CN107828006B - Preparation method of high-heat-resistance water-based acrylic resin and obtained product - Google Patents
Preparation method of high-heat-resistance water-based acrylic resin and obtained product Download PDFInfo
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- C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
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- C09D5/18—Fireproof paints including high temperature resistant paints
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Abstract
The invention belongs to the field of chemical coatings, and particularly relates to a preparation method of a high-heat-resistance water-based acrylic resin. The preparation method of the high-heat-resistance water-based acrylic resin provided by the invention comprises the following steps: and carrying out chain extension reaction on carbonic acid dihydrazide by using phenolic epoxy resin to obtain modified carbonic acid dihydrazide, then obtaining the waterborne acrylic resin with the main chain containing a maleic anhydride ring structure through free radical polymerization, and adding the modified carbonic acid dihydrazide into the waterborne acrylic resin containing the maleic anhydride ring structure for reaction to obtain the acrylic resin. The high-heat-resistance water-based acrylic resin prepared by the invention has high heat resistance, can effectively improve the hardness, oil and pigment leakage resistance, yellowing resistance and water resistance of a paint film when being applied to paint, and has the advantages of high water resistance and corrosion resistance, thereby being an ideal high-heat-resistance water-based acrylic resin for paint.
Description
Technical Field
The invention belongs to the field of chemical coatings, and particularly relates to a preparation method of a high-heat-resistance water-based acrylic resin and an obtained product.
Background
With the enhancement of social environmental awareness, coatings using water-based acrylic resins as main binders are more and more commonly used. At present, there are two methods for improving the heat resistance of such acrylic resins, one is to copolymerize vinyl monomers with imide side groups, and the other is to amidate copolymerized maleic anhydride. The former has no commercial popularization value due to higher cost, and the latter can embody obvious heat resistance only by forming a certain amount of imide structures, thereby greatly limiting the application range of the resin.
Modern researches find that the copolymerization of different types of acrylic monomers can improve the performances of the acrylic resin such as toughness, heat resistance, impact resistance and the like to different degrees. Therefore, the pre-emulsion for industrially preparing the waterborne modified acrylic acid is widely applied at present.
Patent document CN104387511A discloses a temperature-resistant acrylic resin for water-based ink, which is prepared by a solution polymerization method using maleic anhydride, styrene, and (meth) acrylic acid as monomers, and a preparation method thereof. The preparation method comprises the following steps: firstly, uniformly mixing a proper amount of styrene, (methyl) acrylic acid and maleic anhydride, then adding an initiator, and uniformly stirring to obtain a component 1; adding a proper amount of alcohol substances into a reactor, heating until the solvent flows back, keeping the temperature, and slowly dripping the uniformly mixed component 1 into the solvent, wherein the dripping time is controlled to be 0.5-1 hour; and after the dropwise addition is finished, continuously reacting at a constant temperature for 2-3 hours at the reflux temperature, stopping stirring, adjusting the pH value to 7-8 by using a neutralizing agent, preserving the temperature for 1-2 hours, cooling, and discharging to obtain the catalyst. The prepared acrylic resin has moderate price, is green and environment-friendly, has good temperature resistance, and the water-based ink prepared by the acrylic resin as a binder has the advantages of good hardness, good luster and the like of oily ink, and has the advantages of no VOC, good heat resistance, safe production and use and the like.
Patent document CN103087329A discloses a silicone resin modified methacrylic resin and a preparation method and application thereof, wherein the preparation method comprises the steps of uniformly mixing a functional methacrylate copolymer, active MQ silicone resin, an organic solvent and a catalyst to obtain the silicone resin modified methacrylic resin, placing the silicone resin modified methacrylic resin at 70-100 ℃ for 10-20 minutes, and curing at 140-180 ℃ for 1-2 hours to obtain the silicone resin modified methacrylic resin heat-resistant hydrophobic coating. The prepared silicone resin modified methacrylic resin has the advantages of high heat resistance, glass transition temperature of more than 250 ℃ and obviously improved hydrophobicity and stain resistance, and is an ideal silicone resin modified methacrylic resin.
However, the coating using the water-based acrylic resin as the main binder has high requirements on heat resistance, compactness, corrosion resistance, environmental protection, pigment exudation resistance and yellowing resistance.
Therefore, the research and development of the water-based acrylic resin with high compactness, good corrosion resistance, good pigment exudation resistance, good yellowing resistance and high heat resistance are still problems to be solved.
Disclosure of Invention
Aiming at overcoming the defects of poor heat resistance, poor pigment exudation resistance and yellowing resistance, low hardness and poor corrosion resistance of the water-based acrylic resin in the prior art. The invention aims to provide a preparation method of a water-based acrylic resin with high heat resistance and an obtained product, so as to solve the defects.
The invention provides a preparation method of a high-heat-resistance water-based acrylic resin, which comprises the following steps:
s1, adding 25-30 parts of carbolic acid dihydrazide into dimethyl sulfoxide, uniformly stirring, adding 4-5 parts of phenolic epoxy resin, performing chain extension modification reaction, performing reduced pressure distillation, and removing a solvent to obtain modified hydrazide;
s2, adding 160-180 parts of dipropylene glycol methyl ether, 25-35 parts of alpha-methyl styrene, 18-25 parts of acrylic acid, 8-16 parts of butyl acrylate and 10-20 parts of methyl methacrylate into a reaction kettle, introducing nitrogen, fully mixing uniformly at a stirring speed of 100-200 rpm, and heating to 100-130 ℃;
s3, mixing 24-30 parts of maleic anhydride mixed solution with 3-5 parts of dicumyl peroxide, and uniformly stirring to obtain mixed solution;
s4, dropwise adding the mixed liquid obtained in the step S3 into a reaction kettle, and then, preserving the heat for 25-35 min at the temperature of 100-130 ℃ to obtain a polymer solution;
s5, adding 1-3% by mass of hydroquinone into the polymer solution obtained in the step S4 to terminate the reaction, and then performing vacuum devolatilization on the polymer solution while the polymer solution is hot, wherein the devolatilization temperature is 200 +/-10 ℃, and the vacuum degree is controlled to be 0.08-0.1 MPa;
s6, cooling to 80 +/-5 ℃, adding 20-25 parts of amine neutralizer, and dropwise adding 10-20 parts of modified hydrazide obtained in the step S1 and 80-200 parts of water into the reaction kettle at a stirring speed of 100-200 rpm to obtain the modified hydrazide-modified hydrazine hydrate.
Further, the chain extension modification reaction conditions in step S1 are: reacting for 15-20 min at the temperature of 150-160 ℃.
Further, the maleic anhydride mixed solution in the step S3 is composed of maleic anhydride and styrene in a weight ratio of 1: 1.
Further, the dropping speed in the step S4 is 50-60 g/min.
Further, the amine neutralizer in the step S6 is ammonia water or ethanolamine.
Further, the dropping speed in the step S6 is 30-40 g/min.
In addition, the invention also provides the high-heat-resistance water-based acrylic resin prepared by the preparation method of the high-heat-resistance water-based acrylic resin.
The preparation method of the high-heat-resistance water-based acrylic resin provided by the invention comprises the following steps: the method comprises the steps of carrying out chain extension reaction on carbonic acid dihydrazide by using phenolic epoxy resin to obtain modified carbonic acid dihydrazide, then carrying out free radical polymerization to obtain waterborne acrylic resin with a main chain containing a maleic anhydride ring structure, and adding the modified carbonic acid dihydrazide into the waterborne acrylic resin containing the maleic anhydride ring structure for reaction to obtain the modified carbonic acid dihydrazide. When the prepared water-based acrylic resin is applied to a coating, different molecular chains of the coating can be linked together in an imide forming mode in the process of heating, baking and film forming, and the water-based acrylic resin containing an imide structure and a phenolic structure can endow a solid coating with higher heat resistance, so that the water-based acrylic resin is ideal and high in heat resistance.
Further, the preparation of the high-heat-resistance water-based acrylic resin is carried out by preheating dipropylene glycol methyl ether, alpha-methyl styrene, acrylic acid, butyl acrylate and methyl methacrylate, and then dropwise adding the initiator mixed with maleic anhydride at a certain speed, so that the molecular weight and the reaction time of the polymer can be effectively controlled, the polymerization degree and the viscosity of the polymer can be controlled, and the generation of the modified water-based acrylic resin can be promoted.
The water-based acrylic resin prepared by the invention has higher heat resistance, and tests show that the heat resistance of a tubular film made of the water-based acrylic resin with high heat resistance prepared by the invention is more than 283 ℃, which indicates that the water-based acrylic resin prepared by the invention has better heat resistance.
Tests show that the paint film containing the high-heat-resistance water-based acrylic resin prepared by the invention has strong adhesive force and high hardness, the Volatile Organic Compound (VOC) content of the paint film is lower than 110g/L, the coloring rate is 100%, the flexibility (diameter) is smaller than 0.90mm, and the yellowing resistance △ b value is smaller than 0.38.
Compared with the prior art, the preparation method of the high-heat-resistance water-based acrylic resin provided by the invention has the following advantages:
(1) the water-based acrylic resin prepared by the preparation method of the water-based acrylic resin with high heat resistance has the advantages of high adhesive force, strong colorability, good flexibility, and strong heat resistance and corrosion resistance;
(2) the water-based acrylic resin prepared by the preparation method of the water-based acrylic resin with high heat resistance has the advantages of oil leakage resistance, pigment leakage resistance and good yellowing resistance, and is an environment-friendly and healthy water-based acrylic resin for paint;
(3) when the paint prepared from the water-based acrylic resin prepared by the preparation method of the water-based acrylic resin with high heat resistance provided by the invention is applied, the paint has the effects of transparent and bright surface, high fullness and luster, and no fading and no falling after long-term use, and is the paint resin meeting the requirements of modern people.
The specific implementation mode is as follows:
the present invention is further described in the following description of the specific embodiments, which is not intended to limit the invention, but various modifications and improvements can be made by those skilled in the art according to the basic idea of the invention, within the scope of the invention, as long as they do not depart from the basic idea of the invention. The ingredients of the invention are commercially available in conventional compositions such as: the CAS number for novolac epoxy resins is 24969-06-0.
Example 1 preparation of a highly Heat-resistant Water-based acrylic resin
S1, adding 25 parts of carbodihydrazide into dimethyl sulfoxide, uniformly stirring, adding 4 parts of novolac epoxy resin, carrying out chain extension modification reaction for 15min at the temperature of 150 ℃, carrying out reduced pressure distillation, and removing the solvent to obtain modified hydrazide;
s2, adding 160 parts of dipropylene glycol methyl ether, 25 parts of alpha-methyl styrene, 18 parts of acrylic acid, 8 parts of butyl acrylate and 10 parts of methyl methacrylate into a reaction kettle, introducing nitrogen, fully and uniformly mixing under the condition that the stirring speed is 100rpm, and heating to 100 ℃;
s3, mixing 24 parts of maleic anhydride mixed solution and 3 parts of dicumyl peroxide, and uniformly stirring, wherein the maleic anhydride mixed solution is composed of maleic anhydride and styrene according to the weight ratio of 1:1 to obtain mixed solution;
s4, dropwise adding the mixed liquid obtained in the step S3 into a reaction kettle at a speed of 50g/min, and then, preserving heat for 25min at the temperature of 100 ℃ to obtain a polymer solution;
s5, adding hydroquinone with the mass percentage concentration of 1% into the polymer solution obtained in the step S4 to terminate the reaction, and then carrying out vacuum devolatilization on the polymer solution while the polymer solution is hot, wherein the devolatilization temperature is 195 ℃, and the vacuum degree is controlled at 0.08 MPa;
and S6, cooling to 75 ℃, adding 20 parts of ammonia water, and dropwise adding 10 parts of modified hydrazide obtained in the step S1 and 100 parts of water into the reaction kettle at a stirring speed of 100rpm, wherein the dropwise adding speed is 30g/min to obtain the hydrazide-modified hydrazine hydrate.
Example 2 preparation of a highly Heat-resistant waterborne acrylic resin
S1, adding 28 parts of carbonic acid dihydrazide into dimethyl sulfoxide, uniformly stirring, adding 5 parts of phenolic epoxy resin, carrying out chain extension modification reaction for 18min at the temperature of 155 ℃, carrying out reduced pressure distillation, and removing a solvent to obtain modified hydrazide;
s2, adding 170 parts of dipropylene glycol methyl ether, 30 parts of alpha-methyl styrene, 20 parts of acrylic acid, 12 parts of butyl acrylate and 15 parts of methyl methacrylate into a reaction kettle, introducing nitrogen, fully and uniformly mixing under the condition that the stirring speed is 150rpm, and heating to 120 ℃;
s3, mixing 28 parts of maleic anhydride mixed solution and 4 parts of dicumyl peroxide, and uniformly stirring, wherein the maleic anhydride mixed solution is composed of maleic anhydride and styrene according to the weight ratio of 1:1 to obtain mixed solution;
s4, dropwise adding the mixed liquid obtained in the step S3 into a reaction kettle at a speed of 55g/min, and then preserving heat for 30min at 120 ℃ to obtain a polymer solution;
s5, adding hydroquinone with the mass percentage concentration of 2% into the polymer solution obtained in the step S4 to terminate the reaction, and then carrying out vacuum devolatilization on the polymer solution while the polymer solution is hot, wherein the devolatilization temperature is 200 ℃, and the vacuum degree is controlled to be 0.09 MPa;
s6, cooling to 80 ℃, adding 22 parts of ethanolamine, and dropwise adding 15 parts of modified hydrazide obtained in the step S1 and 150 parts of water into the reaction kettle at a stirring speed of 150rpm, wherein the dropwise adding speed is 35 g/min.
Example 3 preparation of a highly Heat-resistant waterborne acrylic resin
S1, adding 30 parts of carbodihydrazide into dimethyl sulfoxide, uniformly stirring, adding 5 parts of novolac epoxy resin, carrying out chain extension modification reaction for 20min at the temperature of 160 ℃, carrying out reduced pressure distillation, and removing the solvent to obtain modified hydrazide;
s2, adding 180 parts of dipropylene glycol methyl ether, 35 parts of alpha-methyl styrene, 25 parts of acrylic acid, 16 parts of butyl acrylate and 20 parts of methyl methacrylate into a reaction kettle, introducing nitrogen, fully and uniformly mixing at a stirring speed of 200rpm, and heating to 130 ℃;
s3, mixing 30 parts of maleic anhydride mixed solution and 5 parts of dicumyl peroxide, and uniformly stirring, wherein the maleic anhydride mixed solution is composed of maleic anhydride and styrene according to the weight ratio of 1:1 to obtain mixed solution;
s4, dropwise adding the mixed liquid obtained in the step S3 into a reaction kettle at a speed of 60g/min, and then, preserving heat for 35min at the temperature of 130 ℃ to obtain a polymer solution;
s5, adding hydroquinone with the mass percentage concentration of 3% into the polymer solution obtained in the step S4 to terminate the reaction, and then carrying out vacuum devolatilization on the polymer solution while the polymer solution is hot, wherein the devolatilization temperature is 205 ℃, and the vacuum degree is controlled to be 0.1 MPa;
and S6, cooling to 85 ℃, adding 25 parts of ammonia water, and dropwise adding 20 parts of the modified hydrazide obtained in the step S1 and 200 parts of water into the reaction kettle at a stirring speed of 200rpm, wherein the dropwise adding speed is 40 g/min.
Comparative example 1 preparation of a Water-based acrylic resin having high Heat resistance
S1, adding 28 parts of carbonic acid dihydrazide into dimethyl sulfoxide, and uniformly stirring to obtain a carbonic acid dihydrazide solution;
s2, adding 170 parts of dipropylene glycol methyl ether, 30 parts of alpha-methyl styrene, 20 parts of acrylic acid, 12 parts of butyl acrylate and 15 parts of methyl methacrylate into a reaction kettle, introducing nitrogen, fully and uniformly mixing under the condition that the stirring speed is 150rpm, and heating to 120 ℃;
s3, mixing 28 parts of maleic anhydride mixed solution and 4 parts of dicumyl peroxide, and uniformly stirring, wherein the maleic anhydride mixed solution is composed of maleic anhydride and styrene according to the weight ratio of 1:1 to obtain mixed solution;
s4, dropwise adding the mixed liquid obtained in the step S3 into a reaction kettle at a speed of 55g/min, and then preserving heat for 30min at 120 ℃ to obtain a polymer solution;
s5, adding hydroquinone with the mass percentage concentration of 2% into the polymer solution obtained in the step S4 to terminate the reaction, and then carrying out vacuum devolatilization on the polymer solution while the polymer solution is hot, wherein the devolatilization temperature is 200 ℃, and the vacuum degree is controlled to be 0.09 MPa;
s6, cooling to 80 ℃, adding 22 parts of ethanolamine, and dropwise adding 15 parts of the carbonic acid dihydrazide solution obtained in the step S1 and 150 parts of water into the reaction kettle at a stirring speed of 150rpm, wherein the dropwise adding speed is 35g/min to obtain the product.
The difference from example 2 is that: the carbonic acid dihydrazide was not modified.
Comparative example 2 preparation of a Water-based acrylic resin having high Heat resistance
S1, adding 28 parts of carbonic acid dihydrazide into dimethyl sulfoxide, uniformly stirring, adding 5 parts of phenolic epoxy resin, carrying out chain extension modification reaction for 18min at the temperature of 155 ℃, carrying out reduced pressure distillation, and removing a solvent to obtain modified hydrazide;
s2, adding 170 parts of dipropylene glycol methyl ether, 30 parts of alpha-methyl styrene, 20 parts of acrylic acid, 12 parts of butyl acrylate and 15 parts of methyl methacrylate into a reaction kettle, introducing nitrogen, fully and uniformly mixing under the condition that the stirring speed is 150rpm, then adding a mixed solution of 8 parts of maleic anhydride mixed solution and 4 parts of dicumyl peroxide, wherein the maleic anhydride mixed solution consists of maleic anhydride and styrene according to the weight ratio of 1:1, and then preserving heat for 30min under the condition of 120 ℃ to obtain a polymer solution;
s3, adding hydroquinone with the mass percentage concentration of 2% into the polymer solution obtained in the step S4 to terminate the reaction, and then carrying out vacuum devolatilization on the polymer solution while the polymer solution is hot, wherein the devolatilization temperature is 200 ℃, and the vacuum degree is controlled to be 0.09 MPa;
s4, cooling to 80 ℃, adding 22 parts of ethanolamine, and dropwise adding 15 parts of modified hydrazide obtained in the step S1 and 150 parts of water into the reaction kettle at a stirring speed of 150rpm, wherein the dropwise adding speed is 35 g/min.
The difference from example 2 is that: the maleic anhydride mixed solution and the initiator are directly added to the step S2 for reaction.
Comparative example 3 preparation of a Water-based acrylic resin having high Heat resistance
S1, adding 28 parts of carbonic acid dihydrazide into dimethyl sulfoxide, uniformly stirring, adding 5 parts of phenolic epoxy resin, carrying out chain extension modification reaction for 18min at the temperature of 155 ℃, carrying out reduced pressure distillation, and removing a solvent to obtain modified hydrazide;
s2, adding 170 parts of dipropylene glycol methyl ether, 30 parts of alpha-methyl styrene, 20 parts of acrylic acid, 12 parts of butyl acrylate and 15 parts of methyl methacrylate into a reaction kettle, introducing nitrogen, fully and uniformly mixing under the condition that the stirring speed is 150rpm, and heating to 120 ℃;
s3, adding 4 parts of dicumyl peroxide into 28 parts of maleic anhydride, and uniformly stirring to obtain a mixed solution;
s4, dropwise adding the mixed liquid obtained in the step S3 into a reaction kettle at a speed of 55g/min, and then preserving heat for 30min at 120 ℃ to obtain a polymer solution;
s5, adding hydroquinone with the mass percentage concentration of 2% into the polymer solution obtained in the step S4 to terminate the reaction, and then carrying out vacuum devolatilization on the polymer solution while the polymer solution is hot, wherein the devolatilization temperature is 200 ℃, and the vacuum degree is controlled to be 0.09 MPa;
s6, cooling to 80 ℃, adding 22 parts of ethanolamine, and dropwise adding 15 parts of modified hydrazide obtained in the step S1 and 150 parts of water into the reaction kettle at a stirring speed of 150rpm, wherein the dropwise adding speed is 35 g/min.
The difference from example 2 is that: maleic anhydride is directly added in step S3.
Test example I Heat resistance test of Water-based acrylic resin having high Heat resistance
1. Test materials:
the water-based acrylic resins with high heat resistance prepared in examples 1, 2, 3, 1, 2 and 3.
2. The test method comprises the following steps:
the highly heat-resistant aqueous acrylic resins prepared in example 1, example 2, example 3, comparative example 1, comparative example 2 and comparative example 3 were applied to the outer peripheries of copper wires having a diameter of about 1.0mm, respectively, and were baked using a baking oven, to obtain heat-resistant resin composites each having a heat-resistant resin film having a thickness of 32 to 34 μm on the surface thereof. The copper wire was removed from the obtained heat-resistant resin composite to obtain a tubular film having a thickness of 32 μm to 34 μm. The measurement was performed using a dynamic mechanical analyzer (DMS6100, manufactured by Seiko Instruments Co., Ltd.) under nitrogen gas at a temperature rising rate of 10 ℃/min. Subsequently, the softening temperature (extrapolated temperature at which the dynamic storage modulus decreases) of each tubular film resin was evaluated to evaluate the heat resistance of the resin.
3. And (3) test results:
the test results are shown in table 1.
TABLE 1 Heat resistance test of Water-based acrylic resin having high Heat resistance
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Heat resistance (. degree.C.) | 286 | 297 | 283 | 198 | 245 | 212 |
As can be seen from Table 1, the tubular films made of the highly heat-resistant aqueous acrylic resins prepared in examples 1 to 3 of the present invention had a heat resistance of more than 283 ℃ while the tubular films made of the highly heat-resistant aqueous acrylic resins prepared in comparative examples 1 to 3 had a significantly reduced heat resistance, indicating that the highly heat-resistant aqueous acrylic resins prepared in the present invention had a better heat resistance.
Test example II Performance test of paint film containing Water-based acrylic resin having high Heat resistance
1. Test materials:
the water-based acrylic resins with high heat resistance prepared in examples 1, 2, 3, 1, 2 and 3.
2. The test method comprises the following steps:
the waterborne acrylic resin with high heat resistance prepared in the example 1, the example 2, the example 3, the comparative example 1, the comparative example 2 and the comparative example 3 is added with components such as a cross-linking agent, a defoaming agent, a dispersing agent, a thickening agent, a leveling agent and the like to prepare the wood lacquer, a paint film is prepared according to a spraying method, and the Volatile Organic Compounds (VOC), the adhesive force, the tinting strength, the flexibility, the hardness and the yellow-penetration resistance value of the paint film are measured,
the method comprises the steps of measuring Volatile Organic Compounds (VOC) by referring to a GB/T23986-2009 method, detecting adhesive force by a grid drawing method, detecting tinting strength by referring to a GB/T14624.2-2008 method, wherein the detection condition temperature is 25 +/-1 ℃, the relative humidity is 65 +/-5%, the calculation formula of the tinting strength percentage is S ═ B/A x 100%, wherein S is the tinting strength percentage, A is the consumption of standard sample diluted white ink, B is the consumption of sample diluted white ink, detecting flexibility by referring to a GB/T1731-93 method, detecting hardness by referring to a GB/T6739-2006 method, and measuring a △ B value (yellow-penetration-preventing value) after drying for 72 hours, wherein the temperature of the yellow-penetration-preventing inspection condition is 25 +/-1 ℃, the relative humidity is 80 +/-5%.
3. And (3) test results:
the test results are shown in table 2.
TABLE 2 test for testing the Properties of paint films containing highly heat-resistant aqueous acrylic resins
From the data of the performance test of the paint films containing the water-based acrylic resin having high heat resistance shown in Table 2:
(1) the paint film containing the high-heat-resistance water-based acrylic resin prepared in the embodiments 1-3 of the invention has strong adhesive force and high hardness, the Volatile Organic Compound (VOC) content of the paint film is less than 110g/L, the coloring rate is 100%, the flexibility (diameter) is less than 0.90mm, the yellow-permeation prevention performance △ b value is less than 0.38, wherein the Volatile Organic Compound (VOC) content of the paint film prepared in the embodiment 2 is 99g/L, the coloring rate is 100%, the flexibility (diameter) is 0.81mm, and the yellow-permeation prevention performance △ b value is 0.22, which is the best embodiment.
(2) The paint films containing the high-heat-resistance water-based acrylic resin prepared in the groups 1-3 have poor Volatile Organic Compound (VOC) content, coloring rate, flexibility and yellow bleeding resistance, and greatly influence the performance of the high-heat-resistance water-based acrylic resin.
Test example III Corrosion resistance test of Water-based acrylic resin paint film containing high Heat resistance
1. Test materials:
the water-based acrylic resins having high heat resistance prepared in examples 1, 2 and 3.
2. The test method comprises the following steps:
the water-based acrylic resin with high heat resistance prepared in the examples 1, 2 and 3 is added with components such as a cross-linking agent, a defoaming agent, a dispersing agent, a thickening agent, a leveling agent and the like to prepare a woodenware paint, a paint film is prepared according to a spraying method, and the sweat resistance, the saliva resistance, the alcohol resistance and the moist heat resistance of the paint film are measured by referring to a method of German standard 64LFGB.B 82.10-1, the alcohol resistance is measured by referring to a method of GB/T13217.7-2009, the paint film is wiped by using 50% alcohol, and the moist heat resistance is measured by referring to a method of GB/T1740-2007.
3. And (3) test results:
the test results are shown in table 3.
TABLE 3 Corrosion resistance test of Water-based acrylic resin paint film containing high Heat resistance
As can be seen from Table 3, the paint films prepared by using the highly heat-resistant water-based acrylic resins prepared in examples 1 to 3 of the present invention have good sweat resistance, saliva resistance, alcohol resistance and moist heat resistance, and the performance of the paint can be greatly improved.
Claims (5)
1. A method for preparing a water-based acrylic resin with high heat resistance is characterized by comprising the following steps: s1, adding 25-30 parts of carbolic acid dihydrazide into dimethyl sulfoxide, uniformly stirring, adding 4-5 parts of phenolic epoxy resin, performing chain extension modification reaction, performing reduced pressure distillation, and removing a solvent to obtain modified hydrazide;
s2, adding 160-180 parts of dipropylene glycol methyl ether, 25-35 parts of alpha-methyl styrene, 18-25 parts of acrylic acid, 8-16 parts of butyl acrylate and 10-20 parts of methyl methacrylate into a reaction kettle, introducing nitrogen, fully mixing uniformly at a stirring speed of 100-200 rpm, and heating to 100-130 ℃;
s3, mixing 24-30 parts of maleic anhydride mixed solution with 3-5 parts of dicumyl peroxide, and uniformly stirring to obtain mixed solution;
s4, dropwise adding the mixed liquid obtained in the step S3 into a reaction kettle, and then, preserving the heat for 25-35 min at the temperature of 100-130 ℃ to obtain a polymer solution;
s5, adding 1-3% by mass of hydroquinone into the polymer solution obtained in the step S4 to terminate the reaction, and then performing vacuum devolatilization on the polymer solution while the polymer solution is hot, wherein the devolatilization temperature is 200 +/-10 ℃, and the vacuum degree is controlled to be 0.08-0.1 MPa;
s6, cooling to 80 +/-5 ℃, adding 20-25 parts of amine neutralizer, and dropwise adding 10-20 parts of modified hydrazide obtained in the step S1 and 80-200 parts of water into the reaction kettle at a stirring speed of 100-200 rpm to obtain the modified hydrazide-containing polyurethane emulsion;
the maleic anhydride mixed solution in the step S3 is composed of maleic anhydride and styrene according to the weight ratio of 1: 1;
the dropping speed in the step S4 is 50-60 g/min.
2. The method for preparing a highly heat-resistant aqueous acrylic resin according to claim 1, wherein the conditions of the chain extension modification reaction in step S1 are as follows: reacting for 15-20 min at the temperature of 150-160 ℃.
3. The method for preparing a highly heat-resistant aqueous acrylic resin according to claim 1, wherein the amine neutralizing agent in step S6 is ammonia or ethanolamine.
4. The method for producing a highly heat-resistant aqueous acrylic resin according to claim 1, wherein the dropping rate in step S6 is 30 to 40 g/min.
5. The highly heat-resistant aqueous acrylic resin obtained by the method for producing a highly heat-resistant aqueous acrylic resin according to any one of claims 1 to 4.
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