Quick-drying acrylic acid modified water-based alkyd resin

Abstract

The invention discloses a quick-drying acrylic acid modified waterborne alkyd resin in the technical field of paint films, which is characterized in that an alkyd precursor with low acid value and large molecular weight is prepared from synthesis of alkyd, and an alkyd resin product with quick air drying, good water resistance and high cost performance is prepared through acrylic acid modification. Then, the water adding amount is increased through a water-soluble solvent and a neutralizer, the cost is further reduced, the acid value of the front-stage alkyd is adjusted through experiments, the ratio of alcohol to acid is changed, the molecular weight is changed, and the optimal state of quick-drying property and gloss water resistance of the alkyd resin is achieved. The water resistance of the alkyd resin prepared by the method can reach 72 hours without blistering, the gloss is 86 or above, and the surface drying time is 30 minutes.

Description

Technical Field

[0001] The invention relates to the technical field of paint films, in particular to a quick-drying acrylic acid-modified waterborne alkyd resin. Background Art

[0002] Nowadays, the pace of life and production is getting faster and faster. Many projects are facing the problem of short construction period and requiring to be completed as soon as possible under the premise of ensuring quality and quantity. Therefore, more and more customers have put forward the requirement: under the premise of guaranteed performance, it can be dried quickly to form a film. Although there are many resins that can achieve fast drying performance, such as nitrocellulose, high vinyl chloride, chlorinated rubber, thermoplastic acrylic, etc., they are all expensive and have more or less some disadvantages in performance: some have poor outdoor weather resistance, such as nitrocellulose paint and chlorinated rubber paint; some have poor film fullness and poor actual working. Various weaknesses make their applicability not strong. Using acrylic acid to modify alkyd resin not only retains the characteristics of alkyd resin such as good fullness and easy construction, but also inherits the characteristics of thermoplastic acrylic fast drying, enhances weather resistance, and has low cost and outstanding cost performance. Environmental awareness is constantly improving worldwide, and the demand for environmentally friendly resins by governments and consumers is increasing. The alkyd resin industry will face the challenge of reducing VOC emissions and improving environmental protection. Water-based alkyd is imperative.

[0003] Alkyd resin is a synthetic resin obtained by the esterification reaction between alcohol (alcohol compounds, such as glycerol, ethylene glycol, etc.) and acid (usually fatty acid, such as oleic acid, tartaric acid, etc.). Alkyd resin is the product of a mixed reaction of polyols and polyacids. By controlling the reaction conditions and raw material ratios, alkyd resins with different properties and characteristics can be obtained. They are usually transparent or translucent, yellow to brown liquids with good solubility and viscosity, and are easy to mix with pigments, fillers and other ingredients to form coatings. Alkyd resins have the characteristics of weather resistance, drying, wear resistance, adhesion and environmental protection, and are often used in coatings, paints, adhesives and other applications.

[0004] However, the current water-based alkyd resins also have some obvious disadvantages: slow coating drying, low hardness, poor water resistance and corrosion resistance, poor outdoor weather resistance, etc., which require modification to meet performance requirements. Summary of the invention

[0005] The purpose of this section is to summarize some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and the invention title of this application to avoid blurring the purpose of this section, the specification abstract and the invention title, and such simplifications or omissions cannot be used to limit the scope of the present invention.

[0006] Therefore, the object of the present invention is to provide a fast-drying acrylic acid-modified waterborne alkyd resin to solve the problems raised in the above background technology.

[0007] To solve the above technical problems, according to one aspect of the present invention, the present invention provides the following technical solutions: A quick-drying acrylic acid modified water-based alkyd resin, comprising the following components in parts by weight: 13-15 parts of trimethylolpropane, 19-20 parts of soybean oleic acid, 3-4 parts of benzoic acid, 1-2 parts of adipic acid, 10-13 parts of phthalic anhydride, 0.05-0.1 parts of a catalyst, 21-24 parts of an acrylic acid monomer, 0.9-1 parts of an initiator, 4-5 parts of a neutralizer, and 22-24 parts of a solvent; The specific preparation steps of the quick-drying acrylic acid-modified waterborne alkyd resin are as follows: S1. After uniformly mixing trimethylolpropane, soybean oleic acid, benzoic acid, phthalic anhydride and adipic acid according to the proportion, add a catalyst and heat to dehydrate. First, heat to 130°C and keep it for 1 hour. At this time, a small amount of water begins to be removed. Then heat to 150°C and keep it for 30 minutes. Heat to 150-180°C for 2 hours, heat to 180-210°C for 3 hours, and heat to 210°C-230°C for 2 hours. When the acid value reaches 12-15 mgKOH / g, vacuumize. S2. When the acid value reaches 2-4 mgKOH / g, use nitrogen to release the pressure and cool down to below 150°C, add a certain amount of solvent, raise the temperature to stabilize at 150°C, add the acrylic acid monomer prepared in proportion at a uniform speed, add it for 4 hours, then keep warm for 0.5 hour, add the initiator once, keep warm for another 1 hour, cool down to 75°C, add the diluted solvent, stir evenly, add the neutralizer and disperse for 0.5 hour, and then discharge the material.

[0008] As a preferred embodiment of the quick-drying acrylic acid-modified waterborne alkyd resin described in the present invention, the catalyst is stannous octoate.

[0009] As a preferred embodiment of the quick-drying acrylic modified waterborne alkyd resin described in the present invention, the acrylic monomer is any one or more of acrylic acid, methyl methacrylate and styrene.

[0010] As a preferred embodiment of the quick-drying acrylic acid-modified waterborne alkyd resin described in the present invention, the initiator is DTBP.

[0011] As a preferred embodiment of the quick-drying acrylic modified waterborne alkyd resin described in the present invention, the neutralizing agent is any one of triethylamine or N,N-dimethylethanolamine.

[0012] As a preferred embodiment of the quick-drying acrylic modified waterborne alkyd resin described in the present invention, the solvent is a mixture of ethylene glycol butyl ether or isopropyl alcohol.

[0013] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention starts with synthesizing alkyd to produce an alkyd precursor with low acid value and large molecular weight, and then prepares an alkyd resin product with fast self-drying, good water resistance and high cost performance through acrylic acid modification. Later, the cost is further reduced by increasing the amount of water added through water-soluble solvents and neutralizers. The acid value of the front-stage alkyd is adjusted through experiments, and the molecular weight is changed by changing the ratio of alcohol to acid, so as to achieve the optimal state of fast drying, gloss and water resistance of the alkyd resin.

[0014] 2. The present invention has the advantages of fast surface drying speed, excellent weather resistance, good water resistance, high gloss and high cost performance. The introduction of acrylate monomer improves the weather resistance and water resistance of the paint film, can prevent the penetration of salt and corrosion of the steel structure substrate, and plays an anti-corrosion role. Compared with traditional alkyd resin, the alkyd resin prepared by this method can achieve 72 hours of water resistance without blistering, gloss above 86, and surface drying for 30 minutes. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the present invention will be described in detail below in combination with the accompanying drawings and detailed embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative labor. Among them: Figure 1 Viscosity and solid content test graphs of alkyd resins prepared in Examples 1-5 and Comparative Examples provided by the present invention; Figure 2 A scale diagram of paint making using alkyd resins prepared in Examples 1-5 and a comparative example provided by the present invention; Figure 3 This is a performance test chart of the alkyd resin paint prepared in Examples 1-5 and the control example provided by the present invention. DETAILED DESCRIPTION

[0016] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0017] Secondly, the present invention is described in detail with reference to schematic diagrams. When describing the embodiments of the present invention in detail, for the sake of convenience, the cross-sectional diagrams showing the device structure will not be partially enlarged according to the general scale, and the schematic diagrams are only examples, which should not limit the scope of protection of the present invention. In addition, in actual production, the three-dimensional dimensions of length, width and depth should be included.

[0018] In order to make the objectives, technical solutions and advantages of the present invention more clear, the embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0019] The invention provides a quick-drying acrylic acid modified water-based alkyd resin, which is composed of the following components in parts by weight: 13-15 parts of trimethylolpropane, 19-20 parts of soybean oleic acid, 3-4 parts of benzoic acid, 1-2 parts of adipic acid, 10-13 parts of phthalic anhydride, 0.05-0.1 parts of catalyst, 21-24 parts of acrylic acid monomer, 0.9-1 parts of initiator, 4-5 parts of neutralizer, and 22-24 parts of solvent. Preferably, in the present embodiment, the catalyst is stannous octoate, the acrylic acid monomer is any one or more of acrylic acid, methyl methacrylate and styrene, the initiator is DTBP, the neutralizer is any one of triethylamine or N,N-dimethylethanolamine, and the solvent is a mixture of ethylene glycol butyl ether or isopropanol.

[0020] In order to verify the performance of the quick-drying acrylic acid-modified waterborne alkyd resin of the present invention, the following Examples 1-5 and a comparative example are provided. Example 1

[0021] S1. Add the first raw material components into a 1000 ml four-necked flask equipped with a stirring device, a dehydrating device, a reflux condenser and a dropping funnel, which contain 13.5% trimethylolpropane, 20.1% soybean oleic acid, 3.6% benzoic acid, 1.8% adipic acid, 12.4% phthalic anhydride and 0.05% stannous octoate by mass percentage; S2, heating the above raw material components to 130°C, keeping the temperature for 1h, at which time a small amount of water begins to escape, then heating to 150°C and keeping the temperature for 30min, heating at 150-180°C for 2h, heating at 180-210°C for 3h, heating at 210°C-230°C for 2h, reacting to an acid value of 12-15mgKOH / g, and evacuating; S3. When the acid value reaches 2-4 mgKOH / g, use nitrogen to release the pressure and cool to below 150°C, add 13.3% ethylene glycol butyl ether, stabilize the temperature at 150°C, slowly drop the second raw material into the first raw material, the second raw material components include 3.3% acrylic acid (AA), 2.5% methyl methacrylate (MMA), 15.4% styrene (ST), 0.85% di-tert-butyl hydroperoxide (DTBP) by mass percentage, dropwise add for 4 hours, keep warm for 0.5 hour, add the remaining 0.1% di-tert-butyl hydroperoxide (DTBP), keep warm for 1 hour, cool to 75°C, add 9% isopropanol as diluent solvent, stir evenly, add 3.7% triethylamine as neutralizer and disperse for 0.5 hour, discharge, and obtain a water-based acrylic modified alkyd resin with a solid content of 75%. Example 2

[0022] S1. Add the first raw material components into a 1000 ml four-necked flask equipped with a stirring device, a dehydrating device, a reflux condenser and a dropping funnel, which contain 14.5% trimethylolpropane, 20.1% soybean oleic acid, 3.6% benzoic acid, 1.8% adipic acid, 12.4% phthalic anhydride and 0.05% stannous octoate by mass percentage; S2, heating the above raw material components to 130°C, keeping the temperature for 1h, at which time a small amount of water begins to escape, then heating to 150°C and keeping the temperature for 30min, heating at 150-180°C for 2h, heating at 180-210°C for 3h, heating at 210°C-230°C for 2h, reacting to an acid value of 12-15mgKOH / g, and evacuating; S3. When the acid value reaches 2-4 mgKOH / g, use nitrogen to release the pressure and cool to below 150°C, add 13.3% ethylene glycol butyl ether, stabilize the temperature at 150°C, slowly drop the second raw material into the first raw material, the second raw material components include 3.3% acrylic acid (AA), 2.5% methyl methacrylate (MMA), 15.4% styrene (ST), 0.85% di-tert-butyl hydroperoxide (DTBP) by mass percentage, dropwise add for 4 hours, keep warm for 0.5 hour, add the remaining 0.1% di-tert-butyl hydroperoxide (DTBP), keep warm for 1 hour, cool to 75°C, add 9% isopropanol as diluent solvent, stir evenly, add 3.7% triethylamine as neutralizer and disperse for 0.5 hour, discharge, and obtain a water-based acrylic modified alkyd resin with a solid content of 75%. Example 3

[0023] S1. Add the first raw material components into a 1000 ml four-necked flask equipped with a stirring device, a dehydrating device, a reflux condenser and a dropping funnel, which contain 13.5% trimethylolpropane, 20.1% soybean oleic acid, 3.6% benzoic acid, 1.8% adipic acid, 11% phthalic anhydride and 0.05% stannous octoate by mass percentage; S2, heating the above raw material components to 130°C, keeping the temperature for 1h, at which time a small amount of water begins to escape, then heating to 150°C and keeping the temperature for 30min, heating at 150-180°C for 2h, heating at 180-210°C for 3h, heating at 210°C-230°C for 2h, reacting to an acid value of 12-15mgKOH / g, and evacuating; S3. When the acid value reaches 2-4 mgKOH / g, use nitrogen to release the pressure and cool to below 150°C, add 13.3% ethylene glycol butyl ether, stabilize the temperature at 150°C, slowly drop the second raw material into the first raw material, the second raw material components include 3.3% acrylic acid (AA), 2.5% methyl methacrylate (MMA), 15.4% styrene (ST), 0.85% di-tert-butyl hydroperoxide (DTBP) by mass percentage, dropwise add for 4 hours, keep warm for 0.5 hour, add the remaining 0.1% di-tert-butyl hydroperoxide (DTBP), keep warm for 1 hour, cool to 75°C, add 9% isopropanol as diluent solvent, stir evenly, add 3.7% triethylamine as neutralizer and disperse for 0.5 hour, discharge, and obtain a water-based acrylic modified alkyd resin with a solid content of 75%. Example 4

[0024] S1. Add the first raw material components into a 1000 ml four-necked flask equipped with a stirring device, a dehydrating device, a reflux condenser and a dropping funnel, which contain 13.5% trimethylolpropane, 20.1% soybean oleic acid, 3.6% benzoic acid, 1.8% adipic acid, 12.4% phthalic anhydride and 0.05% stannous octoate by mass percentage; S2, heating the above raw material components to 130°C, keeping the temperature for 1h, at which time a small amount of water begins to escape, then heating to 150°C and keeping the temperature for 30min, heating at 150-180°C for 2h, heating at 180-210°C for 3h, heating at 210°C-230°C for 2h, reacting to an acid value of 12-15mgKOH / g, and evacuating; S3. When the acid value reaches 8-10 mgKOH / g, use nitrogen to release the pressure and cool to below 150°C, add 13.3% ethylene glycol butyl ether, stabilize the temperature at 150°C, slowly add the second raw material dropwise to the first raw material, the second raw material components include 3.3% acrylic acid (AA), 2.5% methyl methacrylate (MMA), 15.4% styrene (ST), 0.85% di-tert-butyl hydroperoxide (DTBP) by mass percentage, add dropwise for 4 hours, keep warm for 0.5 hour, add the remaining 0.1% di-tert-butyl hydroperoxide (DTBP), keep warm for 1 hour, cool to 75°C, add 9% diluent solvent isopropanol, stir evenly, add 3.7% neutralizing agent triethylamine, disperse for 0.5 hour, discharge, and obtain a water-based acrylic modified alkyd resin with a solid content of 75%. Example 5

[0025] S1. Add the first raw material components into a 1000 ml four-necked flask equipped with a stirring device, a dehydrating device, a reflux condenser and a dropping funnel, which contain 13.5% trimethylolpropane, 20.1% soybean oleic acid, 3.6% benzoic acid, 1.8% adipic acid, 12.4% phthalic anhydride and 0.05% stannous octoate by mass percentage; S2, heating the above raw material components to 130°C, keeping the temperature for 1h, at which time a small amount of water begins to escape, then heating to 150°C and keeping the temperature for 30min, heating at 150-180°C for 2h, heating at 180-210°C for 3h, heating at 210°C-230°C for 2h, reacting to an acid value of 12-15mgKOH / g, and evacuating; S3. When the acid value reaches 1-2 mgKOH / g, use nitrogen to release the pressure and cool to below 150°C, add 13.3% ethylene glycol butyl ether, stabilize the temperature at 150°C, slowly add the second raw material dropwise to the first raw material, the second raw material components include 3.3% acrylic acid (AA), 2.5% methyl methacrylate (MMA), 15.4% styrene (ST), 0.85% di-tert-butyl hydroperoxide (DTBP) by mass percentage, add dropwise for 4 hours, keep warm for 0.5 hour, add the remaining 0.1% di-tert-butyl hydroperoxide (DTBP), keep warm for 1 hour, cool to 75°C, add 9% diluent solvent isopropanol, stir evenly, add 3.7% neutralizing agent triethylamine, disperse for 0.5 hour, discharge, and obtain a water-based acrylic modified alkyd resin with a solid content of 75%.

[0026] Comparison example Competitor's Alkyd Resin The raw materials used in competing alkyd resins include 12.6% soybean oleic acid, 12.6% linseed oil, 16.4% phthalic anhydride, 0.5% maleic anhydride, 6.3% trimethylolpropane, 4.4% pentaerythritol, 0.05% stannous octoate, 3.5% acrylic acid (AA), 6.3% methyl methacrylate (MMA), 6.3% styrene (ST), 0.9% di-tert-butyl hydroperoxide (DTBP), 3% dimethylethanolamine, 13.6% propylene glycol methyl ether, and 13.6% ethylene glycol butyl ether.

[0027] Test: (1) The viscosity and solid content of the alkyd resins of Examples 1-5 and the control example were tested according to GBT2794-95 and GBT2793-95, respectively. The data are as follows: Figure 1 As shown by Figure 1 It can be seen that after increasing trimethylolpropane relative to Example 1, Example 2 has a higher viscosity, a higher degree of reaction after excess alcohol, and a larger molecular weight. After reducing phthalic anhydride relative to Example 2, Example 3 has a lower acid ratio, a lower degree of esterification, a lower viscosity, and a smaller molecular weight. The final acid value of the alkyd also determines the molecular weight. A low acid value has a large molecular weight, and a high acid value has a small molecular weight. The finished product obtained in Example 5 has a too high viscosity and cannot be used normally by customers, so it is not considered. Compared with the resin of the competitor company in the control example, the water-based acrylic acid modified alkyd resin of the present invention has a solid content of 75%, and more water can be added in the later paint making. The same weight of resin can be made into more finished products, with lower cost and more advantages.

[0028] (2) The waterborne acrylic acid modified alkyd resins prepared in Examples 1-5 and the resins of the competitor companies in the control example were prepared according to Figure 2 The paint scraper was used to test its performance. A 200μm wire rod was used to scrape the aluminum plate to make a 40-50μm dry film test. The test results are as follows Figure 3 shown.

[0029] Depend on Figure 3 It can be seen that after increasing trimethylolpropane in Example 2, both the surface drying and water resistance become worse. After reducing phthalic anhydride in Example 3, the viscosity becomes lower, the surface drying becomes worse, and the water resistance also becomes worse. After the acid value becomes higher and the molecular weight becomes smaller in Example 4, the water resistance and surface drying are the worst. The surface drying time of the competitive resin in the control example is longer than that in Example 1, the water resistance is average, and the gloss is similar. In summary, the surface drying and water resistance of Example 1 are better than those of the competitive resin, and it is cheaper and more cost-effective.

[0030] Although the present invention has been described above with reference to the embodiments, various modifications may be made thereto and parts thereof may be replaced by equivalents without departing from the scope of the present invention. In particular, as long as there is no structural conflict, the various features in the embodiments disclosed in the present invention may be used in combination with each other in any manner, and the fact that these combinations are not exhaustively described in this specification is only for the sake of omitting space and saving resources. Therefore, the present invention is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.

Claims

1. A quick-drying acrylic acid-modified waterborne alkyd resin, characterized in that: The invention is composed of the following components in parts by weight: trimethylolpropane: 13-15 parts, soybean oleic acid: 19-20 parts, benzoic acid: 3-4 parts, adipic acid: 1-2 parts, phthalic anhydride: 10-13 parts, catalyst: 0.05-0.1 parts, acrylic acid monomer: 21-24 parts, initiator: 0.9-1 parts, neutralizer: 4-5 parts, solvent: 22-24 parts; The specific preparation steps of the quick-drying acrylic acid-modified waterborne alkyd resin are as follows: S1. After uniformly mixing trimethylolpropane, soybean oleic acid, benzoic acid, phthalic anhydride and adipic acid according to the proportion, add a catalyst and heat to dehydrate. First, heat to 130°C and keep it for 1 hour. At this time, a small amount of water begins to be removed. Then heat to 150°C and keep it for 30 minutes. Heat to 150-180°C for 2 hours, heat to 180-210°C for 3 hours, and heat to 210°C-230°C for 2 hours. When the acid value reaches 12-15 mgKOH / g, vacuumize. S2. When the acid value reaches 2-4 mgKOH / g, use nitrogen to release the pressure and cool down to below 150°C, add a certain amount of solvent, raise the temperature to stabilize at 150°C, add the acrylic acid monomer prepared in proportion at a uniform speed, add it for 4 hours, then keep warm for 0.5 hour, add the initiator once, keep warm for another 1 hour, cool down to 75°C, add the diluted solvent, stir evenly, add the neutralizer and disperse for 0.5 hour, and then discharge the material.

2. A quick-drying acrylic acid modified waterborne alkyd resin according to claim 1, characterized in that: The catalyst is stannous octoate.

3. A quick-drying acrylic acid modified waterborne alkyd resin according to claim 1, characterized in that: The acrylic monomer includes any one or more of acrylic acid, methyl methacrylate and styrene.

4. A quick-drying acrylic acid modified waterborne alkyd resin according to claim 1, characterized in that: The initiator is DTBP.

5. The quick-drying acrylic acid-modified waterborne alkyd resin according to claim 1, characterized in that: The neutralizing agent is any one of triethylamine or N,N-dimethylethanolamine.

6. The quick-drying acrylic acid-modified waterborne alkyd resin according to claim 1, characterized in that: The solvent is a mixture of ethylene glycol butyl ether or isopropanol.

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