stir at a stirring speed of 200 r / min for 30 minutes; Step 2: Slowly add anti-settling agent, defoaming agent, anti-sagging agent and leveling agent during stirring, maintain medium stirring speed of 400r / min, stir for 60 minutes, then add adhesion promoter, stir at 200r / min for 30 minutes; Step 3: Add component B and stir to obtain a modified antibacterial epoxy resin coating.