CN111560201A - Flexible acrylic emulsion - Google Patents
Flexible acrylic emulsion Download PDFInfo
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- CN111560201A CN111560201A CN202010490249.0A CN202010490249A CN111560201A CN 111560201 A CN111560201 A CN 111560201A CN 202010490249 A CN202010490249 A CN 202010490249A CN 111560201 A CN111560201 A CN 111560201A
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
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Abstract
The invention relates to a flexible acrylic emulsion, which relates to the technical field of emulsion, and comprises the following raw materials in parts by weight: 50-60 parts of vinyl acetate, 15-20 parts of acrylic acid, 90-100 parts of butyl acrylate, 10-20 parts of a cross-linking agent, 1-5 parts of an initiator, 400 parts of deionized water 350-plus, 8-12 parts of a dispersing agent, 1-2 parts of a defoaming agent, 10-15 parts of dimethylaminoethanol, 40-55 parts of titanium dioxide, 45-55 parts of composite zinc phosphate, 25-35 parts of talcum powder, 95-105 parts of precipitated barium sulfate, 25-35 parts of an anti-settling agent, 15-25 parts of a film-forming aid, 3-7 parts of a base material wetting agent, 3-7 parts of a leveling agent and 4-8 parts of a thickening agent. The flexible acrylic emulsion prepared by the invention has good cohesiveness, impact resistance, water resistance and low-temperature stability, and can be stored for a long time under the condition of low temperature without deterioration.
Description
Technical Field
The invention relates to the technical field of emulsion, in particular to flexible acrylic emulsion.
Background
The acrylic emulsion has the characteristics of low price and environmental friendliness, and can be divided into pure acrylic emulsion, silicone-acrylic emulsion, styrene-acrylic emulsion, vinyl acetate-acrylic emulsion and the like according to the components, and can be divided into emulsion for interior walls, emulsion for exterior walls, real stone paint emulsion, elastic emulsion, liquid granite paint emulsion, waterproof emulsion, closed emulsion and the like according to the purpose classification.
In the water-based anticorrosive paint, the base material plays a decisive role in the performance of a paint film. Common base materials of the water-based anticorrosive paint are as follows: the water-based epoxy resin paint comprises water-based acrylic emulsion, water-based alkyd resin, a water-based epoxy ester-acrylic resin hybrid, two-component water-based polyurethane and water-based epoxy resin. The water-based acrylic emulsion is a polymer with optimal neutral cost ratio of various water-based paint film-forming substances due to the characteristics of excellent weather resistance, convenient construction and the like. In order to improve the corrosion resistance, phosphate and organosilicon monomers are introduced into some emulsions in a large amount, and the organosilicon monomers are easy to hydrolyze, so that the performance of the acrylic emulsion is unstable, and the acrylic emulsion is not beneficial to long-term storage.
Disclosure of Invention
In view of the disadvantages of the prior art, the present invention provides a flexible acrylic emulsion having good low temperature stability for long term storage.
The above object of the present invention is achieved by the following technical solutions: the flexible acrylic emulsion comprises the following raw materials in parts by weight: 50-60 parts of vinyl acetate, 15-20 parts of acrylic acid, 90-100 parts of butyl acrylate, 10-20 parts of a cross-linking agent, 1-5 parts of an initiator, 400 parts of deionized water 350-plus, 8-12 parts of a dispersing agent, 1-2 parts of a defoaming agent, 10-15 parts of dimethylaminoethanol, 40-55 parts of titanium dioxide, 45-55 parts of composite zinc phosphate, 25-35 parts of talcum powder, 95-105 parts of precipitated barium sulfate, 25-35 parts of an anti-settling agent, 15-25 parts of a film-forming aid, 3-7 parts of a base material wetting agent, 3-7 parts of a leveling agent and 4-8 parts of a thickening agent.
By adopting the technical scheme, the acrylic acid is a functional monomer, has an internal crosslinking effect, can play a role in strengthening the copolymerized vinyl acetate macromolecules, leads polar carboxyl to be introduced into the emulsion, generates space barrier, has an internal plasticizing effect, and improves the bonding strength of the emulsion. Because butyl acrylate has ester group with flexible long chain structure, the copolymerization of butyl acrylate, acrylic acid and vinyl acetate can reduce the glass transition temperature of the emulsion, enhance the motion capability of molecular chains, improve the flexibility of the adhesive film, ensure that the emulsion can still stably exist at lower temperature, and have good low-temperature stability so as to be convenient for the long-term storage of the flexible acrylic emulsion.The compound zinc phosphate is dissociated in the solution to generate phosphate ions, and when the acrylic emulsion is coated on the surface of a steel structure, the phosphate ions are easy to react with Fe3+Form a firmly adhering complex Fe [ Zn ]3(PO4)3]The deposit layer inhibits anode polarization, and zinc ions are combined with carboxyl and hydroxyl in the solution to form a compound, so that the adhesive force and the impermeability of the emulsion are improved. The talcum powder is used as a filler, and can buffer the stretching stress in the coating film, prevent the coating film from cracking and improve the washing resistance, the wear resistance and the durability of the coating film. In addition, the talcum powder is applied to the acrylic emulsion, the talcum powder can form hydrogen bonds with the emulsion by force to synthesize a chain-shaped structure and a net-shaped structure, when the emulsion is subjected to shearing acting force, chain belts among particles are broken, the net-shaped structure is broken, the emulsion can flow freely, and once shearing stops, the chain-shaped structure can form the net-shaped structure again, so that the stability of the acrylic emulsion is enhanced.
In a preferred example, the flexible acrylic emulsion can be further configured such that the raw materials of the flexible acrylic emulsion comprise the following components in parts by weight: 55 parts of vinyl acetate, 17.5 parts of acrylic acid, 95 parts of butyl acrylate, 15 parts of a cross-linking agent, 3 parts of an initiator, 375 parts of deionized water, 10 parts of a dispersing agent, 1.5 parts of a defoaming agent, 12.5 parts of dimethylaminoethanol, 50 parts of titanium dioxide, 50 parts of composite zinc phosphate, 30 parts of talcum powder, 100 parts of precipitated barium sulfate, 30 parts of an anti-settling agent, 20 parts of a film-forming auxiliary agent, 5 parts of a base material wetting agent, 5 parts of a leveling agent and 6 parts of a thickening agent.
The present invention in a preferred example may be further configured to: the cross-linking agent is glyoxal.
By adopting the technical scheme, the glyoxal is used as the cross-linking agent, so that emulsion molecules form a net structure, and the water resistance, the bonding strength and the stability of the emulsion are improved.
The present invention in a preferred example may be further configured to: the initiator is benzoyl peroxide.
By adopting the technical scheme, benzoyl peroxide is selected as an initiator, so that the copolymerization of butyl acrylate, acrylic acid and vinyl acetate is facilitated.
The present invention in a preferred example may be further configured to: the dispersing agent is one of sodium tripolyphosphate, sodium polyphosphate and sodium hexametaphosphate; the defoaming agent is a mineral oil defoaming agent or an organic silicon defoaming agent.
The present invention in a preferred example may be further configured to: the film-forming assistant is propylene glycol butyl ether.
By adopting the technical scheme, the film forming auxiliary agent is also called as a coalescing agent, and can promote the plastic flow and elastic deformation of the acrylic emulsion, improve the coalescing performance and form a film in a wider temperature range.
The present invention in a preferred example may be further configured to: the substrate wetting agent is an ammonium salt wetting dispersant selected from the company santopridae.
By adopting the technical scheme, the surface tension of water is high, so that the wetting and the penetration of the acrylic emulsion to the base material are not facilitated, the problem needs to be solved by adding the base material wetting agent, the ammonium salt wetting dispersant has good corrosion resistance and dispersibility, and the ammonium salt wetting dispersant is used as the base material wetting agent, so that the particle dispersion in an emulsion system is facilitated, the agglomeration of each component of ions is prevented, and the acrylic emulsion keeps good water resistance and adhesion.
The present invention in a preferred example may be further configured to: the flatting agent is polybutyl acrylate; the thickening agent is fatty alcohol thickening agent.
In a preferred embodiment of the present invention, the flexible acrylic emulsion further comprises: 32-40 parts of 12-hydroxystearic acid, 4-5 parts of sodium hydroxide and 5-15 parts of anhydrous sodium sulfate.
The invention in a preferred embodiment can be further configured that the method for preparing the flexible acrylic emulsion comprises the following steps:
(1) preparing a mixed solution: adding 30% of deionized water and 30% of dimethylaminoethanol into a wide-mouth glass container, heating to 75-80 ℃, adjusting the pH to 8, adding 30% of initiator and vinyl acetate under the condition that the rotation speed is 350-400r/min, adding vinyl acetate, sequentially adding vinyl acetate, acrylic acid, butyl acrylate and 30% of initiator after blue fluorescence appears in the system, reacting for 1h, then adding a cross-linking agent and the rest of initiator, continuing stirring at the rotation speed of 350-400r/min, and reacting for 1h to obtain a mixed solution for later use;
(2) preparation of sodium 12-hydroxystearate: in 75% of anhydrous ethanol solution, according to the mass ratio of M12-hydroxystearic acid: weighing 12-hydroxystearic acid and sodium hydroxide at a ratio of M sodium hydroxide to 8:1, adjusting the reaction temperature to 85 ℃, reacting for 3-5h, pouring the reacted solution into cold water, precipitating crystals, and performing suction filtration and drying to obtain 12-sodium hydroxystearate;
(3) preparing modified barium sulfate: weighing anhydrous sodium sulfate according to a proportion, dissolving the anhydrous sodium sulfate into 30-35 parts of deionized water, heating the solution to 80 ℃ in the stirring process, adding 12-sodium hydroxystearate according to a proportion, stirring until the anhydrous sodium sulfate and the 12-sodium hydroxystearate are completely dissolved, adjusting the temperature of the solution to 85 ℃, adding precipitated barium sulfate according to a proportion, stirring at a rotating speed of 500 plus 600r/min for 1-2h, repeatedly washing the stirred solution with deionized water for more than 3 times, drying, grinding and sieving with a sieve of 80-100 meshes to obtain modified barium sulfate;
(4) preparing a finished product: weighing the rest materials in proportion, mixing the mixed solution, the 12-sodium hydroxystearate and the modified barium sulfate, and stirring at the rotating speed of 500-600r/min for 2-3h to obtain the flexible acrylic emulsion.
By adopting the technical scheme, the precipitated barium sulfate is white orthorhombic crystal, has high hardness and high density, but the surface of the unmodified barium sulfate is hydrophilic, has good dispersibility in water, and is precipitated after standing. After the 12-sodium hydroxystearate is added, the surface of the precipitated barium sulfate is embedded with sodium stearate long-chain molecules, so that the surface performance of the precipitated barium sulfate is changed, the dispersibility of the precipitated barium sulfate molecules in the dimethylaminoethanol solution is improved, the phenomenon that the precipitated barium sulfate is precipitated in a solution system is avoided, and the precipitated barium sulfate is favorably and uniformly dispersed in the dimethylaminoethanol solution system.
In summary, the invention includes at least one of the following beneficial technical effects:
1. in the invention, acrylic acid is a functional monomer, has an internal crosslinking function, can play a role in strengthening the copolymerized vinyl acetate macromolecules, leads polar carboxyl to be introduced into the emulsion to generate space obstacle, and has an internal plasticizing function, thereby improving the bonding strength of the emulsion. Because butyl acrylate has ester group with flexible long chain structure, after butyl acrylate, acrylic acid and vinyl acetate are copolymerized, the glass transition temperature of the emulsion can be reduced, the movement capability of a molecular chain is enhanced, the flexibility of the adhesive film is improved, the emulsion can still stably exist at a lower temperature, and the low-temperature stability is good, so that the flexible acrylic emulsion can be stored for a long time;
2. according to the invention, the ammonium salt wetting dispersant has good corrosion resistance and dispersibility, and is used as a base material wetting agent, so that the particle dispersion in an emulsion system is promoted, the agglomeration of each component of ions is prevented, and the acrylic emulsion keeps good water resistance and adhesion;
3. according to the invention, after the 12-sodium hydroxystearate is added, the sodium stearate long-chain molecules are embedded into the surface of the precipitated barium sulfate, so that the surface performance of the precipitated barium sulfate is changed, the dispersibility of the precipitated barium sulfate molecules in the dimethylaminoethanol solution is improved, the phenomenon that the precipitated barium sulfate is precipitated in a solution system is avoided, and the precipitated barium sulfate is favorably and uniformly dispersed in the dimethylaminoethanol solution system.
Detailed Description
The present invention will be described in further detail with reference to examples.
TABLE 1 composition of one of the flexible acrylic emulsions of examples 1-3
Example 1
The raw material ratio of the flexible acrylic emulsion is shown in Table 1, and the preparation method of the flexible acrylic emulsion comprises the following steps:
(1) preparing a mixed solution: adding 125g of deionized water and 4.17g of dimethylaminoethanol into a wide-mouth glass container, heating to 77.5 ℃, adjusting the pH to 8, adding 1g of benzoyl peroxide under the condition that the rotation speed is 375r/min, adding vinyl acetate, sequentially adding vinyl acetate, acrylic acid, butyl acrylate and 1g of benzoyl peroxide after blue fluorescence appears in the system, reacting for 1h, then adding glyoxal and the rest of benzoyl peroxide, continuously stirring at the rotation speed of 375r/min, and reacting for 1h to obtain a mixed solution for later use;
(2) preparation of sodium 12-hydroxystearate: weighing 12-hydroxystearic acid and sodium hydroxide in proportion in 75% of anhydrous ethanol solution, adjusting the reaction temperature to 85 ℃, reacting for 3-5h, pouring the solution after reaction into cold water, precipitating crystals, and performing suction filtration and drying to obtain sodium 12-hydroxystearate;
(3) preparing modified barium sulfate: weighing anhydrous sodium sulfate according to a proportion, dissolving the anhydrous sodium sulfate into 32.5g of deionized water, heating the solution to 80 ℃ in the stirring process, adding 12-sodium hydroxystearate according to a proportion, stirring until the anhydrous sodium sulfate and the 12-sodium hydroxystearate are completely dissolved, adjusting the temperature of the solution to 85 ℃, adding precipitated barium sulfate according to a proportion, stirring at a rotating speed of 550r/min for 1.5h, repeatedly washing the stirred solution with deionized water for 4 times, drying, grinding and sieving with a 90-mesh sieve to obtain modified barium sulfate;
(4) preparing a finished product: weighing the rest materials in proportion, mixing the mixed solution, the 12-sodium hydroxystearate and the modified barium sulfate, and stirring at the rotating speed of 550r/min for 2.5h to obtain the flexible acrylic emulsion.
Example 2
The raw material ratio of the flexible acrylic emulsion is shown in Table 1, and the preparation method of the flexible acrylic emulsion comprises the following steps:
(1) preparing a mixed solution: adding 125g of deionized water and 4.17g of dimethylaminoethanol into a wide-mouth glass container, heating to 75 ℃, adjusting the pH to 8, adding 1g of benzoyl peroxide under the condition that the rotating speed is 350r/min, adding vinyl acetate, sequentially adding vinyl acetate, acrylic acid, butyl acrylate and 1g of benzoyl peroxide after blue fluorescence appears in a system, reacting for 1h, then adding glyoxal and the rest of benzoyl peroxide, continuously stirring at the rotating speed of 350r/min, and reacting for 1h to obtain a mixed solution for later use;
(2) preparation of sodium 12-hydroxystearate: weighing 12-hydroxystearic acid and sodium hydroxide in proportion in 75% of absolute ethyl alcohol solution, adjusting the reaction temperature to 85 ℃, reacting for 3 hours, pouring the solution after reaction into cold water, precipitating crystals, and performing suction filtration and drying to obtain sodium 12-hydroxystearate;
(3) preparing modified barium sulfate: weighing anhydrous sodium sulfate according to a proportion, dissolving the anhydrous sodium sulfate into 30g of deionized water, heating the solution to 80 ℃ in the stirring process, adding 12-sodium hydroxystearate according to a proportion, stirring until the anhydrous sodium sulfate and the 12-sodium hydroxystearate are completely dissolved, adjusting the temperature of the solution to 85 ℃, adding precipitated barium sulfate according to a proportion, stirring at a rotating speed of 500r/min for 1h, repeatedly washing the stirred solution with deionized water for 4 times, drying, grinding and sieving with a 80-mesh sieve to obtain modified barium sulfate;
(4) preparing a finished product: weighing the rest materials in proportion, mixing the mixed solution, the 12-sodium hydroxystearate and the modified barium sulfate, and stirring at the rotating speed of 500r/min for 2h to obtain the flexible acrylic emulsion.
Example 3
The raw material ratio of the flexible acrylic emulsion is shown in Table 1, and the preparation method of the flexible acrylic emulsion comprises the following steps:
(1) preparing a mixed solution: adding 125g of deionized water and 4.17g of dimethylaminoethanol into a wide-mouth glass container, heating to 80 ℃, adjusting the pH to 8, adding 1g of benzoyl peroxide under the condition of a rotation speed of 400r/min, adding vinyl acetate, sequentially adding vinyl acetate, acrylic acid, butyl acrylate and 1g of benzoyl peroxide after blue fluorescence appears in a system, reacting for 1h, then adding glyoxal and the rest of benzoyl peroxide, continuously stirring at a rotation speed of 350r/min, and reacting for 1h to obtain a mixed solution for later use;
(2) preparation of sodium 12-hydroxystearate: weighing 12-hydroxystearic acid and sodium hydroxide in proportion in 75% of absolute ethyl alcohol solution, adjusting the reaction temperature to 85 ℃, reacting for 3 hours, pouring the solution after reaction into cold water, precipitating crystals, and performing suction filtration and drying to obtain sodium 12-hydroxystearate;
(3) preparing modified barium sulfate: weighing anhydrous sodium sulfate according to a proportion, dissolving the anhydrous sodium sulfate into 35g of deionized water, heating the solution to 80 ℃ in the stirring process, adding 12-sodium hydroxystearate according to a proportion, stirring until the anhydrous sodium sulfate and the 12-sodium hydroxystearate are completely dissolved, adjusting the temperature of the solution to 85 ℃, adding precipitated barium sulfate according to a proportion, stirring at a rotating speed of 600r/min for 2 hours, repeatedly washing the stirred solution with deionized water for 4 times, drying, grinding and sieving with a 100-mesh sieve to obtain modified barium sulfate;
(4) preparing a finished product: weighing the rest materials in proportion, mixing the mixed solution, the 12-sodium hydroxystearate and the modified barium sulfate, and stirring at the rotating speed of 600r/min for 3h to obtain the flexible acrylic emulsion.
Example 4
The difference between this example and example 1 is that 12-hydroxystearic acid, sodium hydroxide and anhydrous sodium sulfate were not added.
Example 5
The difference between this example and example 1 is that the dispersant is sodium polyphosphate and the defoamer is a silicone defoamer.
Comparative example 1
The difference between this comparative example and example 1 is that no acrylic acid was added.
Comparative example 2
The difference between this comparative example and example 1 is that no vinyl acetate was added.
Comparative example 3
The difference between this comparative example and example 1 is that no butyl acrylate was added.
Comparative example 4
The comparative example differs from example 1 in that zinc complex phosphate was not added.
Comparative example 5
The difference between this comparative example and example 1 is that no talc was added.
Comparative example 6
The difference between this comparative example and example 1 is that no ammonium salt wetting dispersant was added.
Comparative example 7
The difference between this comparative example and example 1 is that no precipitated barium sulfate was added.
Comparative example 8
The difference between this comparative example and example 1 is that 12-hydroxystearic acid was not added.
Comparative example 9
The difference between this comparative example and example 1 is that no sodium hydroxide was added.
Comparative example 10
The difference between this comparative example and example 1 is that the mass ratio of 12-hydroxystearic acid to sodium hydroxide is 6: 1.
comparative example 11
The difference between this comparative example and example 1 is that the mass ratio of 12-hydroxystearic acid to sodium hydroxide is 7: 1.
comparative example 12
The difference between this comparative example and example 1 is that the mass ratio of 12-hydroxystearic acid to sodium hydroxide is 9: 1.
comparative example 13
The difference between this comparative example and example 1 is that the mass ratio of 12-hydroxystearic acid to sodium hydroxide is 10: 1.
performance detection
The flexible acrylic emulsions obtained in examples 1 to 5 and comparative examples 1 to 13 were subjected to the following property tests, and the test results are shown in Table 2.
Wherein GB/T9286-1998 test for marking the grids of paint films of colored paint and varnish is adopted to detect the binding power of the coating.
The impact resistance of the coating film is tested by GB/T1732-1993 'paint film impact resistance test'.
The water resistance of the coating film is detected by GB/T1733-1993 'determination method for water resistance of paint film'.
The low-temperature stability of the coating film is detected by adopting GBT10222-1988 inorganic building coating for exterior walls.
TABLE 2 results of measuring the Properties of the flexible acrylic emulsions in examples 1 to 5 and comparative examples 1 to 13
As can be seen from Table 2, the flexible acrylic emulsion prepared in the present invention has good adhesive strength, impact resistance, water resistance and low temperature stability.
From comparative examples 1 to 3 in comparison with example 1, it can be seen that the flexible acrylic emulsion of the present invention has high adhesive strength, impact resistance, water resistance and low temperature stability, and the adhesive strength, impact resistance, water resistance and low temperature stability of the flexible acrylic emulsion are lowered without adding acrylic acid, vinyl acetate or butyl acrylate.
From comparison of comparative example 4 with example 1, it can be seen that the addition of no zinc complex phosphate also causes a decrease in the adhesive strength, impact resistance and water resistance of the flexible acrylic emulsion.
From comparison of comparative example 5 with example 1, it can be seen that the absence of talc lowers the impact resistance and water resistance of the flexible acrylic emulsion.
From comparison of comparative example 6 with example 1, it can be seen that no ammonium salt wetting dispersant was added, so that the water resistance of the flexible acrylic emulsion was lowered.
From comparative example 7 compared with example 1, it can be seen that no precipitated barium sulfate was added, so that the water resistance of the flexible acrylic emulsion was lowered.
From comparative examples 8 and 9 in comparison with example 1, it can be seen that the water resistance and low temperature stability of the flexible acrylic emulsion are lowered without adding 12-hydroxystearic acid or sodium hydroxide.
From comparative examples 10 to 13 in comparison with example 1, it can be seen that when the mass ratio of 12-hydroxystearic acid to sodium hydroxide is less than 8:1 or greater than 8:1, the water resistance and low temperature stability of the flexible acrylic emulsion are lowered.
In conclusion, the acrylic acid is a functional monomer, has an internal crosslinking effect, can play a role in reinforcing copolymerized vinyl acetate macromolecules, leads polar carboxyl to be introduced into the emulsion, generates space barrier, and has an internal plasticizing effect, so that the bonding strength of the emulsion is improved. Because butyl acrylate has ester group with flexible long chain structure, the copolymerization of butyl acrylate, acrylic acid and vinyl acetate can reduce the glass transition temperature of the emulsion, enhance the motion capability of molecular chains, improve the flexibility of the adhesive film, ensure that the emulsion can still stably exist at lower temperature and has good low-temperature stability. The ammonium salt wetting dispersant has good corrosion resistance and dispersibility, and is used as a base material wetting agent, so that the particle dispersion in an emulsion system is promoted, the agglomeration of each component of ions is prevented, and the acrylic emulsion keeps good water resistance and adhesion. After the 12-sodium hydroxystearate is added, the surface of the precipitated barium sulfate is embedded with sodium stearate long-chain molecules, so that the surface performance of the precipitated barium sulfate is changed, the dispersibility of the precipitated barium sulfate molecules in the dimethylaminoethanol solution is improved, the phenomenon that the precipitated barium sulfate is precipitated in a solution system is avoided, and the precipitated barium sulfate is favorably and uniformly dispersed in the dimethylaminoethanol solution system.
The present embodiment is only for explaining the present invention, and not for limiting the present invention, and those skilled in the art can make modifications without inventive contribution to the present embodiment as needed after reading the present specification, but all of which are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. The flexible acrylic emulsion is characterized by comprising the following raw materials in parts by weight: 50-60 parts of vinyl acetate, 15-20 parts of acrylic acid, 90-100 parts of butyl acrylate, 10-20 parts of a cross-linking agent, 1-5 parts of an initiator, 400 parts of deionized water 350-plus, 8-12 parts of a dispersing agent, 1-2 parts of a defoaming agent, 10-15 parts of dimethylaminoethanol, 40-55 parts of titanium dioxide, 45-55 parts of composite zinc phosphate, 25-35 parts of talcum powder, 95-105 parts of precipitated barium sulfate, 25-35 parts of an anti-settling agent, 15-25 parts of a film-forming aid, 3-7 parts of a base material wetting agent, 3-7 parts of a leveling agent and 4-8 parts of a thickening agent.
2. The flexible acrylic emulsion according to claim 1, wherein the flexible acrylic emulsion comprises the following raw materials in parts by weight: 55 parts of vinyl acetate, 17.5 parts of acrylic acid, 95 parts of butyl acrylate, 15 parts of a cross-linking agent, 3 parts of an initiator, 375 parts of deionized water, 10 parts of a dispersing agent, 1.5 parts of a defoaming agent, 12.5 parts of dimethylaminoethanol, 50 parts of titanium dioxide, 50 parts of composite zinc phosphate, 30 parts of talcum powder, 100 parts of precipitated barium sulfate, 30 parts of an anti-settling agent, 20 parts of a film-forming auxiliary agent, 5 parts of a base material wetting agent, 5 parts of a leveling agent and 6 parts of a thickening agent.
3. A flexible acrylic emulsion according to claim 1 wherein: the cross-linking agent is glyoxal.
4. A flexible acrylic emulsion according to claim 1 wherein: the initiator is benzoyl peroxide.
5. A flexible acrylic emulsion according to claim 1 wherein: the dispersing agent is one of sodium tripolyphosphate, sodium polyphosphate and sodium hexametaphosphate; the defoaming agent is a mineral oil defoaming agent or an organic silicon defoaming agent.
6. A flexible acrylic emulsion according to claim 1 wherein: the film-forming assistant is propylene glycol butyl ether.
7. A flexible acrylic emulsion according to claim 1 wherein: the substrate wetting agent is an ammonium salt wetting dispersant selected from the company santopridae.
8. A flexible acrylic emulsion according to claim 1 wherein: the flatting agent is polybutyl acrylate; the thickening agent is fatty alcohol thickening agent.
9. The flexible acrylic emulsion according to claim 1, wherein the flexible acrylic emulsion further comprises: 32-40 parts of 12-hydroxystearic acid, 4-5 parts of sodium hydroxide and 5-15 parts of anhydrous sodium sulfate.
10. The method for preparing a flexible acrylic emulsion according to claim 9, comprising the steps of:
(1) preparing a mixed solution: adding 30% of deionized water and 30% of dimethylaminoethanol into a wide-mouth glass container, heating to 75-80 ℃, adjusting the pH to 8, adding 30% of initiator and vinyl acetate under the condition that the rotation speed is 350-400r/min, adding vinyl acetate, sequentially adding vinyl acetate, acrylic acid, butyl acrylate and 30% of initiator after blue fluorescence appears in the system, reacting for 1h, then adding a cross-linking agent and the rest of initiator, continuing stirring at the rotation speed of 350-400r/min, and reacting for 1h to obtain a mixed solution for later use;
(2) preparation of sodium 12-hydroxystearate: in 75% of anhydrous ethanol solution, according to the mass ratio of M12-hydroxystearic acid: m sodium hydroxide =8:1, weighing 12-hydroxystearic acid and sodium hydroxide, adjusting the reaction temperature to 85 ℃, reacting for 3-5h, pouring the reacted solution into cold water, precipitating crystals, and performing suction filtration and drying to obtain 12-sodium hydroxystearate;
(3) preparing modified barium sulfate: weighing anhydrous sodium sulfate according to a proportion, dissolving the anhydrous sodium sulfate into 30-35 parts of deionized water, heating the solution to 80 ℃ in the stirring process, adding 12-sodium hydroxystearate according to a proportion, stirring until the anhydrous sodium sulfate and the 12-sodium hydroxystearate are completely dissolved, adjusting the temperature of the solution to 85 ℃, adding precipitated barium sulfate according to a proportion, stirring at a rotating speed of 500 plus 600r/min for 1-2h, repeatedly washing the stirred solution with deionized water for more than 3 times, drying, grinding and sieving with a sieve of 80-100 meshes to obtain modified barium sulfate;
(4) preparing a finished product: weighing the rest materials in proportion, mixing the mixed solution, the 12-sodium hydroxystearate and the modified barium sulfate, and stirring at the rotating speed of 500-600r/min for 2-3h to obtain the flexible acrylic emulsion.
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