A kind of silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion and preparation method thereof

Abstract

The invention provides a silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion and a preparation method thereof, belonging to the field of coating synthesis, and used to solve the problems of low solid and high viscosity of the waterborne acrylic resin dispersion, poor gloss retention after film formation, poor water resistance and low alkali resistance. The resin dispersion comprises the following raw materials in parts by weight: 10-16 parts of unsaturated fatty acid, 4-6 parts of polyacid, 6-16 parts of polyol, 4.8-8.6 parts of organosilicon, 2-4 parts of hydroxyl vinyl monomer, 40-65 parts of hard monomer, 16.5-40 parts of soft monomer, 4-8 parts of carboxyl vinyl monomer, 1-3 parts of organic fluorine, 34-64 parts of solvent, 1.8-3.6 parts of initiator, 0.2-0.5 parts of tetraisopropyl titanate, 0.1-0.3 parts of cupric chloride, 0.05-0.15 parts of inhibitor, 0.05-0.15 parts of chain transfer agent, 4.5-8.5 parts of neutralizer and 80-165 parts of deionized water.

Description

Technical Field

[0001] The invention belongs to the field of coating synthesis, and particularly relates to a silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion and a preparation method thereof. Background Art

[0002] Traditional solvent-based resins pose a great threat to the environment and human health due to the presence of volatile, flammable and toxic solvents and gases. As environmental standards become more stringent, water-based resins have experienced rapid development, especially environmentally friendly resins represented by water-based acrylic resins, which have become a hot topic of research for scholars. Acrylic resins are mainly copolymerized with (meth) acrylic acid vinyl monomers and have advantages such as good weather resistance and aging resistance. However, their coatings still have problems such as slow surface drying and actual drying time, poor gloss retention, poor water resistance and alkali resistance, poor mechanical properties, and expensive raw materials, which greatly limit their application in many fields.

[0003] Alkyd resin is a polymer formed by the condensation of unsaturated fatty acids from vegetable oils, polyacids, and polyols. It has air-drying properties and can self-oxidize and cross-link during the film-forming process to increase the cross-linking density of the paint film. The raw materials are widely available and inexpensive. The molecules contain a large number of polar groups (ester groups, hydroxyl groups, carboxyl groups, and unsaturated double bonds) and can react with various functional monomers and resins. Chinese patent application number 202111134806.6 discloses an epoxy resin prepolymer-modified water-based alkyd resin and a preparation method thereof. The prepared resin has improved adhesion and medium resistance, but the resin coating has a slow drying time, low hardness, and tends to turn white after immersion in water. Chinese patent application number 202110881209.3 discloses a modified water-based alkyd resin, a preparation method thereof, and an aqueous dispersion containing the same, which solves the technical problem of poor initial water resistance of water-based alkyd resin modified by acrylic acid (ester) monomer in the prior art. However, the paint coating prepared with this resin as the main film-forming substance has a slow surface drying time, low hardness and adhesion. Chinese patent application number 202011380117.9 discloses a hybrid silicon / epoxy ester modified water-based acrylic resin dispersion and a preparation method. The resin dispersion coating has a gloss of more than 90% and an adhesion of level 0. There is no bubbling or shedding after immersion in water for 7-14 days, but the solid content of the dispersion is low. It was found that it was unstable during the addition of a mixed solution of (meth) acrylic acid vinyl monomers, and the gloss retention and alkali resistance after film formation were poor. Chinese patent application number 201610555550.9 discloses a fluorosilicone-modified waterborne alkyd resin and a preparation method thereof. The film-forming hardness and adhesion of the fluorosilicone-modified waterborne alkyd resin reach levels 2H and 0, respectively. However, during the preparation process, "the acrylic monomer mixture B is uniformly added dropwise to the silicon-modified alkyd resin C" may result in an unstable polymerization process. The two are also physically mixed, causing the overall performance of the resin to deteriorate. In addition, the organic fluorine used contains an ester bond and will gradually decompose in an alkaline solution, resulting in a decrease in the alkali resistance of the resin coating prepared therewith. Summary of the Invention

[0004] To address the technical issues of low-solids, high-viscosity waterborne acrylic resin dispersions, poor gloss retention after film formation, poor water resistance, and low alkali resistance, the present invention proposes a silicone-fluorine / alkyd resin-modified waterborne acrylic resin dispersion and a preparation method. The silicone-fluorine / alkyd resin-modified waterborne acrylic resin dispersion exhibits a clear and transparent appearance, high solids and low viscosity, fast surface and through-drying times, and excellent gloss retention and alkali resistance of the film-formed paint film, along with superior mechanical properties and low cost.

[0005] In order to achieve the above object, the technical solution of the present invention is achieved as follows:

[0006] A silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion comprises the following raw materials in parts by weight: 10-16 parts of unsaturated fatty acid, 4-6 parts of polyacid, 6-16 parts of polyol, 4.8-8.6 parts of organosilicon, 2-4 parts of hydroxyl vinyl monomer, 40-65 parts of hard monomer, 16.5-40 parts of soft monomer, 4-8 parts of carboxyl vinyl monomer, 1-3 parts of organofluorine, 34-64 parts of solvent, 1.8-3.6 parts of initiator, 0.2-0.5 parts of tetraisopropyl titanate, 0.1-0.3 parts of cupric chloride, 0.05-0.15 parts of polymerization inhibitor, 0.05-0.15 parts of chain transfer agent, 4.5-8.5 parts of neutralizer and 80-165 parts of deionized water.

[0007] Furthermore, the ratio of the sum of the masses of the unsaturated fatty acids and the polyacid to the mass of the polyol is (1.3-2.4):1, wherein the unsaturated fatty acids are a combination of dehydrated ricinoleic acid and palmitoleic acid, and the mass ratio of dehydrated ricinoleic acid and palmitoleic acid is (2-3):1; the mass ratio of the polyol, the silicone and the hydroxyl-type vinyl monomer is (3-4):(2.1-2.5):1, wherein the silicone is a terminal hydroxyl siloxane, and the hydroxyl-type vinyl monomer is either 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate.

[0008] Furthermore, the polyacid is any one of adipic acid, phthalic anhydride or trimellitic anhydride; the polyol is any one of neopentyl glycol, trimethylolpropane or pentaerythritol; the carboxyl vinyl monomer is any one of methacrylic acid or acrylic acid; the organic fluorine is fluorine-containing polyether acrylate, the basic structural formula is Where R = C n H (2n-1) , R f =C4~C6 perfluoroalkyl, n=1~12, m=2~3, p=1~4.

[0009] Furthermore, the hard monomer is a combination of styrene and methyl methacrylate, and the mass ratio of styrene to methyl methacrylate is (2-2.2):1; the soft monomer is any one of lauryl methacrylate or butyl acrylate; the mass ratio of the hard monomer to the soft monomer is (1.4-2.5):1.

[0010] Furthermore, the solvent is a combination of any three of n-butanol, propylene glycol methyl ether, propylene glycol butyl ether or diethylene glycol butyl ether, and the mass ratio of the three substances in the combination after sorting by volatilization rate of slow, medium and fast is 1:(1:4-2):(2.1-3.5); the initiator is any one of tert-butyl benzoyl peroxide or di-tert-butyl hydroperoxide; the chain transfer agent is any one of 3-mercapto-1-propanol or n-dodecyl mercaptan; the inhibitor is any one of hydroquinone or 4-methoxyphenol; and the neutralizer is any one of triethylamine or NN dimethylethanolamine or a combination of two.

[0011] The present invention also includes a method for preparing the above-mentioned silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion, comprising the following steps:

[0012] (1) organic silicon, tetraisopropyl titanate, copper chloride and solvent are uniformly mixed to obtain a pre-reaction liquid A; hydroxyl vinyl monomer, polymerization inhibitor, tetraisopropyl titanate and solvent are uniformly mixed to obtain a pre-reaction liquid B; hard monomer, soft monomer, carboxyl vinyl monomer, organic fluorine, initiator, chain transfer agent and solvent are uniformly mixed to obtain a pre-reaction liquid C;

[0013] (2) reacting unsaturated fatty acids, polyacids, polyols and solvents to form polymers and esterifying them to obtain unsaturated esters;

[0014] (3) adding the pre-reaction liquid A dropwise to the unsaturated ester of step (2), introducing nitrogen to replace the air for 5-10 minutes, and reacting. After the reaction is completed, adding the pre-reaction liquid B dropwise, introducing nitrogen to replace the air for 5-10 minutes, and reacting again to obtain a reaction liquid;

[0015] (4) The pre-reaction liquid C is added to the reaction liquid of step (3) by a "fast and slow" dropwise addition method. After the reaction is completed, a neutralizing agent and deionized water are added and stirred evenly to obtain a silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion.

[0016] Furthermore, the preparation methods of the pre-reaction liquids A, B and C in the step (1) are respectively: organic silicon, tetraisopropyl titanate with a mass concentration of 50%, copper chloride and a solvent with a mass concentration of 10% are mixed evenly to obtain pre-reaction liquid A; hydroxyl vinyl monomer, polymerization inhibitor, tetraisopropyl titanate with a mass concentration of 50% and a solvent with a mass concentration of 10% are mixed evenly to obtain pre-reaction liquid B; hard monomer, soft monomer, carboxyl vinyl monomer, organic fluorine, an initiator with a mass concentration of 70%, a chain transfer agent and a solvent with a mass concentration of 25% are mixed evenly to obtain pre-reaction liquid C.

[0017] Furthermore, the polymer reaction in step (2) is specifically as follows: after mixing a solvent with a mass concentration of 15%, an unsaturated fatty acid with a mass concentration of 70%, a polyacid and a polyol, heating the oil bath to 210-230° C., continuously stirring at a speed of 100-150 r / min, and reducing the acid value to below 5 mg KOH / g; then adding a solvent with a mass concentration of 10% and an unsaturated fatty acid with a mass concentration of 30%, and continuing the esterification reaction until the acid value is ≤3 mg KOH / g.

[0018] Furthermore, in step (3), the dripping time of the pre-reaction liquid A and the pre-reaction liquid B is controlled to be 10-15 min, the reaction temperature is 120-140° C., and the reaction time is 60-80 min.

[0019] Furthermore, the step (4) is specifically as follows: the temperature is adjusted to 120-140° C., 1 / 5 volume of the pre-reaction liquid C is added dropwise to the reaction liquid of step (3) for 30-40 minutes; the remaining pre-reaction liquid C is then added dropwise for 3-4 hours; the temperature is adjusted to 125-145° C., the remaining solvent and initiator used in the previous step are added, and the reaction is carried out at a constant temperature for 2-4 hours; the temperature is lowered to below 40° C., a neutralizer is added under stirring, the pH is adjusted to 8-9, deionized water is added, and stirring is continued until transparent to obtain a silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion.

[0020] The synthesis mechanism of the silicone fluorine / alkyd resin modified waterborne acrylic resin is as follows Figure 1 As shown: 1) controlling the mass ratio of unsaturated fatty acid, polyacid and polyol, using a polymer method, the unsaturated fatty acid, polyacid and polyol are subjected to an esterification reaction (reaction of carboxyl group with hydroxyl group) under certain conditions to obtain unsaturated ester; 2) adding terminal hydroxyl silicone, and carrying out an etherification reaction with the unsaturated ester under the action of a catalyst (reaction of terminal hydroxyl group with hydroxyl group of the unsaturated ester); 3) adding a hydroxyl type vinyl monomer, and carrying out an etherification reaction with the above product under the action of a catalyst (reaction of terminal hydroxyl group with hydroxyl group of the unsaturated ester). Under these conditions, a small amount of polymerization inhibitor is added to prevent the carbon-carbon double bond of the hydroxyl type vinyl monomer itself from self-polymerization; 4) adding a mixed solution of (meth) acrylic acid vinyl monomer, and carrying out a copolymerization reaction with the above etherified hydroxyl type vinyl monomer under the action of an initiator, and finally obtaining a silicone fluorine / alkyd resin modified waterborne acrylic resin.

[0021] Beneficial effects of the present invention:

[0022] 1. The present invention is based on molecular structure design, uses organic silicon as an intermediate bridge, uses alkyd resin to modify acrylic resin by chemical methods, and adopts in situ polymerization during the synthesis process to polymerize organic fluorine containing carbon-carbon double bonds onto the main chain of acrylic resin, thereby preparing a water-based acrylic resin dispersion with excellent comprehensive properties.

[0023] 2. In the preparation of unsaturated esters, the present invention utilizes a high polymer method for esterification, resulting in a narrower molecular weight distribution for the polymer, which is beneficial for the drying and resistance properties of the resin coating. In the synthesis of acrylic resin, the vinyl monomer is added dropwise in a "fast and slow" manner, which not only ensures a smooth polymerization process but also maintains a stable polymer viscosity, effectively ensuring safety and reproducibility during polymerization. Furthermore, by limiting the ratios of acid, alcohol, organosilicon, and vinyl hard and soft monomers, the orderliness of the polymerization process and the composition of the copolymer are guaranteed. Simultaneously, the restriction and optimization of environmentally friendly solvents ensure the orderly volatilization of the various solvents in the resin coating, resulting in the resin coating having rapid surface drying (≤24 minutes), fast drying (≤19 hours), high gloss (gloss ≥113°), and good gloss retention (the gloss loss rate of the paint film is 11.4%).

[0024] 3. The silicone-fluorine / alkyd resin-modified waterborne acrylic resin dispersion of the present invention eliminates the risk of demulsification, improves the storage stability of the dispersion, and avoids the effects of emulsifiers on the mechanical properties, water resistance, and gloss of the coating. Furthermore, with organosilicon as the intermediate bridge, the Si-O bond is much stronger than C-C and C-O bonds, resulting in superior resin performance and excellent self-cleaning properties. Furthermore, the copolymerization of an acrylic acid organofluorine monomer containing a long-chain ether bond with a (meth)acrylic acid vinyl monomer imparts excellent alkali resistance to the resin. Paint films prepared therefrom exhibit virtually no surface changes after immersion in an alkaline solution for seven days.

[0025] 4. The silicone-fluorine / alkyd resin modified water-based acrylic resin dispersion of the present invention has a clear and transparent appearance, high solid content and low viscosity, fast surface drying (≤24 minutes) and thorough drying (≤19 hours), high hardness (2 hours), good gloss (≥113°), and certain water resistance and storage stability. The paint film after film formation has good gloss retention (gloss loss rate of 11.4%) and good alkali resistance. The raw materials are economical and environmentally friendly, the preparation is simple, and the cost is low, and it has great market application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. 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 paying any creative work.

[0027] Figure 1 It is a synthetic diagram of the silicone-fluorine / alkyd resin modified waterborne acrylic resin of the present invention;

[0028] Figure 2is the molecular weight of a silicone-fluorine / alkyd resin modified waterborne acrylic resin provided in Example 1 of the present invention;

[0029] Figure 3 is the molecular weight of a silicone-fluorine / alkyd resin modified waterborne acrylic resin provided in Example 2 of the present invention;

[0030] Figure 4 is the molecular weight of a silicone-fluorine / alkyd resin modified waterborne acrylic resin provided in Example 3 of the present invention;

[0031] Figure 5 is the molecular weight of a silicone-fluorine / alkyd resin modified waterborne acrylic resin provided in Example 4 of the present invention;

[0032] Figure 6 is the molecular weight of a silicone-fluorine / alkyd resin modified waterborne acrylic resin provided in Example 5 of the present invention;

[0033] Figure 7 This is a particle size distribution diagram of a silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion provided in Example 1 of the present invention;

[0034] Figure 8 This is a particle size distribution diagram of a silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion provided in Example 2 of the present invention;

[0035] Figure 9 This is a particle size distribution diagram of a silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion provided in Example 3 of the present invention;

[0036] Figure 10 This is a particle size distribution diagram of a silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion provided in Example 4 of the present invention;

[0037] Figure 11 This is a particle size distribution diagram of a silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion provided in Example 5 of the present invention. DETAILED DESCRIPTION

[0038] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without creative work are within the scope of protection of the present invention.

[0039] Unless otherwise specified, the experimental methods used in the examples of the present invention are conventional methods.

[0040] Unless otherwise specified, the materials, reagents, etc. used in the examples of the present invention can be obtained from commercial sources.

[0041] In the embodiments of the present invention, the mass concentration of tetraisopropyl titanate used in preparing pre-reaction liquids A and B is 50%, and the mass concentration of the solvent is 10%; the mass concentration of the initiator used in preparing pre-reaction liquid C is 70%, and the mass concentration of the solvent is 25%; the mass concentration of the solvent used for the first time in the polymer reaction is 15%, and the mass concentration of the unsaturated fatty acid is 70%; the mass concentration of the solvent used for the second time is 10%, and the mass concentration of the unsaturated fatty acid is 30%.

[0042] Example 1

[0043] A silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion comprising the following raw materials:

[0044] Unsaturated fatty acids: dehydrated ricinoleic acid and palmitoleic acid, accounting for 7.5g and 2.5g respectively;

[0045] Polyacid; Adipic acid, 4g;

[0046] Polyol: neopentyl glycol, 6g;

[0047] Silicone: Hydroxydimethylsiloxane, 4.8g;

[0048] Hydroxyl vinyl monomer: 2-hydroxyethyl methacrylate, 2g;

[0049] Hard monomers: styrene and methyl methacrylate, accounting for 27g and 13g respectively;

[0050] Soft monomer: lauryl methacrylate, 16.5g;

[0051] Carboxyl vinyl monomer: methacrylic acid, 4g;

[0052] Organic fluorine: FEO-300 (provided by Shanghai Fluorine Technology Co., Ltd.), 1g;

[0053] Solvent: n-butanol, propylene glycol methyl ether, diethylene glycol butyl ether, accounting for 6g, 10g, and 18g respectively;

[0054] Initiator: tert-butyl benzoyl peroxide, 1.8 g;

[0055] Tetraisopropyl titanate: 0.2g;

[0056] Copper chloride: 0.1g;

[0057] Inhibitor: hydroquinone, 0.05g;

[0058] Chain transfer agent: n-dodecyl mercaptan, 0.05 g;

[0059] Neutralizing agent: triethylamine, 4.5g;

[0060] Deionized water: 80g.

[0061] The preparation method of the silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion is as follows:

[0062] (1) 0.6 g of n-butanol, 1 g of propylene glycol methyl ether, 1.8 g of diethylene glycol butyl ether, 4.8 g of terminal hydroxyl polydimethylsiloxane, 0.1 g of tetraisopropyl titanate and 0.1 g of cupric chloride were mixed to obtain a pre-reaction liquid A; 0.6 g of n-butanol, 1 g of propylene glycol methyl ether, 1.8 g of diethylene glycol butyl ether, 2 g of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 0.1 g of tetraisopropyl titanate were mixed to obtain a pre-reaction liquid B; 27 g of styrene, 13 g of methyl methacrylate, 16.5 g of lauryl methacrylate, 4 g of methacrylic acid, 1 g of organic fluorine FEO-300, 1.26 g of tert-butyl peroxide benzoyl, 0.05 g of n-dodecyl mercaptan, 1.5 g of n-butanol, 2.5 g of propylene glycol methyl ether and 4.5 g of diethylene glycol butyl ether were mixed to obtain a pre-reaction liquid C.

[0063] (2) 0.9 g of n-butanol, 1.5 g of propylene glycol methyl ether, 2.4 g of diethylene glycol butyl ether, 5.25 g of dehydrated ricinoleic acid, 1.75 g of palmitic acid, 4 g of adipic acid and 6 g of neopentyl glycol were added to a 500 mL four-necked flask in sequence, the oil bath was heated to 210 °C, and mechanical stirring was continued at a rate of 100 r / min until the acid value dropped to below 5 mg KOH / g. Then, 0.6 g of n-butanol, 1 g of propylene glycol methyl ether, 1.8 g of diethylene glycol butyl ether, 2.25 g of dehydrated ricinoleic acid and 0.75 g of palmitic acid were added, and esterification was continued until the acid value was ≤3 mg KOH / g.

[0064] (3) Cooling to 120°C, slowly adding the pre-reaction liquid A to the above reaction flask, controlling the dropwise addition time to 10 minutes, filling with nitrogen to replace the air for about 6 minutes, and mechanically stirring the reaction for 60 minutes; then slowly adding the pre-reaction liquid B, controlling the dropwise addition time to 10 minutes, filling with nitrogen to replace the air for about 6 minutes, and mechanically stirring the reaction for 60 minutes to obtain a reaction liquid.

[0065] (4) At 120° C., 1 / 5 volume of the pre-reaction liquid C was rapidly added dropwise to the reaction solution of step (3) for 30 min; then the remaining pre-reaction liquid C was slowly added dropwise for 3 h; the temperature was adjusted to 125° C., 1.8 g of n-butanol, 3 g of propylene glycol methyl ether, 5.7 g of diethylene glycol butyl ether and 0.54 g of tert-butyl peroxide benzoyl peroxide were added, and the reaction was carried out at a constant temperature for 2 h; the temperature was lowered to below 40° C., 4.5 g of triethylamine was added under stirring, the pH was adjusted to 8, deionized water was added, and stirring was continued until transparent to obtain a silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion.

[0066] Example 2

[0067] A silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion comprising the following raw materials:

[0068] Unsaturated fatty acids: dehydrated ricinoleic acid and palmitoleic acid, accounting for 11g and 5g respectively;

[0069] Polyacid; Phthalic anhydride, 6g;

[0070] Polyol: trimethylolpropane, 16g;

[0071] Silicone: Hydroxydimethylsiloxane, 8.6g;

[0072] Hydroxyl vinyl monomer: 2-hydroxypropyl methacrylate, 4g;

[0073] Hard monomers: styrene and methyl methacrylate, accounting for 44g and 21g respectively;

[0074] Soft monomer: butyl acrylate, 40g;

[0075] Carboxyl vinyl monomer: acrylic acid, 8g;

[0076] Organic fluorine: FEO-300 (provided by Shanghai Fluorine Technology Co., Ltd.), 3g;

[0077] Solvent: propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, accounting for 14g, 20g, and 30g respectively;

[0078] Initiator: di-tert-butyl hydroperoxide, 3.6 g;

[0079] Tetraisopropyl titanate: 0.5g;

[0080] Copper chloride: 0.3g;

[0081] Inhibitor: 4-methoxyphenol, 0.15g;

[0082] Chain transfer agent: 3-mercapto-1-propanol, 0.15 g;

[0083] Neutralizing agent: NN dimethylethanolamine, 8.5g;

[0084] Deionized water: 165g.

[0085] The preparation method of the silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion is as follows:

[0086] (1) 1.4 g of propylene glycol methyl ether, 2 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 8.6 g of hydroxypolydimethylsiloxane, 0.25 g of tetraisopropyl titanate and 0.3 g of cupric chloride were mixed to obtain a pre-reaction liquid A; 1.4 g of propylene glycol methyl ether, 2 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 4 g of 2-hydroxypropyl methacrylate, 0.15 g of 4-methoxyphenol and 0.25 g of tetraisopropyl titanate were mixed to obtain a pre-reaction liquid B; 44 g of styrene, 21 g of methyl methacrylate, 40 g of butyl acrylate, 8 g of acrylic acid, 3 g of organic fluorine FEO-300, 2.52 g of di-tert-butyl hydroperoxide, 0.15 g of 3-mercapto-1-propanol, 3.5 g of propylene glycol methyl ether, 5 g of propylene glycol butyl ether and 7.5 g of diethylene glycol butyl ether were mixed to obtain a pre-reaction liquid C.

[0087] (2) 2.1 g of propylene glycol methyl ether, 3 g of propylene glycol butyl ether, 4.5 g of diethylene glycol butyl ether, 7.7 g of dehydrated ricinoleic acid, 3.5 g of palmitic acid, 6 g of phthalic anhydride and 16 g of trimethylolpropane were added to a 500 mL four-necked flask in sequence, the oil bath was heated to 230 ° C, and mechanical stirring was continued at a rate of 150 r / min until the acid value dropped to below 5 mg KOH / g. Then 1.4 g of propylene glycol methyl ether, 2 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 3.3 g of dehydrated ricinoleic acid and 1.5 g of palmitic acid were added, and esterification was continued until the acid value was ≤3 mg KOH / g.

[0088] (3) Cooling to 140°C, slowly adding the pre-reaction liquid A to the above reaction flask, controlling the dropwise addition time to 15 minutes, filling with nitrogen to replace the air for about 10 minutes, and mechanically stirring the reaction for 60 minutes; then slowly adding the pre-reaction liquid B, controlling the dropwise addition time to 15 minutes, filling with nitrogen to replace the air for about 10 minutes, and mechanically stirring the reaction for 60 minutes to obtain a reaction liquid.

[0089] (4) At 140° C., 1 / 5 volume of the pre-reaction liquid C was rapidly added dropwise to the reaction solution of step (3) for 40 min; then the remaining pre-reaction liquid C was slowly added dropwise for 4 h; the temperature was adjusted to 145° C., 4.2 g of propylene glycol methyl ether, 6 g of propylene glycol butyl ether, 9 g of diethylene glycol butyl ether and 1.08 g of di-tert-butyl hydroperoxide were added, and the reaction was carried out at a constant temperature for 4 h; the temperature was lowered to below 40° C., 8.5 g of NN dimethylethanolamine was added under stirring, the pH was adjusted to 9, deionized water was added, and stirring was continued until transparent to obtain a silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion.

[0090] Example 3

[0091] A silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion comprising the following raw materials:

[0092] Unsaturated fatty acids: dehydrated ricinoleic acid and palmitoleic acid, accounting for 8.5g and 3.5g respectively;

[0093] Polybasic acid; trimellitic anhydride, 4.5g;

[0094] Polyol: neopentyl glycol, 10 g;

[0095] Silicone: Hydroxyalkyl-terminated polydimethylsiloxane, 7g;

[0096] Hydroxyl vinyl monomer: 2-hydroxyethyl methacrylate, 3g;

[0097] Hard monomers: styrene and methyl methacrylate, accounting for 30g and 15g respectively;

[0098] Soft monomer: lauryl methacrylate, 30g;

[0099] Carboxyl vinyl monomer: acrylic acid, 6g;

[0100] Organic fluorine: FEO-300 (provided by Shanghai Fluorine Technology Co., Ltd.), 2g;

[0101] Solvent: n-butanol, propylene glycol methyl ether, propylene glycol butyl ether, accounting for 8g, 14g, and 28g respectively;

[0102] Initiator: di-tert-butyl hydroperoxide, 3g;

[0103] Tetraisopropyl titanate: 0.4 g;

[0104] Copper chloride: 0.2g;

[0105] Inhibitor: hydroquinone, 0.1g;

[0106] Chain transfer agent: 3-mercapto-1-propanol, 0.1 g;

[0107] Neutralizing agent: triethylamine, 6.5g;

[0108] Deionized water: 115g.

[0109] The preparation method of the silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion is as follows:

[0110] (1) 0.8 g of n-butanol, 1.4 g of propylene glycol methyl ether, 2.8 g of propylene glycol butyl ether, 7 g of hydroxyalkyl-terminated polydimethylsiloxane, 0.2 g of tetraisopropyl titanate and 0.2 g of cupric chloride were mixed to obtain a pre-reaction liquid A; 0.8 g of n-butanol, 1.4 g of propylene glycol methyl ether, 2.8 g of propylene glycol butyl ether, 3 g of 2-hydroxyethyl methacrylate, 0.1 g of hydroquinone and 0.2 g of tetraisopropyl titanate were mixed to obtain a pre-reaction liquid B; 30 g of styrene, 15 g of methyl methacrylate, 30 g of lauryl methacrylate, 6 g of acrylic acid, 2 g of organic fluorine FEO-300, 2.1 g of di-tert-butyl hydroperoxide, 0.1 g of 3-mercapto-1-propanol, 2 g of n-butanol, 3.5 g of propylene glycol methyl ether and 7 g of propylene glycol butyl ether were mixed to obtain a pre-reaction liquid C.

[0111] (2) 1.2 g of n-butanol, 2.1 g of propylene glycol methyl ether, 4.2 g of propylene glycol butyl ether, 5.95 g of dehydrated ricinoleic acid, 2.45 g of palmitic acid, 4.5 g of trimellitic anhydride and 12 g of neopentyl glycol were added to a 500 mL four-necked flask in sequence. The oil bath was heated to 220°C and mechanical stirring was continued at a rate of 135 r / min until the acid value dropped below 5 mg KOH / g. Then, 0.8 g of n-butanol, 1.4 g of propylene glycol methyl ether, 2.8 g of propylene glycol butyl ether, 2.55 g of dehydrated ricinoleic acid and 1.05 g of palmitic acid were added and esterification was continued until the acid value was ≤3 mg KOH / g.

[0112] (3) Cooling to 140°C, slowly adding the pre-reaction liquid A to the above reaction flask, controlling the dropwise addition time to 12 minutes, filling with nitrogen to replace the air for about 8 minutes, and mechanically stirring the reaction for 80 minutes; then slowly adding the pre-reaction liquid B, controlling the dropwise addition time to 12 minutes, filling with nitrogen to replace the air for about 8 minutes, and mechanically stirring the reaction for 80 minutes to obtain a reaction liquid.

[0113] (4) At 140° C., 1 / 5 volume of the pre-reaction liquid C was rapidly added dropwise to the reaction solution of step (3) for 35 min; then the remaining pre-reaction liquid C was slowly added dropwise for 3.5 h; the temperature was adjusted to 142° C., 2.4 g of n-butanol, 4.2 g of propylene glycol methyl ether, 8.4 g of propylene glycol butyl ether and 0.9 g of di-tert-butyl hydroperoxide were added, and the reaction was carried out at a constant temperature for 3 h; the temperature was lowered to below 40° C., 6.5 g of triethylamine was added under stirring, the pH was adjusted to 8.5, deionized water was added, and stirring was continued until transparent to obtain a silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion.

[0114] Example 4

[0115] A silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion comprising the following raw materials:

[0116] Unsaturated fatty acids: dehydrated ricinoleic acid and palmitoleic acid, accounting for 10g and 4g respectively;

[0117] Polyacid; Phthalic anhydride, 5g;

[0118] Polyol: neopentyl glycol, 14g;

[0119] Silicone: hydroxy-terminated polyether polydimethylsiloxane, 8.4g;

[0120] Hydroxyl vinyl monomer: 2-hydroxypropyl methacrylate, 4g;

[0121] Hard monomers: styrene and methyl methacrylate, accounting for 35g and 16g respectively;

[0122] Soft monomer: butyl acrylate, 36g;

[0123] Carboxyl vinyl monomer: methacrylic acid, 7.5g;

[0124] Organic fluorine: FEO-300 (provided by Shanghai Fluorine Technology Co., Ltd.), 1.5 g;

[0125] Solvent: n-butanol, propylene glycol butyl ether, diethylene glycol butyl ether, accounting for 12g, 18g, and 30g respectively;

[0126] Initiator: tert-butyl benzoyl peroxide, 3.4 g;

[0127] Tetraisopropyl titanate: 0.44 g;

[0128] Copper chloride: 0.25g;

[0129] Inhibitor: 4-methoxyphenol, 0.12g;

[0130] Chain transfer agent: n-dodecyl mercaptan, 0.12 g;

[0131] Neutralizing agent: triethylamine, NN dimethylethanolamine, 4.5g, 3.5g respectively;

[0132] Deionized water: 125g.

[0133] The preparation method of the silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion is as follows:

[0134] (1) 1.2 g of n-butanol, 1.8 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 8.4 g of terminal hydroxyl polyether polydimethylsiloxane, 0.22 g of tetraisopropyl titanate and 0.25 g of cupric chloride were mixed to obtain a pre-reaction liquid A; 1.2 g of n-butanol, 1.8 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 4 g of hydroxypropyl acrylate, 0.12 g of 4-methoxyphenol and 0.22 g of tetraisopropyl titanate were mixed to obtain a pre-reaction liquid B; 35 g of styrene, 16 g of methyl methacrylate, 36 g of butyl acrylate, 7.5 g of methacrylic acid, 1.5 g of organic fluorine FEO-300, 2.38 g of tert-butyl peroxide benzoyl, 0.12 g of n-dodecyl mercaptan, 3 g of n-butanol, 4.5 g of propylene glycol butyl ether and 7.5 g of diethylene glycol butyl ether were mixed to obtain a pre-reaction liquid C.

[0135] (2) 1.8 g of n-butanol, 2.7 g of propylene glycol butyl ether, 4.5 g of diethylene glycol butyl ether, 7 g of dehydrated ricinoleic acid, 2.8 g of palmitic acid, 5 g of phthalic anhydride and 14 g of neopentyl glycol were added to a 500 mL four-necked flask in sequence. The oil bath was heated to 215°C and mechanical stirring was continued at a rate of 150 r / min until the acid value dropped below 5 mg KOH / g. Then, 1.2 g of n-butanol, 1.8 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 3 g of dehydrated ricinoleic acid and 1.2 g of palmitic acid were added and esterification was continued until the acid value was ≤3 mg KOH / g.

[0136] (3) Cooling to 125°C, slowly adding the pre-reaction liquid A to the above reaction flask, controlling the dropwise addition time to 15 minutes, filling with nitrogen to replace the air for about 5 minutes, and mechanically stirring the reaction for 70 minutes; then slowly adding the pre-reaction liquid B, controlling the dropwise addition time to 15 minutes, filling with nitrogen to replace the air for about 5 minutes, and mechanically stirring the reaction for 70 minutes to obtain a reaction liquid.

[0137] (4) At 125° C., 1 / 5 volume of the pre-reaction liquid C was rapidly added dropwise to the reaction solution of step (3) for 30 min; then the remaining pre-reaction liquid C was slowly added dropwise for 3 h; the temperature was adjusted to 130° C., 3.6 g of n-butanol, 5.4 g of propylene glycol butyl ether, 9 g of diethylene glycol butyl ether and 1.02 g of tert-butyl peroxide benzoyl peroxide were added, and the reaction was carried out at a constant temperature for 2 h; the temperature was lowered to below 40° C., 4.5 g of triethylamine and 3.5 g of NN dimethylethanolamine were added under stirring, the pH was adjusted to 8, deionized water was added and the mixture was continuously stirred until transparent to obtain a silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion.

[0138] Example 5

[0139] A silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion comprising the following raw materials:

[0140] Unsaturated fatty acids: dehydrated ricinoleic acid and palmitoleic acid, accounting for 8g and 3g respectively;

[0141] Polyacid; Adipic acid, 4.5g;

[0142] Polyol: pentaerythritol, 10g;

[0143] Silicone: Hydroxyalkyl-terminated polydimethylsiloxane, 8g;

[0144] Hydroxyl vinyl monomer: 2-hydroxyethyl methacrylate, 3.2 g;

[0145] Hard monomers: styrene and methyl methacrylate, accounting for 36g and 18g respectively;

[0146] Soft monomer: lauryl methacrylate, 34g;

[0147] Carboxyl vinyl monomer: methacrylic acid, 6.8 g;

[0148] Organic fluorine: FEO-300 (provided by Shanghai Fluorine Technology Co., Ltd.), 1.8 g;

[0149] Solvent: propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol butyl ether; 10g, 14g, 28g respectively;

[0150] Initiator: di-tert-butyl hydroperoxide, 3g;

[0151] Tetraisopropyl titanate: 0.38 g;

[0152] Copper chloride: 0.24g;

[0153] Inhibitor: 4-methoxyphenol, 0.13g;

[0154] Chain transfer agent: n-dodecyl mercaptan, 0.14 g;

[0155] Neutralizing agent: NN dimethylethanolamine, 7g;

[0156] Deionized water: 120g.

[0157] The preparation method of the silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion is as follows:

[0158] (1) 1 g of propylene glycol methyl ether, 1.4 g of propylene glycol butyl ether, 2.8 g of diethylene glycol butyl ether, 7.6 g of hydroxyalkyl-terminated polydimethylsiloxane, 0.19 g of tetraisopropyl titanate and 0.24 g of cupric chloride were mixed to obtain a pre-reaction solution A; 1 g of propylene glycol methyl ether, 1.4 g of propylene glycol butyl ether, 2.8 g of diethylene glycol butyl ether, 3.2 g of 2-hydroxyethyl methacrylate, 0.13 g of 4-methoxyphenol and 0.19 g of tetraisopropyl titanate were mixed uniformly to obtain a pre-reaction liquid B; 36 g of styrene, 18 g of methyl methacrylate, 34 g of lauryl methacrylate, 6.8 g of methacrylic acid, 1.8 g of organic fluorine FEO-300, 2.1 g of di-tert-butyl hydroperoxide, 0.14 g of n-dodecyl mercaptan, 2.5 g of propylene glycol methyl ether, 3.5 g of propylene glycol butyl ether and 7 g of diethylene glycol butyl ether were mixed uniformly to obtain a pre-reaction liquid C.

[0159] (2) 1.5 g of propylene glycol methyl ether, 2.1 g of propylene glycol butyl ether, 4.2 g of diethylene glycol butyl ether, 5.6 g of dehydrated ricinoleic acid, 2.1 g of palmitic acid, 4.5 g of adipic acid and 10 g of pentaerythritol were added to a 500 mL four-necked flask in sequence, the oil bath was heated to 225 °C, and mechanical stirring was continued at a rate of 130 r / min until the acid value dropped below 5 mg KOH / g. Then, 1 g of propylene glycol methyl ether, 1.4 g of propylene glycol butyl ether, 2.8 g of diethylene glycol butyl ether, 2.4 g of dehydrated ricinoleic acid and 0.9 g of palmitic acid were added, and esterification was continued until the acid value was ≤3 mg KOH / g.

[0160] (3) Cooling to 140°C, slowly adding the pre-reaction liquid A to the above reaction flask, controlling the dropwise addition time to 15 minutes, filling with nitrogen to replace the air for about 10 minutes, and mechanically stirring the reaction for 60 minutes; then slowly adding the pre-reaction liquid B, controlling the dropwise addition time to 15 minutes, filling with nitrogen to replace the air for about 10 minutes, and mechanically stirring the reaction for 60 minutes to obtain a reaction liquid.

[0161] (4) 1 / 5 volume of pre-reaction liquid C is rapidly added dropwise to the reaction solution of step (3) over 38 min; the remaining pre-reaction liquid C is then slowly added dropwise over 3.6 h; the temperature is adjusted to 130° C., 3 g of propylene glycol methyl ether, 4.2 g of propylene glycol butyl ether, 8.4 g of diethylene glycol butyl ether and 0.9 g of di-tert-butyl hydroperoxide are added, and the reaction is carried out at a constant temperature for 2.5 h; the temperature is lowered to below 40° C., 7 g of N-N-dimethylethanolamine is added under stirring, the pH is adjusted to 8.2, deionized water is added, and stirring is continued until transparent to obtain a silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion.

[0162] Comparative Example 1

[0163] A fluorine / alkyd resin modified waterborne acrylic resin dispersion comprising the following raw materials:

[0164] Unsaturated fatty acids: dehydrated ricinoleic acid and palmitoleic acid, accounting for 11g and 5g respectively;

[0165] Polyacid; Phthalic anhydride, 6g;

[0166] Polyol: trimethylolpropane, 16g;

[0167] Hydroxyl vinyl monomer: 2-hydroxypropyl methacrylate, 4g;

[0168] Hard monomers: styrene and methyl methacrylate, accounting for 44g and 21g respectively;

[0169] Soft monomer: butyl acrylate, 40g;

[0170] Carboxyl vinyl monomer: acrylic acid, 8g;

[0171] Organic fluorine: FEO-300 (provided by Shanghai Fluorine Technology Co., Ltd.), 3g;

[0172] Solvent: propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, accounting for 14g, 20g, and 30g respectively;

[0173] Initiator: di-tert-butyl hydroperoxide, 3.6 g;

[0174] Tetraisopropyl titanate: 0.25g;

[0175] Inhibitor: 4-methoxyphenol, 0.15g;

[0176] Chain transfer agent: 3-mercapto-1-propanol, 0.15 g;

[0177] Neutralizing agent: NN dimethylethanolamine, 8.5g;

[0178] Deionized water: 165g.

[0179] The preparation method of the fluorine / alkyd resin modified waterborne acrylic resin dispersion is as follows:

[0180] (1) 2.8 g of propylene glycol methyl ether, 4 g of propylene glycol butyl ether, 6 g of diethylene glycol butyl ether, 4 g of 2-hydroxypropyl methacrylate, 0.15 g of 4-methoxyphenol and 0.25 g of tetraisopropyl titanate were mixed to obtain a pre-reaction liquid B; 44 g of styrene, 21 g of methyl methacrylate, 40 g of butyl acrylate, 8 g of acrylic acid, 3 g of organic fluorine FEO-300, 2.52 g of di-tert-butyl hydroperoxide, 0.15 g of 3-mercapto-1-propanol, 3.5 g of propylene glycol methyl ether, 5 g of propylene glycol butyl ether and 7.5 g of diethylene glycol butyl ether were mixed to obtain a pre-reaction liquid C.

[0181] (2) 2.1 g of propylene glycol methyl ether, 3 g of propylene glycol butyl ether, 4.5 g of diethylene glycol butyl ether, 7.7 g of dehydrated ricinoleic acid, 3.5 g of palmitic acid, 6 g of phthalic anhydride and 16 g of trimethylolpropane were added to a 500 mL four-necked flask in sequence, the oil bath was heated to 230 ° C, and mechanical stirring was continued at a rate of 150 r / min until the acid value dropped to below 5 mg KOH / g. Then 1.4 g of propylene glycol methyl ether, 2 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 3.3 g of dehydrated ricinoleic acid and 1.5 g of palmitic acid were added, and esterification was continued until the acid value was ≤3 mg KOH / g.

[0182] (3) Cooling to 140° C., slowly adding the pre-reaction solution B into the above reaction flask, controlling the dropwise addition time to 15 min, filling with nitrogen to replace the air for about 10 min, and mechanically stirring the reaction for 60 min to obtain a reaction solution.

[0183] (4) At 140° C., 1 / 5 volume of the pre-reaction liquid C was rapidly added dropwise to the reaction solution of step (3) for 40 min; then the remaining pre-reaction liquid C was slowly added dropwise for 4 h; the temperature was adjusted to 145° C., 4.2 g of propylene glycol methyl ether, 6 g of propylene glycol butyl ether, 9 g of diethylene glycol butyl ether and 1.08 g of di-tert-butyl hydroperoxide were added, and the reaction was carried out at a constant temperature for 4 h; the temperature was lowered to below 40° C., 8.5 g of NN dimethylethanolamine was added under stirring, the pH was adjusted to 9, deionized water was added, and stirring was continued until transparent to obtain a silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion.

[0184] Comparative Example 2

[0185] A silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion comprising the following raw materials:

[0186] Unsaturated fatty acids: dehydrated ricinoleic acid and palmitoleic acid, accounting for 11g and 5g respectively;

[0187] Polyacid; Phthalic anhydride, 6g;

[0188] Polyol: trimethylolpropane, 16g;

[0189] Silicone: Hydroxydimethylsiloxane, 8.6g;

[0190] Hard monomers: styrene and methyl methacrylate, accounting for 44g and 21g respectively;

[0191] Soft monomer: butyl acrylate, 40g;

[0192] Carboxyl vinyl monomer: acrylic acid, 8g;

[0193] Organic fluorine: FEO-300 (provided by Shanghai Fluorine Technology Co., Ltd.), 3g;

[0194] Solvent: propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, accounting for 14g, 20g, and 30g respectively;

[0195] Initiator: di-tert-butyl hydroperoxide, 3.6 g;

[0196] Tetraisopropyl titanate: 0.25g;

[0197] Chain transfer agent: 3-mercapto-1-propanol, 0.15 g;

[0198] Neutralizing agent: NN dimethylethanolamine, 8.5g;

[0199] Deionized water: 165g.

[0200] The preparation method of the silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion is as follows:

[0201] (1) 2.4 g of propylene glycol methyl ether, 4 g of propylene glycol butyl ether, 6 g of diethylene glycol butyl ether, 8.6 g of hydroxy polydimethylsiloxane, 0.25 g of tetraisopropyl titanate and 0.3 g of cupric chloride were mixed to obtain a pre-reaction liquid A; 44 g of styrene, 21 g of methyl methacrylate, 40 g of butyl acrylate, 8 g of acrylic acid, 3 g of organic fluorine FEO-300, 2.52 g of di-tert-butyl hydroperoxide, 0.15 g of 3-mercapto-1-propanol, 3.5 g of propylene glycol methyl ether, 5 g of propylene glycol butyl ether and 7.5 g of diethylene glycol butyl ether were mixed to obtain a pre-reaction liquid C.

[0202] (2) 2.1 g of propylene glycol methyl ether, 3 g of propylene glycol butyl ether, 4.5 g of diethylene glycol butyl ether, 7.7 g of dehydrated ricinoleic acid, 3.5 g of palmitic acid, 6 g of phthalic anhydride and 16 g of trimethylolpropane were added to a 500 mL four-necked flask in sequence, the oil bath was heated to 230 ° C, and mechanical stirring was continued at a rate of 150 r / min until the acid value dropped to below 5 mg KOH / g. Then 1.4 g of propylene glycol methyl ether, 2 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 3.3 g of dehydrated ricinoleic acid and 1.5 g of palmitic acid were added, and esterification was continued until the acid value was ≤3 mg KOH / g.

[0203] (3) Cooling to 140° C., slowly adding the pre-reaction solution A into the above reaction flask, controlling the dropwise addition time to 15 min, filling with nitrogen to replace the air for about 10 min, and mechanically stirring the reaction for 60 min to obtain a reaction solution.

[0204] (4) At 140° C., 1 / 5 volume of the pre-reaction liquid C was rapidly added dropwise to the reaction solution of step (3) for 40 min; then the remaining pre-reaction liquid C was slowly added dropwise for 4 h; the temperature was adjusted to 145° C., 4.6 g of propylene glycol methyl ether, 6 g of propylene glycol butyl ether, 9 g of diethylene glycol butyl ether and 1.08 g of di-tert-butyl hydroperoxide were added, and the reaction was carried out at a constant temperature for 4 h; the temperature was lowered to below 40° C., 8.5 g of NN dimethylethanolamine was added under stirring, the pH was adjusted to 9, deionized water was added, and stirring was continued until transparent to obtain a silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion.

[0205] Comparative Example 3

[0206] A silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion comprising the following raw materials:

[0207] Unsaturated fatty acids: dehydrated ricinoleic acid and palmitoleic acid, accounting for 11g and 5g respectively;

[0208] Polyacid; Phthalic anhydride, 6g;

[0209] Polyol: trimethylolpropane, 16g;

[0210] Silicone: Hydroxydimethylsiloxane, 8.6g;

[0211] Hydroxyl vinyl monomer: 2-hydroxypropyl methacrylate, 4g;

[0212] Hard monomers: styrene and methyl methacrylate, accounting for 44g and 21g respectively;

[0213] Soft monomer: butyl acrylate, 40g;

[0214] Carboxyl vinyl monomer: acrylic acid, 8g;

[0215] Organic fluorine: FEO-300 (provided by Shanghai Fluorine Technology Co., Ltd.), 3g;

[0216] Solvent: propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, accounting for 14g, 20g, and 30g respectively;

[0217] Initiator: di-tert-butyl hydroperoxide, 3.6 g;

[0218] Tetraisopropyl titanate: 0.5g;

[0219] Copper chloride: 0.3g;

[0220] Inhibitor: 4-methoxyphenol, 0.15g;

[0221] Chain transfer agent: 3-mercapto-1-propanol, 0.15 g;

[0222] Neutralizing agent: NN dimethylethanolamine, 8.5g;

[0223] Deionized water: 165g.

[0224] The preparation method of the silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion is as follows:

[0225] (1) 1.4 g of propylene glycol methyl ether, 2 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 8.6 g of terminal hydroxyl siloxane, 0.25 g of tetraisopropyl titanate and 0.3 g of cupric chloride were mixed to obtain a pre-reaction liquid A; 1.4 g of propylene glycol methyl ether, 2 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 4 g of 2-hydroxypropyl methacrylate, 0.15 g of 4-methoxyphenol and 0.25 g of tetraisopropyl titanate were mixed to obtain a pre-reaction liquid B; 44 g of styrene, 21 g of methyl methacrylate, 40 g of butyl acrylate, 8 g of acrylic acid, 3 g of organic fluorine FEO-300, 2.52 g of di-tert-butyl hydroperoxide, 0.15 g of 3-mercapto-1-propanol, 3.5 g of propylene glycol methyl ether, 5 g of propylene glycol butyl ether and 7.5 g of diethylene glycol butyl ether were mixed to obtain a pre-reaction liquid C.

[0226] (2) 3.5 g of propylene glycol methyl ether, 5 g of propylene glycol butyl ether, 7.5 g of diethylene glycol butyl ether, 11 g of dehydrated ricinoleic acid, 5 g of palmitic acid, 6 g of phthalic anhydride, and 16 g of trimethylolpropane were added to a 500 mL four-necked flask in sequence. The oil bath was heated to 230 °C and mechanical stirring was continued at a rate of 150 r / min until the acid value dropped to below 5 mg KOH / g.

[0227] (3) Cooling to 140°C, slowly adding the pre-reaction liquid A to the above reaction flask, controlling the dropwise addition time to 15 minutes, filling with nitrogen to replace the air for about 10 minutes, and mechanically stirring the reaction for 60 minutes; then slowly adding the pre-reaction liquid B, controlling the dropwise addition time to 15 minutes, filling with nitrogen to replace the air for about 10 minutes, and mechanically stirring the reaction for 60 minutes to obtain a reaction liquid.

[0228] (4) At 140° C., 1 / 5 volume of pre-reaction liquid C was rapidly added dropwise to the reaction solution of step (3) for 40 min; then the remaining pre-reaction liquid C was slowly added dropwise for 4 h; the temperature was adjusted to 145° C., 4.2 g of propylene glycol methyl ether, 6 g of propylene glycol butyl ether, 9 g of diethylene glycol butyl ether and 1.08 g of di-tert-butyl hydroperoxide were added, and the reaction was carried out at a constant temperature for 4 h; the temperature was lowered to below 40° C., 8.5 g of NN dimethylethanolamine was added under stirring, the pH was adjusted to 9, deionized water was added, and the mixture was continuously stirred until transparent to obtain a silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion.

[0229] Comparative Example 4

[0230] A silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion comprising the following raw materials:

[0231] Unsaturated fatty acids: dehydrated ricinoleic acid and palmitoleic acid, accounting for 11g and 5g respectively;

[0232] Polyacid; Phthalic anhydride, 6g;

[0233] Polyol: trimethylolpropane, 16g;

[0234] Silicone: Hydroxydimethylsiloxane, 8.6g;

[0235] Hydroxyl vinyl monomer: 2-hydroxypropyl methacrylate, 4g;

[0236] Hard monomers: styrene and methyl methacrylate, accounting for 44g and 21g respectively;

[0237] Soft monomer: butyl acrylate, 40g;

[0238] Carboxyl vinyl monomer: acrylic acid, 8g;

[0239] Organic fluorine: FEO-300 (provided by Shanghai Fluorine Technology Co., Ltd.), 3g;

[0240] Solvent: propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, accounting for 14g, 20g, and 30g respectively;

[0241] Initiator: di-tert-butyl hydroperoxide, 3.6 g;

[0242] Tetraisopropyl titanate: 0.5g;

[0243] Copper chloride: 0.3g;

[0244] Inhibitor: 4-methoxyphenol, 0.15g;

[0245] Chain transfer agent: 3-mercapto-1-propanol, 0.15 g;

[0246] Neutralizing agent: NN dimethylethanolamine, 8.5g;

[0247] Deionized water: 165g.

[0248] The preparation method of the silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion is as follows:

[0249] (1) 1.4 g of propylene glycol methyl ether, 2 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 8.6 g of terminal hydroxyl siloxane, 0.25 g of tetraisopropyl titanate and 0.3 g of cupric chloride were mixed to obtain a pre-reaction liquid A; 1.4 g of propylene glycol methyl ether, 2 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 4 g of 2-hydroxypropyl methacrylate, 0.15 g of 4-methoxyphenol and 0.25 g of tetraisopropyl titanate were mixed to obtain a pre-reaction liquid B; 44 g of styrene, 21 g of methyl methacrylate, 40 g of butyl acrylate, 8 g of acrylic acid, 3 g of organic fluorine FEO-300, 2.52 g of di-tert-butyl hydroperoxide, 0.15 g of 3-mercapto-1-propanol, 3.5 g of propylene glycol methyl ether, 5 g of propylene glycol butyl ether and 7.5 g of diethylene glycol butyl ether were mixed to obtain a pre-reaction liquid C.

[0250] (2) 2.1 g of propylene glycol methyl ether, 3 g of propylene glycol butyl ether, 4.5 g of diethylene glycol butyl ether, 7.7 g of dehydrated ricinoleic acid, 3.5 g of palmitic acid, 6 g of phthalic anhydride and 16 g of trimethylolpropane were added to a 500 mL four-necked flask in sequence, the oil bath was heated to 230 ° C, and mechanical stirring was continued at a rate of 150 r / min until the acid value dropped to below 5 mg KOH / g. Then 1.4 g of propylene glycol methyl ether, 2 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 3.3 g of dehydrated ricinoleic acid and 1.5 g of palmitic acid were added, and esterification was continued until the acid value was ≤3 mg KOH / g.

[0251] (3) Cooling to 140°C, slowly adding the pre-reaction liquid A to the above reaction flask, controlling the dropwise addition time to 15 minutes, filling with nitrogen to replace the air for about 10 minutes, and mechanically stirring the reaction for 60 minutes; then slowly adding the pre-reaction liquid B, controlling the dropwise addition time to 15 minutes, filling with nitrogen to replace the air for about 10 minutes, and mechanically stirring the reaction for 60 minutes to obtain a reaction liquid.

[0252] (4) At 140° C., pre-reaction solution C is directly added dropwise to the reaction solution of step (3) at a uniform speed for 4 hours; the temperature is adjusted to 145° C., 4.2 g of propylene glycol methyl ether, 6 g of propylene glycol butyl ether, 9 g of diethylene glycol butyl ether and 1.08 g of di-tert-butyl hydroperoxide are added, and the reaction is carried out at a constant temperature for 4 hours; the temperature is lowered to below 40° C., 8.5 g of N-N-dimethylethanolamine is added under stirring, the pH is adjusted to 9, and deionized water is added and stirred continuously until transparent to obtain a silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion.

[0253] Comparative Example 5

[0254] An alkyd resin-modified acrylic resin was prepared by the method disclosed in patent application number CN202110881209.3, and compared with the silicone fluorine / alkyd resin-modified water-based acrylic resin dispersion prepared in Example 2.

[0255] Comparative Example 6

[0256] A silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion comprising the following raw materials:

[0257] Unsaturated fatty acids: dehydrated ricinoleic acid and palmitoleic acid, accounting for 11g and 5g respectively;

[0258] Polyacid; Phthalic anhydride, 6g;

[0259] Polyol: trimethylolpropane, 16g;

[0260] Silicone: Hydroxydimethylsiloxane, 8.6g;

[0261] Hydroxyl vinyl monomer: 2-hydroxypropyl methacrylate, 4g;

[0262] Hard monomers: styrene and methyl methacrylate, accounting for 44g and 21g respectively;

[0263] Soft monomer: butyl acrylate, 40g;

[0264] Carboxyl vinyl monomer: acrylic acid, 8g;

[0265] Solvent: propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, accounting for 14g, 20g, and 30g respectively;

[0266] Initiator: di-tert-butyl hydroperoxide, 3.6 g;

[0267] Tetraisopropyl titanate: 0.5g;

[0268] Copper chloride: 0.3g;

[0269] Inhibitor: 4-methoxyphenol, 0.15g;

[0270] Chain transfer agent: 3-mercapto-1-propanol, 0.15 g;

[0271] Neutralizing agent: NN dimethylethanolamine, 8.5g;

[0272] Deionized water: 165g.

[0273] The preparation method of the silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion is as follows:

[0274] (1) 1.4 g of propylene glycol methyl ether, 2 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 8.6 g of terminal hydroxyl siloxane, 0.25 g of tetraisopropyl titanate and 0.3 g of cupric chloride were mixed to obtain a pre-reaction liquid A; 1.4 g of propylene glycol methyl ether, 2 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 4 g of 2-hydroxypropyl methacrylate, 0.15 g of 4-methoxyphenol and 0.25 g of tetraisopropyl titanate were mixed to obtain a pre-reaction liquid B; 44 g of styrene, 21 g of methyl methacrylate, 40 g of butyl acrylate, 8 g of acrylic acid, 2.52 g of di-tert-butyl hydroperoxide, 0.15 g of 3-mercapto-1-propanol, 3.5 g of propylene glycol methyl ether, 5 g of propylene glycol butyl ether and 7.5 g of diethylene glycol butyl ether were mixed to obtain a pre-reaction liquid C.

[0275] (2) 2.1 g of propylene glycol methyl ether, 3 g of propylene glycol butyl ether, 4.5 g of diethylene glycol butyl ether, 7.7 g of dehydrated ricinoleic acid, 3.5 g of palmitic acid, 6 g of phthalic anhydride and 16 g of trimethylolpropane were added to a 500 mL four-necked flask in sequence, the oil bath was heated to 230 ° C, and mechanical stirring was continued at a rate of 150 r / min until the acid value dropped to below 5 mg KOH / g. Then 1.4 g of propylene glycol methyl ether, 2 g of propylene glycol butyl ether, 3 g of diethylene glycol butyl ether, 3.3 g of dehydrated ricinoleic acid and 1.5 g of palmitic acid were added, and esterification was continued until the acid value was ≤3 mg KOH / g.

[0276] (3) Cooling to 140°C, slowly adding the pre-reaction liquid A to the above reaction flask, controlling the dropwise addition time to 15 minutes, filling with nitrogen to replace the air for about 10 minutes, and mechanically stirring the reaction for 60 minutes; then slowly adding the pre-reaction liquid B, controlling the dropwise addition time to 15 minutes, filling with nitrogen to replace the air for about 10 minutes, and mechanically stirring the reaction for 60 minutes to obtain a reaction liquid.

[0277] (4) At 140° C., 1 / 5 volume of the pre-reaction liquid C is rapidly added dropwise to the reaction solution of step (3) for 30 min; then the remaining pre-reaction liquid C is slowly added dropwise for 3 h; the temperature is adjusted to 145° C., 4.2 g of propylene glycol methyl ether, 6 g of propylene glycol butyl ether, 9 g of diethylene glycol butyl ether and 1.08 g of di-tert-butyl hydroperoxide are added, and the reaction is carried out at a constant temperature for 2 h; the temperature is lowered to below 40° C., 8.5 g of N-N-dimethylethanolamine is added under stirring, the pH is adjusted to 8, deionized water is added, and stirring is continued until transparent to obtain a silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion.

[0278] The resin dispersions prepared in Examples 1-5 and Comparative Examples 1-6 were subjected to the following tests:

[0279] (1) In order to better illustrate the characteristics of the silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion provided in the embodiments of the present invention, the molecular weight and particle size of the silicone fluorine / alkyd resin modified waterborne acrylic resin (dispersion) prepared in Examples 1-5 are tested below. The test results are as follows: Figure 2-11 shown.

[0280] from Figure 2 It can be seen that the Mn of the silicone fluorine / alkyd resin modified waterborne acrylic resin prepared in Example 1 of the present invention is 5011. Figure 3 It can be seen that the Mn of the silicone fluorine / alkyd resin modified waterborne acrylic resin prepared in Example 2 of the present invention is 5697. Figure 4 It can be seen that the Mn of the silicone fluorine / alkyd resin modified waterborne acrylic resin prepared in Example 3 of the present invention is 5815. Figure 5 It can be seen that the Mn of the silicone fluorine / alkyd resin modified waterborne acrylic resin prepared in Example 4 of the present invention is 5145. Figure 6 It can be seen from the above that the Mn of the silicone fluorine / alkyd resin modified waterborne acrylic resin prepared in Example 5 of the present invention is 5043; Figure 7 It can be seen from the figure that the average particle size of the silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion prepared in Example 1 of the present invention is 97.7 nm. Figure 8 It can be seen from the figure that the average particle size of the silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion prepared in Example 2 of the present invention is 103 nm. Figure 9 It can be seen from the figure that the average particle size of the silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion prepared in Example 3 of the present invention is 95.6 nm. Figure 10 It can be seen that the average particle size of the silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion prepared in Example 4 of the present invention is 95 nm. Figure 11It can be seen from the figure that the average particle size of the silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion prepared in Example 1 of the present invention is 98.8 nm.

[0281] (2) To further illustrate the silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion disclosed in the present invention, the present invention also conducted corresponding tests on the resin dispersions and coating properties prepared in Examples 1 to 5 and Comparative Examples 1 to 5. The test methods are as follows:

[0282] Test of surface drying and through-drying time of coating film: The resin dispersion prepared in the examples or comparative examples was evenly applied on a polytetrafluoroethylene plate and dried at a constant temperature of 25°C. The surface drying and through-drying time of the coating film of the resin dispersion prepared in the examples or comparative examples were tested according to the method of GB1728-79.

[0283] Coating film hardness test: The hardness of the coating film of the resin dispersion prepared in the examples or comparative examples was tested according to the method of GB / T6739-2006.

[0284] Coating adhesion test: The adhesion of the coating of the resin dispersion prepared in the examples or comparative examples was tested according to the method of GB / T9286-1998.

[0285] Coating film gloss test: According to GB / T9754-2007 standard, the gloss of the coating film of the resin dispersion in the embodiment or comparative example was tested using the 60-degree specular gloss measurement method.

[0286] Water resistance test of coating film: GB / T1733-1993 standard is used to test the water resistance of the coating film of the resin dispersion prepared in the examples or comparative examples. The coating film is considered to have passed the test if there is no blistering or falling off for 96 hours and slight discoloration is allowed.

[0287] Resin dispersion storage and transportation stability test: The resin dispersion sample prepared in the examples or comparative examples was packed and placed at a constant temperature of 50° C. for 5 weeks. It was then taken out and observed at room temperature. If no gel or separation occurred, it passed the test.

[0288] The test results are shown in Table 1.

[0289] Table 1 Test results of Examples 1-5 and Comparative Examples 1-5

[0290]

[0291] As shown in Table 1, the silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion prepared by the present invention has a clear and transparent appearance with a bluish luster, high solid content and low viscosity, and the surface and through-drying properties of the resin coating are relatively fast, and the hardness and adhesion can reach 2H and 0 levels, respectively.

[0292] (3) In order to further examine the gloss retention of the silicone / fluorine alkyd resin modified waterborne acrylic resin dispersion of the present invention as the main film-forming material in the coating, Example 2 and Comparative Example 3 and the commercially available waterborne acrylic resin dispersion 3EA41Y were ground by mixing vibration at high speed according to the formulation in Table 2. After the coating films were dried, the hiding power was tested. The test results are shown in Table 3.

[0293] Test method: Tested according to GB1740-79. Each cycle was 8 hours at medium and high temperatures and 16 hours at room temperature, for a total of 68 cycles. The gloss changes are shown in the test results in Table 3.

[0294] Table 2 Experimental formula using mixed vibration high-speed grinding

[0295]

[0296] Table 3 Test results of gloss retention

[0297]

[0298] As can be seen from Table 3, the gloss loss rate of the paint film prepared with the silicone / fluorine alkyd resin modified water-based acrylic resin dispersion of Example 2 as the main film-forming substance is 11.4%, while the gloss loss rates of the paint films prepared with Comparative Example 3 and the commercially available resin dispersion as the main film-forming substances are as high as 26.2% and 23.5%, respectively. This shows that the silicone / fluorine alkyd resin modified water-based acrylic resin dispersion prepared by the present invention as the main film-forming substance can make the coating film have excellent gloss retention.

[0299] (4) In order to further examine the alkali resistance of the silicone / fluorine alkyd resin modified water-based acrylic resin dispersion of the present invention as the main film-forming material in the coating, Example 2 and Comparative Example 6 and a core-shell structured room temperature self-crosslinking fluorine-modified acrylic emulsion (application number 201910068202.2) provided by Nanyang Xinggang Paint Co., Ltd. were mixed and vibrated at high speed according to the formula in Table 2, and the alkali resistance of the coating was tested after drying. The test results are shown in Table 4.

[0300] Detection method: At (23±2)℃, prepare an alkaline solution by adding 0.12g of calcium hydroxide to 100mL of distilled water and stir it thoroughly. The pH value of the solution can reach 12-13. Make boards as required on asbestos cement boards and dry them for 7 days under standard conditions or specified test conditions. Take 3 prepared test boards and seal the edges and north sides of the test boards with a mixture of paraffin and rosin (mass ratio is 1:1). Then, 2 / 3 of the test board area is immersed in a saturated calcium hydroxide solution at a temperature of (23±2)℃ for 7 days. After the immersion is completed, take out the test board, rinse it with water, shake off the water droplets on the test board surface, and then dry it with filter paper. Immediately observe whether the coating surface has blistering, cracks, peeling, powdering, dissolution, etc.

[0301] Table 4 Test results of alkali resistance

[0302]

[0303] As shown in Table 4, the paint film prepared with the resin dispersion of Example 2 as the main film-forming material has good alkali resistance, and there is almost no change on the surface after being immersed in the alkaline solution for 7 days; while the paint film prepared with the resin dispersion of Comparative Example 6 (without adding organic fluorine monomer) as the main film-forming material has a little microbubble on the surface after being immersed in the alkaline solution. This is because organic fluorine can reduce the surface tension of the coating surface, and when the resin film without adding organic fluorine is immersed in the alkaline solution, the slight increase in surface tension causes a small amount of alkaline solution to penetrate into the coating film, which eventually causes Slightly microbubbles; the paint coating prepared with the core-shell structure room temperature self-crosslinking fluorine-modified acrylic emulsion provided by Nanyang Xinggang Paint Co., Ltd. as the main film-forming material has microbubbles on the surface and partial shedding after being soaked in an alkaline solution. This is because the ester bond formed between the fluoroalkyl group in other types of organic fluorine molecules and the polymer main chain is unstable to alkali, while the acrylic organic fluorine containing a long-chain ether bond of the present invention does not form an ester bond with the vinyl acrylic monomer. Therefore, the coating with the resin dispersion of the present invention as the main film-forming material exhibits better alkali resistance.

[0304] (5) The present invention also makes a comprehensive comparison between Example 2 and Comparative Examples 1-4, as follows:

[0305] ① Comparing Example 2 with Comparative Example 1, in which no organosilicon-terminated hydroxyl siloxane is added and other ingredients remain unchanged, it can be seen from the test results in Table 1 that the appearance of the resin dispersion in Comparative Example 1 is opaque. This is because the organosilicon-terminated hydroxyl siloxane can react with both unsaturated esters and hydroxyl vinyl monomers (such as Figure 1 ), and then the vinyl monomer is chemically grafted onto the unsaturated ester, so that the final prepared resin is a uniform polymer. If the terminal hydroxyl siloxane is not added, the synthesized resin is mostly a mixture of unsaturated ester and acrylic resin, which is equivalent to physically mixing the two. This will also cause other properties of the resin to deteriorate, such as the hardness of the coating is only HB, and the water resistance and storage stability cannot pass.

[0306] ② Comparing Example 2 and Comparative Example 2, no hydroxyl vinyl monomer was added to Comparative Example 2, and the other components remained unchanged. The test results were similar to those of Comparative Example 1. This is because the hydroxyl vinyl monomer and the terminal hydroxyl silane act similarly, like an intermediate bridge, one end reacting with the terminal hydroxyl silane, and the other end copolymerizing with the vinyl monomer in situ polymerization. The resin finally prepared is a uniform polymer.

[0307] ③ Comparing Example 2 and Comparative Example 3, the unsaturated ester synthesized in Comparative Example 3 was synthesized using a conventional method, while the unsaturated ester synthesized in Example 2 was synthesized using a polymer method. All other factors remained unchanged. As can be seen from the test results in Table 1, the viscosity of the resin dispersion decreased (79KU / 69KU), but the dryness and resistance of the resin coating were significantly reduced. The surface setting and through-drying times increased from 22 minutes and 19 hours to 30 minutes and 25 hours, respectively. Although it is theoretically believed that in the esterification reaction of unsaturated fatty acids, polyacids, and polyols, regardless of the order of addition, the same formula will ultimately produce a product with an equilibrium structure, this patent application has found that this is not the case. This is because the reactivity of the above raw materials varies, and the transesterification between the formed ester structures is very slow. This results in different structures of the final product prepared depending on the order of raw material addition. Therefore, although the viscosity of the resin dispersion prepared using this polymer method is higher, the color is lighter, and the dryness and resistance of the coating are also improved.

[0308] ④ Comparing Example 2 and Comparative Example 4, the ordinary dropping method is adopted when dropping the vinyl monomer mixed solution in Comparative Example 4, while the "fast and slow" dropping method is adopted when dropping the vinyl monomer mixed solution in Example 2, and the others remain unchanged. From the test results, it can be seen that the viscosity of the resin dispersion increased by about 20KU, and the storage stability performance was also reduced. In addition, when the ordinary method is used to drop the vinyl monomer, it is found that the polymerization process is not smooth. The viscosity of the resin is small at the beginning, but after adding 20% ​​of the monomer, the viscosity suddenly increases. When the monomer is added by 80%, the viscosity increases again. The "fast and slow" dropping method is adopted, not only the entire polymerization speed is smooth and safe and reliable, but also the viscosity of the resin is relatively stable, the particle size is uniform, and the viscosity of the resin will not change during storage.

[0309] In summary, the silicone-fluorine / alkyd resin-modified waterborne acrylic resin dispersion and preparation method proposed in this invention can address technical issues such as poor gloss retention, poor water resistance, and low hardness of waterborne acrylic resin dispersions after film formation. The prepared resin dispersion exhibits a good appearance, uniform particle size distribution, low cost, and environmental friendliness, possessing broad market application potential.

[0310] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion, characterized in that: The invention comprises the following raw materials in parts by weight: 10-16 parts of unsaturated fatty acid, 4-6 parts of polyacid, 6-16 parts of polyol, 4.8-8.6 parts of organosilicon, 2-4 parts of hydroxyl vinyl monomer, 40-65 parts of hard monomer, 16.5-40 parts of soft monomer, 4-8 parts of carboxyl vinyl monomer, 1-3 parts of organic fluorine, 34-64 parts of solvent, 1.8-3.6 parts of initiator, 0.2-0.5 parts of tetraisopropyl titanate, 0.1-0.3 parts of cupric chloride, 0.05-0.15 parts of inhibitor, 0.05-0.15 parts of chain transfer agent, 4.5-8.5 parts of neutralizer and 80-165 parts of deionized water; The organosilicon is a hydroxyl-terminated siloxane, The organic fluorine is a fluorine-containing polyether acrylate, and the basic structural formula is Where R = C n H (2n-1) , R f =C4-C6 perfluoroalkyl, n=1-12, m=2-3, p=1-4; The method for preparing the resin dispersion comprises the following steps: (1) mixing organosilicon, tetraisopropyl titanate, cupric chloride and solvent to obtain a pre-reaction liquid A; mixing hydroxyl vinyl monomer, polymerization inhibitor, tetraisopropyl titanate and solvent to obtain a pre-reaction liquid B; mixing hard monomer, soft monomer, carboxyl vinyl monomer, organic fluorine, initiator, chain transfer agent and solvent to obtain a pre-reaction liquid C; (2) subjecting unsaturated fatty acid, polyacid, polyol and solvent to polymer reaction and esterification to obtain unsaturated ester; (3) adding the pre-reaction liquid A dropwise to the unsaturated ester of step (2), introducing nitrogen to replace the air for 5-10 min, and reacting, after the reaction, adding the pre-reaction liquid B dropwise, introducing nitrogen to replace the air for 5-10 min, and reacting again to obtain a reaction liquid; (4) adding the pre-reaction liquid C to the reaction liquid of step (3) by a "fast and slow" dropwise addition method, adding a neutralizing agent and deionized water after the reaction is completed and stirring evenly to obtain a silicone fluorine / alkyd resin modified waterborne acrylic resin dispersion; The polymer reaction in step (2) is specifically as follows: after mixing a solvent with a mass concentration of 15%, an unsaturated fatty acid with a mass concentration of 70%, a polyacid and a polyol, the oil bath is heated to 210-230° C., and the mixture is continuously stirred at a speed of 100-150 r / min until the acid value drops below 5 mg KOH / g; then a solvent with a mass concentration of 10% and an unsaturated fatty acid with a mass concentration of 30% are added, and the esterification reaction is continued until the acid value is ≤3 mg KOH / g.

2. The silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion according to claim 1, characterized in that: The ratio of the sum of the masses of the unsaturated fatty acids and the polyacids to the mass of the polyol is (1.3-2.4):1, wherein the unsaturated fatty acids are a combination of dehydrated ricinoleic acid and palmitoleic acid, and the mass ratio of dehydrated ricinoleic acid and palmitoleic acid is (2-3):1; the mass ratio of the polyol, the silicone and the hydroxyl-type vinyl monomer is (3-4):(2.1-2.5):1, and the hydroxyl-type vinyl monomer is any one of 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate.

3. The silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion according to claim 1, characterized in that: The polyacid is any one of adipic acid, phthalic anhydride or trimellitic anhydride; the polyol is any one of neopentyl glycol, trimethylolpropane or pentaerythritol; and the carboxyl vinyl monomer is any one of methacrylic acid or acrylic acid.

4. The silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion according to claim 1, characterized in that: The hard monomer is a combination of styrene and methyl methacrylate, and the mass ratio of styrene to methyl methacrylate is (2-2.2):1; the soft monomer is any one of lauryl methacrylate or butyl acrylate; the mass ratio of the hard monomer to the soft monomer is (1.4-2.5):

1.

5. The silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion according to claim 1, characterized in that: The solvent is any three combinations of n-butanol, propylene glycol methyl ether, propylene glycol butyl ether or diethylene glycol butyl ether, and the mass ratio of the three substances in the combination in order of slow, medium and fast volatilization rates is 1:(1:4-2):(2.1-3.5); the initiator is any one of tert-butyl benzoyl peroxide or di-tert-butyl hydroperoxide; the chain transfer agent is any one of 3-mercapto-1-propanol or n-dodecyl mercaptan; the inhibitor is any one of hydroquinone or 4-methoxyphenol; the neutralizer is any one of triethylamine or NN dimethylethanolamine or a combination of two.

6. The silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion according to claim 1, characterized in that: The preparation methods of the pre-reaction liquids A, B and C in the step (1) are respectively as follows: organic silicon, tetraisopropyl titanate with a mass concentration of 50%, copper chloride and a solvent with a mass concentration of 10% are mixed evenly to obtain pre-reaction liquid A; hydroxyl vinyl monomer, polymerization inhibitor, tetraisopropyl titanate with a mass concentration of 50% and a solvent with a mass concentration of 10% are mixed evenly to obtain pre-reaction liquid B; hard monomer, soft monomer, carboxyl vinyl monomer, organic fluorine, an initiator with a mass concentration of 70%, a chain transfer agent and a solvent with a mass concentration of 25% are mixed evenly to obtain pre-reaction liquid C.

7. The silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion according to claim 1, characterized in that: In the step (3), the dripping time of the pre-reaction liquid A and the pre-reaction liquid B is controlled to be 10-15 min, the reaction temperature is 120-140° C., and the reaction time is 60-80 min.

8. The silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion according to claim 1, characterized in that: The step (4) specifically comprises: adjusting the temperature to 120-140° C., adding 1 / 5 volume of the pre-reaction liquid C to the reaction liquid of step (3) dropwise for 30-40 min; then adding the remaining pre-reaction liquid C dropwise for 3-4 h; adjusting the temperature to 125-145° C., adding the remaining solvent and initiator used in the previous step, and reacting at a constant temperature for 2-4 h; reducing the temperature to below 40° C., adding a neutralizing agent under stirring, adjusting the pH to 8-9, adding deionized water and continuously stirring until transparent, and obtaining a silicone-fluorine / alkyd resin modified waterborne acrylic resin dispersion.

Images