阅读说明：本技术 一种哑光度可控的超哑光丙烯酸乳液及其制备方法 (Matte degree controllable super-matte acrylic emulsion and preparation method thereof ) 是由 李鑫 黄文武 范理 罗志斌 江德锦 于 2021-08-17 设计创作，主要内容包括：本发明提供一种哑光度可控的超哑光丙烯酸乳液及其制备方法。该乳液由粗粒径乳液和细粒径乳液混合后添加增稠剂制备得到,粗粒径乳液的原料包括纤维素,粗粒径乳液的粒子直径在1-3μm之间,细粒径乳液的粒子直径在70-90nm之间。本发明利用纤维素所制得的粗粒径乳液可以和细粒径乳液实现很好的共混,在无需添加消光粉的情况下,就能得到超哑光丙烯酸乳液。通过单一改变粗粒径乳液中纤维素的用量、釜底乳化剂的用量和预乳化液的滴加速度来改变乳胶粒子的聚并程度,进而控制乳液的哑光度。该乳液在保证光泽度较低的情况下,同时兼具良好的耐水性和耐沾污性。(The invention provides a matte degree controllable super-matte acrylic emulsion and a preparation method thereof. The emulsion is prepared by mixing a coarse-particle-size emulsion and a fine-particle-size emulsion and then adding a thickening agent, wherein the raw material of the coarse-particle-size emulsion comprises cellulose, the particle diameter of the coarse-particle-size emulsion is between 1 and 3 mu m, and the particle diameter of the fine-particle-size emulsion is between 70 and 90 nm. The coarse particle size emulsion prepared by using the cellulose can be well blended with the fine particle size emulsion, and the super-matte acrylic emulsion can be obtained without adding matting powder. The coalescence degree of latex particles is changed by singly changing the dosage of cellulose in the coarse-grain-size emulsion, the dosage of the kettle bottom emulsifier and the dripping speed of the pre-emulsion, so that the matte degree of the emulsion is controlled. The emulsion has good water resistance and stain resistance under the condition of ensuring low glossiness.)

1. The super-matte acrylic emulsion with controllable matte degree is characterized in that: the emulsion is prepared by mixing a coarse-particle-size emulsion and a fine-particle-size emulsion and then adding a thickening agent, wherein the raw material of the coarse-particle-size emulsion comprises cellulose;

the particle diameter of the coarse particle size emulsion is between 1 and 3 mu m;

the particle diameter of the fine particle size emulsion is between 70 and 90 nm.

2. The matte degree controllable super-matte acrylic emulsion according to claim 1, wherein: the solid content of the coarse-particle-size emulsion is 15-20%, and the solid content of the fine-particle-size emulsion is 40-45%;

the mixing ratio of the coarse particle size emulsion to the fine particle size emulsion is 0.55-0.75:1 in parts by mass.

3. The matte degree controllable super-matte acrylic emulsion according to claim 2, wherein the raw materials of the coarse particle size emulsion comprise the following components in parts by weight: 0.8-1.2 parts of cellulose and 0.6-0.9 part of emulsifier.

4. The matte degree controllable super-matte acrylic emulsion according to claim 3, wherein the raw materials of the coarse particle size emulsion further comprise the following components in parts by weight: 15-20 parts of methacrylate, 0.08-0.2 part of PH buffering agent, 0.08-0.1 part of initiator, 0.02-0.04 part of oxidant and 0.02-0.04 part of reducing agent.

5. The matte-degree-controllable super-matte acrylic emulsion according to claim 2, wherein the fine-particle-size emulsion comprises the following components in parts by weight: 25-35 parts of methacrylate, 11-13 parts of acrylate, 0.8-0.9 part of carboxyl monomer, 0.2-0.4 part of functional monomer, 1-2 parts of emulsifier, 0.1-0.3 part of initiator, 0.06-0.1 part of oxidant, 0.06-0.1 part of reducing agent and 0.4-0.6 part of PH regulator.

6. The matte degree controllable super-matte acrylic emulsion according to claim 3, wherein: the cellulose is hydroxyethyl cellulose;

the emulsifier in the coarse particle size emulsion comprises at least one of sodium dodecyl diphenyl ether disulfonate, sodium dodecyl benzene sulfonate and sodium alkylphenol polyoxyethylene ether sulfate.

7. The matte degree controllable super-matte acrylic emulsion according to claim 5, wherein: the carboxyl monomer comprises at least one of acrylic acid, methacrylic acid and itaconic acid; the functional monomer comprises at least one of vinyl trimethoxy silane, vinyl tri (beta-methoxyethoxy) silane, gamma-methacryloxypropyl trimethoxy silane and glycidyl methacrylate.

8. A preparation method of a matte degree controllable super-matte acrylic emulsion is characterized by comprising the following steps:

(1) mixing an emulsifier and a polymerization monomer to prepare a pre-emulsion a;

(2) preparing a reaction solution b by using cellulose and an emulsifier, heating to 75-85 ℃, adding 1-5% of the total weight of the pre-emulsion a into the reaction solution b, then adding an initiator, preserving heat, dropwise adding the rest pre-emulsion a into a reaction system for 50-70min, and continuously preserving heat to obtain a reaction solution c;

(3) when the temperature of the reaction liquid c is reduced to 65-75 ℃, dropwise adding an oxidant and a reducing agent into the reaction liquid c at the same time, and continuously preserving the temperature;

(4) mixing the coarse-particle-size emulsion and the fine-particle-size emulsion, wherein the particle diameter of the adopted fine-particle-size emulsion is 70-90nm, adding a thickening agent into the mixture, and uniformly mixing to obtain the super-matte acrylic emulsion;

wherein the particle diameter in the reaction system is between 1 and 3 mu m by adjusting the dosage of the cellulose, the dosage of the emulsifier and the dropping speed of the pre-emulsion a in the step (2), and the coarse grain size emulsion is obtained after the reaction is finished.

9. The method for preparing the matte-degree-controllable super-matte acrylic emulsion according to claim 8, wherein the fine-particle-size emulsion is prepared by the following steps:

(1) mixing an emulsifier, a polymerization monomer and an initiator to prepare a pre-emulsion d;

(2) preparing a reaction liquid e by using an emulsifier, heating to 80-90 ℃, adding 3-5% of the total weight of the pre-emulsion d into the reaction liquid e, then adding an initiator, preserving heat, dropwise adding the rest pre-emulsion d into a reaction system for 3-4h, and continuously preserving heat to obtain a reaction liquid f;

(3) and (3) when the temperature of the reaction liquid f is reduced to 65-75 ℃, simultaneously dripping an oxidant and a reducing agent into the reaction liquid, continuously preserving the heat, and obtaining the fine-particle-size emulsion after the reaction is finished.

10. The process for preparing a matte degree controllable super-matte acrylic emulsion according to claim 8, wherein: the polymerized monomer in the coarse-particle-size emulsion comprises at least one of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, tert-butyl methacrylate and isoamyl methacrylate;

the raw materials of the fine particle size emulsion comprise polymerized monomers, and the polymerized monomers in the fine particle size emulsion comprise methacrylate, acrylate, carboxyl monomers and functional monomers.

Technical Field

The invention relates to the field of acrylic emulsion, and particularly relates to a matte degree controllable super-matte acrylic emulsion and a preparation method thereof.

Background

The water-based multicolor paint is a mainstream product in the field of decoration of interior and exterior walls of buildings in recent years, has a decoration effect similar to natural granite or marble, and is mainly applied to exterior walls of high-grade buildings. The finishing varnish is used as a protective barrier of the building exterior wall coating, and has the main functions of keeping the exterior wall coating beautiful as new for a long time, resisting the invasion of water, dust and ultraviolet rays, and providing excellent water resistance, stain resistance and weather resistance. The existing finishing varnish on the market is mainly divided into a high-gloss finishing varnish and a matte finishing varnish, and the matte finishing varnish can improve the uniformity and the light shading performance of the gloss of a coating, so that the coating gives a soft visual effect to people and is deeply favored by the market.

Most of the existing emulsion for matte finishing surfaces is prepared by adding matting powder into emulsion or paint or blending two or more immiscible emulsion systems to achieve a matte effect, although matte varnishes with different matte degrees can be prepared, the varnishes prepared by the two methods are easy to layer, the problem of inconsistent glossiness can be caused in the using process, the water resistance and the storage performance are poor, and the application of the emulsion in the fields of water-based colorful paint and the like is greatly limited.

At present, the matte effect can be achieved without adding matting powder emulsion or varnish, and Chinese patent CN106608943B discloses a single-component acrylate matte core-shell emulsion with excellent water-white resistance, and a preparation method and application thereof.

Disclosure of Invention

The invention aims to provide a matte degree controllable super-matte acrylic emulsion and a preparation method thereof, which can improve the matte degree of the emulsion without adding matting powder, so that the emulsion achieves a super-matte effect and the matte degree is controllable.

According to one aspect of the invention, the matte degree controllable super-matte acrylic emulsion is prepared by mixing a coarse particle size emulsion and a fine particle size emulsion and adding a thickening agent, wherein the raw material of the coarse particle size emulsion comprises cellulose; the particle diameter of the coarse particle size emulsion is between 1 and 3 mu m; the particle diameter of the fine particle size emulsion is between 70 and 90 nm.

The acrylic emulsion is prepared by mixing a coarse-particle-size emulsion and a fine-particle-size emulsion and adding a thickening agent. The coarse-particle-size emulsion contains cellulose, and in the emulsion polymerization reaction process, the coarse-particle-size emulsion is grafted with latex particles through the cellulose, so that the latex particles are aggregated to form a micron-sized large-particle structure. In the emulsion film forming process, the cellulose-containing emulsion with coarse particle size and the emulsion with fine particle size are mixed to form a film, and then a micro-phase structure with high roughness can be formed (because the emulsion with coarse particle size has higher glass transition temperature (Tg) and high hardness, the emulsion is not easy to soften after film forming, and the micro-phase structure with coarse film surface can be maintained), so that the emulsion can achieve the super-matte effect, and the glossiness of the emulsion under the incidence angles of 60 degrees and 85 degrees is less than 10%. In addition, the high-roughness micro-phase structure can change the aggregation degree of latex particles by changing the amount of cellulose in the coarse-particle-size emulsion, thereby controlling the matte degree of the emulsion.

Preferably, the solid content of the coarse particle size emulsion is 15-20%, and the solid content of the fine particle size emulsion is 40-45%; the mixing ratio of the coarse particle size emulsion to the fine particle size emulsion is 0.55-0.75:1 in parts by mass.

Preferably, the thickener comprises at least one of polyurethane thickener RM-8W, polyurethane thickener RM-12W and alkali soluble thickener TT-935. According to the invention, a certain amount of thickening agent is added into the blended emulsion, so that the emulsion has good storage stability.

Preferably, the raw material of the coarse grain size emulsion comprises the following components in parts by weight: 0.8-1.2 parts of cellulose and 0.6-0.9 part of emulsifier. The method utilizes the graft polymerization of the cellulose and the latex particles, and the polymerization process is adjusted, so that the polymerization degree of the latex particles can be changed by only singly changing the using amount of the cellulose and the using amount of the emulsifier, and the ultra-matte acrylic emulsion with different matte degrees can be obtained without adding matting powder.

Preferably, the cellulose is hydroxyethyl cellulose.

Preferably, the hydroxyethyl cellulose comprises at least one of Dow QP-100, Ashland 250HBR, Ashland 250 LR.

In the scheme, the cellulose is applied to emulsion polymerization, mainly based on the nonionic nature of the cellulose, the coarse-particle-size emulsion prepared by the method can be well co-dissolved with the fine-particle-size emulsion, the conditions of emulsion layering and mutual insolubility do not exist, and the storage stability of the emulsion is improved.

Preferably, the emulsifier in the coarse particle size emulsion comprises at least one of sodium dodecyl diphenyl oxide disulfonate, sodium dodecyl benzene sulfonate, sodium alkyl phenol polyoxyethylene ether sulfate, reactive emulsifier SR-10 from Ediko, Japan. The emulsifying agent selected by the scheme has better emulsifying capacity, so that the polymerization reaction is more stable, and the emulsion polymerization efficiency can be improved.

Preferably, the raw material of the coarse grain size emulsion also comprises the following components in parts by weight: 15-20 parts of methacrylate, 0.08-0.2 part of PH buffering agent, 0.08-0.1 part of initiator, 0.02-0.04 part of oxidant and 0.02-0.04 part of reducing agent.

Preferably, the methacrylate in the coarse particle size emulsion comprises at least one of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, and isoamyl methacrylate. The methacrylate monomer used in the scheme has high hardness, so that the coarse grain size emulsion has higher Tg in the emulsion film forming process, is mainly distributed on the surface of a coating film as a micro dispersion phase, and provides excellent stain resistance for the coating film.

Preferably, the PH buffering agent comprises at least one of sodium bicarbonate, sodium carbonate.

Preferably, the initiator in the coarse particle size emulsion is a persulfate.

Preferably, the persulfate in the coarse-particle-size emulsion comprises at least one of ammonium persulfate, potassium persulfate, and sodium persulfate.

Preferably, the oxidizing agent in the coarse particle size emulsion is t-butyl hydroperoxide.

Preferably, the reducing agent in the coarse-particle-size emulsion comprises at least one of sodium metabisulfite, sodium bisulfite, and L-ascorbic acid.

Preferably, the raw materials of the fine-particle-size emulsion comprise the following components in parts by weight: 25-35 parts of methacrylate, 11-13 parts of acrylate, 0.8-0.9 part of carboxyl monomer, 0.2-0.4 part of functional monomer, 1-2 parts of emulsifier, 0.1-0.3 part of initiator, 0.06-0.1 part of oxidant, 0.06-0.1 part of reducing agent and 0.4-0.6 part of PH regulator.

The fine particle size emulsion can form a compact emulsion film as a microcosmic continuous phase, and provides excellent water resistance for a coating film. Because the coarse grain size emulsion and the fine grain size emulsion have different characteristics, the low glossiness can be ensured after blending, and the water resistance and the stain resistance of the super-matte emulsion are simultaneously realized.

Preferably, the methacrylate in the fine particle size emulsion comprises at least one of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and pentyl methacrylate.

Preferably, the acrylate comprises at least one of methyl acrylate, ethyl acrylate, butyl acrylate, and isooctyl acrylate. The acrylate monomer used in the scheme has relatively low hardness, so that the film forming performance of the emulsion is good.

Preferably, the carboxyl monomer comprises at least one of acrylic acid, methacrylic acid, itaconic acid. According to the scheme, the specific carboxyl monomer is added into the fine-particle-size emulsion, so that emulsion droplets are charged with negative charges, and due to the electrostatic repulsion effect among the droplets, the probability of collision and mutual combination of the droplets is reduced, and the stability of the emulsion is further improved. In addition, carboxyl in the carboxyl monomer can be self-crosslinked or crosslinked with other groups in an emulsion polymerization system, has high affinity to water, and plays a role of a co-emulsifier to a certain extent.

The functional monomer comprises at least one of vinyl trimethoxy silane, vinyl tri (beta-methoxyethoxy) silane, gamma-methacryloxypropyl trimethoxy silane and glycidyl methacrylate. The functional monomer is matched with other monomers for use, so that the adhesive force, water resistance and the like of the prepared super-matte acrylic emulsion after film formation are enhanced to a certain extent. The addition of a proper amount of functional monomers can enable the copolymer to generate slight cross-linking to form a certain network structure, change the molecular acting force among polymer molecular chains into chemical bonds, improve the rigidity of the copolymer, and hydrophilic groups carried by the functional monomers can reduce the interfacial energy of emulsion particles and water, so that the polymerization process is more stable, and the generation of flocculation is reduced.

Preferably, the emulsifier in the fine particle size emulsion comprises at least one of sodium dodecyl diphenyl oxide disulfonate, sodium dodecyl benzene sulfonate, sodium alkyl phenol polyoxyethylene ether sulfate, reactive emulsifier SR-10 from Ediko, Japan.

Preferably, the initiator in the fine particle size emulsion is a persulfate.

Preferably, the persulfate in the fine particle size emulsion comprises at least one of ammonium persulfate, potassium persulfate, and sodium persulfate.

Preferably, the oxidizing agent in the fine particle size emulsion is t-butyl hydroperoxide.

Preferably, the reducing agent in the fine particle size emulsion comprises at least one of sodium metabisulfite, sodium bisulfite, and L-ascorbic acid.

Preferably, the pH adjuster is ammonia. This scheme selects for use the aqueous ammonia as the PH regulator, can make the stability of emulsion increase to aqueous ammonia can volatilize at emulsion film forming in-process, can not remain in the membrane, consequently can not cause the influence to its performance.

According to a second aspect of the invention, a preparation method of a matte degree controllable super-matte acrylic emulsion is provided, which comprises the following steps:

(1) mixing an emulsifier and a polymerization monomer to prepare a pre-emulsion a;

(2) preparing a reaction solution b by using cellulose and an emulsifier, heating to 75-85 ℃, adding 1-5% of the total weight of the pre-emulsion a into the reaction solution b, then adding an initiator, preserving heat, dropwise adding the rest pre-emulsion a into a reaction system for 50-70min, and continuously preserving heat to obtain a reaction solution c;

(3) when the temperature of the reaction liquid c is reduced to 65-75 ℃, dropwise adding an oxidant and a reducing agent into the reaction liquid c at the same time, and continuously preserving the temperature;

adjusting the cellulose dosage, the emulsifier dosage and the dropping speed of the pre-emulsion a in the step (2) to ensure that the particle diameter in a reaction system is between 1 and 3 mu m, and obtaining a coarse grain size emulsion after the reaction is finished;

(4) and mixing the coarse-particle-size emulsion and the fine-particle-size emulsion, wherein the particle diameter of the adopted fine-particle-size emulsion is 70-90nm, adding a thickening agent into the mixture, and uniformly mixing to obtain the super-matte acrylic emulsion.

Preferably, the polymerized monomer in the coarse particle size emulsion comprises at least one of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, and isoamyl methacrylate.

Preferably, the fine particle size emulsion is prepared by the following steps:

(1) mixing an emulsifier, a polymerization monomer and an initiator to prepare a pre-emulsion d;

(2) preparing a reaction liquid e by using an emulsifier, heating to 80-90 ℃, adding 3-5% of the total weight of the pre-emulsion d into the reaction liquid e, then adding an initiator, preserving heat, dropwise adding the rest pre-emulsion d into a reaction system for 3-4h, and continuously preserving heat to obtain a reaction liquid f;

(3) and (3) when the temperature of the reaction liquid f is reduced to 65-75 ℃, simultaneously dripping an oxidant and a reducing agent into the reaction liquid, continuously preserving the heat, and obtaining the fine-particle-size emulsion after the reaction is finished.

Preferably, the starting material of the fine particle size emulsion comprises polymerized monomers, and the polymerized monomers in the fine particle size emulsion comprise methacrylate, acrylate, carboxyl monomers and functional monomers.

Detailed Description

Technical features in the technical solutions provided by the present invention are further clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Comparative example 1

The preparation method of the matte degree controllable super-matte acrylic emulsion specifically comprises the following steps:

the method comprises the following steps: preparation of coarse particle size emulsion

(1) Mixing 0.7 part of sodium dodecyl benzene sulfonate and 7 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, then adding 17.5 parts of methyl methacrylate, and stirring at high speed for 30 minutes to obtain a pre-emulsion for later use;

(2) adding 0.05 part of sodium dodecyl benzene sulfonate, 0.14 part of sodium carbonate and 70 parts of deionized water into the bottom of a reaction kettle, heating to 80 ℃ while stirring, adding 3 percent of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding 0.09 part of potassium persulfate and 5 parts of deionized water to prepare a primary initiator aqueous solution, keeping the temperature for 10min, then beginning to dropwise add the residual pre-emulsion obtained in the step (1), keeping the temperature for 60min, keeping the reaction temperature at 80 ℃, and keeping the temperature for 1h at 80 ℃ after dropwise addition;

(3) cooling to 70 ℃, simultaneously dropwise adding 0.03 part of tert-butyl hydroperoxide dissolved by 1.5 parts of deionized water and 0.03 part of sodium bisulfite dissolved by 1.5 parts of deionized water, wherein the dropwise adding time is 30min, and keeping the temperature for 20min after the dropwise adding;

(4) cooling to 50 ℃, filtering and discharging to obtain coarse grain size emulsion;

step two: preparation of fine particle size emulsions

(1) Mixing 1.1 parts of sodium dodecyl benzene sulfonate and 16 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, then sequentially adding 30 parts of methyl methacrylate, 4.5 parts of butyl acrylate, 7.5 parts of isooctyl acrylate, 0.85 part of methacrylic acid, 0.3 part of vinyl tri (beta-methoxyethoxy) silane and 0.13 part of potassium persulfate, and stirring at high speed for 30min to obtain a pre-emulsion for later use;

(2) adding 0.4 part of sodium dodecyl benzene sulfonate and 32 parts of deionized water into the bottom of a reaction kettle, heating to 85 ℃ while stirring, adding 4% of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding 0.07 part of potassium persulfate and 1.5 parts of deionized water to prepare a primary initiator aqueous solution, keeping the temperature for 25min, then beginning to dropwise add the residual pre-emulsion obtained in the step (1), keeping the dropwise adding time for 3.5h, keeping the reaction temperature at 85 ℃, and keeping the temperature for 1h after the dropwise adding is finished at 85 ℃;

(3) cooling to 70 ℃, simultaneously dropwise adding 0.08 part of tert-butyl hydroperoxide dissolved by 2.5 parts of deionized water and 0.08 part of sodium bisulfite dissolved by 2.5 parts of deionized water, wherein the dropwise adding time is 30min, and keeping the temperature for 20min after the dropwise adding;

(4) cooling to 50 ℃, adding 0.5 part of ammonia water, stirring for 10min, filtering and discharging to obtain fine-particle-size emulsion;

step three: mixing the coarse-particle-size emulsion and the fine-particle-size emulsion according to the mass ratio of 0.65:1, adding 0.9 part of polyurethane thickener RM-12W, and stirring for 15min to obtain acrylic emulsion;

the parts of the components are calculated according to the parts by weight;

the particle diameter of the coarse-particle-size emulsion is 400nm, and the solid content is 18%; the particle diameter of the fine particle size emulsion was 80nm, and the solid content was 42%.

Example 1

The preparation method of the matte degree controllable super-matte acrylic emulsion specifically comprises the following steps:

the method comprises the following steps: preparation of coarse particle size emulsion

(1) Mixing 0.7 part of sodium dodecyl benzene sulfonate and 7 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, then adding 17.5 parts of methyl methacrylate, and stirring at high speed for 30min to obtain a pre-emulsion for later use;

(2) adding 1.0 part of hydroxyethyl cellulose methylene blue 250HBR, 0.05 part of sodium dodecyl benzene sulfonate, 0.14 part of sodium carbonate and 70 parts of deionized water into the bottom of a reaction kettle, heating to 80 ℃ while stirring, adding 3% of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding a primary initiator aqueous solution prepared from 0.09 part of potassium persulfate and 5 parts of deionized water, keeping the temperature for 10min, then beginning to dropwise add the residual pre-emulsion obtained in the step (1), keeping the dropwise adding time for 60min, keeping the reaction temperature at 80 ℃, and keeping the temperature for 1h at 80 ℃ after the dropwise addition is finished;

(3) cooling to 70 ℃, simultaneously dropwise adding 0.03 part of tert-butyl hydroperoxide dissolved by 1.5 parts of deionized water and 0.03 part of sodium bisulfite dissolved by 1.5 parts of deionized water, wherein the dropwise adding time is 30min, and keeping the temperature for 20min after the dropwise adding;

(4) cooling to 50 ℃, filtering and discharging to obtain coarse grain size emulsion;

step two: preparation of fine particle size emulsions

(1) Mixing 1.1 parts of sodium dodecyl benzene sulfonate and 16 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, then sequentially adding 30 parts of methyl methacrylate, 4.5 parts of butyl acrylate, 7.5 parts of isooctyl acrylate, 0.85 part of methacrylic acid, 0.3 part of vinyl tri (beta-methoxyethoxy) silane and 0.13 part of potassium persulfate, and stirring at high speed for 30min to obtain a pre-emulsion for later use;

(2) adding 0.4 part of sodium dodecyl benzene sulfonate and 32 parts of deionized water into the bottom of a reaction kettle, heating to 85 ℃ while stirring, adding 4% of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding 0.07 part of potassium persulfate and 1.5 parts of deionized water to prepare a primary initiator aqueous solution, keeping the temperature for 25min, then beginning to dropwise add the residual pre-emulsion obtained in the step (1), keeping the dropwise adding time for 3.5h, keeping the reaction temperature at 85 ℃, and keeping the temperature for 1h after the dropwise adding is finished at 85 ℃;

(3) cooling to 70 ℃, simultaneously dropwise adding 0.08 part of tert-butyl hydroperoxide dissolved by 2.5 parts of deionized water and 0.08 part of sodium bisulfite dissolved by 2.5 parts of deionized water, wherein the dropwise adding time is 30min, and keeping the temperature for 20min after the dropwise adding;

(4) cooling to 50 ℃, adding 0.5 part of ammonia water, stirring for 10min, filtering and discharging to obtain fine-particle-size emulsion;

step three: mixing the coarse-particle-size emulsion and the fine-particle-size emulsion according to the mass ratio of 0.65:1, adding 0.9 part of polyurethane thickener RM-12W, and stirring for 15min to obtain acrylic emulsion;

the parts of the components are calculated according to the parts by weight;

the particle diameter of the coarse-particle-size emulsion is 2 mu m, and the solid content is 18 percent; the particle diameter of the fine particle size emulsion was 80nm, and the solid content was 42%.

Example 2

The preparation method of the matte degree controllable super-matte acrylic emulsion specifically comprises the following steps:

the method comprises the following steps: preparation of coarse particle size emulsion

(1) Mixing 0.6 part of sodium dodecyl diphenyl ether disulfonate and 6 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, then adding 15 parts of methyl methacrylate, and stirring at high speed for 30min to obtain a pre-emulsion for later use;

(2) adding 0.8 part of hydroxyethyl cellulose Dow QP-100, 0.08 part of sodium bicarbonate and 75 parts of deionized water into the bottom of a reaction kettle, heating to 75 ℃ while stirring, adding 1% of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding a primary initiator aqueous solution prepared from 0.08 part of ammonium persulfate and 4 parts of deionized water, keeping the temperature for 5min, then beginning to dropwise add the residual pre-emulsion obtained in the step (1), keeping the temperature for 50min, keeping the reaction temperature at 75 ℃, and keeping the temperature for 1h at 75 ℃ after dropwise addition;

(3) cooling to 65 ℃, simultaneously dropwise adding 0.02 part of tert-butyl hydroperoxide dissolved by 1 part of deionized water and 0.02 part of sodium metabisulfite dissolved by 1 part of deionized water, wherein the dropwise adding time is 30min, and keeping the temperature for 20min after the dropwise adding;

(4) cooling to 50 ℃, filtering and discharging to obtain coarse grain size emulsion;

step two: preparation of fine particle size emulsions

(1) Mixing 0.7 part of sodium dodecyl diphenyl ether disulfonate and 17 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, then sequentially adding 25 parts of methyl methacrylate, 4 parts of butyl acrylate, 7 parts of isooctyl acrylate, 0.8 part of acrylic acid, 0.2 part of vinyl trimethoxy silane and 0.06 part of ammonium persulfate, and stirring at high speed for 30min to obtain a pre-emulsion for later use;

(2) adding 0.3 part of sodium dodecyl diphenyl ether disulfonate and 36 parts of deionized water into the bottom of a reaction kettle, heating to 80 ℃ while stirring, adding 3 percent of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding an initial initiator aqueous solution prepared from 0.04 part of ammonium persulfate and 1 part of deionized water, beginning to dropwise add the residual pre-emulsion obtained in the step (1) after preserving heat for 20min, dropwise adding for 3h, reacting at the temperature of 80 ℃, and preserving heat for 1h at the temperature of 80 ℃ after dropwise adding;

(3) cooling to 65 ℃, simultaneously dropwise adding 0.06 part of tert-butyl hydroperoxide dissolved by 2 parts of deionized water and 0.06 part of sodium metabisulfite dissolved by 2 parts of deionized water for 30min, and keeping the temperature for 20min after dropwise adding;

(4) cooling to 50 ℃, adding 0.4 part of ammonia water, stirring for 10min, filtering and discharging to obtain fine-particle-size emulsion;

step three: mixing the coarse-particle-size emulsion and the fine-particle-size emulsion according to the mass ratio of 0.75:1, adding 1.0 part of polyurethane thickener RM-8W, and stirring for 15min to obtain acrylic emulsion;

the parts of the components are calculated according to the parts by weight;

the particle diameter of the coarse-particle-size emulsion is 1 mu m, and the solid content is 15 percent; the particle diameter of the fine particle size emulsion was 70nm, and the solid content was 40%.

Example 3

The preparation method of the matte degree controllable super-matte acrylic emulsion specifically comprises the following steps:

the method comprises the following steps: preparation of coarse particle size emulsion

(1) Mixing 0.8 part of alkylphenol polyoxyethylene ether sodium sulfate and 8 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, then adding 20 parts of methyl methacrylate, and stirring at high speed for 30min to obtain a pre-emulsion for later use;

(2) adding 1.2 parts of hydroxyethyl cellulose methylene blue 250LR, 0.1 part of sodium alkylphenol polyoxyethylene ether sulfate, 0.2 part of sodium carbonate and 65 parts of deionized water into the bottom of a reaction kettle, heating to 85 ℃ while stirring, adding 5% of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding a primary initiator aqueous solution prepared from 0.1 part of sodium persulfate and 6 parts of deionized water, keeping the temperature for 15min, then beginning to dropwise add the residual pre-emulsion obtained in the step (1), keeping the dropwise adding time for 70min, keeping the reaction temperature at 85 ℃, and keeping the temperature for 1h at 85 ℃ after the dropwise adding is finished;

(3) cooling to 75 ℃, simultaneously dropwise adding 0.04 part of tert-butyl hydroperoxide dissolved by 2 parts of deionized water and 0.04 part of L-ascorbic acid dissolved by 2 parts of deionized water, wherein the dropwise adding time is 30min, and keeping the temperature for 20min after the dropwise adding;

(4) cooling to 50 ℃, filtering and discharging to obtain coarse grain size emulsion;

step two: preparation of fine particle size emulsions

(1) Mixing 1.5 parts of alkylphenol polyoxyethylene ether sodium sulfate and 15 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, and then sequentially adding 35 parts of methyl methacrylate, 5 parts of butyl acrylate, 8 parts of isooctyl acrylate, 0.9 part of itaconic acid, 0.4 part of gamma-methacryloxypropyl trimethoxysilane and 0.2 part of sodium persulfate, and stirring at high speed for 30min to obtain a pre-emulsion for later use;

(2) adding 0.5 part of sodium alkylphenol polyoxyethylene ether sulfate and 28 parts of deionized water into the bottom of a reaction kettle, heating to 90 ℃ while stirring, adding 5% of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding 0.1 part of sodium persulfate and 2 parts of deionized water to prepare a primary initiator aqueous solution, keeping the temperature for 30min, then beginning to dropwise add the residual pre-emulsion obtained in the step (1), dropwise adding for 4h, keeping the reaction temperature at 90 ℃, and keeping the temperature for 1h at 90 ℃ after dropwise adding;

(3) cooling to 75 ℃, simultaneously dropwise adding 0.1 part of tert-butyl hydroperoxide dissolved by 3 parts of deionized water and 0.1 part of L-ascorbic acid dissolved by 3 parts of deionized water, wherein the dropwise adding time is 30min, and keeping the temperature for 20min after the dropwise adding;

(4) cooling to 50 ℃, adding 0.6 part of ammonia water, stirring for 10min, and filtering and discharging to obtain a fine-particle-size emulsion;

step three: mixing the coarse-particle-size emulsion and the fine-particle-size emulsion according to the mass ratio of 0.55:1, adding 0.8 part of polyurethane thickener TT-935, and stirring for 15min to obtain acrylic emulsion;

the parts of the components are calculated according to the parts by weight;

the particle diameter of the coarse-particle-size emulsion is 3 mu m, and the solid content is 20 percent; the particle diameter of the fine particle size emulsion was 90nm and the solid content was 45%.

Example 4

The preparation method of the matte degree controllable super-matte acrylic emulsion specifically comprises the following steps:

the method comprises the following steps: preparation of coarse particle size emulsion

(1) Mixing 0.7 part of sodium dodecyl benzene sulfonate and 7 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, then adding 17.5 parts of methyl methacrylate, and stirring at high speed for 30min to obtain a pre-emulsion for later use;

(2) adding 0.9 part of hydroxyethyl cellulose methylene blue 250HBR, 0.05 part of sodium dodecyl benzene sulfonate, 0.14 part of sodium carbonate and 70 parts of deionized water into the bottom of a reaction kettle, heating to 80 ℃ while stirring, adding 3% of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding a primary initiator aqueous solution prepared from 0.09 part of potassium persulfate and 5 parts of deionized water, keeping the temperature for 10min, then beginning to dropwise add the residual pre-emulsion obtained in the step (1), keeping the dropwise adding time for 60min, keeping the reaction temperature at 80 ℃, and keeping the temperature for 1h at 80 ℃ after the dropwise addition is finished;

(3) cooling to 70 ℃, simultaneously dropwise adding 0.03 part of tert-butyl hydroperoxide dissolved by 1.5 parts of deionized water and 0.03 part of sodium bisulfite dissolved by 1.5 parts of deionized water, wherein the dropwise adding time is 30min, and keeping the temperature for 20min after the dropwise adding;

(4) cooling to 50 ℃, filtering and discharging to obtain coarse grain size emulsion;

step two: preparation of fine particle size emulsions

(1) Mixing 1.1 parts of sodium dodecyl benzene sulfonate and 16 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, then sequentially adding 30 parts of methyl methacrylate, 4.5 parts of butyl acrylate, 7.5 parts of isooctyl acrylate, 0.85 part of methacrylic acid, 0.3 part of vinyl tri (beta-methoxyethoxy) silane and 0.13 part of potassium persulfate, and stirring at high speed for 30min to obtain a pre-emulsion for later use;

(2) adding 0.4 part of sodium dodecyl benzene sulfonate and 32 parts of deionized water into the bottom of a reaction kettle, heating to 85 ℃ while stirring, adding 4% of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding 0.07 part of potassium persulfate and 1.5 parts of deionized water to prepare a primary initiator aqueous solution, keeping the temperature for 25min, then beginning to dropwise add the residual pre-emulsion obtained in the step (1), keeping the dropwise adding time for 3.5h, keeping the reaction temperature at 85 ℃, and keeping the temperature for 1h after the dropwise adding is finished at 85 ℃;

(3) cooling to 70 ℃, simultaneously dropwise adding 0.08 part of tert-butyl hydroperoxide dissolved by 2.5 parts of deionized water and 0.08 part of sodium bisulfite dissolved by 2.5 parts of deionized water, wherein the dropwise adding time is 30min, and keeping the temperature for 20min after the dropwise adding;

(4) cooling to 50 ℃, adding 0.5 part of ammonia water, stirring for 10min, filtering and discharging to obtain fine-particle-size emulsion;

step three: mixing the coarse-particle-size emulsion and the fine-particle-size emulsion according to the mass ratio of 0.65:1, adding 0.9 part of polyurethane thickener RM-12W, and stirring for 15min to obtain acrylic emulsion;

the parts of the components are calculated according to the parts by weight;

the particle diameter of the coarse-particle-size emulsion is 2 mu m, and the solid content is 18 percent; the particle diameter of the fine particle size emulsion was 80nm, and the solid content was 42%.

Example 5

The preparation method of the matte degree controllable super-matte acrylic emulsion specifically comprises the following steps:

the method comprises the following steps: preparation of coarse particle size emulsion

(1) Mixing 0.7 part of sodium dodecyl benzene sulfonate and 7 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, then adding 17.5 parts of methyl methacrylate, and stirring at high speed for 30min to obtain a pre-emulsion for later use;

(2) adding 1.0 part of hydroxyethyl cellulose methylene blue 250HBR, 0.1 part of sodium dodecyl benzene sulfonate, 0.14 part of sodium carbonate and 70 parts of deionized water into the bottom of a reaction kettle, heating to 80 ℃ while stirring, adding 3% of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding a primary initiator aqueous solution prepared from 0.09 part of potassium persulfate and 5 parts of deionized water, keeping the temperature for 10min, then beginning to dropwise add the residual pre-emulsion obtained in the step (1), keeping the dropwise adding time for 60min, keeping the reaction temperature at 80 ℃, and keeping the temperature for 1h at 80 ℃ after the dropwise addition is finished;

(3) cooling to 70 ℃, simultaneously dropwise adding 0.03 part of tert-butyl hydroperoxide dissolved by 1.5 parts of deionized water and 0.03 part of sodium bisulfite dissolved by 1.5 parts of deionized water, wherein the dropwise adding time is 30min, and keeping the temperature for 20min after the dropwise adding;

(4) cooling to 50 ℃, filtering and discharging to obtain coarse grain size emulsion;

step two: preparation of fine particle size emulsions

(1) Mixing 1.1 parts of sodium dodecyl benzene sulfonate and 16 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, then sequentially adding 30 parts of methyl methacrylate, 4.5 parts of butyl acrylate, 7.5 parts of isooctyl acrylate, 0.85 part of methacrylic acid, 0.3 part of vinyl tri (beta-methoxyethoxy) silane and 0.13 part of potassium persulfate, and stirring at high speed for 30min to obtain a pre-emulsion for later use;

(2) adding 0.4 part of sodium dodecyl benzene sulfonate and 32 parts of deionized water into the bottom of a reaction kettle, heating to 85 ℃ while stirring, adding 4% of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding 0.07 part of potassium persulfate and 1.5 parts of deionized water to prepare a primary initiator aqueous solution, keeping the temperature for 25min, then beginning to dropwise add the residual pre-emulsion obtained in the step (1), keeping the dropwise adding time for 3.5h, keeping the reaction temperature at 85 ℃, and keeping the temperature for 1h after the dropwise adding is finished at 85 ℃;

(3) cooling to 70 ℃, simultaneously dropwise adding 0.08 part of tert-butyl hydroperoxide dissolved by 2.5 parts of deionized water and 0.08 part of sodium bisulfite dissolved by 2.5 parts of deionized water, wherein the dropwise adding time is 30min, and keeping the temperature for 20min after the dropwise adding;

(4) cooling to 50 ℃, adding 0.5 part of ammonia water, stirring for 10min, filtering and discharging to obtain fine-particle-size emulsion;

step three: mixing the coarse-particle-size emulsion and the fine-particle-size emulsion according to the mass ratio of 0.65:1, adding 0.9 part of polyurethane thickener RM-12W, and stirring for 15min to obtain acrylic emulsion;

the parts of the components are calculated according to the parts by weight;

the particle diameter of the coarse-particle-size emulsion is 2 mu m, and the solid content is 18 percent; the particle diameter of the fine particle size emulsion was 80nm, and the solid content was 42%.

Example 6

The preparation method of the matte degree controllable super-matte acrylic emulsion specifically comprises the following steps:

the method comprises the following steps: preparation of coarse particle size emulsion

(1) Mixing 0.7 part of sodium dodecyl benzene sulfonate and 7 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, then adding 17.5 parts of methyl methacrylate, and stirring at high speed for 30 minutes to obtain a pre-emulsion for later use;

(2) adding 1.0 part of hydroxyethyl cellulose methylene blue 250HBR, 0.05 part of sodium dodecyl benzene sulfonate, 0.14 part of sodium carbonate and 70 parts of deionized water into the bottom of a reaction kettle, heating to 80 ℃ while stirring, adding 3% of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding a primary initiator aqueous solution prepared from 0.09 part of potassium persulfate and 5 parts of deionized water, keeping the temperature for 10min, then beginning to dropwise add the residual pre-emulsion in the step (1), keeping the dropwise adding time for 65min, keeping the reaction temperature at 80 ℃, and keeping the temperature for 1h at 80 ℃ after the dropwise addition is finished;

(3) cooling to 70 ℃, simultaneously dropwise adding 0.03 part of tert-butyl hydroperoxide dissolved by 1.5 parts of deionized water and 0.03 part of sodium bisulfite dissolved by 1.5 parts of deionized water, wherein the dropwise adding time is 30min, and keeping the temperature for 20min after the dropwise adding;

(4) cooling to 50 ℃, filtering and discharging to obtain coarse grain size emulsion;

step two: preparation of fine particle size emulsions

(1) Mixing 1.1 parts of sodium dodecyl benzene sulfonate and 16 parts of deionized water in an emulsifying cylinder at normal temperature and normal pressure, fully stirring and dissolving, then sequentially adding 30 parts of methyl methacrylate, 4.5 parts of butyl acrylate, 7.5 parts of isooctyl acrylate, 0.85 part of methacrylic acid, 0.3 part of vinyl tri (beta-methoxyethoxy) silane and 0.13 part of potassium persulfate, and stirring at high speed for 30min to obtain a pre-emulsion for later use;

(2) adding 0.4 part of sodium dodecyl benzene sulfonate and 32 parts of deionized water into the bottom of a reaction kettle, heating to 85 ℃ while stirring, adding 4% of the total weight of the pre-emulsion obtained in the step (1) as a seed emulsion, adding 0.07 part of potassium persulfate and 1.5 parts of deionized water to prepare a primary initiator aqueous solution, keeping the temperature for 25min, then beginning to dropwise add the residual pre-emulsion obtained in the step (1), keeping the dropwise adding time for 3.5h, keeping the reaction temperature at 85 ℃, and keeping the temperature for 1h after the dropwise adding is finished at 85 ℃;

(3) cooling to 70 ℃, simultaneously dropwise adding 0.08 part of tert-butyl hydroperoxide dissolved by 2.5 parts of deionized water and 0.08 part of sodium bisulfite dissolved by 2.5 parts of deionized water, wherein the dropwise adding time is 30min, and keeping the temperature for 20min after the dropwise adding;

(4) cooling to 50 ℃, adding 0.5 part of ammonia water, stirring for 10min, filtering and discharging to obtain fine-particle-size emulsion;

step three: mixing the coarse-particle-size emulsion and the fine-particle-size emulsion according to the mass ratio of 0.65:1, adding 0.9 part of polyurethane thickener RM-12W, and stirring for 15min to obtain acrylic emulsion;

the parts of the components are calculated according to the parts by weight;

the particle diameter of the coarse-particle-size emulsion is 2 mu m, and the solid content is 18 percent; the particle diameter of the fine particle size emulsion was 80nm, and the solid content was 42%.

Test example

1. Experimental construction mode

The test subjects used in this test example were the super-matt acrylic emulsions prepared in examples 1 to 7, and the above-obtained super-matt acrylic emulsions were used to prepare matt top varnishes, the formulations of which are shown in Table 1. The detection of the relevant parameters is then carried out.

TABLE 1 formulation of matte finish varnish

The detection method according to the test example is as follows:

(1) gloss: the emulsion obtained by the invention is prepared into a film on black-and-white cardboard by a 100-micron wire rod, and then is cured in an oven at 50 ℃ for 20min, and then is measured by a gloss meter with a standard Kgada model of BGD515 and data is recorded.

(2) Stain resistance: the coating is carried out according to the standard of the finishing varnish for HB/T5065-2016 architectural coating, and the stain resistance is tested twice by adopting an oven rapid method (the lower the reduction rate coefficient is, the better the performance is shown).

(3) Water resistance: spraying a layer of multicolor paint on a 150 x 70 x 5mm asbestos-free fiber cement pressure plate, after curing for 3 days at constant temperature and humidity, brushing the finish varnish, curing for 1 day in a constant temperature and humidity environment, dripping deionized water on the surface of a paint film, observing and recording the foaming condition and the time required by color change.

2. Results of the experiment

TABLE 2 gloss, stain resistance and Water resistance test results

Analysis of the test results in table 2 shows that the matte acrylic emulsion obtained by blending the coarse grain size emulsion prepared from the cellulose and the coarse grain size emulsion has low glossiness, the glossiness of the acrylic emulsion at the incidence angles of 60 degrees and 85 degrees is less than 10%, and the acrylic emulsion has excellent water resistance and stain resistance. Meanwhile, the super-matte acrylic emulsion with different matte degrees can be obtained by singly changing the cellulose dosage, the dosage of the kettle bottom emulsifier and the dropping speed of the pre-emulsion in the coarse-grain-size emulsion.

Although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.