CN110964152B - Quick-drying core-shell structure hydroxyl acrylic emulsion and preparation method and application thereof - Google Patents
Quick-drying core-shell structure hydroxyl acrylic emulsion and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a quick-drying core-shell structure hydroxyl acrylic emulsion and a preparation method and application thereof. The quick-drying type core-shell structure hydroxyl acrylic emulsion is prepared from the following components in percentage by mass of 1: and (1) carrying out emulsion polymerization twice on a core layer monomer and a shell layer monomer continuously to obtain the core layer monomer, wherein the core layer monomer consists of methyl methacrylate, styrene, butyl acrylate and ethylene glycol diacrylate, and the shell layer monomer consists of methyl methacrylate, styrene, butyl acrylate, acrylic acid or/and methacrylic acid, hydroxypropyl acrylate or/and hydroxyethyl methacrylate, hydroxyethyl acrylate, isobornyl acrylate or/and isobornyl methacrylate or/and cyclohexyl acrylate or/and cyclohexyl methacrylate. The coating prepared from the hydroxyl acrylic emulsion has the advantages of high drying speed, high compactness of the formed coating, good corrosion resistance, high glossiness and high distinctness of image, and can be applied to quick-drying acrylic polyurethane coatings.
Description
Technical Field
The invention relates to a quick-drying core-shell structure hydroxyl acrylic emulsion and a preparation method and application thereof.
Background
The bi-component acrylic polyurethane coating has good decorative performance and corrosion resistance, and is widely applied to the fields of heavy-duty anticorrosive coatings, automobile coatings, wood coatings and the like. In recent years, under the pressure of environmental protection, water-based acrylic polyurethane coatings gradually replace solvent-based acrylic polyurethane coatings, and are widely popularized and applied.
The two-component water-based acrylic polyurethane coating consists of water-based hydroxyl acrylic resin (hydroxypropyl resin for short) and an isocyanate curing agent. The water-based hydroxypropyl resin comprises a water dispersion type and an emulsion type, wherein the water dispersion type hydroxypropyl resin is a water dispersion formed by dispersing acrylic monomers in water through hydrophilic groups in the resin after polymerization in a solvent, the VOC content of the water-based hydroxypropyl resin is high, the production process is complex, the production cost is high, the emulsion type hydroxypropyl resin is prepared through emulsion polymerization, the molecular weight of the emulsion type hydroxypropyl resin is high, a formed paint film has good mechanical performance, and the VOC content is extremely low. Therefore, the emulsion type hydroxypropyl resin has better application prospect.
However, the coating prepared from the emulsion type hydroxypropyl resin contains more hydrophilic substances (such as an emulsifier, a dispersant, a wetting agent and the like), and the latent heat of evaporation of water is high, so that the drying speed of a coating film is slow. At present, the method for improving the drying speed of the coating mainly comprises the following two methods: 1) the addition amount of the isocyanate curing agent is increased, but the price of the curing agent is very high, and the increase of the dosage of the curing agent can cause the cost of the coating to be greatly increased; 2) increasing T of resin g But high T g The crosslinking is insufficient, the glossiness of the coating is low, the distinctness of image is poor, and the decorative performance and the corrosion resistance of the coating are reduced.
Both CN 101942269A, CN 102153691A, CN 102161770a and CN 102627720a disclose methods for synthesizing hydroxypropyl resin aqueous dispersion for quick-drying coating, but the synthesized resin is aqueous dispersion type resin, and the preparation process is complex, the cost is high, and the VOC content is high.
Therefore, it is necessary to develop an emulsion type hydroxy acrylic resin suitable for a quick-drying type coating.
Disclosure of Invention
The invention aims to provide a quick-drying type core-shell structure hydroxyl acrylic emulsion and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a quick-drying type hydroxyl acrylic emulsion with a core-shell structure is prepared from the following components in percentage by mass of 1: (1-9) carrying out emulsion polymerization twice on the core layer monomer and the shell layer monomer continuously to obtain the polymer;
the core layer monomer comprises the following components in percentage by mass:
methyl methacrylate: 60% -94%;
styrene: 0 to 15 percent;
butyl acrylate: 6 to 25 percent;
ethylene glycol diacrylate: 0 to 1.2 percent;
the shell layer monomer comprises the following components in percentage by mass:
methyl methacrylate: 0 to 37 percent;
styrene: 0 to 15 percent;
butyl acrylate: 30% -46%;
acrylic acid and/or methacrylic acid: 0.5 to 4 percent;
hydroxypropyl acrylate or/and hydroxyethyl methacrylate: 15% -52%;
hydroxyethyl acrylate: 0 to 26 percent;
isobornyl acrylate or/and isobornyl methacrylate or/and cyclohexyl acrylate or/and cyclohexyl methacrylate: 1 to 8 percent.
Preferably, the hydroxyl content of the quick-drying type core-shell structure hydroxyl acrylic emulsion is 1.5-4%.
Preferably, the glass transition temperature of the latex particles in the quick-drying core-shell structure hydroxyl acrylic emulsion is 10-30 ℃, the glass transition temperature of the core layer of the latex particles is 50-90 ℃, and the glass transition temperature of the shell layer of the latex particles is-15-5 ℃.
Note: glass transition temperature (T) g ) Calculated according to Fox formula: 1/T g ＝W 1 /T g1 +W 2 /T g2 +…+W n /T gn Wherein W is i Is the mass fraction of the i-th monomer, T gi The glass transition temperature of the ith monomer, corresponding to the homopolymer, is reported in units of K.
The preparation method of the quick-drying type core-shell structure hydroxyl acrylic emulsion comprises the following steps:
1) adding water into a core layer monomer and an emulsifier, and uniformly dispersing to obtain a pre-emulsion A;
2) adding water into a shell monomer, a chain transfer agent and an emulsifier, and uniformly dispersing to obtain a pre-emulsion B;
3) adding water into an initiator to disperse uniformly to obtain an initiator solution;
4) adding water into a pH buffering agent and an emulsifier, uniformly dispersing and heating to 75-85 ℃, adding a part of pre-emulsion A and a part of initiator solution, performing seed polymerization, adding the rest of pre-emulsion A and a part of initiator solution, performing emulsion polymerization of a core layer, adding a part of pre-emulsion B and the rest of initiator solution, performing emulsion polymerization of a shell layer, cooling to 70-74 ℃, adjusting the pH value to 4-5, adding a post-elimination initiator and a post-elimination reducing agent, performing heat preservation reaction to eliminate residual monomers, cooling to 40-50 ℃, adjusting the pH value to 7-9, cooling to room temperature, and filtering to obtain the quick-drying core-shell structure hydroxyl acrylic emulsion.
Preferably, the emulsifier in the steps 1), 2) and 4) is alkylphenol polyoxyethylene ether sulfate, and the total addition amount is 0.8-2% of the total mass of the core layer monomer and the shell layer monomer.
Preferably, the chain transfer agent in the step 2) is dodecyl mercaptan, and the addition amount of the dodecyl mercaptan is 0.2-1.5% of the total mass of the core layer monomer and the shell layer monomer.
Preferably, the initiator in the step 3) is ammonium persulfate, and the addition amount of the initiator is 0.1-0.6% of the total mass of the core layer monomer and the shell layer monomer.
Preferably, the pH buffering agent in the step 4) is baking soda, and the addition amount of the pH buffering agent is 0.1-2% of the total mass of the core layer monomer and the shell layer monomer.
Preferably, the post-elimination initiator in the step 4) is tert-butyl hydroperoxide, and the addition amount of the post-elimination initiator is 0.1-0.5% of the total mass of the core layer monomer and the shell layer monomer.
Preferably, the post-elimination reducing agent in the step 4) is at least one of sodium thiosulfate and sodium bisulfite, and the addition amount is 0.1-0.5% of the total mass of the core layer monomer and the shell layer monomer.
A quick-drying water-based acrylic polyurethane coating contains the quick-drying core-shell structure hydroxyl acrylic emulsion.
Preferably, the quick-drying water-based acrylic polyurethane coating consists of a component A and a component B, wherein the component A comprises the quick-drying core-shell structure hydroxy acrylic emulsion, a filler, a pigment, a dispersing agent, a wetting agent, a defoaming agent, a thickening agent and water, and the component B comprises hydrophilic modified isocyanate and a diluting agent.
Preferably, the hydrophilic modified isocyanate is at least one of bayer 2655 and warfarin 269.
The beneficial effects of the invention are: the coating prepared from the hydroxyl acrylic emulsion has the advantages of high drying speed, high compactness of the formed coating, good corrosion resistance, high glossiness and high distinctness of image, and can be applied to quick-drying acrylic polyurethane coatings.
1) The latex particles in the hydroxy acrylic emulsion have a hard core and soft shell structure, and the T of the core layer g High and glass state at room temperature, and can make the coating film quickly reach surface dry and T of shell layer g The coating is low and viscous at room temperature, can provide long opening time for crosslinking, is easy to crosslink with an isocyanate curing agent because the surface of the shell layer is enriched with hydroxyl, can accelerate the drying speed of the coating, and improves the compactness, the corrosion resistance, the glossiness and the distinctness of the coating;
2) the hydroxyl acrylic emulsion has simple production process and low production cost, and is suitable for large-area popularization and application.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a quick-drying core-shell structure hydroxyl acrylic emulsion is obtained by continuously carrying out emulsion polymerization twice on a core-layer monomer and a shell-layer monomer in a mass ratio of 1: 1;
the composition of the core layer monomers is shown in the following table:
TABLE 1 composition of core layer monomers
| Raw materials | Mass percent (%) |
| Methacrylic acid methyl ester | 61 |
| Styrene (meth) acrylic acid ester | 15 |
| Acrylic acid butyl ester | 22.8 |
| Ethylene glycol diacrylate | 1.2 |
The compositions of the shell monomers are shown in the following table:
TABLE 2 composition of shell monomers
| Raw materials | Mass percent (%) |
| Methacrylic acid methyl ester | 6 |
| Styrene (meth) acrylic acid ester | 15 |
| Acrylic acid butyl ester | 44 |
| Methacrylic acid | 4 |
| Hydroxyethyl methacrylate | 23 |
| Acrylic acid isobornyl ester | 8 |
The preparation method of the quick-drying type core-shell structure hydroxyl acrylic emulsion comprises the following steps:
1) adding water into a nuclear layer monomer and alkylphenol polyoxyethylene ether sulfate to disperse uniformly to obtain a pre-emulsion A;
2) adding water to the shell monomer, dodecyl mercaptan and alkylphenol polyoxyethylene ether sulfate, and uniformly dispersing to obtain a pre-emulsion B;
3) adding water into ammonium persulfate to disperse uniformly to obtain an ammonium persulfate solution with the mass fraction of 0.67%;
4) adding water into baking soda and alkylphenol polyoxyethylene ether sulfate, dispersing uniformly, heating to 80 ℃, adding 1/5 pre-emulsion A and 1/2 ammonium persulfate solution, reacting for 30min under heat preservation after the reaction solution turns blue, then dropwise adding the rest pre-emulsion A, simultaneously dropwise adding the rest ammonium persulfate solution, finishing adding the pre-emulsion A for 60min, suspending dropwise adding the ammonium persulfate solution after finishing adding the pre-emulsion A, carrying out heat preservation reaction for 60min, then dropwise adding the pre-emulsion B, meanwhile, continuously dropwise adding an ammonium persulfate solution, adding the pre-emulsion B and the ammonium persulfate solution after 150min, carrying out heat preservation reaction for 60min, then cooling to 72 ℃ and adjusting the pH value to 5, adding tert-butyl hydroperoxide and sodium thiosulfate, carrying out heat preservation reaction for 30min, then cooling to 40 ℃ and adjusting the pH value to 8, then cooling to room temperature, and filtering with a 200-mesh filter screen to obtain the quick-drying core-shell structure hydroxyacrylic acid emulsion;
in the step 1), the addition amount of alkylphenol polyoxyethylene ether sulfate is 0.4% of the total mass of the nuclear layer monomer and the shell layer monomer, and the addition amount of water is 25% of the total mass of the nuclear layer monomer and the shell layer monomer;
in the step 2), the addition amount of dodecyl mercaptan is 0.2 percent of the total mass of the core layer monomer and the shell layer monomer, the addition amount of alkylphenol polyoxyethylene ether sulfate is 0.8 percent of the total mass of the core layer monomer and the shell layer monomer, and the addition amount of water is 25 percent of the total mass of the core layer monomer and the shell layer monomer;
in the step 3), the adding amount of ammonium persulfate is 0.6 percent of the total mass of the core layer monomer and the shell layer monomer;
in the step 4), the addition amount of the small soda ash is 1% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of the alkylphenol polyoxyethylene ether sulfate is 0.3% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of the water is 35% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of the tert-butyl hydroperoxide is 0.1% of the total mass of the core layer monomer and the shell layer monomer, and the addition amount of the sodium thiosulfate is 0.1% of the total mass of the core layer monomer and the shell layer monomer.
Example 2:
a quick-drying core-shell structure hydroxyl acrylic emulsion is obtained by continuously carrying out emulsion polymerization twice on a core-layer monomer and a shell-layer monomer in a mass ratio of 1: 9;
the composition of the core layer monomers is shown in the following table:
TABLE 3 composition of core layer monomers
| Raw materials | Mass percent (%) |
| Methacrylic acid methyl ester | 94 |
| Acrylic acid butyl ester | 6 |
The compositions of the shell monomers are shown in the following table:
TABLE 4 composition of shell monomers
| Raw materials | Mass percent (%) |
| Methacrylic acid methyl ester | 36.1 |
| Acrylic acid butyl ester | 38.8 |
| Acrylic acid | 0.6 |
| Hydroxypropyl acrylate | 16.7 |
| Acrylic acid hydroxy ethyl ester | 5.6 |
| Isobornyl methacrylate | 2.2 |
The preparation method of the quick-drying type core-shell structure hydroxyl acrylic emulsion comprises the following steps:
1) adding water into a core layer monomer and alkylphenol polyoxyethylene ether sulfate to disperse uniformly to obtain a pre-emulsion A;
2) adding water to the shell monomer, dodecyl mercaptan and alkylphenol polyoxyethylene ether sulfate, and uniformly dispersing to obtain a pre-emulsion B;
3) adding water into ammonium persulfate to disperse uniformly to obtain an ammonium persulfate solution with the mass fraction of 1%;
4) adding water into baking soda and alkylphenol polyoxyethylene sulfate, dispersing uniformly, heating to 80 ℃, adding 1/5 pre-emulsion A and 1/2 ammonium persulfate solution, keeping the temperature for reaction for 30min after the reaction solution turns blue, then dropwise adding the rest pre-emulsion A, simultaneously dropwise adding the rest ammonium persulfate solution, finishing adding the pre-emulsion A for 60min, suspending dropwise adding the ammonium persulfate solution after finishing adding the pre-emulsion A, carrying out heat preservation reaction for 60min, then dropwise adding the pre-emulsion B, continuously dropwise adding an ammonium persulfate solution, adding the pre-emulsion B and the ammonium persulfate solution after 150min, carrying out heat preservation reaction for 60min, cooling to 72 ℃ and adjusting the pH value to 5, adding tert-butyl hydroperoxide and sodium thiosulfate, carrying out heat preservation reaction for 30min, cooling to 40 ℃ and adjusting the pH value to 8, cooling to room temperature, and filtering with a 200-mesh filter screen to obtain the fast-drying core-shell structure hydroxyacrylic acid emulsion;
in the step 1), the addition amount of alkylphenol polyoxyethylene ether sulfate is 0.1 percent of the total mass of the nuclear layer monomer and the shell layer monomer, and the addition amount of water is 10 percent of the total mass of the nuclear layer monomer and the shell layer monomer;
in the step 2), the addition amount of dodecyl mercaptan is 1% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of alkylphenol polyoxyethylene ether sulfate is 1.2% of the total mass of the core layer monomer and the shell layer monomer, and the addition amount of water is 50% of the total mass of the core layer monomer and the shell layer monomer;
in the step 3), the adding amount of ammonium persulfate is 0.4 percent of the total mass of the nuclear layer monomer and the shell layer monomer;
in the step 4), the addition amount of the small soda ash is 0.1% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of the alkylphenol polyoxyethylene ether sulfate is 0.3% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of the water is 30% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of the tert-butyl hydroperoxide is 0.1% of the total mass of the core layer monomer and the shell layer monomer, and the addition amount of the sodium thiosulfate is 0.1% of the total mass of the core layer monomer and the shell layer monomer.
Example 3:
a quick-drying core-shell structure hydroxyl acrylic emulsion is obtained by continuously carrying out emulsion polymerization twice on a core-layer monomer and a shell-layer monomer in a mass ratio of 3: 7;
the composition of the core layer monomers is shown in the following table:
TABLE 5 composition of core layer monomers
| Raw materials | Mass percent (%) |
| Methacrylic acid methyl ester | 77.7 |
| Styrene (meth) acrylic acid ester | 6.6 |
| Acrylic acid butyl ester | 14.7 |
| Ethylene glycol diacrylate | 1 |
The compositions of the shell monomers are shown in the following table:
TABLE 6 composition of shell monomers
The preparation method of the quick-drying type core-shell structure hydroxyl acrylic emulsion comprises the following steps:
1) adding water into a core layer monomer and alkylphenol polyoxyethylene ether sulfate to disperse uniformly to obtain a pre-emulsion A;
2) adding water to the shell monomer, dodecyl mercaptan and alkylphenol polyoxyethylene ether sulfate, and uniformly dispersing to obtain a pre-emulsion B;
3) adding water into ammonium persulfate, and uniformly dispersing to obtain an ammonium persulfate solution with the mass fraction of 0.5%;
4) adding water into baking soda and alkylphenol polyoxyethylene sulfate, dispersing uniformly, heating to 80 ℃, adding 1/5 pre-emulsion A and 1/2 ammonium persulfate solution, keeping the temperature for reaction for 30min after the reaction solution turns blue, then dropwise adding the rest pre-emulsion A, simultaneously dropwise adding the rest ammonium persulfate solution, finishing adding the pre-emulsion A for 60min, suspending dropwise adding the ammonium persulfate solution after finishing adding the pre-emulsion A, carrying out heat preservation reaction for 60min, then dropwise adding the pre-emulsion B, meanwhile, continuously dropwise adding an ammonium persulfate solution, adding the pre-emulsion B and the ammonium persulfate solution after 150min, carrying out heat preservation reaction for 60min, then cooling to 72 ℃ and adjusting the pH value to 5, adding tert-butyl hydroperoxide and sodium thiosulfate, carrying out heat preservation reaction for 30min, then cooling to 40 ℃ and adjusting the pH value to 8, then cooling to room temperature, and filtering with a 200-mesh filter screen to obtain the quick-drying core-shell structure hydroxyacrylic acid emulsion;
in the step 1), the addition amount of alkylphenol polyoxyethylene ether sulfate is 0.3 percent of the total mass of the nuclear layer monomer and the shell layer monomer, and the addition amount of water is 15 percent of the total mass of the nuclear layer monomer and the shell layer monomer;
in the step 2), the addition amount of dodecyl mercaptan is 0.5 percent of the total mass of the core layer monomer and the shell layer monomer, the addition amount of alkylphenol polyoxyethylene ether sulfate is 0.9 percent of the total mass of the core layer monomer and the shell layer monomer, and the addition amount of water is 25 percent of the total mass of the core layer monomer and the shell layer monomer;
in the step 3), the adding amount of ammonium persulfate is 0.2 percent of the total mass of the nuclear layer monomer and the shell layer monomer;
in the step 4), the addition amount of the small soda ash is 0.2% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of the alkylphenol polyoxyethylene ether sulfate is 0.3% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of the water is 30% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of the tert-butyl hydroperoxide is 0.1% of the total mass of the core layer monomer and the shell layer monomer, and the addition amount of the sodium thiosulfate is 0.1% of the total mass of the core layer monomer and the shell layer monomer.
Example 4:
a quick-drying core-shell structure hydroxyl acrylic emulsion is obtained by continuously carrying out emulsion polymerization twice on a core-layer monomer and a shell-layer monomer in a mass ratio of 4: 6;
the composition of the core layer monomers is shown in the following table:
TABLE 7 composition of core layer monomers
| Starting materials | Mass percent (%) |
| Methacrylic acid methyl ester | 83.2 |
| Styrene (meth) acrylic acid ester | 7.5 |
| Acrylic acid butyl ester | 8.5 |
| Ethylene glycol diacrylate | 0.8 |
The compositions of the shell monomers are shown in the following table:
TABLE 8 composition of shell monomers
| Raw materials | Mass percent (%) |
| Styrene (meth) acrylic acid ester | 6.7 |
| Acrylic acid butyl ester | 32.5 |
| Methacrylic acid | 1.7 |
| Hydroxypropyl acrylate | 51.1 |
| Methacrylic acid cyclohexyl ester | 8 |
The preparation method of the quick-drying type core-shell structure hydroxyl acrylic emulsion comprises the following steps:
1) adding water into a core layer monomer and alkylphenol polyoxyethylene ether sulfate to disperse uniformly to obtain a pre-emulsion A;
2) adding water into the shell monomer, dodecyl mercaptan and alkylphenol polyoxyethylene ether sulfate to disperse uniformly to obtain a pre-emulsion B;
3) adding water into ammonium persulfate to disperse uniformly to obtain an ammonium persulfate solution with the mass fraction of 0.5%;
4) adding water into baking soda and alkylphenol polyoxyethylene ether sulfate, dispersing uniformly, heating to 80 ℃, adding 1/5 pre-emulsion A and 1/2 ammonium persulfate solution, reacting for 30min under heat preservation after the reaction solution turns blue, then dropwise adding the rest pre-emulsion A, simultaneously dropwise adding the rest ammonium persulfate solution, finishing adding the pre-emulsion A for 60min, suspending dropwise adding the ammonium persulfate solution after finishing adding the pre-emulsion A, carrying out heat preservation reaction for 60min, then dropwise adding the pre-emulsion B, meanwhile, continuously dropwise adding an ammonium persulfate solution, adding the pre-emulsion B and the ammonium persulfate solution after 150min, carrying out heat preservation reaction for 60min, then cooling to 72 ℃ and adjusting the pH value to 5, adding tert-butyl hydroperoxide and sodium thiosulfate, carrying out heat preservation reaction for 30min, then cooling to 40 ℃ and adjusting the pH value to 8, then cooling to room temperature, and filtering with a 200-mesh filter screen to obtain the quick-drying core-shell structure hydroxyacrylic acid emulsion;
in the step 1), the addition amount of alkylphenol polyoxyethylene ether sulfate is 0.4% of the total mass of the nuclear layer monomer and the shell layer monomer, and the addition amount of water is 20% of the total mass of the nuclear layer monomer and the shell layer monomer;
in the step 2), the addition amount of dodecyl mercaptan is 1% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of alkylphenol polyoxyethylene ether sulfate is 0.8% of the total mass of the core layer monomer and the shell layer monomer, and the addition amount of water is 20% of the total mass of the core layer monomer and the shell layer monomer;
in the step 3), the adding amount of ammonium persulfate is 0.3 percent of the total mass of the nuclear layer monomer and the shell layer monomer;
in the step 4), the addition amount of the small soda is 0.2% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of the alkylphenol polyoxyethylene ether sulfate is 0.5% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of the water is 30% of the total mass of the core layer monomer and the shell layer monomer, the addition amount of the tert-butyl hydroperoxide is 0.1% of the total mass of the core layer monomer and the shell layer monomer, and the addition amount of the sodium thiosulfate is 0.1% of the total mass of the core layer monomer and the shell layer monomer.
Comparative example 1:
the commercial hydroxyl acrylic emulsion A has the solid content of 42 percent, the hydroxyl content of 3.0 percent and the viscosity of 250cP and is used for self-drying metal anticorrosive finish.
Comparative example 2:
the commercial hydroxyl acrylic emulsion B has the solid content of 45 percent, the hydroxyl content of 2.6 percent and the viscosity of 180cP, and is used for self-drying metal anticorrosion finish paint.
And (3) performance testing:
the quick-drying type hydroxyl acrylic emulsion with the core-shell structure in the embodiment 1-4 and the hydroxyl acrylic emulsion in the comparative example 1-2 are prepared into water-based acrylic polyurethane coating according to the formula shown in the table 9, and are marked as the sample 1-4 and the comparative sample 1-2, and then the performance test is carried out, wherein the test result is shown in the table 10:
TABLE 9 composition of aqueous acrylic polyurethane coatings
TABLE 10 Performance test results for waterborne acrylic polyurethane coatings
Note:
surface drying time: the test is carried out according to the cotton blowing ball method in GB/T1728-;
the actual drying time is as follows: the test is carried out according to the cotton ball pressing method in GB/T1728-;
hardness: testing is carried out according to GB/T6739-2006;
gloss: the test was performed with reference to GB/T9754-2007;
adhesion force: the test was performed with reference to GB/T9286-1998;
flexibility: the test was performed with reference to GB/T1731-1993.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A quick-drying type hydroxyl acrylic emulsion with a core-shell structure is characterized in that: the mass ratio of 1: (1-9) carrying out emulsion polymerization twice on the core layer monomer and the shell layer monomer continuously to obtain the polymer;
the core layer monomer comprises the following components in percentage by mass:
methyl methacrylate: 60% -94%;
styrene: 0 to 15 percent;
butyl acrylate: 6 to 25 percent;
ethylene glycol diacrylate: 0 to 1.2 percent;
the shell layer monomer comprises the following components in percentage by mass:
methyl methacrylate: 0 to 37 percent;
styrene: 0 to 15 percent;
butyl acrylate: 30% -46%;
acrylic acid and/or methacrylic acid: 0.5 to 4 percent;
hydroxypropyl acrylate or/and hydroxyethyl methacrylate: 15% -52%;
hydroxyethyl acrylate: 0 to 26 percent;
isobornyl acrylate or/and isobornyl methacrylate or/and cyclohexyl acrylate or/and cyclohexyl methacrylate: 1% -8%;
the glass transition temperature of latex particles in the quick-drying core-shell structure hydroxyl acrylic emulsion is 10-30 ℃, the glass transition temperature of a core layer of the latex particles is 50-90 ℃, and the glass transition temperature of a shell layer of the latex particles is-15-5 ℃; the preparation method of the quick-drying type core-shell structure hydroxyl acrylic emulsion comprises the following steps: 1) adding water into a core layer monomer and an emulsifier, and uniformly dispersing to obtain a pre-emulsion A; 2) adding water into a shell monomer, a chain transfer agent and an emulsifier, and uniformly dispersing to obtain a pre-emulsion B; 3) adding water into an initiator to disperse uniformly to obtain an initiator solution; 4) adding water into a pH buffering agent and an emulsifier, uniformly dispersing and heating to 75-85 ℃, adding a part of pre-emulsion A and a part of initiator solution, performing seed polymerization, adding the rest of pre-emulsion A and a part of initiator solution, performing emulsion polymerization of a core layer, adding a part of pre-emulsion B and the rest of initiator solution, performing emulsion polymerization of a shell layer, cooling to 70-74 ℃, adjusting the pH value to 4-5, adding a post-elimination initiator and a post-elimination reducing agent, performing heat preservation reaction to eliminate residual monomers, cooling to 40-50 ℃, adjusting the pH value to 7-9, cooling to room temperature, and filtering to obtain the quick-drying core-shell structure hydroxyl acrylic emulsion.
2. The quick-drying hydroxyl acrylic emulsion with the core-shell structure according to claim 1, which is characterized in that: the hydroxyl content of the quick-drying type core-shell structure hydroxyl acrylic emulsion is 1.5-4%.
3. The quick-drying type core-shell structure hydroxyacrylic acid emulsion according to claim 1, characterized in that: the emulsifier in the steps 1), 2) and 4) is alkylphenol polyoxyethylene ether sulfate, and the total addition amount is 0.8-2% of the total mass of the core layer monomer and the shell layer monomer.
4. The quick-drying hydroxyl acrylic emulsion with the core-shell structure according to claim 1, which is characterized in that: in the step 2), the chain transfer agent is dodecyl mercaptan, and the addition amount of the dodecyl mercaptan is 0.2-1.5% of the total mass of the core layer monomer and the shell layer monomer.
5. The quick-drying type core-shell structure hydroxyacrylic acid emulsion according to claim 1, characterized in that: and 3) the initiator is ammonium persulfate, and the addition amount of the initiator is 0.1-0.6% of the total mass of the core layer monomer and the shell layer monomer.
6. The quick-drying type core-shell structure hydroxyacrylic acid emulsion according to claim 1, characterized in that: and 4) the pH buffering agent is baking soda, and the addition amount of the pH buffering agent is 0.1-2% of the total mass of the core layer monomer and the shell layer monomer.
7. The quick-drying type core-shell structure hydroxyacrylic acid emulsion according to claim 1, characterized in that: step 4), the post-elimination initiator is tert-butyl hydroperoxide, and the addition amount of the post-elimination initiator is 0.1 to 0.5 percent of the total mass of the core layer monomer and the shell layer monomer; the post-elimination reducing agent in the step 4) is at least one of sodium thiosulfate and sodium bisulfite, and the addition amount is 0.1-0.5 percent of the total mass of the core layer monomer and the shell layer monomer.
8. A quick-drying water-based acrylic polyurethane coating is characterized in that: the quick-drying type hydroxyl acrylic emulsion with the core-shell structure, which contains the quick-drying type hydroxyl acrylic emulsion with the core-shell structure, as claimed in any one of claims 1 to 7.
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