CN109705256B - Acrylic ester emulsion with lotus leaf effect for high-gloss water-based finish varnish and preparation method thereof - Google Patents
Acrylic ester emulsion with lotus leaf effect for high-gloss water-based finish varnish and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an acrylic ester emulsion with lotus leaf effect for high-gloss water-based finish varnish and a preparation method thereof, wherein the emulsion comprises the following raw materials in parts by weight: 20-30 parts of methyl methacrylate, 10-20 parts of isooctyl acrylate, 0.1-3 parts of crosslinking monomer, 1-3 parts of carboxyl monomer, 1-3 parts of organosilicon monomer, 1.1-3 parts of emulsifier, 0.2-1 part of initiator, 1-5 parts of film-forming assistant, 0.5-5.5 parts of pH regulator and 50-65 parts of deionized water. The paint film has a lotus leaf effect structure by proper core-shell proportion and Tg difference, complete hydrophobicity of the hard core and relative hydrophobicity of the soft shell, and completely avoids the use of inorganic compounds, so that the finishing varnish prepared from the emulsion has excellent water resistance, stain resistance, yellowing resistance, stability and universality.
Description
Technical Field
The invention relates to the technical field of organic polymer polymerization, in particular to an acrylate emulsion with lotus leaf effect for high-gloss water-based finish varnish and a preparation method thereof.
Background
In recent years, along with the development of technical level and the promotion of living standard, the requirements of people on exterior architectural coatings are also more and more strict, not only the requirements of simply meeting the use are met, but also the performances of all aspects are expected to be further promoted under the condition of controlling the cost, such as simpler and more convenient construction, more natural and harmonious color and luster, longer service life, more excellent water resistance, easier washing and cleaning of surface dust and dirt, and the like. The exterior wall coating represented by the stone-like paint and the multicolor paint is deeply favored by users due to attractive appearance, natural color and stereoscopic impression, but the exterior wall stone-like paint and the multicolor paint have the defects of water resistance, water-white resistance, stain resistance, relatively poor weather resistance and the like generally, so that a layer of finish coat varnish is required to be matched on the surface of the exterior wall stone-like paint and the multicolor paint to solve the problems, maintain the aesthetic feeling of the exterior wall stone-like paint and prolong the service life of the exterior wall paint. The existing water-based emulsion for the cover surface mainly comprises pure acrylic emulsion, silicone acrylic emulsion and organic-inorganic composite emulsion, wherein the pure acrylic emulsion has the phenomena of hot stickiness and cold brittleness, the stain resistance is rapidly reduced due to the fact that the temperature is high, the stickiness of a paint film is rapidly reduced, the problem of stickiness can be solved by increasing the glass transition temperature of the emulsion, and the emulsion is easy to crack when being used under the condition of low temperature. The silicone-acrylic emulsion has relatively excellent comprehensive performance, but has relatively high price, and the organic-inorganic composite emulsion is easy to have the problems of poor storage stability and the like, so that a cover emulsion which is waterproof, excellent in stain resistance, relatively low in price, good in stability and strong in universality is urgently needed in the market at present to meet the market demand at present.
Disclosure of Invention
In order to solve the problem that the stability of a polymer synthesized by organic and inorganic composite materials and having a lotus leaf effect structure is easy to appear relatively poor, the invention aims to provide the acrylate emulsion for the high-gloss water-based finish varnish synthesized by all organic materials and having the lotus leaf effect, which does not need to add modified inorganic compound materials, has good compatibility and reaction performance among organic raw materials, and has the advantages of low cost, stable production batch, high storage stability, wide application prospect and the like in practical industrial application. The emulsion disclosed by the invention has excellent water resistance, water-white resistance, stain resistance and yellowing resistance, and simultaneously has better stability and universality.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the acrylic ester emulsion with the lotus leaf effect for the highlight water-based finish paint comprises the following raw materials in parts by weight:
20-30 parts of methyl methacrylate, 10-20 parts of isooctyl acrylate, 0.1-3 parts of crosslinking monomer, 1-3 parts of carboxyl monomer, 1-3 parts of organosilicon monomer, 1.1-3 parts of emulsifier, 0.3-1 part of initiator, 1-5 parts of film-forming assistant, 0.5-5.5 parts of pH regulator and 50-65 parts of deionized water.
The crosslinking monomer includes but is not limited to one or more of ethylene glycol dimethacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate and acrylamide.
The carboxyl monomer includes but is not limited to one or more of acrylic acid, methacrylic acid and itaconic acid.
The organosilicon monomer comprises one or more than two of vinyl trimethoxy silane, methacryloxy propyl trimethoxy silane and vinyl tri (beta-methoxy ethoxy) silane.
The emulsifier includes, but is not limited to, one or more of sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkyl polyoxyethylene ether sulfate, sodium allyloxy hydroxypropanesulfonate, sodium 2-acrylamido-2-methylpropanesulfonate, SR-10, SR-20 of Edaceae, Japan.
The initiator comprises one or more than two of ammonium persulfate, potassium persulfate and sodium persulfate.
The film forming auxiliary agent comprises one or more than two of 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, propylene glycol phenyl ether, propylene glycol butyl ether and OE-300 of Issman company.
The pH regulator includes but is not limited to one or more of ammonia water, sodium hydroxide and potassium hydroxide.
The invention also provides a preparation method of the acrylic ester emulsion with the lotus leaf effect for the high-gloss finish varnish, which comprises the following steps:
(1) under the conditions of normal temperature and normal pressure, adding 3-15 parts of methyl methacrylate, 0-3 parts of isooctyl acrylate, 0-1 part of crosslinking monomer, 0.2-1.5 parts of carboxyl monomer, 0.3-0.8 part of organosilicon monomer, 0.1-0.6 part of emulsifier, 0.1-0.3 part of initiator and 5-15 parts of deionized water into an emulsifying cylinder one by one, stirring at high speed for 30min to uniformly mix the materials to be used as a nuclear layer pre-emulsion for later use;
(2) adding 20-30 parts of deionized water into a normal-pressure reaction kettle, adding 0.5-1.5 parts of emulsifier, stirring and heating to 80-85 ℃;
(3) taking 5-20% of the nuclear layer pre-emulsion in the step (1) to the reaction kettle in the step (2), adding 0.1-0.5 part of initiator aqueous solution, preserving heat for 10-30 minutes at the temperature of 80-85 ℃, then dropwise adding the rest of the nuclear layer pre-emulsion for 30-60 minutes, and preserving heat for 1 hour;
(4) uniformly mixing the rest parts of methyl methacrylate, isooctyl acrylate, a crosslinking monomer, a carboxyl monomer, an organic silicon monomer, an emulsifier, an initiator, deionized water and 0-0.5 part of pH regulator in an emulsifying cylinder with the same scale according to the mode of the step (1) to obtain a shell pre-emulsion for later use;
(5) maintaining the temperature of the reaction kettle at 80-85 ℃, dropwise adding the shell layer pre-emulsion in the step (4) for 4 hours, and continuously preserving the heat for 1 hour at the temperature after dropwise adding the shell layer pre-emulsion;
(6) cooling to 50 ℃, adding 0.5-5 parts of pH regulator, regulating the pH value of the emulsion to 7-9, slowly adding 1-5 parts of film-forming assistant, keeping the temperature at 50 ℃, stirring for 0.5 hour, and discharging.
Further, the preparation method maintains a mechanical stirring state in the whole process.
The acrylic ester emulsion for the high-gloss water-based finishing varnish with the lotus leaf effect, which is prepared by the method, has the solid content of 35-45 percent, the particle size of the emulsion is 50-120nm, the viscosity is within 1000CPS (3#12r), and the lowest film forming temperature is 5-15 ℃. The emulsion can be mainly used as the outer wall building coating finish coat.
The application mechanism of the invention is as follows: the unique proportion of the hard core and the soft shell and the Tg difference enable the synthesized acrylate emulsion to form a film, the hard core is difficult to deform greatly due to high glass transition temperature to form a convex structure, the soft shell is easy to deform, the film is formed to be relatively flat, so that a structure similar to a lotus effect is formed, the convex part is of a hydrophobic structure, the water repellent effect is good, water molecules can be slowed down from spreading to the surface of a paint film, the soft section is of a relatively hydrophobic structure, and the acrylate emulsion has some special functional groups and has the water locking property, when water permeates to the moment, the inward permeation of the water molecules can be further slowed down, and therefore the acrylate emulsion has excellent water resistance integrally. Meanwhile, special water-locking groups such as phosphoric acid, sulfonic acid, amide groups and the like can form a water film on the surface of the paint film, so that the surface of the paint film is relatively wetted to eliminate static electricity on the surface of the paint film, the electrostatic adsorption force of pollutants is reduced, in addition, the protrusions also reduce the direct contact of pollution sources such as a dust layer and the like and the large area of the surface of the paint film, so that dust is difficult to firmly adhere to the surface of the paint film, and can be easily taken away after being washed by rainwater, and therefore, the paint film has excellent stain resistance.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a pure acrylic emulsion with high glass transition temperature (Tg) and low film forming temperature, which is characterized in that a hard core and a soft shell are matched with each other, when a film is formed, the hard core is difficult to deform greatly due to high glass transition temperature, a convex structure is formed, the soft shell is easy to deform, and the formed film is relatively flat, so that the emulsion has a structure similar to a lotus effect after the film is formed, the use of inorganic matters is avoided, the emulsion has better stability and universality, the purpose of water locking and wetting can be achieved by proper amount of functional groups on the surface of the soft shell, the varnish is endowed with excellent water resistance and stain resistance by matching the lotus effect structure, meanwhile, a proper amount of organic silicon is added, the cost is controlled, the stain resistance can be further improved, and some problems of the prior high-gloss finishing varnish in application are well solved.
The invention is a common acrylate monomer, does not contain inorganic functional compounds, can achieve the polymer with lotus effect synthesized by organic and inorganic composite synthesis only by designing proper core-shell proportion and poor Tg through a core-shell emulsion polymerization process, has the advantages of easily obtained raw materials, simple operation process, no need of considering the problems of compatibility, stability and the like brought by inorganic matters, simultaneously, the core-shell structure enables the emulsion to have lower film forming temperature under the condition of higher Tg, the construction season and the construction temperature are not limited, special functional groups not only can lock water and provide stain resistance, but also have better thickening effect, thereby using less thickener, varnish can achieve the viscosity required by construction, and reducing the production cost of finish paint. Generally, the acrylate emulsion has excellent water resistance, water white resistance, stain resistance and yellowing resistance, has good stability and universality, and is a product which is in urgent shortage in the current market.
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention. The following reagents or starting materials, unless otherwise specified, were obtained from publicly available commercial sources.
Example 1:
an acrylic ester emulsion with a lotus leaf effect for a high-gloss water-based finish varnish is composed of the following raw materials in parts by weight: 30 parts of methyl methacrylate, 14 parts of isooctyl acrylate, 2 parts of a crosslinking monomer (comprising ethylene glycol dimethacrylate and glycidyl methacrylate), 1 part of a carboxyl monomer (methacrylic acid), 1.6 parts of an organosilicon monomer (vinyl trimethoxy silane), 2 parts of an emulsifier (comprising sodium dodecyl sulfate, 2-acrylamido-2-methyl sodium propane sulfonate and SR-10 of Japan Aidicco), 0.3 part of an initiator (ammonium persulfate), 5 parts of a film-forming assistant (2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate), 0.8 part of a pH regulator (ammonia water) and 55 parts of deionized water.
The preparation method of the acrylic ester emulsion with the lotus leaf effect for the high-gloss finishing varnish comprises the following steps:
(1) under the conditions of normal temperature and normal pressure, 12 parts of methyl methacrylate, 3 parts of isooctyl acrylate, 0.8 part of ethylene glycol dimethacrylate, 0.4 part of methacrylic acid, 0.6 part of vinyl trimethoxy silane, 0.2 part of SR-10 emulsifier of Ideca corporation of Japan, 0.4 part of 2-acrylamide-2-methyl sodium propane sulfonate, 0.1 part of ammonium persulfate and 14 parts of deionized water are added into an emulsifying cylinder one by one and stirred at high speed for 30min to be uniformly mixed to be used as a nuclear layer pre-emulsion for standby;
(2) adding 20 parts of deionized water into a normal-pressure reaction kettle, adding 0.5 part of lauryl sodium sulfate, stirring and heating to 80-82 ℃;
(3) taking 5% of the nuclear layer pre-emulsion in the step (1) to the reaction kettle in the step (2), adding 0.1 part of initiator aqueous solution, preserving heat for 15 minutes at the temperature of 80-82 ℃, then dropwise adding the rest of the nuclear layer pre-emulsion for 60 minutes, and preserving heat for 1 hour;
(4) uniformly mixing 18 parts of methyl methacrylate, 11 parts of isooctyl acrylate, 1.2 parts of glycidyl methacrylate, 0.6 part of methacrylic acid, 1 part of vinyl trimethoxy silane, 0.3 part of SR-10 emulsifier of Idiaceae company, 0.6 part of 2-acrylamide-2-methyl sodium propane sulfonate, 0.1 part of ammonium persulfate, 21 parts of deionized water and 0.05 part of ammonia water in an emulsion tank with the same scale according to the mode of the step (1) to be used as a shell layer pre-emulsion for later use;
(5) maintaining the temperature of the reaction kettle at 80-82 ℃, dropwise adding the shell layer pre-emulsion in the step (4) for 4 hours, and continuously preserving the heat for 1 hour at the temperature after dropwise adding the shell layer pre-emulsion;
(6) cooling to 50 ℃, adding 0.75 part of ammonia water, adjusting the pH value of the emulsion to 7-9, slowly adding 5 parts of 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, keeping the temperature at 50 ℃, stirring for 0.5 hour, and discharging.
Further, the above preparation method maintains the mechanical stirring state in the whole process
The acrylic ester emulsion for the high-gloss water-based finishing varnish with the lotus leaf effect, which is prepared by the method, has the solid content of 44.5 percent, the particle size of the emulsion is 110nm, the viscosity is within 1000CPS (3#12r), and the lowest film forming temperature is 5 ℃.
Example 2:
an acrylic ester emulsion with a lotus leaf effect for a high-gloss water-based finish varnish is composed of the following raw materials in parts by weight: 25 parts of methyl methacrylate, 10 parts of isooctyl acrylate, 1 part of a crosslinking monomer (ethylene glycol dimethacrylate), 0.8 part of a carboxyl monomer (comprising methacrylic acid and acrylic acid), 1.4 parts of an organosilicon monomer (comprising vinyl trimethoxy silane and methacryloxypropyl trimethoxy silane), 2.2 parts of an emulsifier (comprising sodium dodecyl benzene sulfonate, 2-acrylamido-2-methyl propyl sulfonate and SR-10 of Idiaceae company, Japan), 0.4 part of an initiator (ammonium persulfate), 2.5 parts of a film-forming aid (2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate), 0.7 part of a pH regulator (ammonia water) and 60 parts of deionized water.
The preparation method of the acrylic ester emulsion with the lotus leaf effect for the high-gloss finishing varnish comprises the following steps:
(1) under the conditions of normal temperature and normal pressure, adding 8 parts of methyl methacrylate, 1 part of isooctyl acrylate, 0.4 part of ethylene glycol dimethacrylate, 0.3 part of methacrylic acid, 0.2 part of vinyl trimethoxy silane, 0.3 part of methacryloxypropyl trimethoxy silane, 0.4 part of SR-10 emulsifier of Japan Aidicke company, 0.1 part of ammonium persulfate and 12 parts of deionized water into an emulsifying cylinder one by one, stirring at high speed for 30min to uniformly mix the materials to be used as a nuclear layer pre-emulsion for standby;
(2) adding 25 parts of deionized water into a normal-pressure reaction kettle, adding 1 part of sodium dodecyl benzene sulfonate, stirring and heating to 80-82 ℃;
(3) taking 7% of the nuclear layer pre-emulsion in the step (1) to the reaction kettle in the step (2), adding 0.1 part of initiator aqueous solution, preserving heat for 15 minutes at the temperature of 80-82 ℃, then dropwise adding the rest of the nuclear layer pre-emulsion for 45 minutes, and preserving heat for 1 hour;
(4) uniformly mixing 17 parts of methyl methacrylate, 9 parts of isooctyl acrylate, 0.6 part of ethylene glycol dimethacrylate, 0.5 part of acrylic acid, 0.4 part of vinyl trimethoxy silane, 0.5 part of methacryloxypropyl trimethoxy silane, 0.4 part of SR-10 emulsifier of Idiaceae, 0.4 part of 2-acrylamido-2-methyl sodium propanesulfonate, 0.2 part of ammonium persulfate, 23 parts of deionized water and 0.04 part of ammonia water in an emulsifying cylinder with the same size according to the mode of the step (1) to prepare a shell layer pre-emulsion for later use;
(5) maintaining the temperature of the reaction kettle at 80-82 ℃, dropwise adding the shell layer pre-emulsion in the step (4) for 4 hours, and continuously preserving the heat for 1 hour at the temperature after dropwise adding the shell layer pre-emulsion;
(6) cooling to 50 ℃, adding 0.66 part of ammonia water, adjusting the pH value of the emulsion to 7-9, slowly adding 2.5 parts of 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, keeping the temperature at 50 ℃, stirring for 0.5 hour, and discharging.
Further, the above preparation method maintains the mechanical stirring state in the whole process
The acrylic ester emulsion for the high-gloss water-based finishing varnish with the lotus leaf effect, which is prepared by the method, has the solid content of 38.5 percent, the particle size of the emulsion is 85nm, the viscosity is within 1000CPS (3#12r), and the lowest film forming temperature is 15 ℃.
Example 3:
an acrylic ester emulsion with lotus leaf effect for high-gloss water-based finish varnish comprises the following raw materials in parts by weight: 28 parts of methyl methacrylate, 16 parts of isooctyl acrylate, 1.5 parts of crosslinking monomer (comprising ethylene glycol dimethacrylate and hydroxyethyl methacrylate), 1.5 parts of carboxyl monomer (methacrylic acid), 2 parts of organosilicon monomer (comprising vinyl trimethoxy silane and methacryloxypropyl trimethoxy silane), 1.9 parts of emulsifier (comprising sodium dodecyl sulfate, alkyl polyoxyethylene ether sulfate, 2-acrylamido-2-methyl propane sodium sulfonate and SR-10 of Idiaceae company, Japan), 0.5 part of initiator (potassium persulfate), 1 part of film-forming aid (2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate), 1.05 parts of pH regulator (ammonia water) and 65 parts of deionized water.
The preparation method of the acrylic ester emulsion with the lotus leaf effect for the high-gloss finishing varnish comprises the following steps:
(1) under the conditions of normal temperature and normal pressure, adding 6 parts of methyl methacrylate, 0.5 part of ethylene glycol dimethacrylate, 0.3 part of methacrylic acid, 0.3 part of vinyl trimethoxy silane, 0.3 part of methacryloxypropyl trimethoxy silane, 0.2 part of SR-10 emulsifier of Aidic corporation of Japan, 0.1 part of potassium persulfate and 10 parts of deionized water into an emulsifying cylinder one by one, stirring at high speed for 30min, and uniformly mixing to obtain a nuclear layer pre-emulsion for later use;
(2) adding 25 parts of deionized water into a normal-pressure reaction kettle, adding 0.4 part of lauryl sodium sulfate and 0.2 part of alkyl polyoxyethylene ether sulfate, stirring and heating to 82-84 ℃;
(3) taking 10% of the nuclear layer pre-emulsion in the step (1) to the reaction kettle in the step (2), adding 0.1 part of initiator aqueous solution, preserving heat for 15 minutes at the temperature of 82-84 ℃, then dropwise adding the rest of the nuclear layer pre-emulsion for 30 minutes, and preserving heat for 1 hour;
(4) uniformly mixing 22 parts of methyl methacrylate, 16 parts of isooctyl acrylate, 1 part of hydroxyethyl methacrylate, 1.2 parts of methacrylic acid, 0.7 part of vinyl trimethoxy silane, 0.7 part of methacryloxypropyl trimethoxy silane, 0.4 part of SR-10 emulsifier of Idiaceae, 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 0.3 part of potassium persulfate, 30 parts of deionized water and 0.05 part of ammonia water in an emulsifying cylinder with the same size according to the mode of the step (1) to prepare a shell layer pre-emulsion for later use;
(5) maintaining the temperature of the reaction kettle at 82-84 ℃, dropwise adding the shell layer pre-emulsion in the step (4), wherein the dropwise adding time is 4 hours, and continuously preserving the heat for 1 hour at the temperature after the dropwise adding of the shell layer pre-emulsion is completed;
(6) cooling to 50 ℃, adding 1 part of ammonia water, adjusting the pH value of the emulsion to 7-9, slowly adding 1 part of 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, keeping the temperature at 50 ℃, stirring for 0.5 hour, and discharging.
Further, the above preparation method maintains the mechanical stirring state in the whole process
The acrylic ester emulsion for the high-gloss water-based finishing varnish with the lotus leaf effect, which is prepared by the method, has the solid content of 42.5 percent, the particle size of the emulsion of 105nm, the viscosity of within 1000CPS (3#12r), and the lowest film forming temperature of 5 ℃.
Example 4:
an acrylic ester emulsion with lotus leaf effect for high-gloss water-based finish varnish comprises the following raw materials in parts by weight: 20 parts of methyl methacrylate, 10 parts of isooctyl acrylate, 2.5 parts of crosslinking monomer (comprising glycidyl methacrylate and acrylamide), 2 parts of carboxyl monomer (methacrylic acid and itaconic acid), 1 part of organosilicon monomer (comprising vinyl trimethoxy silane and vinyl tri (beta-methoxy ethoxy) silane), 2.5 parts of emulsifier (comprising sodium dodecyl benzene sulfonate, alkyl polyoxyethylene ether sulfate, sodium allyloxy hydroxy propane sulfonate and SR-20 of Idiaceae company, Japan), 0.4 part of initiator (sodium persulfate), 2 parts of film-forming assistant (OE-300 of Issman company), 1.4 parts of pH regulator (ammonia water) and 57 parts of deionized water.
The preparation method of the acrylic ester emulsion with the lotus leaf effect for the high-gloss finishing varnish comprises the following steps:
(1) under the conditions of normal temperature and normal pressure, adding 7 parts of methyl methacrylate, 1 part of isooctyl acrylate, 0.5 part of glycidyl methacrylate, 0.2 part of methacrylic acid, 0.1 part of vinyl trimethoxy silane, 0.2 part of vinyl tri (beta-methoxyethoxy) silane, 0.4 part of SR-20 emulsifier of Japanese Adeca company, 0.1 part of sodium persulfate and 9 parts of deionized water into an emulsifying cylinder one by one, stirring at high speed for 30min, and uniformly mixing to obtain a nuclear layer pre-emulsion for later use;
(2) adding 27 parts of deionized water into a normal-pressure reaction kettle, adding 0.8 part of sodium dodecyl benzene sulfonate and 0.3 part of alkyl polyoxyethylene ether sulfate, stirring and heating to 81-83 ℃;
(3) taking 10% of the nuclear layer pre-emulsion in the step (1) to the reaction kettle in the step (2), adding 0.1 part of initiator aqueous solution, preserving heat for 15 minutes at the temperature of 81-83 ℃, then dropwise adding the rest nuclear layer pre-emulsion for 40 minutes, and preserving heat for 1 hour;
(4) uniformly mixing 13 parts of methyl methacrylate, 9 parts of isooctyl acrylate, 2 parts of acrylamide, 1 part of methacrylic acid, 0.8 part of itaconic acid, 0.3 part of vinyl trimethoxy silane, 0.4 part of vinyl tri (beta-methoxyethoxy) silane, 0.4 part of SR-20 emulsifier of Idecaco, Japan, 0.6 part of sodium allyloxy hydroxypropane sulfonate, 0.2 part of sodium persulfate, 21 parts of deionized water and 0.05 part of ammonia water in an emulsifying cylinder with the same size according to the mode of the step (1) to prepare a pre-emulsion of a shell layer for later use;
(5) maintaining the temperature of the reaction kettle at 81-83 ℃, dropwise adding the shell layer pre-emulsion in the step (4) for 4 hours, and continuously preserving the heat for 1 hour at the temperature after dropwise adding the shell layer pre-emulsion;
(6) after the temperature is reduced to 50 ℃, 1.35 parts of ammonia water is added, the pH value of the emulsion is adjusted to 7-9, then 2 parts of OE-300 of Islam company is slowly added, the temperature is kept at 50 ℃, and the mixture is stirred for 0.5 hour and then discharged.
Further, the above preparation method maintains the mechanical stirring state in the whole process
The acrylic ester emulsion for the high-gloss water-based finishing varnish with the lotus leaf effect prepared by the method has the solid content of 40 percent, the particle size of the emulsion is 95nm, the viscosity is within 1000CPS (3#12r), and the lowest film forming temperature is 5 ℃.
Example 5:
an acrylic ester emulsion with lotus leaf effect for high-gloss water-based finish varnish comprises the following raw materials in parts by weight: 29 parts of methyl methacrylate, 20 parts of isooctyl acrylate, 0.5 part of a crosslinking monomer (acrylamide), 3 parts of a carboxyl monomer (acrylic acid and itaconic acid), 2.5 parts of an organosilicon monomer (comprising methacryloxypropyltrimethoxysilane and vinyl tris (beta-methoxyethoxy) silane), 3 parts of an emulsifier (comprising sodium dodecyl sulfate, 2-acrylamido-2-methylpropanesulfonic acid, SR-10 and SR-20 of Idiaceae, Japan), 0.6 part of an initiator (ammonium persulfate), 2 parts of a film-forming aid (2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate), 5 parts of a pH regulator (a 15% mass fraction sodium hydroxide solution), and 65 parts of deionized water.
The preparation method of the acrylic ester emulsion with the lotus leaf effect for the high-gloss finishing varnish comprises the following steps:
(1) under the conditions of normal temperature and normal pressure, adding 6 parts of methyl methacrylate, 0.5 part of isooctyl acrylate, 0.6 part of acrylic acid, 0.5 part of methacryloxypropyltrimethoxysilane, 0.3 part of SR-10 emulsifier of Idecaco, Japan, 0.1 part of ammonium persulfate and 13 parts of deionized water into an emulsifying cylinder one by one, stirring at a high speed for 30min to uniformly mix the components to be used as a nuclear layer pre-emulsion for later use;
(2) adding 25 parts of deionized water into a normal-pressure reaction kettle, adding 1 part of sodium dodecyl sulfate, stirring and heating to 83-85 ℃;
(3) taking 10% of the nuclear layer pre-emulsion in the step (1) to the reaction kettle in the step (2), adding 0.2 part of initiator aqueous solution, preserving heat for 15 minutes at the temperature of 83-85 ℃, then dropwise adding the rest of the nuclear layer pre-emulsion for 55 minutes, and preserving heat for 1 hour;
(4) uniformly mixing 23 parts of methyl methacrylate, 19.5 parts of isooctyl acrylate, 0.5 part of acrylamide, 1.4 parts of acrylic acid, 1 part of itaconic acid, 1 part of methacryloxypropyltrimethoxysilane, 1 part of vinyl tri (beta-methoxyethoxy) silane, 0.6 part of SR-20 emulsifier of Japan Aidicco, 1.1 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 0.3 part of ammonium persulfate and 27 parts of deionized water in an emulsifying cylinder with the same scale according to the mode of the step (1) to prepare a shell layer pre-emulsion for later use;
(5) maintaining the temperature of the reaction kettle at 83-85 ℃, dropwise adding the shell layer pre-emulsion in the step (4) for 4 hours, and continuously preserving the heat for 1 hour at the temperature after dropwise adding the shell layer pre-emulsion;
(6) cooling to 50 ℃, adding 5 parts of 15% sodium hydroxide solution by mass, adjusting the pH value of the emulsion to 7-9, slowly adding 2 parts of 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, keeping the temperature at 50 ℃, stirring for 0.5 hour, and discharging.
Further, the above preparation method maintains the mechanical stirring state in the whole process
The acrylic ester emulsion for the high-gloss water-based finishing varnish with the lotus leaf effect, which is prepared by the method, has the solid content of 42 percent, the particle size of the emulsion is 85nm, the viscosity is within 1000CPS (3#12r), and the lowest film forming temperature is 5 ℃.
Example 6:
the emulsions prepared in examples 1 to 5 were formulated into aqueous high gloss finishes according to the following formulation Table 1.
TABLE 1 aqueous high gloss finish varnish formulation
The detection method comprises the following steps: the coating is carried out according to the standard of the finishing varnish for HB/T5065-2016 architectural coatings, the stain resistance is carried out by a B method (the lower the reduction rate coefficient is, the better the performance is), the water resistance and the water white resistance are carried out on a multi-color paint base material, and the bubbling and the discoloration conditions are observed.
The test results are shown in table 2:
TABLE 2 detection results of water-based high-gloss top-coat varnish
The above results show that: compared with the products sold in the market, the product of the invention has more excellent stain resistance, water resistance and water-white resistance, and is completely suitable for being used as exterior wall high-gloss finishing varnish.
Although the preferred embodiments of the present invention have been disclosed, it should be understood that they are not intended to limit the invention, but various changes and modifications may be made therein by those skilled in the art without departing from the spirit and scope of the invention, and it is intended that the scope of the invention be defined by the appended claims.
Claims (10)
1. The acrylic ester emulsion with the lotus leaf effect for the high-gloss water-based finish paint is characterized by comprising the following raw materials in parts by weight: 20-30 parts of methyl methacrylate, 10-20 parts of isooctyl acrylate, 0.1-3 parts of crosslinking monomer, 1-3 parts of carboxyl monomer, 1-3 parts of organosilicon monomer, 1.1-3 parts of emulsifier, 0.3-1 part of initiator, 1-5 parts of film-forming assistant, 0.5-5.5 parts of pH regulator and 50-65 parts of deionized water;
the preparation method of the acrylate emulsion comprises the following steps:
(1) under the conditions of normal temperature and normal pressure, adding 3-15 parts of methyl methacrylate, 0-3 parts of isooctyl acrylate, 0-1 part of crosslinking monomer, 0.2-1.5 parts of carboxyl monomer, 0.3-0.8 part of organosilicon monomer, 0.1-0.6 part of emulsifier, 0.1-0.3 part of initiator and 5-15 parts of deionized water into an emulsifying cylinder one by one, stirring at high speed for 30min to uniformly mix the materials to be used as a nuclear layer pre-emulsion for later use;
(2) adding 20-30 parts of deionized water into a normal-pressure reaction kettle, adding 0.5-1.5 parts of emulsifier, stirring and heating to 80-85 ℃;
(3) adding 5-20% of the nuclear layer pre-emulsion prepared in the step (1) into the reaction kettle in the step (2), adding 0.1-0.5 part of initiator aqueous solution, preserving heat for 10-30 minutes at the temperature of 80-85 ℃, then dropwise adding the rest of the nuclear layer pre-emulsion for 30-60 minutes, and preserving heat for 1 hour;
(4) uniformly mixing the rest parts of methyl methacrylate, isooctyl acrylate, a crosslinking monomer, a carboxyl monomer, an organic silicon monomer, an emulsifier, an initiator, deionized water and 0-0.5 part of pH regulator in an emulsification cylinder with the same scale according to the mode of the step (1) to obtain a shell pre-emulsion for later use;
(5) maintaining the temperature of the reaction kettle at 80-85 ℃, dropwise adding the shell layer pre-emulsion prepared in the step (4) for 4 hours, and continuously preserving heat for 1 hour at the temperature after dropwise adding the shell layer pre-emulsion;
(6) cooling to 50 ℃, adding 0.5-5 parts of pH regulator, regulating the pH value of the emulsion to 7-9, slowly adding 1-5 parts of film-forming assistant, keeping the temperature at 50 ℃, stirring for 0.5 hour, and discharging.
2. The acrylic ester emulsion for high gloss water-based finish with lotus effect of claim 1, wherein the crosslinking monomer is one or more of ethylene glycol dimethacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate and acrylamide.
3. The acrylic ester emulsion for high gloss water-based finish with lotus effect of claim 1, wherein the carboxyl monomer is one or more of acrylic acid, methacrylic acid and itaconic acid.
4. The acrylic ester emulsion for high gloss water-based finish paint with lotus leaf effect according to claim 1, wherein the organosilicon monomer is one or more of vinyl trimethoxy silane, methacryloxypropyl trimethoxy silane, and vinyl tri (beta-methoxyethoxy) silane.
5. The acrylic ester emulsion for high gloss water-based finish paint with lotus leaf effect according to claim 1, wherein the emulsifier is one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, alkyl polyoxyethylene ether sulfate, sodium allyloxy hydroxypropane sulfonate, sodium 2-acrylamido-2-methylpropane sulfonate, SR-10, SR-20 of adi corporation of japan.
6. The acrylic ester emulsion for high gloss water-based finish paint with lotus effect according to claim 1, wherein the initiator is one or more of ammonium persulfate, potassium persulfate and sodium persulfate.
7. The acrylic ester emulsion for high gloss water-based finish paint with lotus leaf effect according to claim 1, wherein the film forming assistant is one or more than two of 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, propylene glycol phenyl ether, propylene glycol butyl ether, OE-300 of Iseman.
8. The acrylic ester emulsion for high gloss water-based finish paint with lotus leaf effect of claim 1, wherein the pH regulator is one or more of ammonia, sodium hydroxide and potassium hydroxide.
9. A method for preparing the acrylic ester emulsion with lotus leaf effect for high gloss finishing varnish of any one of claims 1 to 8, which is characterized by comprising the following steps:
(1) under the conditions of normal temperature and normal pressure, adding 3-15 parts of methyl methacrylate, 0-3 parts of isooctyl acrylate, 0-1 part of crosslinking monomer, 0.2-1.5 parts of carboxyl monomer, 0.3-0.8 part of organosilicon monomer, 0.1-0.6 part of emulsifier, 0.1-0.3 part of initiator and 5-15 parts of deionized water into an emulsifying cylinder one by one, stirring at high speed for 30min to uniformly mix the materials to be used as a nuclear layer pre-emulsion for later use;
(2) adding 20-30 parts of deionized water into a normal-pressure reaction kettle, adding 0.5-1.5 parts of emulsifier, stirring and heating to 80-85 ℃;
(3) adding 5-20% of the nuclear layer pre-emulsion prepared in the step (1) into the reaction kettle in the step (2), adding 0.1-0.5 part of initiator aqueous solution, preserving heat for 10-30 minutes at the temperature of 80-85 ℃, then dropwise adding the rest of the nuclear layer pre-emulsion for 30-60 minutes, and preserving heat for 1 hour;
(4) uniformly mixing the rest parts of methyl methacrylate, isooctyl acrylate, a crosslinking monomer, a carboxyl monomer, an organic silicon monomer, an emulsifier, an initiator, deionized water and 0-0.5 part of pH regulator in an emulsification cylinder with the same scale according to the mode of the step (1) to obtain a shell pre-emulsion for later use;
(5) maintaining the temperature of the reaction kettle at 80-85 ℃, dropwise adding the shell layer pre-emulsion prepared in the step (4) for 4 hours, and continuously preserving heat for 1 hour at the temperature after dropwise adding the shell layer pre-emulsion;
(6) cooling to 50 ℃, adding 0.5-5 parts of pH regulator, regulating the pH value of the emulsion to 7-9, slowly adding 1-5 parts of film-forming assistant, keeping the temperature at 50 ℃, stirring for 0.5 hour, and discharging.
10. The method of claim 9, wherein the mechanical agitation is maintained throughout the method.
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| CN110358015B (en) * | 2019-06-26 | 2022-01-07 | 嘉宝莉化工集团股份有限公司 | Self-lubricating hydrophobic silicone-acrylic emulsion and preparation method and application thereof |
| CN111087546B (en) * | 2019-12-24 | 2022-08-19 | 佛山市顺德区巴德富实业有限公司 | Industrial water-based high-gloss light-weight anticorrosive acrylic emulsion and preparation method thereof |
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| CN111363081A (en) * | 2020-04-29 | 2020-07-03 | 广东巴德富新材料有限公司 | Acrylate emulsion for stain-resistant water-based finish varnish and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575398A (en) * | 2009-06-05 | 2009-11-11 | 天津碧海蓝天水性高分子材料有限公司 | Organosilicon-modified acrylate emulsion and preparation method of coating agent for powder-free gloves |
| JP2010059379A (en) * | 2008-09-08 | 2010-03-18 | Asahi Kasei Chemicals Corp | Highly durable acrylic emulsion |
| CN106519126A (en) * | 2016-10-27 | 2017-03-22 | 华南理工大学 | Fluorosilicone-modified polyacrylate emulsion as well as preparing method and application thereof |
| CN106608943A (en) * | 2016-11-22 | 2017-05-03 | 佛山市顺德区巴德富实业有限公司 | One-component acrylic ester matte core-shell emulsions with good anti-water-white performance and preparation method and application thereof |
| CN106749934A (en) * | 2016-12-12 | 2017-05-31 | 上海三瑞高分子材料股份有限公司 | A kind of terrace polishing agent polyacrylate dispersion and preparation method |
-
2018
- 2018-12-13 CN CN201811523010.8A patent/CN109705256B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010059379A (en) * | 2008-09-08 | 2010-03-18 | Asahi Kasei Chemicals Corp | Highly durable acrylic emulsion |
| CN101575398A (en) * | 2009-06-05 | 2009-11-11 | 天津碧海蓝天水性高分子材料有限公司 | Organosilicon-modified acrylate emulsion and preparation method of coating agent for powder-free gloves |
| CN106519126A (en) * | 2016-10-27 | 2017-03-22 | 华南理工大学 | Fluorosilicone-modified polyacrylate emulsion as well as preparing method and application thereof |
| CN106608943A (en) * | 2016-11-22 | 2017-05-03 | 佛山市顺德区巴德富实业有限公司 | One-component acrylic ester matte core-shell emulsions with good anti-water-white performance and preparation method and application thereof |
| CN106749934A (en) * | 2016-12-12 | 2017-05-31 | 上海三瑞高分子材料股份有限公司 | A kind of terrace polishing agent polyacrylate dispersion and preparation method |
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