CN109517104B - Emulsion for exterior wall coating and preparation method thereof - Google Patents
Emulsion for exterior wall coating and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Abstract
The invention discloses an emulsion for exterior wall coating and a preparation method thereof; the preparation method comprises the following steps: (1) respectively and uniformly mixing the component A and the component B to obtain a pre-emulsified component A and a pre-emulsified component B; (2) in the presence of water, an emulsifier, a pH regulator and an initiator, dropwise adding the pre-emulsified component A into a reactor at a speed of 50-100ml/h for polymerization reaction, dropwise adding the pre-emulsified component B into the reactor, and simultaneously adjusting the dropwise adding speed of the component A to ensure that A, B components are completely dropwise added at the same time, and continuously reacting after the dropwise adding is completed to obtain the emulsion for the exterior wall coating; wherein, the component A comprises soft monomers, optional hard monomers, acrylic acid, an emulsifier and water; the component B comprises hard monomers, optional soft monomers, acrylonitrile, an emulsifier and water. The emulsion synthesized by the method has a structure similar to a core-shell structure, and the structure of a soft core and a hard shell determines that the prepared emulsion has the characteristics of good flexibility and high modulus.
Description
Technical Field
The invention belongs to the technical field of water-based emulsion, and particularly relates to emulsion for an exterior wall coating and a preparation method thereof.
Background
The stain resistance of the coating is an important performance index of the exterior wall coating in the practical application process, the insufficient stain resistance seriously affects the decorative effect and the service life of the exterior wall coating, and simultaneously is a key factor for restricting the application range of the coating. Especially in recent years, the air quality of cities in China is generally poor, and after a paint film is used for a period of time, dust deposition pollution of different degrees generally exists, which seriously influences the application and popularization of the paint in the fields of exposed engineering and decoration.
The polymer emulsion is used as a main film forming substance in a water-based paint formula, is also a key factor influencing and determining the stain resistance of the paint, and the paint can have excellent stain resistance only by improving the glass transition temperature of the emulsion and ensuring that the emulsion has higher modulus at normal temperature after film forming. However, the high glass transition temperature leads to a high film-forming temperature of the coating, which makes the coating difficult to form at normal temperature or low temperature, and even if the coating is formed, the modulus is too high, which causes the problems of poor elasticity and easy cracking.
Disclosure of Invention
The invention aims to provide an emulsion for an exterior wall coating and a preparation method thereof; the prepared emulsion for the exterior wall coating is easy to form a film at low temperature, has good stain resistance and excellent aging resistance, and solves the problem that the low-temperature film forming and the stain resistance of the aqueous emulsion for the exterior wall coating and the roof coating cannot be compatible; the synthesis process is simple, and industrial production can be realized.
In order to achieve the above objects, one aspect of the present invention provides a method for preparing an emulsion for exterior wall coating materials, the method comprising:
(1) respectively and uniformly mixing the component A and the component B to obtain a pre-emulsified component A and a pre-emulsified component B;
(2) dropwise adding the pre-emulsified component A into a reactor at a speed of 50-100ml/h in the presence of water, an emulsifier, a pH regulator and an initiator for polymerization reaction, then dropwise adding the pre-emulsified component B into the reactor, and simultaneously adjusting the dropwise adding speed of the component A to ensure that the components AB are dropwise added simultaneously and then continuously react after the dropwise adding is finished, thus obtaining the emulsion for the exterior wall coating;
wherein the component A comprises: soft monomers, optionally hard monomers, acrylic acid, emulsifiers and water; the component B comprises: hard monomers, optionally soft monomers, acrylonitrile, emulsifiers and water.
The invention also provides an emulsion for the exterior wall coating prepared by the preparation method.
The technical scheme of the invention has the following advantages:
(1) the emulsion synthesized by the method has a structure similar to a core-shell structure, and the structure of a soft core and a hard shell determines that the prepared emulsion has the characteristics of good flexibility and high modulus.
(2) The invention adopts a continuous polymerization method, realizes the continuous change of the high polymer glass transition temperature in the latex particles and enhances the compatibility among molecules in the latex particles.
(3) The emulsion synthesized by the method has no obvious glass transition temperature (Tg value), has the characteristic of obviously reducing the lowest film forming temperature compared with the conventional emulsion, and effectively improves the low-temperature film forming property of the emulsion. The prepared emulsion has lower modulus at low temperature, better flexibility, higher modulus at normal temperature or high temperature, stronger toughness and excellent stain resistance of the emulsion film.
(4) The invention adopts the pre-emulsification process and selects proper emulsifier, which can well control the particle size and viscosity of the emulsion, thereby improving the low-temperature film-forming property of the emulsion to a certain extent.
(5) The synthesis process is simple and controllable, and industrial production can be realized.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
One aspect of the present invention provides a method for preparing an emulsion for exterior wall coatings, the method comprising:
(1) respectively and uniformly mixing the component A and the component B to obtain a pre-emulsified component A and a pre-emulsified component B;
(2) dropwise adding the pre-emulsified component A into a reactor at a speed of 50-100ml/h in the presence of water, an emulsifier, a pH regulator and an initiator for polymerization reaction, then dropwise adding the pre-emulsified component B into the reactor, and simultaneously adjusting the dropwise adding speed of the component A to ensure that the components AB are dropwise added simultaneously and then continuously react after the dropwise adding is finished, thus obtaining the emulsion for the exterior wall coating;
wherein the component A comprises: soft monomers, optionally hard monomers, acrylic acid, emulsifiers and water; the component B comprises: hard monomers, optionally soft monomers, acrylonitrile, emulsifiers and water.
The invention realizes the synthesis process of continuously changing the proportion of soft and hard monomers in the polymerization process, the polymer particles form a similar core-shell structure, the core is soft and hard, more emulsion shows rigidity and good stain resistance because the hard monomers have higher surface content in the emulsion particles, the glass transition temperature of the emulsion particles is continuously changed, and the formed adhesive film has a wider temperature transfer interval, thereby reducing the glass transition temperature (MFT) of the emulsion. At the beginning of the polymerization reaction, the soft monomer content is high and the hard monomer content is low, forming the "core" of the latex particles. In the middle section of the polymerization reaction, the soft monomer and the hard monomer are continuously consumed, and the hard monomer and the soft monomer are continuously added, so that the amounts of the soft monomer and the hard monomer are nearly equal. At the end of the polymerization reaction, the soft monomer is depleted and the hard monomer content is at its maximum, continuing to form a "shell" on the surface of the latex particles. The content of the soft and hard monomers is continuously changed in the whole reaction process, so that the molecular chain of the part in the finally generated latex particle is continuously changed from the core to the shell, the glass transition temperature of the generated polymer molecule is continuously changed from low to high, and the formed latex film has a wider temperature transfer range, so that the MFT of the latex is reduced.
In the invention, the particle size of the emulsion particles has obvious influence on the MFT of the emulsion, the smaller the particle size is, the larger the capillary pressure and the total specific surface area of the particles are in the emulsion film forming process, which is beneficial to promoting the deformation of the emulsion particles to form a film, and further reducing the MFT of the emulsion to a certain extent.
In the invention, a pre-emulsification process is adopted in the step (1), so that a plurality of small micelles are formed in the pre-emulsified A, B component, the polydispersity of an emulsion system of a polymerization reaction is excellent, the acting force and the steric hindrance effect of an emulsifier on molecules are further improved, the particle size and the viscosity of the finally formed emulsion are further influenced, and the MFT of the emulsion is further reduced.
According to the invention, preferably, in the step (2), the pre-emulsified component A is dripped into the reactor at the speed of 50-100ml/h for polymerization, the pre-emulsified component B is dripped into the reactor after 15-45min, and the dripping of the pre-emulsified component B is controlled within 1.5-3 h.
According to the present invention, it is preferable that, in the step (2), the reaction temperature is controlled to be 80 to 85 ℃.
According to the invention, preferably, the soft monomer is butyl acrylate and the hard monomer is methyl methacrylate.
According to the invention, preferably, the emulsifier is a mixture of sodium dodecyl sulfate and alkylphenol ethoxylates, and the mass ratio of the sodium dodecyl sulfate to the alkylphenol ethoxylates is 1-2: 1.
the emulsifier system of the invention is a mixed complex system of an anionic emulsifier (sodium dodecyl sulfate) and a nonionic emulsifier (alkylphenol ethoxylates); the nonionic emulsifier can not be dissociated into ions in water, an adsorption layer is formed on the surface of the polymer to prevent polymer molecules from colliding with each other, the dispersion stability of the polymer particles is improved, the anionic emulsifier is hydrolyzed into anionic groups in water, an electric double layer is formed on the surface of the emulsion particles, the emulsion particles are stabilized by electrostatic repulsion, and the two emulsifiers are mixed according to a certain proportion for use, so that the emulsification of monomers and the temperature of the polymer are facilitated, and the viscosity and the particle size of the emulsion can be well controlled, so that the MFT of the emulsion is influenced.
According to the present invention, preferably, the PH adjusting agent is sodium bicarbonate; the initiator is persulfate, preferably ammonium persulfate.
According to the present invention, preferably, in the a component, the mass ratio of the soft monomer, the optional hard monomer, acrylic acid, the emulsifier and water is (40-80): (0-30): (1-3): 1: (40-60);
in the component B, the mass ratio of the hard monomer, the optional soft monomer, the acrylonitrile, the emulsifier and the water is (75-115): (0-25): (4-7): 1: (40-65);
in the step (2), the mass ratio of the water, the emulsifier, the pH regulator and the initiator is (50-90): 1: (0.2-0.4): (0.4-0.8).
According to the present invention, it is preferable that, in the step (2), the polymerization reaction is carried out in the presence of water, an emulsifier, a pH adjuster, an initiator and nitrogen.
Preferably, in the step (2), water, an emulsifier and a pH regulator are added into a reactor, the reactor is stirred and heated to 80-85 ℃, nitrogen is introduced into the reactor to form protective gas, then an initiator is added, and finally the emulsified A, B components are sequentially added dropwise to carry out polymerization reaction.
According to the invention, preferably, in step (1), the mixing time is 10-20 min;
in the step (2), the time for continuing the reaction after the dripping is finished is 2-3 h.
The invention also provides an emulsion for the exterior wall coating prepared by the preparation method.
The invention is further illustrated by the following examples:
the emulsifiers used in the following examples and comparative examples are mixtures of sodium lauryl sulfate and alkylphenol ethoxylates, the mass ratio of sodium lauryl sulfate to alkylphenol ethoxylates being 2: 1.
examples 1 to 4
The dosage of each raw material of the emulsion for the exterior wall coating provided in the examples 1 to 4 is specifically shown in table 1, and the preparation method comprises the following steps:
(1) stirring all the substances of the component A for 15min at normal temperature, uniformly mixing, and pre-emulsifying to obtain a pre-emulsified component A;
(2) stirring all the substances of the component B for 15min at normal temperature, uniformly mixing and pre-emulsifying to obtain a pre-emulsified component B;
(3) adding deionized water, an emulsifier and sodium bicarbonate into a reactor according to a ratio, stirring and heating to 83 ℃, introducing nitrogen into the reactor, and adding ammonium persulfate after 2 min; slowly dripping the pre-emulsified component A into a reactor at a speed of 75ml/h, after dripping for 30min, dripping the pre-emulsified component B into the reactor at a constant speed, controlling the dripping speed of the component B to be 2h, regulating the dripping speed of the component A to ensure that A, B components are dripped simultaneously, finally keeping the temperature at 83 ℃ for 2h, naturally cooling, filtering and discharging; the reaction temperature was controlled to 83 ℃ throughout the reaction.
TABLE 1
Comparative example 1
The dosage of the raw materials of the emulsion for the exterior wall coating provided by the comparative example is the same as that of the emulsion in the example 1, and the preparation method comprises the following steps:
(1) stirring all the substances of the component A for 15min at normal temperature, uniformly mixing, and pre-emulsifying to obtain a pre-emulsified component A;
(2) stirring all the substances of the component B for 15min at normal temperature, uniformly mixing and pre-emulsifying to obtain a pre-emulsified component B;
(3) adding deionized water, an emulsifier and sodium bicarbonate into a reactor according to a ratio, stirring and heating to 83 ℃, introducing nitrogen into the reactor, and adding ammonium persulfate after 2 min; then, slowly dripping the pre-emulsified A, B into the reactor at the speed of 75ml/h, accelerating the dripping speed of A, B components after 30min to ensure that A, B components are completely dripped within 2h, finally keeping the temperature at 83 ℃ for 2h, naturally cooling, filtering and discharging; the reaction temperature was controlled to 83 ℃ throughout the reaction.
Test example
The emulsions prepared in examples 1 to 4 and comparative example 1 were subjected to a performance test in accordance with GB T11175-2002 Standard "synthetic resin emulsion test method", the specific test results are shown in Table 2. The theoretical Tg values in Table 2 are calculated from the amounts of monomers and are not measured (the emulsions of examples 1 to 4 were tested and had no significant glass transition temperature, only film formation temperature).
TABLE 2
As shown in Table 2, the film forming temperature of examples 1 to 4 was significantly lower than that of comparative example 1, and the stain resistance was better than that of comparative example 1, and since examples 1 to 4 were prepared by the method of the present invention and comparative example 1 was prepared by the conventional method, while the emulsion of example 1 was the same in the components and amounts as those of comparative example 1 except for the preparation method, it was found that the film forming temperature of the emulsion prepared by the method of the present invention was lower than that of the emulsion prepared by the conventional method, and the stain resistance was better than that of the emulsion prepared by the conventional method.
As can be seen from tables 1 and 2, examples 1 and 2 were distinguished in terms of the amount of emulsifier used, and the others were kept consistent, and it can be seen that the amount of emulsifier used was increased, the particle size of the emulsion became smaller, the film-forming temperature of the emulsion was further decreased, and the low-temperature film-forming property was improved.
As can be seen from tables 1 and 2, examples 4, 1 and 3 were adjusted in the amounts of soft and hard monomers in A, B components, and the amounts of soft monomers in A component were decreased and the amounts of hard monomers in A component were increased, while those in B component were reversed, and the types of monomers and the total amounts of monomers in the three formulations were completely the same. From the test results, the reduction of the hard monomer dosage in the component B can cause the film forming temperature of the emulsion to be reduced, the storage modulus to be reduced at normal temperature and the stain resistance of the emulsion to be reduced, which is mainly caused by the change of the molecular structure of the latex particles and the reduction of the Tg value of the polymer chain of the shell layer.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (9)
1. A preparation method of emulsion for exterior wall coating is characterized by comprising the following steps:
(1) respectively and uniformly mixing the component A and the component B to obtain a pre-emulsified component A and a pre-emulsified component B;
(2) dropwise adding the pre-emulsified component A into a reactor at a speed of 50-100ml/h in the presence of water, an emulsifier, a pH regulator and an initiator for polymerization reaction, then dropwise adding the pre-emulsified component B into the reactor, and simultaneously adjusting the dropwise adding speed of the component A to ensure that A, B components are completely dropwise added at the same time and continuously react after the dropwise adding is completed to obtain the emulsion for the exterior wall coating;
wherein the component A consists of the following components: soft monomers, optionally hard monomers, acrylic acid, emulsifiers and water; the component B consists of the following components: hard monomers, optionally soft monomers, acrylonitrile, emulsifiers and water;
the emulsifier is a mixture of sodium dodecyl sulfate and alkylphenol polyoxyethylene, and the mass ratio of the sodium dodecyl sulfate to the alkylphenol polyoxyethylene is (1-2): 1;
in the component A, the mass ratio of the soft monomer, the optional hard monomer, the acrylic acid, the emulsifier and the water is (40-80): (0-30): (1-3): 1: (40-60);
in the component B, the mass ratio of the hard monomer, the optional soft monomer, the acrylonitrile, the emulsifier and the water is (75-115): (0-25): (4-7): 1: (40-65);
the soft monomer is butyl acrylate, and the hard monomer is methyl methacrylate.
2. The preparation method according to claim 1, wherein in the step (2), the pre-emulsified component A is dropwise added into the reactor at a speed of 50-100ml/h for polymerization, the pre-emulsified component B is dropwise added into the reactor after 15-45min, and the pre-emulsified component B is controlled to be completely dropwise added within 1.5-3 h.
3. The production process according to claim 1, wherein in the step (2), the reaction temperature is controlled to 80 to 85 ℃.
4. The production method according to claim 1, wherein the pH adjuster is sodium bicarbonate; the initiator is persulfate.
5. The production method according to claim 4, wherein the initiator is ammonium persulfate.
6. The production method according to claim 1,
in the step (2), the mass ratio of the water, the emulsifier, the pH regulator and the initiator is (50-90): 1: (0.2-0.4): (0.4-0.8).
7. The production method according to claim 1, wherein in the step (2), the polymerization reaction is carried out in the presence of water, an emulsifier, a pH adjuster, an initiator and nitrogen.
8. The production method according to claim 1,
in the step (1), the mixing time is 10-20 min;
in the step (2), the time for continuing the reaction after the dripping is finished is 2-3 h.
9. The emulsion for exterior wall coating prepared by the preparation method of any one of claims 1 to 8.
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