A reactive phosphate functional emulsifier and preparation method thereof

Abstract

The present invention relates to a reactive phosphate functional emulsifier and a preparation method thereof, and belongs to the technical field of emulsifiers. A reactive phosphate functional emulsifier is prepared by using vinyl salicylaldehyde, phenyl phosphoryl dichloride, 2-amino-4-fluorothiophenol and glycidyl methacrylate as raw materials. The present invention is modified by grafting vinyl salicylaldehyde with phenyl phosphoryl dichloride, and then connected with 2-amino-4-fluorothiophenol to form an imine bond, and a polymer is generated with glycidyl methacrylate. The emulsifier can enhance the material structure density and thermal stability of the coating system. At the same time, the cross-linking carbonization ability of the imine structure, the synergistic flame retardancy of fluorine, nitrogen, phosphorus and sulfur elements, promote the dehydration of the coating into carbon, and enhance its flame retardant effect.

Description

Technical Field

[0001] The invention belongs to the technical field of emulsifiers and relates to a reactive phosphate functional emulsifier and a preparation method thereof. Background Art

[0002] Water-based coatings can be divided into four categories: acrylic coatings, alkyd coatings, epoxy coatings and polyurethane coatings, based on the differences in water-based resins. Among them, water-based acrylic resin coatings have become the leading product in the market with their outstanding market share. This product has excellent light resistance, weather resistance and heat resistance, elegant colors, and convenient construction. It is widely used in automobile manufacturing, furniture making and construction.

[0003] However, water-based acrylic coatings also have shortcomings, such as long drying cycle, easy to become sticky under high temperature environment, easy to become brittle under low temperature conditions, and inherently flammable. These defects limit its wide application to a certain extent. In particular, its flammability can easily cause fire accidents, resulting in casualties and property losses, which has become a serious obstacle to the promotion and application of water-based acrylic coatings. Therefore, it is extremely important to strengthen the research on water-based acrylic flame-retardant coatings.

[0004] In recent years, the flammability of waterborne acrylic coatings has gradually attracted the attention of all sectors of society, and the research on related flame-retardant coatings has also gradually increased. However, the current reports on waterborne acrylic flame-retardant coatings are still insufficient, and there is a lack of in-depth research results, which is not conducive to the further promotion and application of waterborne acrylic coatings. The flame retardant effect of waterborne acrylic coatings on the market using a single flame retardant is not ideal. Different flame retardant systems have their own advantages and disadvantages. Combining two or more different types of flame retardants to exert synergistic flame retardancy can achieve better flame retardant effects. Summary of the invention

[0005] The object of the present invention is to provide a reactive phosphate functional emulsifier and a preparation method thereof. The present invention utilizes vinyl salicylaldehyde and phenylphosphoryl dichloride for graft modification, and then forms an imine bond connection with 2-amino-4-fluorobenzenethiol, and generates a polymer with glycidyl methacrylate. The emulsifier can participate in the reaction in the coating system, improve the density of the material structure, and improve the thermal stability. In addition, the present invention promotes the dehydration and carbonization of the coating through the cross-linking carbonization ability of the imine structure, the action of fluorine-containing and phosphorus free radicals, and the synergistic flame retardancy of nitrogen and sulfur elements, thereby enhancing its flame retardant effect.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A method for preparing a reactive phosphate functional emulsifier comprises the following steps:

[0008] 1) placing vinyl salicylaldehyde, a solvent and a catalyst in a reaction kettle and stirring and mixing, slowly adding phenylphosphoryl dichloride under an inert atmosphere and an ice bath, heating and stirring, centrifuging, washing, and freeze-drying to obtain a preform;

[0009] 2) ultrasonically mixing the preform, anhydrous ethanol and 2-amino-4-fluorobenzenethiol and subjecting the mixture to a constant temperature treatment, cooling the mixture to room temperature, removing the solvent by rotary evaporation, washing the mixture, and freeze-drying the mixture to obtain a mixture;

[0010] 3) The mixture, anhydrous ethanol and an initiator are stirred and mixed, glycidyl methacrylate is added and heated, and then centrifuged, washed, and dried in an oven to obtain a product.

[0011] As a preferred technical solution of the present invention, in step 1), the stirring and mixing is stirring at a speed of 300-400 r / min for 30-45 min; and the inert atmosphere is a nitrogen atmosphere.

[0012] As a preferred technical solution of the present invention, in step 1), the heating and stirring is stirring at a temperature of 65-70° C. for 12-15 hours; and the washing is washing with saturated sodium chloride.

[0013] As a preferred technical solution of the present invention, in step 1), the mass ratio of the vinyl salicylaldehyde, the solvent, the catalyst and phenylphosphoryl dichloride is 12-15:125-140:8.0-9.2:7.5-9.0;

[0014] The solvent is ethyl acetate; the catalyst is triethylamine.

[0015] As a preferred technical solution of the present invention, in step 2), the ultrasonic mixing is performed at a frequency of 120-150W for 7-10 minutes; the constant temperature treatment is performed at a temperature of 60-65°C for 5-6 hours; and the washing is performed by alcohol washing.

[0016] As a preferred technical solution of the present invention, in step 2), the mass ratio of the preform, anhydrous ethanol and 2-amino-4-fluorobenzenethiol is 10-10.5:40-50:2.3-2.6.

[0017] As a preferred technical solution of the present invention, in step 3), the stirring and mixing time is 30-45 minutes; the heating treatment is heating at 80-85°C for 5-6 hours; the washing is washing with alcohol; and the drying is drying at 80°C to constant weight.

[0018] As a preferred technical solution of the present invention, in step 3), the mass ratio of the mixture, anhydrous ethanol, initiator and glycidyl methacrylate is 12-15:45-50:0.32-0.35:2.5-2.8.

[0019] As a preferred technical solution of the present invention, in step 3), the initiator is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, ammonium persulfate, potassium persulfate, sodium persulfate, benzoyl peroxide and peracetic acid.

[0020] The invention discloses a reactive phosphate functional emulsifier prepared by the above-mentioned preparation method.

[0021] Beneficial effects of the present invention:

[0022] The present invention utilizes vinyl salicylaldehyde and phenylphosphoryl dichloride for graft modification, and then forms an imine bond connection with 2-amino-4-fluorobenzenethiol, and generates a polymer with glycidyl methacrylate. The emulsifier can participate in the reaction in the coating system, improve the density of the material structure, and improve the thermal stability. In addition, the present invention promotes the dehydration and carbonization of the coating through the cross-linking carbonization ability of the imine structure, the action of fluorine-containing and phosphorus free radicals, and the synergistic flame retardancy of N and S elements, thereby enhancing its flame retardant effect. DETAILED DESCRIPTION

[0023] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0024] Example 1

[0025] A method for preparing a reactive phosphate functional emulsifier comprises the following steps:

[0026] 1) Vinyl salicylaldehyde, a solvent and a catalyst are placed in a reaction kettle and stirred and mixed, and then phenylphosphoryl dichloride is slowly added in an inert atmosphere and an ice bath, heated and stirred, centrifuged, washed, and freeze-dried to obtain a preform; wherein the stirring and mixing is stirring at a speed of 300 r / min for 30 minutes; the inert atmosphere is a nitrogen atmosphere; the heating and stirring is stirring at a temperature of 65° C. for 12 hours; the washing is washing with saturated sodium chloride; the mass ratio of vinyl salicylaldehyde, solvent, catalyst and phenylphosphoryl dichloride is 12:125:8.0:7.5; the solvent is ethyl acetate; and the catalyst is triethylamine.

[0027] 2) ultrasonically mixing the preform, anhydrous ethanol and 2-amino-4-fluorobenzenethiol, and then subjecting the preform to a constant temperature treatment. After cooling to room temperature, the solvent is removed by rotary evaporation, and then washed and freeze-dried to obtain a mixture; the ultrasonic mixing is performed at a frequency of 120 W for 7 minutes; the constant temperature treatment is performed at a temperature of 60° C. for 5 hours; the washing is performed 3 times with anhydrous ethanol; the mass ratio of the preform, anhydrous ethanol and 2-amino-4-fluorobenzenethiol is 10:40:2.3;

[0028] 3) stirring and mixing the mixture, anhydrous ethanol and initiator, adding glycidyl methacrylate and heating, centrifuging, washing, and drying in an oven to obtain; wherein the stirring and mixing time is 30 minutes; the heating treatment is heating at 80°C for 5 hours; the washing is washing 3 times with anhydrous ethanol; the drying is drying at 80°C to constant weight; the mass ratio of the mixture, anhydrous ethanol, initiator and glycidyl methacrylate is 12:45:0.32:2.5; the initiator is azobisisobutyronitrile.

[0029] Example 2

[0030] A method for preparing a reactive phosphate functional emulsifier comprises the following steps:

[0031] 1) Vinyl salicylaldehyde, a solvent and a catalyst are placed in a reaction kettle and stirred and mixed, and then phenylphosphoryl dichloride is slowly added in an inert atmosphere and an ice bath, heated and stirred, centrifuged, washed, and freeze-dried to obtain a preform; wherein the stirring and mixing is stirring at a speed of 330 r / min for 35 minutes; the inert atmosphere is a nitrogen atmosphere; the heating and stirring is stirring at a temperature of 67° C. for 13 hours; the washing is washing with saturated sodium chloride; the mass ratio of vinyl salicylaldehyde, solvent, catalyst and phenylphosphoryl dichloride is 13:130:8.4:8; the solvent is ethyl acetate; and the catalyst is triethylamine.

[0032] 2) ultrasonically mixing the preform, anhydrous ethanol and 2-amino-4-fluorobenzenethiol, and then subjecting the preform to a constant temperature treatment. After cooling to room temperature, the solvent is removed by rotary evaporation, and then washed and freeze-dried to obtain a mixture; the ultrasonic mixing is performed at a frequency of 130 W for 8 minutes; the constant temperature treatment is performed at a temperature of 62° C. for 5.5 hours; the washing is performed 3 times with anhydrous ethanol; the mass ratio of the preform, anhydrous ethanol and 2-amino-4-fluorobenzenethiol is 10.2:43:2.4;

[0033] 3) stirring and mixing the mixture, anhydrous ethanol and initiator, adding glycidyl methacrylate and heating, centrifuging, washing, and drying in an oven to obtain; wherein the stirring and mixing time is 35 minutes; the heating treatment is heating at 82°C for 5.5 hours; the washing is washing 3 times with anhydrous ethanol; the drying is drying at 80°C to constant weight; the mass ratio of the mixture, anhydrous ethanol, initiator and glycidyl methacrylate is 13:47:0.33:2.6; the initiator is azobisisobutyronitrile.

[0034] Example 3

[0035] A method for preparing a reactive phosphate functional emulsifier comprises the following steps:

[0036] 1) Vinyl salicylaldehyde, a solvent and a catalyst are placed in a reaction kettle and stirred and mixed, and then phenylphosphinoyl dichloride is slowly added in an inert atmosphere and an ice bath, heated and stirred, centrifuged, washed, and freeze-dried to obtain a preform; wherein the stirring and mixing is stirring at a speed of 360r / min for 40min; the inert atmosphere is a nitrogen atmosphere; the heating and stirring is stirring at a temperature of 68°C for 14h; the washing is washing with saturated sodium chloride; the mass ratio of vinyl salicylaldehyde, solvent, catalyst and phenylphosphinoyl dichloride is 14:135:8.8:8.5; the solvent is ethyl acetate; and the catalyst is triethylamine.

[0037] 2) ultrasonically mixing the preform, anhydrous ethanol and 2-amino-4-fluorobenzenethiol and subjecting them to constant temperature treatment, cooling to room temperature, rotary evaporating to remove the solvent, washing, and freeze-drying to obtain a mixture; the ultrasonic mixing is ultrasonically mixed at a frequency of 140 W for 9 minutes; the constant temperature treatment is constant temperature at 63° C. for 5.5 hours; the washing is washed 3 times with anhydrous ethanol; the mass ratio of the preform, anhydrous ethanol and 2-amino-4-fluorobenzenethiol is 10.3:47:2.5;

[0038] 3) stirring and mixing the mixture, anhydrous ethanol and initiator, adding glycidyl methacrylate and heating, centrifuging, washing, and drying in an oven to obtain; wherein the stirring and mixing time is 40 minutes; the heating treatment is heating at 83°C for 5.5 hours; the washing is washing 3 times with anhydrous ethanol; the drying is drying at 80°C to constant weight; the mass ratio of the mixture, anhydrous ethanol, initiator and glycidyl methacrylate is 14:48:0.34:2.7; the initiator is azobisisobutyronitrile.

[0039] Example 4

[0040] A method for preparing a reactive phosphate functional emulsifier comprises the following steps:

[0041] 1) Vinyl salicylaldehyde, a solvent and a catalyst are placed in a reaction kettle and stirred and mixed, and then phenylphosphoryl dichloride is slowly added under an inert atmosphere and an ice bath, heated and stirred, centrifuged, washed, and freeze-dried to obtain a preform; wherein the stirring and mixing is stirring at a speed of 400 r / min for 45 minutes; the inert atmosphere is a nitrogen atmosphere; the heating and stirring is stirring at a temperature of 70° C. for 15 hours; the washing is washing with saturated sodium chloride; the mass ratio of vinyl salicylaldehyde, solvent, catalyst and phenylphosphoryl dichloride is 15:140:9.2:9.0; the solvent is ethyl acetate; and the catalyst is triethylamine.

[0042] 2) ultrasonically mixing the preform, anhydrous ethanol and 2-amino-4-fluorobenzenethiol, and then subjecting the preform to a constant temperature treatment. After cooling to room temperature, the solvent is removed by rotary evaporation, and then washed and freeze-dried to obtain a mixture; the ultrasonic mixing is performed at a frequency of 150 W for 10 minutes; the constant temperature treatment is performed at a temperature of 65° C. for 6 hours; the washing is performed 3 times with anhydrous ethanol; the mass ratio of the preform, anhydrous ethanol and 2-amino-4-fluorobenzenethiol is 10.5:50:2.6;

[0043] 3) stirring and mixing the mixture, anhydrous ethanol and initiator, adding glycidyl methacrylate and heating, centrifuging, washing, and drying in an oven to obtain; wherein the stirring and mixing time is 45 minutes; the heating treatment is heating at 85°C for 6 hours; the washing is washing 3 times with anhydrous ethanol; the drying is drying at 80°C to constant weight; the mass ratio of the mixture, anhydrous ethanol, initiator and glycidyl methacrylate is 15:50:0.35:2.8; the initiator is azobisisobutyronitrile.

[0044] Comparative Example 1

[0045] Compared with Example 2, Comparative Example 1 is different in that salicylaldehyde is used instead of vinyl salicylaldehyde, and the other components, preparation steps and parameters are the same.

[0046] Comparative Example 2

[0047] Compared with Example 2, Comparative Example 2 is different in that 2-aminothiophenol is used instead of 2-amino-4-fluorothiophenol, and the other components, preparation steps and parameters are the same.

[0048] Comparative Example 3

[0049] Compared with Example 2, Comparative Example 3 is different in that aniline is used instead of 2-amino-4-fluorobenzenethiol, and the other components, preparation steps and parameters are the same.

[0050] Comparative Example 4

[0051] Compared with Example 2, Comparative Example 4 is different in that 4-fluorothiophenol is used instead of 2-amino-4-fluorothiophenol, and the other components, preparation steps and parameters are the same.

[0052] Comparative Example 5

[0053] Compared with Example 2, Comparative Example 5 is different in that 2-amino-4-fluorobenzenethiol is not used, and the remaining components, preparation steps and parameters are the same.

[0054] Comparative Example 6

[0055] Compared with Example 2, Comparative Example 6 is different in that glycidyl methacrylate is not used, and the other components, preparation steps and parameters are the same.

[0056] The emulsifiers obtained in Examples 1-4 and Comparative Examples 1-6 were used to prepare coatings according to the following method.

[0057] Emulsifier (Example 1-4 and Comparative Example 1-6), n-butanol, epoxy resin (E-44) and calcium carbonate are placed in a reaction kettle, the temperature is raised to 105°C, methyl methacrylate, butyl acrylate, hydroxyethyl acrylate and acrylic acid are added, benzoyl peroxide is slowly added, the temperature is raised to 115°C, and the reaction is kept warm for 3 hours; the temperature is lowered to 70°C, and ammonium polyphosphate is added under stirring, and then diluted with deionized water, and the pH value is adjusted to 7 to obtain a coating; wherein the mass ratio of emulsifier, n-butanol, epoxy resin, calcium carbonate, butyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, benzoyl peroxide, ionized water and ammonium polyphosphate is 3:3:12:4:40:15:8:2:2.5:0.8:50:1.

[0058] The coatings prepared with the emulsifiers of Examples 1-4 and Comparative Examples 1-6 were cured to form films, and the limiting oxygen index was tested using a JF-3 oxygen index tester in accordance with GB / T 2406.2-2009. The test results are shown in Table 1.

[0059] Table 1

[0060] Limiting oxygen index (%) Example 1 31.5 Example 2 32.1 Example 3 31.6 Example 4 31.8 Comparative Example 1 28.3 Comparative Example 2 25.5 Comparative Example 3 23.1 Comparative Example 4 23.8 Comparative Example 5 18.9 Comparative Example 6 27.9

[0061] From the test results in Table 1, it can be seen that compared with Comparative Examples 1-6, the limiting oxygen index of the coating prepared by using the emulsifier of Examples 1-4 of the present invention after curing is significantly higher than that of Comparative Examples 1-6. From the comparative analysis of Examples 1-4 and Comparative Examples 1-6 and combined with Table 1, it can be seen that the present invention introduces an active carbon-carbon double bond and a P element with a flame retardant function through the phenolic hydroxyl group of vinyl salicylaldehyde and phenylphosphoryl dichloride, and then forms an imide bond connection between the aldehyde group and the amino group of 2-amino-4-fluorobenzenethiol, and introduces F, N and S elements with a flame retardant function at the same time, and finally generates a polymer with glycidyl methacrylate through the carbon-carbon double bond. The benzene ring structure and carbon ester in the polymer are hydrophobic, which increases its dispersibility in the system. The carbon-carbon double bond in the emulsifier polymer can participate in the reaction of the acrylic acid system and enter the polymer chain, and the epoxy group can increase its affinity with pigments and fillers. While maintaining compatibility, the active epoxy group can also participate in a variety of chemical reactions, increase its dispersion stability and compatibility in the system, significantly improve the crosslinking density of the coating, and improve the compactness and thermal stability of the coating structure. In addition, the emulsifier contains an imine structure, which can undergo a self-crosslinking reaction at high temperature to form a nitrogen-containing six-membered ring structure. The special structure gives the acrylic coating a more excellent carbon-forming performance, which can effectively improve thermal stability and high temperature resistance. The present invention can better promote the dehydration and carbonization of the acrylic coating through the excellent crosslinking and carbon-forming ability of the imine structure, the role of fluorine and phosphorus free radicals in capturing gas phase free radicals, and the synergistic flame retardancy of F, N, P and S elements, thereby enhancing its condensed phase flame retardancy.

[0062] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a reactive phosphate functional emulsifier, characterized in that: The preparation method comprises the following steps: 1) placing vinyl salicylaldehyde, a solvent and a catalyst in a reaction kettle and stirring and mixing, then slowly adding phenylphosphoryl dichloride under an inert atmosphere and an ice bath, heating and stirring, centrifuging, washing, and freeze-drying to obtain a preform; the mass ratio of the vinyl salicylaldehyde, the solvent, the catalyst and phenylphosphoryl dichloride is 12-15:125-140:8.0-9.2:7.5-9.0; the solvent is ethyl acetate; and the catalyst is triethylamine; 2) ultrasonically mixing the preform, anhydrous ethanol and 2-amino-4-fluorobenzenethiol and subjecting the mixture to a constant temperature treatment, cooling the mixture to room temperature, removing the solvent by rotary evaporation, washing the mixture, and freeze-drying the mixture to obtain a mixture; wherein the mass ratio of the preform, anhydrous ethanol and 2-amino-4-fluorobenzenethiol is 10-10.5:40-50:2.3-2.6; 3) stirring and mixing the mixture, anhydrous ethanol and an initiator, adding glycidyl methacrylate and heating, centrifuging, washing, and drying in an oven to obtain the mixture; the mass ratio of the mixture, anhydrous ethanol, initiator and glycidyl methacrylate is 12-15:45-50:0.32-0.35:2.5-2.

8.

2. The method for preparing a reactive phosphate functional emulsifier according to claim 1, characterized in that: In step 1), the stirring and mixing is stirring at a speed of 300-400 r / min for 30-45 min; and the inert atmosphere is a nitrogen atmosphere.

3. The method for preparing a reactive phosphate functional emulsifier according to claim 1, characterized in that: In step 1), the heating and stirring is stirring at 65-70° C. for 12-15 hours; and the washing is washing with saturated sodium chloride.

4. The method for preparing a reactive phosphate functional emulsifier according to claim 1, characterized in that: In step 2), the ultrasonic mixing is performed at a frequency of 120-150W for 7-10 minutes; the constant temperature treatment is performed at a temperature of 60-65°C for 5-6 hours; and the washing is performed by alcohol washing.

5. The method for preparing a reactive phosphate functional emulsifier according to claim 1, characterized in that: In step 3), the stirring and mixing time is 30-45 minutes; the heating treatment is heating at 80-85°C for 5-6 hours; the washing is washing with alcohol; and the drying is drying at 80°C to constant weight.

6. The method for preparing a reactive phosphate functional emulsifier according to claim 1, characterized in that: In step 3), the initiator is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, ammonium persulfate, potassium persulfate, sodium persulfate, benzoyl peroxide and peracetic acid.

7. A reactive phosphate functional emulsifier prepared by the preparation method according to any one of claims 1 to 6.