阅读说明：本技术 玄武岩鳞片丙烯酸树脂复合改性聚偏氟乙烯涂料 (Basalt flake acrylic resin composite modified polyvinylidene fluoride coating ) 是由 白永平 曹柏青 安英斌 王建伟 张小娟 于 2021-10-29 设计创作，主要内容包括：本发明涉及聚偏氟乙烯涂料技术领域,尤其涉及玄武岩鳞片丙烯酸树脂复合改性聚偏氟乙烯涂料,涂料组合物按质量百分数计算含量,至少包括：聚偏氟乙烯水性乳液：10-20％；改性填料：5-25％；聚丙烯酸树脂：1-8％；溶剂：47-76％；涂料的制备方法包括以下步骤：S1、聚偏氟乙烯水性乳液的制备,S2、改性填料的制备,S3、涂料制备,该发明制备的涂料具有良好的机械韧性、高硬度、耐紫外辐射、耐候性,玄武岩鳞片的添加,其在涂料中产生的“迷宫效应”可有效提高腐蚀介质的渗透路径,且改性后玄武岩鳞片与涂料的结合性好,易分散,且稳定性高,其自身优异的耐氯侵蚀性、耐辐射性、耐酸碱性等也发挥作用,进一步加强了涂料的性能。(The invention relates to the technical field of polyvinylidene fluoride coatings, in particular to a basalt flake acrylic resin composite modified polyvinylidene fluoride coating, which comprises the following components in percentage by mass: polyvinylidene fluoride aqueous emulsion: 10 to 20 percent; modified filler: 5 to 25 percent; polyacrylic acid resin: 1 to 8 percent; solvent: 47-76%; the preparation method of the coating comprises the following steps: s1, preparing polyvinylidene fluoride aqueous emulsion, S2, preparing modified filler, S3 and preparing coating, wherein the coating prepared by the invention has good mechanical toughness, high hardness, ultraviolet radiation resistance and weather resistance, and the addition of basalt flakes can effectively improve the permeation path of corrosive media due to the labyrinth effect generated in the coating, and the modified basalt flakes are good in binding property with the coating, easy to disperse and high in stability, and play a role in excellent chlorine corrosion resistance, radiation resistance, acid and alkali resistance and the like, so that the performance of the coating is further enhanced.)

1. The basalt crystalline flake acrylic resin composite modified polyvinylidene fluoride coating is characterized in that the coating composition at least comprises the following components in percentage by mass: polyvinylidene fluoride aqueous emulsion: 10 to 20 percent; modified filler: 5 to 25 percent; polyacrylic acid resin: 1 to 8 percent; solvent: 47-76%;

the preparation method of the coating comprises the following steps:

s1, preparing polyvinylidene fluoride aqueous emulsion: mixing acrylic emulsion with polyvinylidene fluoride to form polyvinylidene fluoride aqueous emulsion, wherein the acrylic emulsion accounts for 20-30% of the total mass of the polyvinylidene fluoride aqueous emulsion;

s2, preparation of modified filler: adding the basalt flakes into an auxiliary agent, adding a surface treatment catalyst, dropwise adding a surface treatment agent while stirring, controlling the reaction temperature to be 30-60 ℃, controlling the dropwise adding time to be 0.5-3h, keeping the temperature for 1-4h after dropwise adding, filtering out the auxiliary agent, and performing forced convection drying to obtain a modified filler for later use, wherein the mass ratio of the surface treatment agent to the basalt flakes is (0.3-2): 1;

s3, preparing the coating: adding the polyvinylidene fluoride aqueous emulsion, the modified filler, the polyacrylic resin and the solvent into a batching container, preliminarily mixing uniformly, and preparing coating dispersion slurry in a high-speed dispersion mode for 30-90min to obtain the basalt crystalline flake acrylic resin composite modified polyvinylidene fluoride coating.

2. The basalt scale acrylic resin composite modified polyvinylidene fluoride coating of claim 1, wherein the solvent is one or a mixture of methyl isobutyl ketone, N-methyl pyrrolidone, xylene, toluene, dimethylformamide, butyl acetate, ethyl acetate, and cyclohexanone.

3. The basalt scale acrylic resin composite modified polyvinylidene fluoride coating of claim 1, wherein the additive is one or a mixture of methanol, ethanol, ethyl acetate and acetone.

4. The basalt flake acrylic resin composite modified polyvinylidene fluoride coating of claim 1, wherein the surface treatment catalyst is one or a mixture of cobalt naphthenate, zinc naphthenate, calcium naphthenate, potassium isooctate, zinc acetate, sodium ethoxide, potassium hydroxide and calcium hydroxide.

5. The basalt scale acrylic resin composite modified polyvinylidene fluoride coating of claim 1, wherein the mass ratio of the surface treatment catalyst to the basalt scale is (0.005-0.03): 1.

6. the basalt scale acrylic resin composite modified polyvinylidene fluoride coating of claim 1, wherein the surface treating agent is: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, methacryloxymethyldiethoxysilane and methacryloxymethyldimethoxysilane, or a mixture of several of them.

7. The basalt scale acrylic resin composite modified polyvinylidene fluoride coating of claim 1, wherein the stirring speed of the initial mixing is 500-700rpm, and the stirring speed of the high-speed dispersion is 3600-4500 rpm.

Technical Field

The invention relates to the technical field of polyvinylidene fluoride coatings, in particular to a basalt flake acrylic resin composite modified polyvinylidene fluoride coating.

Background

Polyvinylidene fluoride (PVDF) coating has excellent weather resistance and insulation performance, and excellent impact resistance, heat resistance, chemical resistance, oil resistance and pollution resistance, and is widely applied to coating outdoor furniture, equipment, chemical equipment, pipelines and the like at present. With the development of society, people put higher requirements on the performance of the coating, and the anti-corrosion performance of the existing polyvinylidene fluoride coating needs to be further improved.

The basalt flake is a novel flake material, is a novel material prepared by selecting natural basalt ore with excellent performance through special processing technologies such as high-temperature melting, clarification, homogenization molding, screening and the like, has a transparent or dark green sheet-shaped structure, is generally about 3 mu m thick and is generally 25 mu m-3mm in size. The basalt scales have high content of iron oxide, titanium dioxide, aluminum oxide and calcium oxide and low content of alkaline oxides, so that the basalt scales not only can generate a shielding effect, but also have unique advantages in acid-base resistance and corrosion resistance. The basalt scales are added into the resin, so that the resin can be divided into a plurality of small spaces, the phenomenon of stress concentration in the resin is effectively improved, staggered arrangement is formed among the scales, the medium infiltration can become circuitous and tortuous, the path of corroding medium diffusing to matrix resin and the time of corroding medium infiltrating into a matrix are increased, and the corrosion resistance of the coating is improved.

Therefore, the basalt flake acrylic resin composite modified polyvinylidene fluoride coating is provided for solving the problems.

Disclosure of Invention

The invention aims to solve the defects in the prior art, and provides a basalt flake acrylic resin composite modified polyvinylidene fluoride coating.

The basalt crystalline flake acrylic resin composite modified polyvinylidene fluoride coating at least comprises the following components in percentage by mass: polyvinylidene fluoride aqueous emulsion: 10 to 20 percent; modified filler: 5 to 25 percent; polyacrylic acid resin: 1 to 8 percent; solvent: 47-76%;

the preparation method of the coating comprises the following steps:

s1, preparing polyvinylidene fluoride aqueous emulsion: mixing acrylic emulsion with polyvinylidene fluoride to form polyvinylidene fluoride aqueous emulsion, wherein the acrylic emulsion accounts for 20-30% of the total mass of the polyvinylidene fluoride aqueous emulsion;

s2, preparation of modified filler: adding the basalt flakes into an auxiliary agent, adding a surface treatment catalyst, dropwise adding a surface treatment agent while stirring, controlling the reaction temperature to be 30-60 ℃, controlling the dropwise adding time to be 0.5-3h, keeping the temperature for 1-4h after dropwise adding, filtering out the auxiliary agent, and performing forced convection drying to obtain a modified filler for later use, wherein the mass ratio of the surface treatment agent to the basalt flakes is (0.3-2): 1;

s3, preparing the coating: adding the polyvinylidene fluoride aqueous emulsion, the modified filler, the polyacrylic resin and the solvent into a batching container, preliminarily mixing uniformly, and preparing coating dispersion slurry in a high-speed dispersion mode for 30-90min to obtain the basalt crystalline flake acrylic resin composite modified polyvinylidene fluoride coating.

Preferably, the solvent is one or a mixture of several of methyl isobutyl ketone, N-methyl pyrrolidone, xylene, toluene, dimethylformamide, butyl acetate, ethyl acetate and cyclohexanone.

Preferably, the auxiliary agent is one or a mixture of methanol, ethanol, ethyl acetate and acetone.

Preferably, the surface treatment catalyst is one or a mixture of more of cobalt naphthenate, zinc naphthenate, calcium naphthenate, potassium isooctanoate, zinc acetate, sodium ethoxide, potassium hydroxide and calcium hydroxide, and the mass ratio of the surface treatment catalyst to the basalt scales is (0.005-0.03): 1.

preferably, the surface treatment agent is: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, methacryloxymethyldiethoxysilane and methacryloxymethyldimethoxysilane, or a mixture of several of them.

Preferably, the stirring speed of the preliminary mixing is 500-700rpm, and the stirring speed of the high-speed dispersion is 3600-4500 rpm.

The invention has the beneficial effects that: the coating prepared by the invention has good mechanical toughness, high hardness, ultraviolet radiation resistance and weather resistance, and the addition of the basalt flakes can effectively improve the permeation path of corrosive media due to the labyrinth effect generated in the coating, and the modified basalt flakes are good in binding property with the coating, easy to disperse and high in stability, can also compensate the problem of poor binding force between a polytetrafluoroethylene coating and a substrate, and also play a role in excellent chlorine corrosion resistance, radiation resistance, acid and alkali resistance and the like, so that the performance of the coating is further enhanced.

Detailed Description

The present invention will be further illustrated with reference to the following specific examples.

Example 1

The basalt crystalline flake acrylic resin composite modified polyvinylidene fluoride coating comprises the following components in percentage by mass: polyvinylidene fluoride aqueous emulsion: 10 percent; modified filler: 13 percent; polyacrylic acid resin: 1 percent; ethyl acetate solvent: 76%;

the preparation method of the coating comprises the following steps:

s1, preparing polyvinylidene fluoride aqueous emulsion: mixing acrylic emulsion with polyvinylidene fluoride to form polyvinylidene fluoride aqueous emulsion, wherein the acrylic emulsion accounts for 20% of the total mass of the polyvinylidene fluoride aqueous emulsion;

s2, preparation of modified filler:

adding the basalt flakes into a methanol auxiliary agent;

adding a calcium naphthenate surface treatment catalyst, wherein the mass ratio of the surface treatment catalyst to the basalt flakes is 0.005: 1;

dropwise adding a 3-methacryloxypropyltrimethoxysilane surface treating agent while stirring, wherein the mass ratio of the surface treating agent to the basalt flakes is 0.3: 1, controlling the reaction temperature to be 30 ℃, dropwise adding for 0.5h, preserving heat for 1h after dropwise adding, and filtering out the auxiliary agent;

after forced convection drying, obtaining modified filler for later use;

s3, preparing the coating: adding polyvinylidene fluoride aqueous emulsion, modified filler, polyacrylic resin and solvent into a batching container, stirring at 500rpm for preliminary mixing, preparing coating dispersion slurry in a high-speed dispersion mode after preliminary mixing is uniform, wherein the stirring speed for high-speed dispersion is 3600rpm, and the high-speed dispersion time is 30min, thus obtaining the basalt crystalline flake acrylic resin composite modified polyvinylidene fluoride coating.

Further, the solvent is one or a mixture of several of methyl isobutyl ketone, N-methyl pyrrolidone, xylene, toluene, dimethylformamide, butyl acetate, ethyl acetate and cyclohexanone.

Further, the auxiliary agent is one or a mixture of more of methanol, ethanol, ethyl acetate and acetone.

Further, the surface treatment catalyst is one or a mixture of more of cobalt naphthenate, zinc naphthenate, calcium naphthenate, potassium isooctanoate, zinc acetate, sodium ethoxide, potassium hydroxide and calcium hydroxide.

Further, the surface treating agent is: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, methacryloxymethyldiethoxysilane and methacryloxymethyldimethoxysilane, or a mixture of several of them.

Example 2

The basalt crystalline flake acrylic resin composite modified polyvinylidene fluoride coating comprises the following components in percentage by mass: polyvinylidene fluoride aqueous emulsion: 20 percent; modified filler: 25 percent; polyacrylic acid resin: 8 percent; n-methylpyrrolidone solvent: 47%;

the preparation method of the coating comprises the following steps:

s1, preparing polyvinylidene fluoride aqueous emulsion: mixing acrylic emulsion with polyvinylidene fluoride to form polyvinylidene fluoride aqueous emulsion, wherein the acrylic emulsion accounts for 30% of the total mass of the polyvinylidene fluoride aqueous emulsion;

s2, preparation of modified filler:

adding the basalt flakes into an acetone auxiliary agent;

adding a potassium hydroxide surface treatment catalyst, wherein the mass ratio of the surface treatment catalyst to the basalt flakes is 0.03: 1;

dropwise adding a 3-methacryloxypropyltriethoxysilane surface treating agent while stirring, wherein the mass ratio of the surface treating agent to the basalt flakes is 2: 1, controlling the reaction temperature to be 60 ℃, dropwise adding for 3 hours, preserving heat for 4 hours after dropwise adding, and filtering out an auxiliary agent;

after forced convection drying, obtaining modified filler for later use;

s3, preparing the coating: adding the polyvinylidene fluoride aqueous emulsion, the modified filler, the polyacrylic resin and the solvent into a batching container, stirring at 700rpm for preliminary mixing, preparing coating dispersion slurry in a high-speed dispersion mode after preliminary mixing is uniform, wherein the stirring speed for high-speed dispersion is 4500rpm, and the high-speed dispersion time is 90min, so as to obtain the basalt crystalline flake acrylic resin composite modified polyvinylidene fluoride coating.

Example 3

The basalt crystalline flake acrylic resin composite modified polyvinylidene fluoride coating comprises the following components in percentage by mass: polyvinylidene fluoride aqueous emulsion: 15 percent; modified filler: 20 percent; polyacrylic acid resin: 6 percent; xylene solvent: 59 percent of water;

the preparation method of the coating comprises the following steps:

s1, preparing polyvinylidene fluoride aqueous emulsion: mixing acrylic emulsion with polyvinylidene fluoride to form polyvinylidene fluoride aqueous emulsion, wherein the acrylic emulsion accounts for 25% of the total mass of the polyvinylidene fluoride aqueous emulsion;

s2, preparation of modified filler:

adding the basalt flakes into an auxiliary agent, wherein the auxiliary agent is a mixture of ethyl acetate and ethanol;

adding a cobalt naphthenate surface treatment catalyst, wherein the mass ratio of the surface treatment catalyst to the basalt flakes is 0.02: 1;

dropwise adding a methacryloxymethyltriethoxysilane surface treating agent while stirring, wherein the mass ratio of the surface treating agent to the basalt flakes is 1: 1, controlling the reaction temperature to be 45 ℃, dropwise adding for 2 hours, preserving the temperature for 2 hours after dropwise adding, and filtering out the auxiliary agent;

after forced convection drying, obtaining modified filler for later use;

s3, preparing the coating: adding polyvinylidene fluoride aqueous emulsion, modified filler, polyacrylic resin and solvent into a batching container, stirring at 600rpm for preliminary mixing, preparing coating dispersion slurry in a high-speed dispersion mode after preliminary mixing is uniform, wherein the stirring speed for high-speed dispersion is 4000rpm, and the high-speed dispersion time is 60min, thus obtaining the basalt crystalline flake acrylic resin composite modified polyvinylidene fluoride coating.

In the comparative example 1,

in comparison with example 3, the modified filler was not added, and the rest was the same as example 3.

In a comparative example 2,

compared with the embodiment 3, the basalt flakes with equal mass are added to replace the modified filler, and the rest is the same as the embodiment 3.

The coatings of the three examples and the two comparative examples are tested, and the statistics of the test results are shown in table 1;

TABLE 1

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.