阅读说明：本技术 一种丙烯酸酯聚合物乳液及其在制备硅酸盐涂料中的应用 (Acrylate polymer emulsion and application thereof in preparation of silicate coating ) 是由 陈爱民 张信 魏金晶 区英强 林杰生 于 2019-10-29 设计创作，主要内容包括：本发明公开了一种丙烯酸酯聚合物乳液及其在制备硅酸盐涂料中的应用,所述乳液由如下质量配比的原料组成：甲基丙烯酸酯单体10％-20％,丙烯酸酯单体10％-20％,功能性单体1％-3％,引发剂0.1％-0.3％,阴离子乳化剂0.5％-1.0％,非离子乳化剂0.7％-1.5％,余量为水,总加料量为100％；本发明制备的丙烯酸酯聚合物乳液干燥后的乳胶膜吸水率稳定在5％左右、热解温度为357.40℃,适用于涂料装饰,制备的硅酸盐无机涂料的涂膜表干时间均小于1h。本发明制备的硅酸盐无机涂料,外表观正常无异味,硬度均保持在3H及以上,附着力达到一级,在施工过程中涂刷二道无障碍,综合性能良好。(The invention discloses an acrylate polymer emulsion and application thereof in preparing silicate paint, wherein the emulsion is prepared from the following raw materials in parts by mass: 10-20% of methacrylate monomer, 10-20% of acrylate monomer, 1-3% of functional monomer, 0.1-0.3% of initiator, 0.5-1.0% of anionic emulsifier, 0.7-1.5% of nonionic emulsifier and the balance of water, wherein the total addition amount is 100%; the water absorption of the emulsion film of the dried acrylate polymer emulsion is stabilized at about 5 percent, the pyrolysis temperature is 357.40 ℃, the emulsion film is suitable for paint decoration, and the surface drying time of the film of the prepared silicate inorganic paint is less than 1 h. The silicate inorganic paint prepared by the invention has normal appearance without peculiar smell, the hardness is kept at 3H or above, the adhesive force reaches the first level, no obstacle exists when the paint is coated for two times in the construction process, and the comprehensive performance is good.)

1. The acrylic ester polymer emulsion is characterized by comprising the following raw materials in parts by mass: 10 to 20 percent of methacrylate monomer, 10 to 20 percent of acrylate monomer, 0.5 to 3 percent of functional monomer, 0.1 to 0.5 percent of initiator, 0.5 to 1.5 percent of anionic emulsifier, 0.7 to 1.5 percent of nonionic emulsifier and the balance of water, wherein the total feeding amount is 100 percent; the anionic emulsifier is one of special alkyl alcohol polyether sulfate ES-430S or branched alkyl alcohol polyether sulfate ES-730; the non-ionic emulsifier is one of alkyl polyglycoside or alcohol ether glucoside; the functional monomer is one or more of acrylamide or N, N-diethylacrylamide; the initiator is one of potassium persulfate or ammonium persulfate; the methacrylate monomer is one of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, n-octyl methacrylate or isooctyl methacrylate; the acrylate is one of ethyl acrylate, propyl acrylate, butyl acrylate or isooctyl acrylate.

2. The acrylate polymer emulsion according to claim 1, wherein the acrylate polymer emulsion comprises the following raw materials by mass: 10-20% of methacrylate monomer, 10-20% of acrylate monomer, 1-2.5% of functional monomer, 0.1-0.25% of initiator, 0.7-1.0% of anionic emulsifier, 0.7-1.2% of nonionic emulsifier and the balance of water, wherein the total addition amount is 100%.

3. The acrylate polymer emulsion according to claim 1, wherein the acrylate polymer emulsion comprises the following raw materials by mass: 13-15% of methyl methacrylate, 13-15% of butyl acrylate, 1-2.5% of N, N-diethyl acrylamide, 0.1-0.25% of potassium persulfate, 0.7-1.2% of alkyl alcohol polyether sulfate ES-7300.7%, 0.7-1.2% of alcohol ether glycoside and the balance of water, wherein the total feeding amount is 100%.

4. A method for preparing the acrylate polymer emulsion of claim 1, characterized in that the method comprises: firstly, mixing an anionic emulsifier, a nonionic emulsifier and part of water according to the formula amount, stirring, heating to 70-85 ℃ in a water bath, respectively dripping 10-30% of acrylate monomer according to the formula amount, 10-30% of methacrylate monomer according to the formula amount, 10-30% of functional monomer according to the formula amount, 10-30% of initiator according to the formula amount and part of water according to the formula amount within 15min, and continuously preserving heat for 10-30min after dripping is finished; then dropwise adding the water, the initiator, the acrylate monomer, the methacrylate monomer and the functional monomer in the rest formula amount within 2.0-4.0h, heating to 90 ℃ after dropwise adding, and continuously preserving heat for 30-50 min; cooling to 40 ℃, filtering and discharging, and taking the filtrate to obtain the acrylic ester polymer emulsion.

5. A silicate inorganic coating prepared from the acrylate polymer emulsion as claimed in claim 1, which is characterized by comprising the following raw materials in percentage by mass: 30-45% of water, 25-40% of pigment and filler, 15-30% of inorganic silicate film-forming base material, 1-5% of acrylate polymer emulsion, 0.5-1.3% of defoaming agent, 0.5-1.3% of dispersing agent, 0.4-1.1% of flatting agent, 0.5-1.0% of thickening agent and 100% of total feeding amount; the pigment and filler is one or more of titanium dioxide, calcined kaolin, heavy calcium carbonate and talcum powder; the inorganic silicate film-forming base material is one or more of alkaline silica sol, potassium silicate and sodium silicate; the defoaming agent is one of a mineral oil defoaming agent CK-231, a mineral oil defoaming agent CK-232 and a mineral oil defoaming agent CK-233; the dispersing agent is one of fatty acid dispersing agent CK-921 or fatty acid dispersing agent CK-922; the leveling agent is one of an organic silicon leveling agent CK-113 or an organic silicon leveling agent CK-114, and the thickening agent is one of carboxymethyl cellulose or hydroxyethyl cellulose.

6. The silicate inorganic paint as claimed in claim 5, wherein the pigment and filler is a mixture of ground calcium carbonate, talc, kaolin and titanium dioxide in a mass ratio of 1:0.4-0.6:0.3-0.6: 1.0-1.2.

7. The silicate inorganic paint as claimed in claim 5, wherein the silicate inorganic paint is prepared from the following raw materials in parts by mass: 30 to 45 percent of water, 25 to 38 percent of pigment and filler, 15 to 27 percent of inorganic silicate film-forming base material, 1 to 4 percent of acrylate polymer emulsion, 0.5 to 1.2 percent of defoaming agent, 0.5 to 1.2 percent of dispersant, 0.4 to 1.0 percent of flatting agent, 0.5 to 1.0 percent of thickening agent and 100 percent of total feeding amount.

8. The silicate inorganic paint as claimed in claim 5, wherein the silicate inorganic paint is prepared from the following raw materials in parts by mass: 40-45% of water, 25-28% of pigment and filler, 21-25% of inorganic silicate film-forming base material, 3-4% of acrylate polymer emulsion, 1.1-1.2% of defoaming agent, 1.2-1.3% of dispersing agent, 1.1-1.3% of flatting agent, 1.3-1.5% of thickening agent and 100% of total feeding amount; the pigment and filler is prepared by mixing heavy calcium carbonate, talcum powder, kaolin and titanium dioxide according to the mass ratio of 1:0.4-0.6:0.3-0.6: 1.0-1.2; the inorganic silicate film-forming base material is formed by mixing organic silica sol JN-30, sodium silicate and liquid potassium silicate in a mass ratio of 1:0.1-2:0.1-2, and the defoaming agent is a mineral oil defoaming agent CK-231; the dispersing agent is a fatty acid dispersing agent CK-921; the leveling agent is an organic silicon leveling agent CK-113, and the thickening agent is carboxymethyl cellulose.

9. The silicate inorganic paint according to claim 5, wherein the silicate inorganic paint is prepared by the following method: according to the formula amount, firstly adding water, a dispersing agent and a defoaming agent accounting for 1/2 formula amount into a stirring tank, and stirring for 5-15min at the rotation speed of 600-1500 rpm; then adding the pigment and filler, and stirring for 30-55min at the speed of 1000-; then adding inorganic silicate film-forming base material and acrylate polymer emulsion, and stirring for 15-30min at the rotating speed of 1000-2000 rpm; and finally, adding a thickening agent, a flatting agent and the remaining defoaming agent accounting for 1/2 of the formula amount, stirring for 20-50min at the rotating speed of 900-2500rpm, and discharging to obtain the modified silicate coating.

10. Use of the acrylate polymer emulsion according to claim 1 for the preparation of silicate inorganic coatings.

(I) technical field

The invention belongs to the building coating industry, relates to an interior wall coating used for interior decoration, and particularly relates to an acrylate polymer emulsion modified general silicate inorganic coating.

(II) technical background

With the continuous development of society, the living standard of people is continuously improved, the performance is excellent, the environment is friendly, and the requirements of people on decoration articles are increased due to diversified trends of no toxicity, no harm and the like. The polyurethane coating prepared by the bear weiwei inventor in the patent of 'epoxy resin cured precoating anticorrosive coating polyurethane and preparation method thereof' has certain corrosion resistance, but has the defects of easy aging, easy combustion and the like, and has certain influence on the air quality. Meanwhile, the organic latex paint can mildew in a humid environment, and the VOC content is high. The inorganic silicate coating takes inorganic silicate as a main film forming substance, has the advantages of high temperature resistance, weather resistance, no pollution, low VOC, rich raw materials and the like, and meets the requirements of the existing market on the performance and environmental protection of the inorganic coating. However, the common inorganic paint has the defects of long coating drying time, easy cracking and the like, which not only affects the construction performance of the paint, but also has certain influence on the appearance of the paint, thereby causing inconvenience for users. The acrylate polymer emulsion has the advantages of strong water resistance, good temperature resistance, low volatility and the like, is suitable for coating decoration, can shorten the surface drying time of the coating while meeting the market demand after modifying the silicate inorganic coating, and improves the friction resistance, the thermal stability and the brushing performance.

Therefore, the invention provides a polyacrylate emulsion modified silicate water-based interior wall coating, which is simple in preparation method, has the advantages of no toxicity, low VOC content, better flame retardance, better adhesive force than pure inorganic silicate coatings, shorter surface drying time, coating film hardness of 3H or above and the like, can effectively improve the performance of the coating, is suitable for coating decoration, meets the requirement of low VOC content, and has good industrial application.

Disclosure of the invention

Aiming at the problems, the invention aims to provide an acrylate polymer emulsion, a preparation method and application thereof in preparing silicate inorganic coating, wherein the emulsion has strong water resistance, good temperature resistance and low volatility, is suitable for coating decoration, meets the requirement of low VOC content, and simultaneously improves the defects of pure inorganic coating. The silicate inorganic coating prepared by the invention is nontoxic, has low VOC content, better flame retardance, better adhesive force than pure inorganic silicate coating, shorter surface drying time, normal coating appearance and no obstacle when coated for two times in construction, has the hardness of 3H or more, is an environment-friendly and easily-decorated silicate inorganic coating, and also meets the requirements of the current market on the performance and the environment protection of the inorganic coating.

The technical scheme adopted by the invention is as follows:

the invention provides an acrylate polymer emulsion, which is prepared from the following raw materials in parts by mass: 10 to 20 percent of methacrylate monomer, 10 to 20 percent of acrylate monomer, 0.5 to 3 percent of functional monomer, 0.1 to 0.3 percent of initiator, 0.5 to 1.5 percent of anionic emulsifier, 0.5 to 1.5 percent of nonionic emulsifier and the balance of water, wherein the total feeding amount is 100 percent; the anionic emulsifier is one of special alkyl alcohol polyether sulfate ES-430S or branched alkyl alcohol polyether sulfate ES-730, preferably ES-730; the non-ionic emulsifier is one of alkyl polyglycoside or Alcohol Ether Glycoside (AEG), preferably alcohol ether glycoside; the functional monomer is one or more of acrylamide or N, N-diethylacrylamide, preferably N, N-diethylacrylamide; the initiator is one of potassium persulfate or ammonium persulfate, preferably potassium persulfate; the methacrylate monomer is one of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, n-octyl methacrylate or isooctyl methacrylate, preferably methyl methacrylate; the acrylate is one of ethyl acrylate, propyl acrylate, butyl acrylate or isooctyl acrylate, and butyl acrylate is preferred.

Further, the acrylate polymer emulsion is prepared from the following raw materials in parts by mass: 10-20% of methacrylate monomer, 10-20% of acrylate monomer, 1-2.5% of functional monomer, 0.1-0.25% of initiator, 0.7-1.0% of anionic emulsifier, 0.7-1.2% of nonionic emulsifier and the balance of water, wherein the total addition amount is 100%.

More preferably, the acrylate polymer emulsion is prepared from the following raw materials in parts by mass: 13 to 15 percent of methacrylate monomer, 13 to 15 percent of acrylate monomer, 1 to 2.5 percent of functional monomer, 0.1 to 0.25 percent of initiator, 0.7 to 1.0 percent of anionic emulsifier, 0.7 to 1.2 percent of nonionic emulsifier and the balance of water, wherein the total feeding amount is 100 percent.

Most preferably, the acrylate polymer emulsion is prepared from the following raw materials in parts by mass: 13-15% of methyl methacrylate, 13-15% of butyl acrylate, 1-2.5% of N, N-diethyl acrylamide, 0.1-0.25% of potassium persulfate, 0.7-1.2% of branched alkyl alcohol polyether sulfate ES-7300.7%, 0.7-1.2% of alcohol ether glycoside and the balance of water, wherein the total feeding amount is 100%.

The invention also provides a preparation method of the acrylate polymer emulsion, which comprises the following steps: firstly, mixing an anionic emulsifier, a nonionic emulsifier and part of water according to the formula amount, stirring, heating to 70-85 ℃ in a water bath, respectively dripping 10-30% of acrylate monomer according to the formula amount, 10-30% of methacrylate monomer according to the formula amount, 10-30% of functional monomer according to the formula amount, 10-30% of initiator according to the formula amount and part of water according to the formula amount within 15min, and continuously preserving heat for 10-30min after dripping is finished; then dropwise adding the water, the initiator, the acrylate monomer, the methacrylate monomer and the functional monomer in the rest formula amount within 2.0-4.0h, heating to 90 ℃ after dropwise adding, and continuously preserving heat for 30-50 min; cooling to 40 ℃, filtering and discharging, and taking the filtrate to obtain the acrylic ester polymer emulsion.

The invention also provides an application of the acrylate polymer emulsion in preparation of silicate inorganic paint.

The invention also provides a silicate inorganic coating prepared from the acrylate polymer emulsion, which comprises the following raw materials in parts by mass: 30-45% of water, 25-40% of pigment and filler, 15-30% of inorganic silicate film-forming base material, 1-5% of acrylate polymer emulsion, 0.5-1.3% of defoaming agent, 0.5-1.3% of dispersing agent, 0.4-1.1% of flatting agent, 0.5-1.0% of thickening agent and 100% of total feeding amount; the pigment and filler is one or more of titanium dioxide, calcined kaolin, heavy calcium carbonate and talcum powder, more preferably the pigment and filler is prepared by mixing the heavy calcium carbonate, the talcum powder, the kaolin and the titanium dioxide in a mass ratio of 1:0.4-0.6:0.3-0.6:1.0-1.2, and preferably the pigment and filler is the heavy calcium carbonate, the talcum powder, the kaolin and the titanium dioxide in a mass ratio of 1: 0.4: 0.36: 1.17; the mesh number of the heavy calcium carbonate is 400-1400, the mesh number of the titanium dioxide is 300-800, the mesh number of the kaolin is 500-1500, and the mesh number of the talcum powder is 500-1500; the inorganic silicate film-forming base material is one or more of alkaline silica sol, potassium silicate and sodium silicate, and preferably the inorganic silicate film-forming base material is a mixture of organic silica sol JN-30, sodium silicate and liquid potassium silicate in a mass ratio of 1:0.1-2: 0.1-2; the modulus of potassium silicate is 2.0-4.0, and the modulus of sodium silicate is 2.0-4.0. The defoaming agent is one of mineral oil defoaming agents CK-231, CK-232 and CK-233; the dispersing agent is one of fatty acid dispersing agents CK-921 or CK-922; the leveling agent is one of organic silicon leveling agents CK-113 or CK-114, and the thickening agent is one of carboxymethyl cellulose or hydroxyethyl cellulose.

Further, the silicate inorganic coating is preferably composed of the following raw materials in parts by mass: 30 to 45 percent of water, 25 to 38 percent of pigment and filler, 15 to 27 percent of inorganic silicate film-forming base material, 1 to 4 percent of acrylate polymer emulsion, 0.5 to 1.2 percent of defoaming agent, 0.5 to 1.2 percent of dispersant, 0.4 to 1.0 percent of flatting agent, 0.5 to 1.0 percent of thickening agent and 100 percent of total feeding amount.

Furthermore, the silicate inorganic coating is preferably composed of the following raw materials in parts by mass: 40-45% of water, 25-28% of pigment and filler, 21-25% of inorganic silicate film-forming base material, 3-4% of acrylate polymer emulsion, 1.1-1.2% of defoaming agent, 1.2-1.3% of dispersing agent, 1.1-1.3% of flatting agent, 1.3-1.5% of thickening agent and 100% of total feeding amount; the pigment and filler is prepared by mixing heavy calcium carbonate, talcum powder, kaolin and titanium dioxide according to the mass ratio of 1:0.4-0.6:0.3-0.6: 1.0-1.2; the inorganic silicate film-forming base material is preferably a mixture of organic silica sol JN-30, sodium silicate and liquid potassium silicate in a mass ratio of 1:0.1-2:0.1-2, more preferably 1:0.977: 0.935; the defoaming agent is a mineral oil defoaming agent CK-231; the dispersing agent is a fatty acid dispersing agent CK-921; the leveling agent is an organic silicon leveling agent CK-113, and the thickening agent is carboxymethyl cellulose.

The preparation method of the silicate inorganic coating comprises the following steps: according to the formula amount, firstly adding water, a dispersing agent and a defoaming agent accounting for 1/2 formula amount into a stirring tank, and stirring for 5-15min at the rotation speed of 600-1500 rpm; then adding the pigment and filler, and stirring for 30-55min at the speed of 1000-; then adding inorganic silicate film-forming base material and acrylate polymer emulsion, and stirring for 15-30min at the rotating speed of 1000-2000 rpm; and finally, adding a thickening agent, a flatting agent and the remaining defoaming agent accounting for 1/2 of the formula amount, stirring for 20-50min at the rotating speed of 900-2500rpm, and discharging to obtain the modified silicate coating.

The molecular formula of the acrylate polymer emulsion is as follows:

a. b and c represent the molecular numbers of three monomers of methyl methacrylate, butyl acrylate and N, N-diethylacrylamide required for synthesizing the polymer emulsion respectively.

Compared with the prior art, the invention has the following beneficial effects:

the water absorption of the emulsion film of the dried acrylate polymer emulsion is stabilized at about 5 percent, the pyrolysis temperature is 357.40 ℃, the emulsion film is suitable for paint decoration, and the surface drying time of the film of the prepared silicate inorganic paint is less than 1 h.

The inorganic coating has little pollution, hardly releases volatile gases such as formaldehyde, benzene and the like, and the raw materials for producing the silicate inorganic coating have rich sources, high quality and low price.

The silicate inorganic paint prepared by the invention has normal appearance without peculiar smell, the hardness is kept at 3H or above, the adhesive force reaches the first level, no obstacle exists when the paint is coated for two times in the construction process, and the comprehensive performance is good.

(IV) description of the drawings

FIG. 1: example 1 the acrylate polymer emulsion prepared in step 1 is dried to form a film and then the infrared spectrogram is obtained.

FIG. 2: example 2 thermogravimetry of acrylic ester polymer emulsion after drying and film forming made in step 1, a is acrylic ester polymer emulsion without functional monomer modification, b is acrylic ester polymer emulsion modified by functional monomer.

FIG. 3: example 2 the contact angle of the emulsion prepared in step 1 after drying to form a film is a functional monomer-unmodified acrylate polymer emulsion and b is a functional monomer-modified acrylate polymer emulsion.

FIG. 4: coating film pattern of the silicate inorganic paint obtained in example 1.

(V) detailed description of the preferred embodiments

The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.

The branched alkyl alcohol polyether sulfate (ES-730) and the specific alkyl alcohol polyether sulfate (ES-430S) used in the examples of the present invention were obtained from Shanghai loyal Fine chemical Co., Ltd.

The defoaming agent and the leveling agent in the embodiment of the invention are purchased from Tianjin Gaitan New Material science and technology Limited.