CN111363082B - Preparation method of water-based acrylate emulsion - Google Patents
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- CN111363082B CN111363082B CN202010127167.XA CN202010127167A CN111363082B CN 111363082 B CN111363082 B CN 111363082B CN 202010127167 A CN202010127167 A CN 202010127167A CN 111363082 B CN111363082 B CN 111363082B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
Abstract
The invention relates to a preparation method of a water-based acrylate emulsion, which comprises the following steps: mixing the monomer with part of emulsifier, diacetone acrylamide and deionized water, pre-emulsifying to obtain pre-emulsion, stirring sodium bicarbonate, deionized water and the rest emulsifier at constant temperature, adding the pre-emulsion and the initiator aqueous solution in batches, keeping the temperature, cooling, adjusting the pH, adding organic silicon, stirring for dissolving, stopping heating, and filtering to obtain the final product. The invention has the characteristic of remarkably reducing the gel amount in the synthesis process, and the prepared emulsion has high monomer conversion rate, good stability, strong mechanical property of the coating film, wide application range and excellent application prospect.
Description
Technical Field
The invention belongs to the field of preparation of aqueous polymer emulsion materials, and particularly relates to a preparation method of an aqueous acrylate emulsion.
Background
The water-based acrylate emulsion not only has the characteristics of light color, high transparency, strong color and light retention, high hardness, excellent flexibility, strong adhesion and the like, but also has the performances of excellent weather resistance, stain resistance and chemical resistance, and is gradually the mainstream direction of paint development due to the advantages of various aspects such as environmental friendliness and the like.
Due to the particularity of the water-based acrylate, the water-based acrylate is prepared by adopting a seed emulsion polymerization method in the current production and preparation process. In the initial stage of the reaction, a large amount of heat is generated in the reaction system due to the generation of new bonds, and the generation of free radicals and the reaction progress are further accelerated. When the reaction temperature exceeds a certain limit value, the branching and crosslinking degree of polymer molecular chains is easily increased, so that insoluble particles appear in the emulsion, on one hand, the waste of materials is caused, the quality of resin is influenced, and even the accident of pot flushing and material overflowing in the synthesis process is caused; on the other hand, the difficulty and cost of waste treatment are greatly increased. Leyao is introduced into the analysis of the influence factors in the seed emulsion polymerization process in the text of the analysis of the influence factors of the production process and the polymerization reaction process of the aqueous acrylic emulsion, and the main factor of the emulsion bumping is classified as the influence of the temperature factor, so that the phenomena of uneven particle size distribution and gel precipitation in the emulsion are reduced to a certain extent; in Pengchen, the gel fraction of the acrylic ester emulsion is reduced to 0.165% by regulating and controlling the emulsifier in the 'influence of the emulsifier on the performance of the acrylic emulsion', but the water absorption and the storage stability of the emulsion are adversely affected by a method of adding the emulsifier; the invention starts from controlling the generation rate of new bonds in the initial stage of emulsion polymerization, regulates and controls the production process by reasonably distributing the proportion of the emulsifier, the initiator and the pre-emulsion, and the like, thereby stabilizing a reaction system simply, conveniently and efficiently and obviously reducing or even eliminating the generation of gel.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of water-based acrylate emulsion, overcoming the defects that insoluble particles appear in the emulsion, the resin quality is influenced, and the waste treatment difficulty and cost are increased in the seed emulsion polymerization method in the prior art.
The preparation method of the water-based acrylate emulsion comprises the following steps:
(1) uniformly mixing monomers of n-butyl acrylate, styrene, methyl methacrylate, methacrylic acid, a part of emulsifier, diacetone acrylamide and deionized water, and pre-emulsifying to obtain pre-emulsion; wherein part of the emulsifier accounts for 1-7% of the total mass of the monomers;
(2) stirring sodium bicarbonate, deionized water and the rest of emulsifier at constant temperature, adding 7-15% of partial pre-emulsion and 45-55% of initiator aqueous solution by mass, stirring at constant temperature, dropwise adding the rest of pre-emulsion and initiator aqueous solution, keeping the temperature, cooling, adjusting pH, adding organic silicon, stirring for dissolving, stopping heating, and filtering to obtain the final product.
The preferred mode of the above preparation method is as follows:
the mass ratio of the n-butyl acrylate, the styrene, the methyl methacrylate and the methacrylic acid in the step (1) is 40-45:24-22:33-30: 3; the mass of the diacetone acrylamide is 1-4% of the total mass of the monomers (n-butyl acrylate, styrene, methyl methacrylate and methacrylic acid, the same below); the partial emulsifier accounts for 70-90% of the total mass of the emulsifier. Further, preferably, the mass ratio of the n-butyl acrylate, the styrene, the methyl methacrylate and the methacrylic acid is 43:22:32: 3; the partial emulsifier accounts for 90 percent of the total mass of the emulsifier.
In the step (1), the emulsifier accounts for 70-90% of the total mass of the sodium dodecyl sulfate and 70-90% of the total mass of the polyoxyethylene octyl phenol ether-10.
In the step (1), the emulsifier is sodium dodecyl sulfate and polyoxyethylene octyl phenol ether-10; wherein the lauryl sodium sulfate accounts for 1-3% of the total mass of the monomers; polyoxyethylene octyl phenol ether-10 accounts for 2-4% of the total mass of the monomers.
Further, preferably, the mass of the sodium dodecyl sulfate in the step (1) is 2.0% of the total mass of the monomers; the mass of the polyoxyethylene octyl phenol ether-10 is 3.0 percent of the total mass of the monomers; the mass of diacetone acrylamide was 1.9% of the total mass of the monomers.
The pre-emulsification in the step (1) is specifically that firstly a high-speed dispersion homogenizer is used for stirring for 0.5-1min, and then magnetic stirring is carried out for 20 min.
The initiator in the step (2) is potassium persulfate; the silicone is a polyorganosiloxane.
The mass of the sodium bicarbonate in the step (2) is 3-7 per mill of the total mass of the monomers; the total mass of the initiator is 0.5-1.5% of the total mass of the monomer; the mass of the organic silicon is 4-9% of the total mass of the monomers; the mass fractions of the added pre-emulsion and the rest pre-emulsion are 7: 93%, 8: 92%, 9: 89% and 15: 85% respectively.
Further, preferably, the mass of the sodium bicarbonate in the step (2) is 4.0 per mill of the total mass of the monomers; the mass of the initiator is 0.7 percent of the total mass of the monomers; the mass of the silicone was 6.0% of the total mass of the monomers.
Adding part of the pre-emulsion and the initiator aqueous solution in the step (2) at one time, and dripping the rest of the pre-emulsion and the initiator aqueous solution for 2.5 to 3 hours respectively; wherein, part of the initiator aqueous solution accounts for 45 to 55 percent of the mass of the initiator aqueous solution; part of the pre-emulsion is 85-93% of the total mass of the emulsion.
The constant-temperature stirring temperature in the step (2) is 80-84 ℃, and the stirring speed is 200-500 rpm.
Further, preferably, the stirring temperature at constant temperature in the step (2) is 82 ℃.
And (3) keeping the temperature in the step (2) for 1-3h, and cooling to about 55 +/-5 ℃.
Further, preferably, the temperature keeping time in the step (2) is 1.5 h.
And (3) adjusting the pH value to be 8.0-9.0 by ammonia water in the step (2).
And (3) stopping heating after stirring and dissolving for 30-60min in the step (2).
The invention provides a water-based acrylate emulsion prepared by the method.
The invention provides an application of the water-based acrylate emulsion.
Advantageous effects
(1) The production process of the water-based acrylate emulsion is optimized based on the seed liquid forming stage by adopting a pre-emulsification semi-continuous process, and the method has the characteristics of remarkably stabilizing a reaction system and reducing the generation of gel in the production process.
(2) The optimization method of the production process of the water-based acrylate emulsion based on seed liquid regulation and control has the following excellent characteristics:
the production of gel in the production process is obviously reduced, and the reaction system is stabilized, for example, the gel rate of the reaction system is 0.07 percent in the preparation process.
Secondly, the stability of the emulsion is inspected under the following conditions, and the phenomena of layering and emulsion breaking do not occur: standing at normal temperature for more than 6 months; placing in a refrigerator at 4 ℃ for 72h in a sealed manner; centrifuging at 4000rpm for 30 min; the emulsion is diluted to 200 times of the original emulsion, and the emulsion prepared after the process optimization has good stability.
Thirdly, after the prepared composite emulsion is dried to form a film, the formed film has good mechanical property, for example, the tensile strength can reach 9.02MPa, and the elongation at break can reach 1207%.
The composite emulsion prepared has wide application range, has excellent strippability when being respectively coated on 3 resin paint boards, and has no adhesive residue on the attached surface.
The prepared composite emulsion is dried to form a film, the film coating temperature adaptability is good, the film coating is respectively placed in a refrigerator freezing chamber at the temperature of minus 20 ℃ for 92 hours and a forced air drying oven at the temperature of 90 ℃ for 92 hours, the physical performance of the film coating is excellent, and the strippability is not affected.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a picture of the stability of the product of example 2, (stored for 6 months at room temperature);
FIG. 3 is a graph showing the temperature adaptability of the product of example 3, wherein a, the emulsion is dried and then placed in a 90 ℃ forced air drying oven for standing for 92 hours; b, placing the emulsion in a freezing chamber of a refrigerator at the temperature of-20 ℃ after coating and drying the emulsion, and standing for 92 hours;
FIG. 4 is a strippable picture of the product of example 3; wherein a is an oily polyurethane plate; b: an oily epoxy board; and c, a water-based acrylic plate.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims. The additives such as monomers, emulsifiers and the like come from the national medicine group and are chemically pure.
Example 1
(1) 99.9g of n-butyl acrylate, 48.84g of styrene, 73.26g of methyl methacrylate, 7.44g of methacrylic acid, 4.14g of sodium dodecyl sulfate, 0.60g of polyoxyethylene octylphenol ether-10, 4.38g of diacetone acrylamide and 109.2g of deionized water are uniformly mixed in a beaker, stirred by a high-speed dispersion homogenizer for 0.5-1min, and then stirred magnetically for 20min for pre-emulsification. 0.72g of potassium persulfate was dissolved in 21g of deionized water, and 0.90g of potassium persulfate was dissolved in 54g of deionized water for further use.
(2) Uniformly mixing 0.9g of sodium bicarbonate, 96g of deionized water, 0.456g of sodium dodecyl sulfate and 0.66g of polyoxyethylene octyl phenol ether-10 in a four-neck flask, controlling the temperature to be 82 ℃, and stirring at constant temperature for 15min at the rotating speed of 350 rpm; when the emulsifier is completely dissolved, 24.68g of pre-emulsion and 21.72g of potassium persulfate aqueous solution are added at one time, and the mixture is stirred for 30min at constant temperature.
(3) And respectively and simultaneously dripping the residual emulsion and 54.9g of potassium persulfate solution into the four-neck flask, finishing dripping within 3 hours, then preserving the temperature for 1.5 hours, cooling to 55 ℃, and adjusting the pH value to 8-9 by using ammonia water.
(4) Adding 13.8g of polyorganosiloxane, fully stirring for 30min, stopping heating, filtering, and discharging.
FIG. 1 is a process flow diagram for its synthesis.
Example 2
(1) 99.9g of n-butyl acrylate, 48.84g of styrene, 73.26g of methyl methacrylate, 7.44g of methacrylic acid, 4.14g of sodium dodecyl sulfate, 0.60g of polyoxyethylene octylphenol ether-10, 4.38g of diacetone acrylamide and 109.2g of deionized water are uniformly mixed in a beaker, stirred by a high-speed dispersion homogenizer for 0.5-1min, and then stirred magnetically for 20min for pre-emulsification. 0.72g of potassium persulfate was dissolved in 21g of deionized water, and 0.90g of potassium persulfate was dissolved in 54g of deionized water for further use.
(2) Uniformly mixing 0.9g of sodium bicarbonate, 96g of deionized water, 0.456g of sodium dodecyl sulfate and 0.66g of polyoxyethylene octyl phenol ether-10 in a four-neck flask, controlling the temperature to be 82 ℃, and stirring at constant temperature for 15min at the rotation speed of 350 rpm; when the emulsifier is completely dissolved, 28.2g of pre-emulsion and 21.72g of potassium persulfate aqueous solution are added at one time, and the mixture is stirred for 30min at constant temperature.
(3) And respectively and simultaneously dripping the residual emulsion and 54.9g of potassium persulfate solution into the four-neck flask, finishing dripping within 3 hours, then preserving the temperature for 1.5 hours, cooling to 55 ℃, and adjusting the pH value to 8-9 by using ammonia water.
(4) Adding 13.8g of polyorganosiloxane, fully stirring for 30min, stopping heating, filtering, and discharging.
Figure 2 is a picture of the stability of the resulting emulsion. As can be seen, the obtained emulsion has good stability and no delamination after being stored for six months at normal temperature.
Example 3
(1) 99.9g of n-butyl acrylate, 48.84g of styrene, 73.26g of methyl methacrylate, 7.44g of methacrylic acid, 4.14g of sodium dodecyl sulfate, 0.60g of polyoxyethylene octylphenol ether-10, 4.38g of diacetone acrylamide and 109.2g of deionized water are uniformly mixed in a beaker, stirred by a high-speed dispersion homogenizer for 0.5-1min, and then stirred magnetically for 20min for pre-emulsification. 0.72g of potassium persulfate was dissolved in 21g of deionized water, and 0.90g of potassium persulfate was dissolved in 54g of deionized water for further use.
(2) Uniformly mixing 0.9g of sodium bicarbonate, 96g of deionized water, 0.456g of sodium dodecyl sulfate and 0.66g of polyoxyethylene octyl phenol ether-10 in a four-neck flask, controlling the temperature to be 82 ℃, and stirring at constant temperature for 15min at the rotating speed of 350 rpm; when the emulsifier is completely dissolved, 31.73g of pre-emulsion and 21.72g of potassium persulfate aqueous solution are added at one time, and the mixture is stirred for 30min at constant temperature.
(3) And respectively and simultaneously dripping the residual emulsion and 54.9g of potassium persulfate solution into the four-neck flask, finishing dripping within 3 hours, then preserving the temperature for 1.5 hours, cooling to 55 ℃, and adjusting the pH value to 8-9 by using ammonia water.
(4) Adding 13.8g of polyorganosiloxane, fully stirring for 30min, stopping heating, filtering, and discharging.
Fig. 3 and 4 show the temperature stability and strippability thereof. The stability of the coating film is good between minus 20 ℃ and 90 ℃, and the strippability on various paint boards is good.
Comparative example 1
(1) 99.9g of n-butyl acrylate, 48.84g of styrene, 73.26g of methyl methacrylate, 7.44g of methacrylic acid, 4.14g of sodium dodecyl sulfate, 0.60g of polyoxyethylene octylphenol ether-10, 4.38g of diacetone acrylamide and 109.2g of deionized water are uniformly mixed in a beaker, stirred by a high-speed dispersion homogenizer for 0.5-1min, and then stirred magnetically for 20min for pre-emulsification. 0.72g of potassium persulfate was dissolved in 21g of deionized water, and 0.90g of potassium persulfate was dissolved in 54g of deionized water for further use.
(2) Uniformly mixing 0.9g of sodium bicarbonate, 96g of deionized water, 0.456g of sodium dodecyl sulfate and 0.66g of polyoxyethylene octyl phenol ether-10 in a four-neck flask, controlling the temperature to be 82 ℃, and stirring at constant temperature for 15min at the rotating speed of 350 rpm; when the emulsifier is completely dissolved, 52.88g of pre-emulsion and 21.72g of potassium persulfate aqueous solution are added at one time, and the mixture is stirred for 30min at constant temperature.
(3) And respectively and simultaneously dripping the residual emulsion and 54.9g of potassium persulfate solution into the four-neck flask, finishing dripping within 3 hours, then preserving the temperature for 1.5 hours, cooling to 55 ℃, and adjusting the pH value to 8-9 by using ammonia water.
(4) Adding 13.8g of polyorganosiloxane, fully stirring for 30min, stopping heating, filtering, and discharging.
The aqueous acrylate micro-nano composite emulsion prepared in the examples 1-3 and the comparative example 1 is subjected to various performance tests according to HG/T4758-:
gel fraction: after emulsion polymerization reaction is finished, filtering the emulsion by using a 200-mesh nylon filtering gauze, collecting filter residues and solid condensate attached to reaction equipment and equipment, fully washing the filter residues and the solid condensate by using deionized water, drying the filter residues and the solid condensate in a 90-DEG C blast drying oven to constant weight, weighing, and calculating the emulsion gel rate according to a formula.
In the formula: w 1 -mass after drying of the solid agglomerate (g);
W 0 -total mass of monomer (g).
Conversion rate: accurately weighing 2.50g of emulsion, placing the emulsion in a watch glass which is dried to constant weight, uniformly placing a sample on the bottom surface of the watch glass, placing the watch glass in a 105 ℃ blast drying oven for drying for 4 hours, weighing the emulsion once every 1 hour until the mass difference of two times is not more than 0.001g, and calculating the conversion rate of the emulsion according to a formula.
In the formula: b-conversion (%);
W 1 -total mass of raw materials in the reactor (g);
W 2 -total mass of non-volatile matter in the starting materials (g);
W 3 -total mass of monomers (g).
Tensile strength and elongation at break:
the water-borne paint film was cut to a specification of (10. + -. 1) mm X (50. + -.5) mm, and the thickness was measured accurately with a vernier caliper. The resulting mixture was placed in a constant temperature and humidity chamber for 24 hours, and the tensile strength and elongation at break were measured by using a universal material tester model H5K-S from Hounsfield, UK. The drawing speed was 50mm/min and each sample was measured in triplicate and the average value was recorded. The results are as follows:
table 1 shows the gel rate, conversion rate and mechanical properties of the emulsions prepared in comparative example 1 in the preparation process of examples 1 to 3:
| example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Gel fraction (%) | 0.10 | 0.07 | 0.09 | 3.80 |
| Conversion (%) | 97.46 | 97.55 | 97.11 | 93.41 |
| Tensile Strength (MPa) | 8.82 | 9.02 | 8.77 | 7.02 |
| Elongation at Break (%) | 1149 | 1207 | 1166 | 984 |
Therefore, compared with a comparative example, the product obtained by the method has the advantages of low gel rate, high conversion rate, strong tensile property and large elongation at break.
Claims (9)
1. A method of preparing an aqueous acrylate emulsion comprising:
(1) uniformly mixing monomers of n-butyl acrylate, styrene, methyl methacrylate, methacrylic acid, a part of emulsifier, diacetone acrylamide and deionized water, and pre-emulsifying to obtain pre-emulsion; wherein part of the emulsifier accounts for 1-7% of the total mass of the monomers; part of the emulsifier accounts for 70-90% of the total mass of the emulsifier;
(2) stirring sodium bicarbonate, deionized water and the rest of emulsifier at constant temperature, adding part of pre-emulsion and initiator aqueous solution at one time, stirring at constant temperature, dripping the rest of pre-emulsion and initiator aqueous solution for 2.5-3h, keeping the temperature, cooling, adjusting pH, adding organic silicon, stirring for dissolving, stopping heating, and filtering to obtain the final product; wherein the mass ratio of the added part of pre-emulsion to the rest of pre-emulsion is respectively 7 percent to 93 percent, 8 percent to 92 percent or 9 percent to 91 percent; wherein the content ratio of the initiator in the partial initiator aqueous solution to the initiator in the remaining initiator aqueous solution is 0.72: 0.90.
2. The method according to claim 1, wherein the mass of diacetone acrylamide in the step (1) is 1 to 4% of the total mass of n-butyl acrylate, styrene, methyl methacrylate and methacrylic acid.
3. The method according to claim 1, wherein the emulsifier in step (1) is sodium lauryl sulfate and polyoxyethylene octylphenol ether-10, wherein the sodium lauryl sulfate is 1-3% of the total mass of the monomers.
4. The method according to claim 1, wherein the pre-emulsification in step (1) is performed by stirring with a high-speed dispersion homogenizer for 0.5-1min, and then magnetic stirring for 20 min.
5. The production method according to claim 1, wherein the initiator in the step (2) is potassium persulfate; the silicone is a polyorganosiloxane.
6. The preparation method according to claim 1, wherein the mass of the sodium bicarbonate in the step (2) is 3-7% of the total mass of the monomers; the total mass of the initiator is 0.5-1.5% of the total mass of the monomer; the mass of the organic silicon is 4-9% of the total mass of the monomer.
7. The preparation method according to claim 1, wherein the stirring temperature at constant temperature in the step (2) is 80-84 ℃, and the stirring speed is 200-500 rpm.
8. An aqueous acrylate emulsion prepared according to the method of claim 1.
9. Use of the aqueous acrylate emulsion of claim 8 in aqueous coatings.
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| US3542585A (en) * | 1968-02-23 | 1970-11-24 | Dow Corning | Method for adhering acrylate finishes to silicone impregnated leather and resulting article |
| CN101096400A (en) * | 2006-06-30 | 2008-01-02 | 天津市振东涂料有限公司 | Synthesizing method for confecting inner-outer wall coating water-proof stain-resistant latex |
| CN102060954B (en) * | 2010-11-23 | 2013-04-03 | 广州慧谷化学有限公司 | Acrylic emulsion as well as preparation method and application thereof |
| CN103193922B (en) * | 2013-03-27 | 2016-01-20 | 长兴三伟热熔胶有限公司 | A kind of water polyacrylic acid emulsion |
| CN103864976B (en) * | 2014-04-08 | 2016-05-11 | 中山职业技术学院 | The pre-emulsification semi-continuous seed emulsion polymerization technique of self-crosslinking styrene-acrylic emulsion for a kind of nonwoven |
| CN104177939A (en) * | 2014-09-05 | 2014-12-03 | 上海展辰涂料有限公司 | Room-temperature self-crosslinking wood lacquer emulsion and preparation method thereof |
| CN105085792B (en) * | 2015-09-17 | 2018-06-19 | 安徽森普新型材料发展有限公司 | A kind of preparation method of the monomer modified acrylic emulsion of Organic fluoride |
| CN106117407A (en) * | 2016-07-28 | 2016-11-16 | 上海维凯光电新材料有限公司 | Ambient self cross-linkable acrylic emulsion and preparation method thereof |
| CN106118319A (en) * | 2016-08-04 | 2016-11-16 | 东华大学 | A kind of aqueous stripping lacquer and preparation method thereof |
| CN106749875A (en) * | 2016-12-31 | 2017-05-31 | 上海巴德富实业有限公司 | A kind of self-crosslinking aqueous acrylic emulsion of low ammonia and preparation method thereof |
| CN106632823B (en) * | 2016-12-31 | 2019-02-01 | 上海巴德富实业有限公司 | A kind of acrylic ester elastic emulsion and preparation method thereof with superior low temperature elongation at break |
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