A method for preparing a nano-titanium dioxide and acrylic modified water-based alkyd resin
By introducing four-arm polyethylene glycol and modified nano-titanium dioxide into alkyd resin, the problems of low hardness of alkyd resin and poor dispersibility of nano-titanium dioxide were solved, thus improving the performance of the coating.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHANDONG QILU PAINT CO LTD
- Filing Date
- 2023-09-11
- Publication Date
- 2026-08-04
AI Technical Summary
Existing alkyd resins have low hardness and are easily decomposed. Nano-titanium dioxide has poor dispersibility in coatings, affecting the gloss, hardness, wear resistance and stability of the coatings.
Four-arm polyethylene glycol was used as the hyperbranched main chain of the alkyd resin, and nano-titanium dioxide was modified by triisostearate titanate isopropyl ester and combined with acrylic resin branches to improve the uniformity and hardness of the resin, while also improving the dispersibility of nano-titanium dioxide.
It improves the hardness and flexibility of alkyd resin, prevents coating cracking, enhances the dispersibility of nano titanium dioxide in coating, and improves the gloss, hardness and stability of coating.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of alkyd resin technology, specifically a method for preparing a waterborne alkyd resin modified with nano-titanium dioxide and acrylic acid. Background Technology
[0002] Alkyd resin is a polyester resin mainly composed of vegetable oils. Its raw materials are widely available, production costs are low, the preparation process is stable, and its performance is excellent, making it widely used in the coatings industry. However, existing alkyd resins often contain a large amount of pentaerythritol during preparation. Pentaerythritol has a small molecular weight and high molecular flexibility, resulting in low hardness and easy decomposition of the prepared alkyd resin. Therefore, it is necessary to add other components during the resin preparation process to improve the resin's hardness.
[0003] Nano-titanium dioxide, as an additive, can improve the gloss, hardness, wear resistance, and stability of coatings, and has a very broad application prospect in the coatings industry. However, nano-titanium dioxide solid is insoluble, resulting in poor dispersibility when directly added to coatings, and sedimentation occurs after long-term storage. Therefore, how to improve the dispersibility of nano-titanium dioxide in coatings and maximize its effects on gloss, hardness, wear resistance, and stability has always been a problem that technicians have been constantly exploring to solve. Summary of the Invention
[0004] To address the above problems, the present invention aims to provide a method for preparing nano-titanium dioxide and acrylic acid-modified waterborne alkyd resin.
[0005] To achieve the above objectives, the present invention employs the following technical solution: A method for preparing a waterborne alkyd resin modified with nano-titanium dioxide and acrylic acid includes the following steps: ① By weight, add 100-150 parts of vegetable oil, 10-20 parts of tetraethylene glycol, 5-15 parts of pentaerythritol, 5-10 parts of benzoic acid, and 30-40 parts of phthalic anhydride to a reaction vessel, stir and heat to 150-160℃, stir and react for 1-2 hours, continue to heat to 200-210℃, stir and react for 3-5 hours, cool to 20-35℃ to obtain an alkyd resin solution for later use; The vegetable oil is one or two of soybean oil, castor oil, or linseed oil; ② Add 5-15 parts of nano titanium dioxide, 0.1-1 parts of triisostearate titanate isopropyl triisostearate, 30-50 parts of ethanol, and 20-30 parts of water to a mixing reactor, and stir and mix at 25-45℃ for 1-2 hours to obtain a nano titanium dioxide solution. ③ Add 30-40 parts of organic solvent, 30-40 parts of styrene, 10-15 parts of butyl acrylate, 10-20 parts of hydroxyethyl acrylate, 20-30 parts of methyl methacrylate, and 1-5 parts of initiator to a reaction vessel, stir and heat to 90℃, add the alkyd resin solution obtained in step ① in several portions, controlling the temperature of the reaction vessel to not exceed 120℃ during the addition, and continue to add the nano titanium dioxide solution obtained in step ② to the reaction vessel, stir and react at 100-120℃ for 2-5 hours, add organic amine to neutralize to an acidity of 20-26 mg KOH / g, cool to 25-45℃, and disperse at high speed for 0.5-1 hour to obtain nano titanium dioxide and acrylic acid modified waterborne alkyd resin.
[0006] Preferably, the vegetable oil is composed of castor oil and linseed oil in a mass ratio of 1:2 to 5.
[0007] Preferably, the organic solvent is obtained by mixing an alcohol ether solvent and No. 100 solvent oil at a mass ratio of 1:2~4; the preferred alcohol ether is diethylene glycol monomethyl ether, propylene glycol methyl ether or dipropylene glycol dimethyl ether. The organic amine is dimethylethanolamine or AMP-95.
[0008] Preferably, the molecular weight of the four-armed polyethylene glycol is 3000-5000.
[0009] Preferably, the nano-titanium dioxide is activated before use, specifically by calcining at 200-250°C for 2-3 hours.
[0010] Preferably, the initiator is benzoyl peroxide or azobisisobutyronitrile.
[0011] The present invention has the following advantages over the prior art: The modified alkyd resin of this invention uses four-arm polyethylene glycol as the main chain of the hyperbranched structure of the alkyd resin. Because four-arm polyethylene glycol contains a large number of oxygen atoms, after polymerization, a large number of voids are generated throughout the alkyd resin molecule. These voids allow acrylic resin branches and nano-titanium dioxide to enter, thereby improving the uniformity of the resin. Furthermore, using four-arm polyethylene glycol as the main chain of the hyperbranched structure of the alkyd resin can improve the hardness and flexibility of the alkyd resin, preventing cracking in the coating. On the other hand, this invention uses isopropyl triisostearate titanate to modify nano-titanium dioxide, overcoming the problem of insufficient uniformity of nano-titanium dioxide and preventing the precipitation of nano-titanium dioxide in the alkyd resin. Through the acrylic resin branches interspersed in the alkyd resin, the mechanical properties of the alkyd resin can be improved, the drying speed of the resin can be increased, and the stability of the resin can be enhanced. Detailed Implementation
[0012] The purpose of this invention is to provide a method for preparing nano-titanium dioxide and acrylic acid-modified waterborne alkyd resin. The invention will be further described below with reference to specific embodiments.
[0013] Example 1: A method for preparing a waterborne alkyd resin modified with nano-titanium dioxide and acrylic acid, comprising the following steps: ① Add 100 kg of vegetable oil, 10 kg of tetraethylene glycol, 5 kg of pentaerythritol, 5 kg of benzoic acid, and 30 kg of phthalic anhydride to a reaction vessel, stir and heat to 150°C, stir and react for 1 hour, continue to heat to 200°C, stir and react for 3 hours, cool to 20°C to obtain an alkyd resin solution for later use. The vegetable oil is soybean oil; ② Add 5 kg of nano titanium dioxide, 0.1 kg of triisostearate titanate isopropyl triisostearate, 30 kg of ethanol and 20 kg of water to a mixing reactor, stir and mix at 25°C for 2 hours to obtain a nano titanium dioxide solution. ③ Add 10 kg of diethylene glycol monomethyl ether, 26 kg of No. 100 solvent oil, 30 kg of styrene, 10 kg of butyl acrylate, 10 kg of hydroxyethyl acrylate, 20 kg of methyl methacrylate, and 1 kg of initiator to the reaction vessel, stir and heat to 90°C, add the alkyd resin solution obtained in step ① in 5 portions, and control the temperature of the reaction vessel to not exceed 120°C during the addition. After the addition is completed, continue to add the nano titanium dioxide solution obtained in step ② to the reaction vessel, stir and react at 100°C for 5 hours, cool down to 25°C, add dimethylethanolamine to neutralize to an acidity of 20 mg KOH / g, disperse at high speed for 0.5 hours to obtain nano titanium dioxide and acrylic acid modified waterborne alkyd resin; The initiator is benzoyl peroxide.
[0014] Example 2: A method for preparing a waterborne alkyd resin modified with nano-titanium dioxide and acrylic acid, comprising the following steps: ① Add 150 kg of vegetable oil, 20 kg of tetraethylene glycol, 15 kg of pentaerythritol, 10 kg of benzoic acid, and 40 kg of phthalic anhydride to a reaction vessel, stir and heat to 160°C, stir and react for 2 hours, continue to heat to 210°C, stir and react for 5 hours, cool to 35°C to obtain an alkyd resin solution for later use. The vegetable oil is castor oil; ② Add 15 kg of nano titanium dioxide, 1 kg of triisostearate titanate isopropyl triisostearate, 50 kg of ethanol and 30 kg of water to a mixing reactor, stir and mix at 45°C for 1 hour to obtain a nano titanium dioxide solution. ③ Add 10 kg of propylene glycol methyl ether, 24 kg of No. 100 solvent oil, 40 kg of styrene, 15 kg of butyl acrylate, 20 kg of hydroxyethyl acrylate, 30 kg of methyl methacrylate, and 5 kg of initiator to the reaction vessel, stir and heat to 90°C, add the alkyd resin solution obtained in step ① in 8 portions, and control the temperature of the reaction vessel to not exceed 120°C during the addition. After the addition is completed, continue to add the nano titanium dioxide solution obtained in step ② to the reaction vessel, stir and react at 120°C for 2 hours, cool down to 45°C, add AMP-95 to neutralize to an acidity of 26 mg KOH / g, disperse at high speed for 1 hour to obtain nano titanium dioxide and acrylic acid modified waterborne alkyd resin; The initiator is azobisisobutyronitrile.
[0015] Example 3 A method for preparing a waterborne alkyd resin modified with nano-titanium dioxide and acrylic acid, comprising the following steps: ① Add 120 kg of vegetable oil, 18 kg of tetraethylene glycol, 8 kg of pentaerythritol, 6 kg of benzoic acid, and 32 kg of phthalic anhydride to a reaction vessel, stir and heat to 152°C, stir and react for 1.5 hours, continue to heat to 205°C, stir and react for 3.5 hours, cool to 25°C to obtain an alkyd resin solution for later use; The vegetable oil is composed of castor oil and linseed oil in a mass ratio of 1:2; the molecular weight of the four-armed polyethylene glycol is 3000; ② 8 kg of nano titanium dioxide was calcined at 200°C for 3 hours. Then, the treated nano titanium dioxide, 0.5 kg of triisostearate isopropyl titanate, 32 kg of ethanol and 22 kg of water were added to a mixing reactor and stirred at 30°C for 1.5 hours to obtain a nano titanium dioxide solution. ③ Add 10 kg of dipropylene glycol dimethyl ether, 25 kg of No. 100 solvent oil, 32 kg of styrene, 12 kg of butyl acrylate, 12 kg of hydroxyethyl acrylate, 28 kg of methyl methacrylate, and 2 kg of initiator to the reaction vessel, stir and heat to 90°C, add the alkyd resin solution obtained in step ① in 3 portions, and control the temperature of the reaction vessel to not exceed 120°C during the addition. After the addition is completed, continue to add the nano titanium dioxide solution obtained in step ② to the reaction vessel, stir and react at 105°C for 3 hours, cool down to 30°C, add AMP-95 to neutralize to an acidity of 22 mg KOH / g, disperse at high speed for 45 minutes to obtain nano titanium dioxide and acrylic acid modified waterborne alkyd resin; The initiator is benzoyl peroxide.
[0016] Example 4: A method for preparing a waterborne alkyd resin modified with nano-titanium dioxide and acrylic acid, comprising the following steps: ① Add 130 kg of vegetable oil, 12 kg of tetraethylene glycol, 10 kg of pentaerythritol, 8 kg of benzoic acid, and 34 kg of phthalic anhydride to a reaction vessel, stir and heat to 155°C, stir and react for 1 hour, continue to heat to 202°C, stir and react for 4 hours, cool to 30°C to obtain an alkyd resin solution for later use. The vegetable oil is composed of castor oil and linseed oil in a mass ratio of 1:5; the molecular weight of the tetra-armed polyethylene glycol is 5000. ② 12 kg of nano titanium dioxide was calcined at 250°C for 2 hours. Then, the treated nano titanium dioxide, 0.6 kg of triisostearate isopropyl titanate, 35 kg of ethanol and 26 kg of water were added to a mixing reactor and stirred at 40°C for 1.5 hours to obtain a nano titanium dioxide solution. ③ Add 9 kg of diethylene glycol monomethyl ether, 23 kg of No. 100 solvent oil, 38 kg of styrene, 12 kg of butyl acrylate, 14 kg of hydroxyethyl acrylate, 28 kg of methyl methacrylate, and 2 kg of initiator to the reaction vessel, stir and heat to 90°C, add the alkyd resin solution obtained in step ① in 4 portions, and control the temperature of the reaction vessel to not exceed 120°C during the addition. After the addition is completed, continue to add the nano titanium dioxide solution obtained in step ② to the reaction vessel, stir and react at 110°C for 4 hours, cool down to 40°C, add dimethyl ethanolamine to neutralize to an acidity of 23 mg KOH / g, disperse at high speed for 40 minutes to obtain nano titanium dioxide and acrylic acid modified waterborne alkyd resin; The initiator is azobisisobutyronitrile.
[0017] Example 5: A method for preparing a waterborne alkyd resin modified with nano-titanium dioxide and acrylic acid, comprising the following steps: ① Add 135 kg of vegetable oil, 15 kg of tetraethylene glycol, 12 kg of pentaerythritol, 7 kg of benzoic acid, and 36 kg of phthalic anhydride to a reaction vessel, stir and heat to 154°C, stir and react for 1.5 hours, continue to heat to 208°C, stir and react for 4 hours, cool to 32°C to obtain an alkyd resin solution for later use; The vegetable oil is obtained by mixing castor oil and linseed oil in a mass ratio of 1:4; the molecular weight of the tetra-armed polyethylene glycol is 4000; ② 8 kg of nano titanium dioxide was calcined at 220°C for 2.5 hours. Then, the treated nano titanium dioxide, 0.6 kg of triisostearate isopropyl titanate, 45 kg of ethanol and 24 kg of water were added to a mixing reactor and stirred at 35°C for 1.5 hours to obtain a nano titanium dioxide solution. ③ Add 12 kg of propylene glycol methyl ether, 24 kg of No. 100 solvent oil, 36 kg of styrene, 12 kg of butyl acrylate, 18 kg of hydroxyethyl acrylate, 24 kg of methyl methacrylate, and 4 kg of initiator to the reaction vessel, stir and heat to 90°C, add the alkyd resin solution obtained in step ① in 5 portions, and control the temperature of the reaction vessel to not exceed 120°C during the addition. After the addition is completed, continue to add the nano titanium dioxide solution obtained in step ② to the reaction vessel, stir and react at 110°C for 3 hours, cool down to 40°C, add dimethyl ethanolamine to neutralize to an acidity of 25 mg KOH / g, disperse at high speed for 40 minutes to obtain nano titanium dioxide and acrylic acid modified waterborne alkyd resin; The initiator is benzoyl peroxide.
[0018] The modified waterborne alkyd resins with added benzyl glycerol obtained in Examples 1-5 were prepared into alkyd resin paints according to the following weight formulas. The drying time of the paint film was tested according to GB / T 1728-79. The surface drying time was determined by the cotton ball blowing method, and the actual drying time was determined by the filter paper pressing method. The hardness of the paint film was tested according to GB / T 6739-2006. The impact resistance of the paint film was tested according to GB / T 1732-1993. The adhesion of the paint film was tested according to GB / T 9286-1998. The water resistance and salt water resistance of the paint film were tested according to GB / T 1733-1993.
[0019] The recipe is as follows: The modified waterborne alkyd resin with added benzyl glycerol obtained in Examples 1-5 consisted of 35 parts, organic bismuth environmentally friendly catalyst SDJT-20 0.5 parts, SD5040 dispersant 0.3 parts, deionized water 50 parts, light calcium carbonate 10 parts, and BYK-066N defoamer 0.2 parts; the film properties are shown in Table 1.
[0020]
Claims
1. A method for preparing nano-titanium dioxide and acrylic acid-modified waterborne alkyd resin, characterized in that: Includes the following steps: ① By weight, add 100-150 parts of vegetable oil, 10-20 parts of tetraethylene glycol, 5-15 parts of pentaerythritol, 5-10 parts of benzoic acid, and 30-40 parts of phthalic anhydride to a reaction vessel, stir and heat to 150-160℃, stir and react for 1-2 hours, continue to heat to 200-210℃, stir and react for 3-5 hours, cool to 20-35℃ to obtain an alkyd resin solution for later use; The vegetable oil is one or two of soybean oil, castor oil, or linseed oil; ② Add 5-15 parts of nano titanium dioxide, 0.1-1 parts of triisostearate titanate isopropyl triisostearate, 30-50 parts of ethanol, and 20-30 parts of water to a mixing reactor, and stir and mix at 25-45℃ for 1-2 hours to obtain a nano titanium dioxide solution. ③ Add 30-40 parts of organic solvent, 30-40 parts of styrene, 10-15 parts of butyl acrylate, 10-20 parts of hydroxyethyl acrylate, 20-30 parts of methyl methacrylate, and 1-5 parts of initiator to a reaction vessel, stir and heat to 90℃, add the alkyd resin solution obtained in step ① in several portions, controlling the temperature of the reaction vessel to not exceed 120℃ during the addition, and continue to add the nano titanium dioxide solution obtained in step ② to the reaction vessel, stir and react at 100-120℃ for 2-5 hours, cool down to 25-45℃, add organic amine to neutralize to an acidity of 20-26 mg KOH / g, disperse at high speed for 0.5-1 hour to obtain nano titanium dioxide and acrylic acid modified waterborne alkyd resin.
2. The method for preparing a nano-titanium dioxide and acrylic acid-modified waterborne alkyd resin according to claim 1, characterized in that: The vegetable oil is composed of castor oil and linseed oil in a mass ratio of 1:2 to 5.
3. The method for preparing a nano-titanium dioxide and acrylic acid-modified waterborne alkyd resin according to claim 1, characterized in that: The organic solvent is obtained by mixing alcohol ether solvent and No. 100 solvent oil in a mass ratio of 1:2~4.
4. The method for preparing a nano-titanium dioxide and acrylic acid-modified waterborne alkyd resin according to claim 1, characterized in that: The organic amine is dimethylethanolamine or AMP-95.
5. The method for preparing a nano-titanium dioxide and acrylic acid-modified waterborne alkyd resin according to claim 1, characterized in that: The molecular weight of the four-armed polyethylene glycol is 3000-5000.
6. The method for preparing a nano-titanium dioxide and acrylic acid-modified waterborne alkyd resin according to claim 1, characterized in that: The nano-titanium dioxide is activated before use, specifically by calcining at 200-250°C for 2-3 hours.
7. The method for preparing a nano-titanium dioxide and acrylic acid-modified waterborne alkyd resin according to claim 1, characterized in that: The initiator is benzoyl peroxide or azobisisobutyronitrile.