阅读说明：本技术 一种水性氟改性丙烯酸乳液及其制备方法、应用 (Aqueous fluorine modified acrylic emulsion and preparation method and application thereof ) 是由 魏克海 侯树伟 朱克 于 2019-10-15 设计创作，主要内容包括：本发明属于乳液技术领域,具体涉及一种水性氟改性丙烯酸乳液的及其制备方法、应用。具体配方为：水56％,乳化剂1-2％,含氟单体1-6％,丙烯酸丁酯11-16％,甲基丙烯酸甲酯8-15％,苯乙烯3-11％,β-丙烯酰氧基丙酸0.25-0.5%,丙烯酸0.25-0.5％,丙烯酸羟乙酯1-4％,叔碳酸乙烯酯0.5-3％,丙烯酰胺0.3-0.8％,双丙酮丙烯酰胺(DAAM)1-2.5％,己二酸二酰肼(ADH)0.5-1.25％,过硫酸盐0.2-0.4％,有机胺AMP-95 0.6%-1.5%。本发明制备的乳液,耐溶剂性、耐候性、耐沾污性、耐人工老化性、耐水性好,且抗刮伤、T弯、冲击性能优异。(The invention belongs to the technical field of emulsion, and particularly relates to a water-based fluorine modified acrylic emulsion, and a preparation method and application thereof. The specific formula is as follows: 56% of water, 1-2% of emulsifier, 1-6% of fluorine-containing monomer, 11-16% of butyl acrylate, 8-15% of methyl methacrylate, 3-11% of styrene, 0.25-0.5% of beta-acryloxypropionic acid, 0.25-0.5% of acrylic acid, 1-4% of hydroxyethyl acrylate, 0.5-3% of vinyl versatate, 0.3-0.8% of acrylamide, 1-2.5% of diacetone acrylamide (DAAM), 0.5-1.25% of Adipic Dihydrazide (ADH), 0.2-0.4% of persulfate and 1.5% of organic amine AMP-950.6%. The emulsion prepared by the invention has good solvent resistance, weather resistance, stain resistance, artificial aging resistance and water resistance, and has excellent scratch resistance, T-bend resistance and impact resistance.)

1. The water-based fluorine modified acrylic emulsion is characterized by comprising the following components: 56% of water, 1-2% of emulsifier, 1-6% of fluorine-containing monomer, 11-16% of butyl acrylate, 8-15% of methyl methacrylate, 3-11% of styrene, 0.25-0.5% of beta-acryloxypropionic acid, 0.25-0.5% of acrylic acid, 1-4% of hydroxyethyl acrylate, 0.5-3% of vinyl versatate, 0.3-0.8% of acrylamide, 1-2.5% of diacetone acrylamide (DAAM), 0.5-1.25% of Adipic Dihydrazide (ADH), 0.2-0.4% of persulfate and 1.5% of organic amine AMP-950.6%; the percentage is mass fraction.

2. The aqueous fluorine-modified acrylic emulsion according to claim 1, wherein the emulsifier is one or a mixture of two or more of sodium lauryl sulfate, sodium alkylphenol ethoxylate sulfate and ammonium alkylphenol ethoxylate sulfate.

3. The aqueous fluorine-modified acrylic emulsion according to claim 1, wherein the fluorine-containing monomer is any one or a mixture of two or more of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, and octafluoropentyl methacrylate.

4. The aqueous fluorine-modified acrylic emulsion according to claim 1, wherein said vinyl versatate is C₉Vinyl versatate, C₁₀Vinyl versatate, C₁₁Any one or a mixture of more than two of ethylene versatate.

5. The aqueous fluorine-modified acrylic emulsion according to claim 1, wherein the persulfate is one or a mixture of two or more of potassium persulfate, sodium persulfate and ammonium persulfate.

6. A process for the preparation of an aqueous fluorine-modified acrylic emulsion according to any of claims 1 to 5, comprising the steps of:

(1) 1/2-2/3 water and 1/4-1/2 emulsifier are weighed and added into a reaction kettle, stirring and heating are started, and the temperature is raised to 83-88 ℃;

(2) adding 1/3-1/2 water and 1/2-3/4 emulsifier into an emulsification tank, starting stirring, sequentially adding a fluorine-containing monomer, butyl acrylate, methyl methacrylate, styrene, beta-acryloxypropionic acid, acrylic acid, hydroxyethyl acrylate, vinyl versatate, acrylamide, diacetone acrylamide and 2/3 persulfate, and continuously stirring for 40 minutes to prepare an emulsion for later use;

(3) when the temperature of the reaction kettle is raised to 83-88 ℃, adding the residual persulfate into the reaction kettle, beginning to dropwise add the emulsion into the reaction kettle at a constant speed, and controlling the temperature to 83-88 ℃;

(4) when the emulsion is completely added into the reaction kettle, controlling the temperature to be 83-90 ℃, and preserving the heat for 1-2 hours;

(5) and (3) cooling after the heat preservation is finished, adding AMP-95 when the temperature is reduced to be below 45 ℃, stirring for 15 minutes, adding adipic dihydrazide, continuing stirring for 15 minutes, stopping stirring, filtering, and discharging.

7. The production method according to claim 6, wherein in the step (3), the dropping time of the emulsion is controlled to be 2 to 3 hours.

8. Use of the aqueous fluorine-modified acrylic emulsion according to claims 1 to 7 for the preparation of color plate paints.

Technical Field

The invention belongs to the technical field of emulsion, relates to a fluorine modified acrylic emulsion, and particularly relates to a water-based fluorine modified acrylic emulsion and a preparation method and application thereof.

Background

The coil coating is different from the common industrial coating, and adopts a production process of coating before processing, so that a lot of cost can be saved. The requirements for coatings are very high, on the one hand, sufficient hardness to prevent scratching, and on the other hand, sufficient flexibility to prevent cracking of the coating during processing. The coating after coating also has excellent weather resistance, water resistance and the like so as to meet different requirements of users.

At present, almost all the coatings for the coiled materials are oil-based paints, and because the coatings contain a large amount of solvents, the coatings have great influence on the environment and workers, and are not in accordance with the environmental protection advocated by the nation. In the prior art, the acid and alkali resistance and other properties of the aqueous fluorine modified acrylic emulsion are greatly improved due to the existence of fluorine atoms, but the existing aqueous fluorine resin paint film has soft hardness, poor fullness and easy defects in the construction process, and the existing fluorine modified paint has insufficient adhesive force of the paint and a base material. Coil coatings need to be fast-curing, able to withstand shaping and impact operations without cracking, and the coating must have sufficient strength after curing, the coil coating should have the correct pigment content, and optimum hiding power is required even in the case of thinner paint films. At present, the coil coating mostly adopts oil polyester paint, the VOC content is high, and the development of a water-based coating which meets the environmental protection requirement and has the performance comparable to that of the oil paint is urgently needed.

Disclosure of Invention

The invention aims to solve the problems and provides the water-based fluorine modified acrylic emulsion which can be prepared into water-based coiled material color plate paint, has excellent solvent resistance, weather resistance, stain resistance, artificial aging resistance and water resistance, and has the advantages of scratch resistance, T bend resistance, excellent impact performance and good paint film adhesion.

The invention also provides a preparation method of the water-based fluorine modified acrylic emulsion.

The invention also provides an application of the water-based fluorine modified acrylic emulsion in preparing color plate paint.

The technical scheme adopted by the invention for realizing the purpose is as follows:

the invention provides a water-based fluorine modified acrylic emulsion, which comprises the following components: 56% of water, 1-2% of emulsifier, 1-6% of fluorine-containing monomer, 11-16% of butyl acrylate, 8-15% of methyl methacrylate, 3-11% of styrene, 0.25-0.5% of beta-acryloxypropionic acid, 0.25-0.5% of acrylic acid, 1-4% of hydroxyethyl acrylate, 0.5-3% of vinyl versatate, 0.3-0.8% of acrylamide, 1-2.5% of diacetone acrylamide (DAAM), 0.5-1.25% of Adipic Dihydrazide (ADH), 0.2-0.4% of persulfate and 1.5% of organic amine AMP-950.6%; the percentage is mass fraction.

Further, the emulsifier is any one or a mixture of more than two of sodium dodecyl sulfate, sodium alkylphenol polyoxyethylene ether sulfate and ammonium alkylphenol polyoxyethylene ether sulfate.

Further, the fluorine-containing monomer is any one or a mixture of more than two of hexafluorobutyl acrylate, hexafluorobutyl methacrylate and octafluoropentyl methacrylate.

Further, the vinyl versatate is C₉Vinyl versatate, C₁₀Vinyl versatate, C₁₁Any one or a mixture of more than two of ethylene versatate.

Further, the persulfate is any one or a mixture of more than two of potassium persulfate, sodium persulfate and ammonium persulfate.

The invention also provides a preparation method of the water-based fluorine modified acrylic emulsion, which comprises the following steps:

(1) 1/2-2/3 water and 1/4-1/2 emulsifier are weighed and added into a reaction kettle, stirring and heating are started, and the temperature is raised to 83-88 ℃;

(2) adding 1/3-1/2 water and 1/2-3/4 emulsifier into an emulsification tank, starting stirring, sequentially adding a fluorine-containing monomer, butyl acrylate, methyl methacrylate, styrene, beta-acryloxypropionic acid, acrylic acid, hydroxyethyl acrylate, vinyl versatate, acrylamide, diacetone acrylamide and 2/3 persulfate, and continuously stirring for 40 minutes to prepare an emulsion for later use;

(3) when the temperature of the reaction kettle is raised to 83-88 ℃, adding the residual persulfate into the reaction kettle, beginning to dropwise add the emulsion into the reaction kettle at a constant speed, and controlling the temperature to 83-88 ℃;

(4) when the emulsion is completely added into the reaction kettle, controlling the temperature to be 83-90 ℃, and preserving the heat for 1-2 hours;

(5) and (3) cooling after the heat preservation is finished, adding AMP-95 when the temperature is reduced to be below 45 ℃, stirring for 15 minutes, adding adipic dihydrazide, continuing stirring for 15 minutes, stopping stirring, filtering, and discharging.

Further, in the step (3), the dropping time of the emulsion is controlled to be 2-3 h.

The invention also provides an application of the water-based fluorine modified acrylic emulsion in preparing color plate paint.

Because the fluorine atom has smaller radius and very high electronegativity, the F-C bond has higher bond energy, thereby endowing the coating with excellent chemical resistance, solvent resistance, water resistance, weather resistance, salt mist resistance, stain resistance, corrosion resistance and the like. The coating film can be endowed with excellent comprehensive performance on the premise of not changing the glass transition temperature of the acrylic emulsion. The cross-linking monomer diacetone acrylamide is added in the emulsion polymerization, and the diacetone acrylamide and the adipic acid dihydrazide added subsequently can be stably stored for a long time in an emulsion state, and the diacetone acrylamide and the adipic acid dihydrazide are cross-linked in the drying process of a paint film. After crosslinking, the film-forming substances in the paint film change from a linear structure to a three-dimensional network structure. When a sufficient amount of crosslinking monomers of diacetone acrylamide and adipic dihydrazide are added, the water resistance, stain resistance, weather resistance, chemical resistance, scratch resistance and impact resistance of the coating film can be greatly improved. Adding tertiary ethylene carbonate into the emulsion polymerization to copolymerize with the acrylate monomer. Three alkyl groups with larger volume on the alpha carbon atom in the tertiary ethylene carbonate have large steric hindrance, so that an ester group can be protected from being attacked by acid, alkali and water, and the hydrolysis of the ester group on a polymer side chain can be prevented. Thereby endowing the paint film with excellent water resistance, chemical resistance and weather resistance. The side chain with high branching degree provides flexibility for the formed copolymer, forms a tough and hard coating surface, and can improve the fullness of a coating film and the wettability to pigment and filler. Beta-acryloxypropionic acid is added in the emulsion polymerization and can be copolymerized with propionate monomers. Beta-acryloxypropionic acid has longer pendant carboxylic chains giving good flexibility, promoting more efficient interaction between the polymer and the substrate, thus enhancing adhesion and peel strength.

The invention has the beneficial effects that: the fluorine modified acrylic emulsion is used for preparing the color plate paint, has excellent solvent resistance, weather resistance, stain resistance, artificial aging resistance and water resistance, has excellent scratch resistance, T bend resistance and impact resistance, and can completely replace the oil polyester color plate paint widely used at present.

Detailed Description

The invention will be further explained and illustrated with reference to specific examples.