CN1844270A - Nano antibacterial powder coating and its micro-suspension one-step manufacturing method - Google Patents

Abstract

The invention relates to a manufacturing domain of nanopowder composite, especially to a nano antibacterial powder coating and one-step manufacturing method of microsuspension. The nano antibacterial powder coating consists of water, mixture monomer, pigment, surface processing agent, nanometre-sized inorganic antiseptic particle and auxiliary agent. The method comprises dispersing components such as water and suspending disperser by ultra-audio wave, then performing dispersion by high-shear emulsifier to prepare the predispersion; afterwards, adding the other components into polymerization kettle according to priority, after agitation and heating, adding the said predispersion at one time, reacting at a constant temperature, then cooling, discharge, centrifugally dewatering and drying to obtain the product. The invention solves the problems that the nanoparticles are easy to aggregate inside the organic polymer existed in present technology and the manufacturing engineering of the traditional powder coating is difficult, and has advantages that the process flow is short, the equipment investment is low, and can save working hours and energy resource, is of no dust pollution, the prepared powder coating particles is of regular shape, and has better levelling property in application.

Description

Nano antibacterial powder coating and its micro-suspension one-step manufacturing method

technical field

The invention relates to the field of manufacturing nano powder composite materials, in particular to a nano antibacterial powder coating and a microsuspension one-step manufacturing method thereof.

Background technique

In recent years, with the extensive use of antibiotics and chemical drugs and the aggravation of environmental pollution, bacteria and viruses are causing more and more serious harm to humans. From the 0-157 Escherichia coli infection that broke out in a large area in Japan in 1996 to today's "atypical pneumonia" and "bird flu", all of them have proved to us the urgency and severity of resisting the harm of bacteria and viruses. To effectively prevent the growth of bacteria, the use of antibacterial materials is the simplest and most effective method. Therefore, the use of antibacterial coatings for coatings that are closely related to people's lives is of great significance for protecting human health and reducing diseases. Powder coatings are widely used in the fields of home furnishing, building materials, household goods and transportation equipment. With the improvement of people's living standards and the increasing concern for health, the demand for antibacterial coatings is also becoming stronger and stronger.

Antibacterial agents must be used in the manufacture of antibacterial coatings. Antibacterial agents are mainly divided into three categories: natural, organic and inorganic. Natural antibacterial agents have a short service life and poor heat resistance (carbonization and decomposition at 150°C to 180°C). Organic antibacterial agents are prone to microbial resistance (resistance), and have disadvantages such as easy migration and poor heat resistance. They are easy to decompose and fail at the processing temperature of powder coatings, and the decomposition products may cause secondary pollution. Inorganic oxide nanoparticle antibacterial agents can use both the antibacterial ability of metal ions and the antibacterial properties of nanoparticles. It does not produce drug resistance and is safe and non-toxic, especially its outstanding heat resistance (> 600 ° C), It has obvious advantages in the application of various antibacterial products.

The traditional process of preparing nano-antibacterial powder coatings includes six major process steps: resin synthesis, material mixing, heating and melting, cooling granulation, mechanical crushing, and sieving and grading. However, due to the small particle size of nanoparticles, the specific surface area and surface energy are very large. It is easy to agglomerate, even if the size of primary particles obtained by chemical methods reaches the nanometer level, these primary particles will still agglomerate during the processing of powder coatings and become agglomerated particles with a size of hundreds of nanometers or even larger, so pure inorganic nanoparticles It is not easy to disperse in organic polymers, and there is often serious phase separation between organic polymers and inorganic particles. This seriously hinders the performance of nanoparticles, so it is particularly important to improve the dispersion of nanoparticles in powder coating polymers. In addition, the shape of powder coating particles prepared by melt extrusion pulverization method is irregular, including triangular, square or spherical, etc., which will affect the leveling of powder coatings in use.

Powder coatings are one of the environmentally friendly coatings and are widely used in oil fields and natural gas pipelines for anti-corrosion, automobile manufacturing, refrigerators, washing machines, hardware appliances and other manufacturing fields. Nano-antibacterial powder coatings are generally prepared by adding antibacterial agents (such as inorganic nano-titanium dioxide, oxidized Zinc particles), the traditional manufacturing method of powder coating belongs to the physical and mechanical crushing method, its main disadvantages are long process, large investment in equipment, waste of working hours, waste of energy and serious dust pollution, etc., and the nano antibacterial agent particles are not easy to disperse, affecting The performance of its function will further affect the quality of the product. It can be seen that it is very necessary to develop a new process to manufacture powder coatings.

Contents of the invention

The purpose of the present invention is to overcome the shortcomings of the traditional powder coating manufacturing process and the nano-particles are easy to agglomerate, and provide a nano-antibacterial powder coating and its micro-suspension one-step manufacturing method.

Nano antibacterial powder coating is made from the component of following weight part among the present invention:

Water 150～300 Mixed monomer 80～150 Nano antibacterial agent particles 10～20

Pigment and filler 30-50 Auxiliary 3-20 Surface treatment agent 1-10

The mixed monomer is a compound of hard monomer, soft monomer and functional monomer, and the auxiliary agent is a suspension dispersant, initiator, auxiliary dispersant and water phase polymerization inhibitor.

Wherein the concrete composition of each component is:

The weight ratio of each component in the mixed monomer is:

Hard monomer 60～90 Soft monomer 20～50 Functional monomer 2～10

The hard monomer is one or more mixtures of methyl methacrylate, methyl acrylate, styrene, methyl styrene, vinyl acetate, acrylonitrile, and methacrylonitrile; the soft monomer is ethyl acrylate One or more mixtures of ester, butyl acrylate, hexyl acrylate, octyl acrylate, isooctyl acrylate, and 2-ethylhexyl acrylate; functional monomers are acrylic acid, itaconic acid, methacrylic acid , β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate, N-methylolacrylamide, N-methoxymethacrylamide one or a mixture of more than one.

The inorganic nano antibacterial agent particles are one or more mixtures of nano-titanium dioxide, nano-zinc oxide, nano-calcium oxide, nano-alumina and other particles.

Pigments and fillers include coloring pigments and extender pigments. The coloring pigments are one or more mixtures of titanium dioxide, lithopone, zinc oxide, iron red, iron yellow, ultramarine blue, and chrome green. The extender pigments are calcium carbonate and china clay. , talcum powder, barite powder, superfine aluminum silicate or a mixture of more than one, and the coloring pigment and extender pigment are treated lipophilic and water-repellent pigments.

Suspending and dispersing agents in auxiliary agents are gelatin, bone glue, polyvinyl alcohol 1788, polyvinyl alcohol 1799, polyvinyl alcohol 1793, polyvinyl alcohol 1778, polyvinyl alcohol 2088, carboxymethyl cellulose, polyvinylpyrrolidone One or more than one of the mixture, the auxiliary dispersant is one or more of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, OP-10, OP-40, MS-1 The mixture, the initiator is benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptylonitrile One or more mixtures, the aqueous phase polymerization inhibitor is one or more mixtures of potassium chloride, sodium chloride, copper chloride and sodium sulfate.

The surface treatment agent is stearic acid, polyvinylpyrrolidone, trichlorovinylsilane, triethoxysilane, titanate and other coupling agents, alkylphenol polyoxyethylene ether series, alkyl alcohol polyoxygen One or more mixtures of vinyl ether series surfactants.

The preparation method of the present invention is:

It consists of the following process steps:

A. Disperse 40% to 80% of water, 50% to 80% of suspending and dispersing agent, initiator, auxiliary dispersing agent, mixed monomer and surface-treated inorganic nano-antibacterial agent particles and pigments and fillers by ultrasonic dispersion, Then disperse through a high-shear emulsifier to make a pre-dispersed liquid for use;

B. Add the rest of the water, suspension dispersant and water phase polymerization inhibitor in sequence to the reactor, start stirring to dissolve the suspension dispersant, heat to 60-90°C, add the pre-dispersion in step A at one time, React at 70°C-85°C for 1.5-5 hours, raise the temperature to 80°C-85°C and react for 4-6 hours, cool down, discharge, centrifuge and dry to obtain the product.

The technical progress achieved by the present invention lies in:

Changing the traditional powder coating manufacturing method from 6-step method to 1-step method, compared with the traditional manufacturing process of powder coating, the process flow is shorter, equipment investment is less, man-hours and energy are saved, and dust pollution is lighter. At the same time, the problems of easy aggregation of nanoparticles and compatibility with polymers are solved. The nano antibacterial powder coating has good leveling property in use.

Detailed ways

The present invention will be further described below in conjunction with embodiment:

Example

The distribution ratio for each group is:

Deionized water 250 Mixed monomer 102 Inorganic nano antibacterial particles 10

Pigment and filler 30 Auxiliary 5.6 Surface treatment agent 1.0

The proportioning ratio of the ingredients contained in the above-mentioned mixed monomers is:

Hard monomer 80 soft monomer 30 functional monomer 2.

Among them, the inorganic nano-antibacterial particles use nano-zinc oxide powder, and the composition of the hard monomer is:

Methyl methacrylate (polymer grade) 65 Styrene (polymer grade) 15

The soft monomer is butyl acrylate (polymerization grade), the functional monomer is acrylic acid (polymerization grade), the suspension and dispersant in the auxiliary agent is polyvinyl alcohol 1788, the auxiliary dispersant is OP-10 (polymerization grade), and the initiator is Azoisobutyronitrile is selected for use, potassium chloride is selected as the aqueous phase polymerization inhibitor, and the composition of the auxiliary agent is:

Polyvinyl alcohol 1788 2.5 OP-10 (polymer grade) 0.1 Azoisobutyronitrile 2.5

Potassium chloride 0.5

The preparation method is:

A. Add 150 ml of water, 3 g of polyvinyl alcohol and 0.1 g of OP-10 into a stirred 500 ml reactor, heat and stir to dissolve the polyvinyl alcohol for use. Weigh methyl methacrylate, styrene, butyl acrylate, and acrylic acid, add initiator, dissolve and add surface-treated inorganic nano-antibacterial particles and pigments and fillers, disperse with ultrasonic waves for 30 minutes, and disperse in a high-shear emulsifier In the case of , add the suspending agent solution and disperse for 20 minutes to make a pre-dispersion liquid for use;

B. Add the remaining 100 ml of water, 2 g of polyvinyl alcohol, and potassium chloride into the polymerization kettle, start stirring to dissolve the polyvinyl alcohol, heat to 80°C, add the pre-dispersion liquid at one time, and react at a constant temperature of 80°C for 2 hours and then react at 83° C. for 3 hours, cool down, discharge, centrifugally dehydrate, and dry to obtain the product.

Sample performance:

[1] Appearance: white powder;

[Particle size]: 20～50μm;

[3] Particle shape: regular spherical or ellipsoidal.

Claims (7)

1, nano-antibacterial powder coating is characterized in that it is made by following components in part by weight:

Water 150～300 mix monomers 80～150 nano antibacterial agent particles 10～20

Color stuffing 30-50 auxiliary agent 3～20 surface treatment agents 1～10

Wherein mix monomer is the mixed thing of hard monomer, soft monomer and function monomer, and auxiliary agent is suspension dispersive agent, initiator, dispersion aids and water stopper.

2, nano-antibacterial powder coating according to claim 1 is characterized in that each composition weight proportioning is in the described mix monomer:

Hard monomer 60～90 soft monomers 20～50 function monomers 2～10

Wherein hard monomer is one or more the mixture in methyl methacrylate, methyl acrylate, vinylbenzene, vinyl toluene, vinyl acetate between to for plastic, acrylonitrile, the methacrylic eyeball; Soft monomer is one or more the mixture in ethyl propenoate, butyl acrylate, Ethyl acrylate, Octyl acrylate, Isooctyl acrylate monomer, the 2-EHA; Function monomer is one or more the mixture in vinylformic acid, itaconicacid, methacrylic acid, propenoic acid beta-hydroxy ethyl ester, propenoic acid beta-hydroxy propyl ester, Jia Jibingxisuanβ-Qiang Yizhi, methacrylic acid β-hydroxypropyl acrylate, N hydroxymethyl acrylamide, the N-methoxymethyl acrylamide.

3, nano-antibacterial powder coating according to claim 1 is characterized in that described inorganic nano antiseptic particle is one or more mixtures of particles such as nano titanium oxide, nano zine oxide, nano calcium oxide, nano aluminium oxide.

4, nano-antibacterial powder coating according to claim 1, it is characterized in that described color stuffing comprises tinting pigment and pigment extender, tinting pigment is one or more the mixture in titanium dioxide, zinc sulfide white, zinc oxide, iron oxide red, iron oxide yellow, ultramarine, the chrome green, pigment extender is one or more the mixture in lime carbonate, china clay, talcum powder, ground barium sulfate, the superfine alumina silicate, and tinting pigment and pigment extender are oleophylic water repellency pigment after treatment.

5, nano-antibacterial powder coating according to claim 1, it is characterized in that the suspension dispersive agent in the described auxiliary agent is a gelatinum, gelatine, polyvinyl alcohol 1788, polyvinyl alcohol 1799, polyvinyl alcohol 1793, polyvinyl alcohol 1778, polyvinyl alcohol 2088, carboxymethyl cellulose, the mixture of one or more in the polyethylene pyrrolidone, dispersion aids is a sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, OP-10, OP-40, the mixture of one or more among the MS-1, initiator is a benzoyl peroxide, lauroyl peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, azo two isobutyls are fine, the mixture of one or more during two different heptan of azo are fine, the water stopper is a Repone K, sodium-chlor, the mixture of one or more in cupric chloride and the sodium sulfate.

6, nano-antibacterial powder coating according to claim 1 is characterized in that surface treatment agent is one or more the mixture in coupling agent, alkylphenol polyoxyethylene series, the alkyl alcohol Soxylat A 25-7 series of surfactants such as stearic acid, polyethylene pyrrolidone, trieline base silane, triethoxyl silane, titanate ester.

7, the micro-suspension one-step manufacturing process of nano-antibacterial powder coating according to claim 1 is characterized in that it is made up of following processing step:

A, water with 40%～80%, 50%～80% suspension dispersive agent, initiator, dispersion aids, mix monomer and through surface-treated inorganic nano antiseptic particle and color stuffing pass through ultrasonic dispersing, disperse through high-shear emulsion machine again, make that to give dispersion liquid stand-by;

B, with remaining water, suspension dispersive agent and water stopper, add reactor successively according to the order of sequence, start to stir and make the suspension dispersive agent dissolving, be heated to 60～90 ℃, disposable adding A step give dispersion liquid, 70 ℃～85 ℃ reactions 1.5～5 hours, be warming up to 80 ℃～85 ℃ afterreactions 4～6 hours, cooling, discharging, centrifuge dehydration, oven dry promptly get product.