Wear-resistant water-based alkyd resin and preparation method thereof

Abstract

The invention discloses wear-resistant waterborne alkyd resin and a preparation method thereof, and belongs to the technical field of alkyd resin, a polyamide structure polymer with a hyperbranched structure and hydroxylated carbon nanotubes are introduced in the preparation process of the alkyd resin, the polyamide structure polymer has excellent wear resistance, the introduced carbon nanotubes have high strength, and the wear resistance of the alkyd resin is improved. The water-based alkyd resin also has good toughness, and the wear resistance of the water-based alkyd resin is improved; besides, hydrogen-bond interaction is formed between the hydroxylated carbon nanotubes and amido and ether groups on the polyamide structure polymer, so that the interface bonding strength between the resin and the carbon nanotubes is improved, and the dispersion of the carbon nanotubes is more stable; the wear-resistant water-based alkyd resin prepared by the invention has excellent mechanical properties and wear resistance on the basis of keeping the original excellent properties of the resin.

Description

Technical Field

[0001] The invention belongs to the technical field of alkyd resins, and in particular relates to a wear-resistant water-based alkyd resin and a preparation method thereof. Background Art

[0002] Water-based alkyd resin is an environmentally friendly resin that uses water as its main solvent. It has the advantages of low volatile organic matter content, non-flammability, low odor, and low toxicity. After film formation, it also has good corrosion resistance, weather resistance, adhesion and drying properties, and is widely used in coatings and paints.

[0003] However, the main chain structure of waterborne alkyd resin is relatively soft and its mechanical properties are relatively weak. Therefore, it is easily affected by external friction stress during use, resulting in problems such as scratches and wear. On the other hand, during the curing process of waterborne alkyd resin, due to the presence of water, the degree of crosslinking is low, which also leads to poor mechanical strength and wear resistance, thus affecting the performance of waterborne alkyd resin. Therefore, how to modify waterborne alkyd resin to improve its defects in wear resistance and thus extend the service life of waterborne alkyd resin is of great significance. Summary of the invention

[0004] To solve the above problems, the present invention aims to provide a wear-resistant waterborne alkyd resin and a preparation method thereof.

[0005] In order to achieve the above object, the present invention is implemented through the following technical solutions:

[0006] A wear-resistant water-based alkyd resin is composed of the following raw materials, measured in parts by weight: 10 to 15 parts of polyol, 10 to 13 parts of phthalic anhydride, 12 to 20 parts of fatty acid, 2 to 3 parts of carboxyl-terminated polyamide structure polymer, 3 to 5 parts of trimellitic anhydride, 1 to 2 parts of xylene, 10 to 15 parts of cosolvent, 4 to 5 parts of neutralizer and 0.1 to 0.3 parts of hydroxylated carbon nanotube;

[0007] The carboxyl-terminated polyamide structural polymer is prepared according to the following method:

[0008] 1) 3-amino-2-hydroxy-5-methylbenzoic acid methyl ester and amino-triethylene glycol are added to tetrahydrofuran, and after stirring and dissolving, triphenylphosphine and diisopropyl azodicarboxylate are added, and the reaction is carried out at 30-40° C. for 5-8 hours. After the reaction is completed, the solvent is removed by distillation under reduced pressure, and the obtained residue is dissolved by adding dichloromethane and then filtered. The obtained filtrate is extracted with water for 3-5 times, and the organic layers are combined, and the solvent is removed by distillation under reduced pressure, and dried to obtain a methyl bisaminobenzoate derivative;

[0009] 2) Add the methyl bis(amino)benzoate derivative prepared in step 1) and trimellitic acid into an organic solvent. After stirring and mixing evenly, add diethyl azodicarboxylate and 1-hydroxybenzotriazole, and react at 30 - 40 °C for 5 - 12 h. After the reaction is completed, remove the solvent by distillation under reduced pressure. The obtained residue is washed 2 - 3 times with petroleum ether and then added to methanol. Then add sodium hydroxide and react at 25 - 30 °C for 5 - 10 h. After the reaction is completed, add water and dichloromethane for extraction. The obtained organic phase is distilled under reduced pressure to remove the solvent, and a polymer with a terminal carboxyl polyamide structure is obtained.

[0010] In step 1), the mass ratio of methyl 3-amino-2-hydroxy-5-methylbenzoate, amino-triethylene glycol, tetrahydrofuran, triphenylphosphine, diisopropyl azodicarboxylate, dichloromethane and water is 1:0.8 - 1.2:10 - 15:1.5 - 2:1.2 - 1.5:5 - 10:5 - 10.

[0011] In step 2), the organic solvent is dimethyl sulfoxide or dimethylformamide.

[0012] In step 2), the mass ratio of the methyl bis(amino)benzoate derivative, trimellitic acid, organic solvent, diethyl azodicarboxylate, 1-hydroxybenzotriazole, methanol, sodium hydroxide, water and dichloromethane is 1:0.5 - 0.8:8 - 15:0.4 - 0.6:0.3 - 0.5:5 - 10:0.4 - 0.8:10 - 15:10 - 15.

[0013] The polyol is glycerol, pentaerythritol or trimethylolpropane.

[0014] The fatty acid is linseed oil or soya-bean oil fatty acid.

[0015] The cosolvent is ethylene glycol monobutyl ether or propylene glycol monomethyl ether.

[0016] The neutralizing agent is triethylamine or dimethylethanolamine.

[0017] The preparation method of the wear-resistant waterborne alkyd resin includes the following steps:

[0018] Add 12 - 20 parts by weight of fatty acid, 10 - 15 parts of polyol, 10 - 13 parts of phthalic anhydride, 2 - 3 parts of a polymer with a terminal carboxyl polyamide structure, and 1 - 2 parts of xylene into a reactor. Heat it to 180 - 190 °C under nitrogen protection, keep the temperature for reaction for 1 - 2 h, raise the temperature to 195 - 210 °C for reaction for 2 - 3 h, continue to raise the temperature to 220 - 230 °C, react until the acid value reaches 10 - 15 mgKOH / g, evacuate to remove xylene, cool down to 170 - 180 °C, add 3 - 5 parts of trimellitic anhydride, continue to keep the temperature for reaction until the acid value reaches 40 - 60 mgKOH / g, cool down to 100 - 120 °C, add 10 - 15 parts of cosolvent and 0.1 - 0.3 parts of hydroxyl-terminated carbon nanotubes, stir and disperse for 0.5 h, continue to cool down to 60 - 70 °C, add 4 - 5 parts of neutralizer for neutralization reaction for 0.5 - 1 h, and finally add water for high-speed emulsification and dispersion for 30 min to obtain a wear-resistant waterborne alkyd resin.

[0019] The present invention has the following advantages compared with the prior art:

[0020] For the wear-resistant waterborne alkyd resin of the present invention, a polyamide structure polymer with a hyperbranched structure and hydroxylated carbon nanotubes are introduced during the preparation of the alkyd resin. The polyamide structure polymer has excellent wear resistance. The introduction of ether bonds increases the toughness of the resin, reduces cracks caused by impact, and thus improves wear resistance. The introduction of rigid benzene rings increases the hardness of the resin; in addition, the hyperbranched structure enables the prepared resin to crosslink to form a three-dimensional network structure, further improving the strength and wear resistance of the material; the introduced carbon nanotubes not only have high strength but also good toughness, improving the wear resistance of the waterborne alkyd resin; hydrogen bonding is formed between the hydroxylated carbon nanotubes and the amide groups and ether groups on the polyamide structure polymer, improving the interfacial bonding strength between the resin and the carbon nanotubes and making the carbon nanotubes more stably dispersed; the wear-resistant waterborne alkyd resin prepared by the present invention has excellent mechanical properties and wear resistance on the basis of maintaining the original excellent properties of the resin. Specific Embodiments

[0021] In order to better understand the technical solution of the present invention, the above content of the present invention will be further described in detail through specific embodiments in the form of examples, but this should not be construed as limiting the scope of the above subject matter of the present invention to the following examples. Any technology implemented based on the above content of the present invention belongs to the scope of the present invention.

[0022] Example 1 Preparation of a polymer with a terminal carboxyl polyamide structure:

[0023] Dissolve 1 kg of methyl 3-amino-2-hydroxy-5-methylbenzoate and 0.8 kg of amino-triethylene glycol in 10 kg of tetrahydrofuran. After stirring and dissolving, add 1.5 kg of triphenylphosphine and 1.2 kg of diisopropyl azodicarboxylate, and react at 30 °C for 5 h. After the reaction is completed, remove the solvent by distillation under reduced pressure. Dissolve the obtained residue in 5 kg of dichloromethane and filter by suction. Extract the obtained filtrate with 5 kg of water three times, combine the organic layers, remove the solvent by distillation under reduced pressure, and dry to obtain a bis-aminobenzoate derivative; 1 H NMR(300MHz,DMSO-d 6 ,298K)δ7.55(s,2H),6.98(s,1H),6.54(s,1H),4.32(t,2H),3.91(s,3H),3.75(t,2H),3.63(t,2H),3.45 - 3.56(m,4H),3.09(t,2H),2.29(s,3H),1.79(s,2H).

[0024] Dissolve 1 kg of the bis-aminobenzoate derivative and 0.5 kg of trimesic acid in 8 kg of dimethylformamide. After stirring and mixing evenly, add 0.4 kg of diethyl azodicarboxylate and 0.3 kg of 1-hydroxybenzotriazole, and react at 30 °C for 5 h. After the reaction is completed, remove the solvent by distillation under reduced pressure. Wash the obtained residue twice with petroleum ether and then add it to 5 kg of methanol. Then add 0.4 kg of sodium hydroxide and react at 25 °C for 5 h. After the reaction is completed, add 10 kg of water and 10 kg of dichloromethane for extraction. Distill off the solvent from the obtained organic phase under reduced pressure to obtain a terminal carboxyl polyamide structure polymer.

[0025] Preparation of wear-resistant waterborne alkyd resin:

[0026] Add 12 kg of soybean oil fatty acid, 10 kg of glycerol, 10 kg of phthalic anhydride, 2 kg of the terminal carboxyl polyamide structure polymer and 1 kg of xylene to a reactor. Heat to 180 °C under nitrogen protection and hold the reaction for 1 h. Raise the temperature to 195 °C and react for 2 h. Continue to raise the temperature to 220 °C and react until the acid value reaches 15 mg KOH / g. Evacuate to remove xylene, cool to 170 °C, add 3 kg of trimellitic anhydride, continue to hold the reaction until the acid value reaches 40 mg KOH / g, cool to 100 °C, add 10 kg of propylene glycol methyl ether and 0.1 kg of terminal hydroxyl carbon nanotubes, stir and disperse for 0.5 h. Continue to cool to 60 °C, add 4 kg of dimethylethanolamine for neutralization reaction for 0.5 h, and finally add water for high-speed emulsification and dispersion for 30 min to obtain a wear-resistant waterborne alkyd resin.

[0027] Preparation of the terminal carboxyl polyamide structure polymer in Example 2:

[0028] 1 kg of methyl 3-amino-2-hydroxy-5-methylbenzoate and 0.9 kg of amino-triethylene glycol were added to 11 kg of tetrahydrofuran. After stirring and dissolving, 1.6 kg of triphenylphosphine and 1.3 kg of diisopropyl azodicarboxylate were added, and the reaction was carried out at 35 °C for 7 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure. The obtained residue was dissolved in 7 kg of dichloromethane and filtered by suction. The obtained filtrate was extracted 5 times with 6 kg of water. The organic layers were combined, the solvent was removed by distillation under reduced pressure, and dried to obtain a bis-aminobenzoate derivative;

[0029] 1 kg of the bis-aminobenzoate derivative and 0.6 kg of trimesic acid were added to 10 kg of dimethyl sulfoxide. After stirring and mixing evenly, 0.5 kg of diethyl azodicarboxylate and 0.35 kg of 1-hydroxybenzotriazole were added, and the reaction was carried out at 35 °C for 10 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure. The obtained residue was washed 3 times with petroleum ether and then added to 6 kg of methanol. Then 0.5 kg of sodium hydroxide was added, and the reaction was carried out at 26 °C for 9 h. After the reaction was completed, 11 kg of water and 12 kg of dichloromethane were added for extraction. The obtained organic phase was distilled under reduced pressure to remove the solvent to obtain a polymer with a terminal carboxyl polyamide structure.

[0030] Preparation of wear-resistant waterborne alkyd resin:

[0031] 14 kg of soya fatty acid, 11 kg of pentaerythritol, 11 kg of phthalic anhydride, 2.2 kg of the polymer with a terminal carboxyl polyamide structure and 1.5 kg of xylene were added to a reactor. Under nitrogen protection, it was heated to 185 °C and kept warm for reaction for 1.5 h, then the temperature was raised to 200 °C and reacted for 2 h, and then the temperature was further raised to 230 °C and reacted until the acid value reached 11 mg KOH / g. The xylene was removed by vacuum pumping, and the temperature was lowered to 170 °C. 3.5 kg of trimellitic anhydride was added, and the reaction was continued to be kept warm until the acid value reached 45 mg KOH / g. The temperature was lowered to 110 °C, 11 kg of propylene glycol methyl ether and 0.2 kg of hydroxyl-terminated carbon nanotubes were added, and stirred and dispersed for 0.5 h. Then the temperature was further lowered to 65 °C, 4.5 kg of triethylamine was added for neutralization reaction for 0.6 h, and finally water was added for high-speed emulsification and dispersion for 30 min to obtain a wear-resistant waterborne alkyd resin.

[0032] Preparation of the polymer with a terminal carboxyl polyamide structure in Example 3:

[0033] 1 kg of methyl 3-amino-2-hydroxy-5-methylbenzoate and 1 kg of amino-triethylene glycol were added to 13 kg of tetrahydrofuran. After stirring and dissolving, 1.8 kg of triphenylphosphine and 1.3 kg of diisopropyl azodicarboxylate were added, and the reaction was carried out at 38 °C for 6 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure. The obtained residue was dissolved in 9 kg of dichloromethane and filtered by suction. The obtained filtrate was extracted 4 times with 8 kg of water. The organic layers were combined, the solvent was removed by distillation under reduced pressure, and dried to obtain a bis-aminobenzoate derivative;

[0034] 1 kg of methyl bis(aminobenzoate) derivative and 0.7 kg of trimellitic acid are added to 12 kg of dimethyl sulfoxide. After stirring and mixing evenly, 0.55 kg of diethyl azodicarboxylate and 0.4 kg of 1-hydroxybenzotriazole are added. The reaction is carried out at 33 °C for 11 h. After the reaction is completed, the solvent is removed by vacuum distillation. The obtained residue is washed 3 times with petroleum ether and then added to 7 kg of methanol. Then 0.65 kg of sodium hydroxide is added, and the reaction is carried out at 28 °C for 7 h. After the reaction ends, 13 kg of water and 13 kg of dichloromethane are added for extraction. The obtained organic phase is distilled under reduced pressure to remove the solvent, and a polymer with a terminal carboxyl polyamide structure is obtained.

[0035] Preparation of wear-resistant waterborne alkyd resin:

[0036] 15 kg of linseed oil, 13 kg of trimethylolpropane, 12 kg of phthalic anhydride, 2.5 kg of the polymer with a terminal carboxyl polyamide structure and 1.5 kg of xylene are added to a reactor. Under nitrogen protection, it is heated to 185 °C and kept at this temperature for reaction for 1.5 h. Then the temperature is raised to 200 °C and reacted for 1.5 h. The temperature is further raised to 225 °C and the reaction is carried out until the acid value reaches 13 mg KOH / g. Xylene is removed by vacuum pumping. The temperature is lowered to 175 °C, 4 kg of trimellitic anhydride is added, and the reaction is continued under insulation until the acid value reaches 55 mg KOH / g. The temperature is lowered to 110 °C, 13 kg of ethylene glycol monobutyl ether and 0.2 kg of hydroxyl-terminated carbon nanotubes are added, and they are stirred and dispersed for 0.5 h. The temperature is further lowered to 65 °C, 4.5 kg of triethylamine is added for neutralization reaction for 0.7 h. Finally, water is added and high-speed emulsification and dispersion are carried out for 30 min to obtain the wear-resistant waterborne alkyd resin.

[0037] Preparation of the polymer with a terminal carboxyl polyamide structure in Example 4:

[0038] 1 kg of methyl 3-amino-2-hydroxy-5-methylbenzoate and 1.1 kg of amino-triethylene glycol are added to 14 kg of tetrahydrofuran. After stirring and dissolving, 1.9 kg of triphenylphosphine and 1.4 kg of diisopropyl azodicarboxylate are added. The reaction is carried out at 34 °C for 7 h. After the reaction ends, the solvent is removed by vacuum distillation. The obtained residue is dissolved in 9 kg of dichloromethane and then filtered by suction. The obtained filtrate is extracted 5 times with 9 kg of water. The organic layers are combined and the solvent is removed by vacuum distillation and dried to obtain the methyl bis(aminobenzoate) derivative;

[0039] Add 1 kg of methyl bis(aminobenzoate) derivative and 0.75 kg of trimellitic acid to 14 kg of dimethylformamide. After stirring and mixing evenly, add 0.55 kg of diethyl azodicarboxylate and 0.45 kg of 1-hydroxybenzotriazole, and react at 38 °C for 6 h. After the reaction is completed, remove the solvent by vacuum distillation. The obtained residue is washed 3 times with petroleum ether and then added to 9 kg of methanol. Then add 0.7 kg of sodium hydroxide and react at 29 °C for 6 h. After the reaction is completed, add 14 kg of water and 13 kg of dichloromethane for extraction. The obtained organic phase is subjected to vacuum distillation to remove the solvent, and a polymer with a terminal carboxyl polyamide structure is obtained.

[0040] Preparation of wear-resistant waterborne alkyd resin:

[0041] Add 18 kg of soya fatty acid, 13 kg of trimethylolpropane, 11 kg of phthalic anhydride, 2.8 kg of the polymer with a terminal carboxyl polyamide structure and 1.8 kg of xylene to a reactor. Heat to 188 °C under nitrogen protection and keep the temperature for 1.8 h. Then raise the temperature to 205 °C and react for 2.5 h. Continue to raise the temperature to 225 °C and react until the acid value reaches 14 mg KOH / g. Evacuate to remove xylene, cool to 175 °C, add 4.5 kg of trimellitic anhydride, and continue to keep the temperature for reaction until the acid value reaches 50 mg KOH / g. Cool to 115 °C, add 14 kg of ethylene glycol monobutyl ether and 0.25 kg of carboxyl-terminated carbon nanotubes, stir and disperse for 0.5 h. Continue to cool to 65 °C, add 4.5 kg of triethylamine for neutralization reaction for 0.9 h. Finally, add water and emulsify and disperse at high speed for 30 min to obtain the wear-resistant waterborne alkyd resin.

[0042] Preparation of the polymer with a terminal carboxyl polyamide structure in Example 5:

[0043] Add 1 kg of methyl 3-amino-2-hydroxy-5-methylbenzoate and 1.2 kg of amino-triethylene glycol to 15 kg of tetrahydrofuran. After stirring and dissolving, add 2 kg of triphenylphosphine and 1.5 kg of diisopropyl azodicarboxylate, and react at 40 °C for 5 h. After the reaction is completed, remove the solvent by vacuum distillation. The obtained residue is dissolved in 10 kg of dichloromethane and then filtered by suction. The obtained filtrate is extracted 3 times with 10 kg of water. The organic layers are combined and the solvent is removed by vacuum distillation and dried to obtain the methyl bis(aminobenzoate) derivative;

[0044] 1 kg of methyl bis(aminobenzoate) derivative and 0.8 kg of trimesic acid were added to 15 kg of dimethylformamide. After stirring and mixing evenly, 0.6 kg of diethyl azodicarboxylate and 0.5 kg of 1-hydroxybenzotriazole were added. The reaction was carried out at 40 °C for 5 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure. The obtained residue was washed 3 times with petroleum ether and then added to 10 kg of methanol. Then 0.8 kg of sodium hydroxide was added, and the reaction was carried out at 30 °C for 5 h. After the reaction ended, 15 kg of water and 15 kg of dichloromethane were added for extraction. The obtained organic phase was distilled under reduced pressure to remove the solvent, and a polymer with a terminal carboxyl polyamide structure was obtained.

[0045] Preparation of wear-resistant waterborne alkyd resin:

[0046] 20 kg of soya fatty acid, 15 kg of pentaerythritol, 13 kg of phthalic anhydride, 3 kg of polymer with a terminal carboxyl polyamide structure and 2 kg of xylene were added to a reactor. Under nitrogen protection, it was heated to 190 °C and kept at this temperature for reaction for 2 h. Then the temperature was raised to 210 °C and reacted for 3 h. The temperature was further raised to 230 °C and reacted until the acid value reached 15 mg KOH / g. Xylene was removed by vacuum distillation. The temperature was lowered to 180 °C, and 5 kg of trimellitic anhydride was added. The reaction was continued under insulation until the acid value reached 60 mg KOH / g. The temperature was lowered to 120 °C, 15 kg of propylene glycol methyl ether and 0.3 kg of carboxyl-terminated carbon nanotubes were added, and they were stirred and dispersed for 0.5 h. Then the temperature was further lowered to 70 °C, 5 kg of triethylamine was added for neutralization reaction for 1 h. Finally, water was added for high-speed emulsification and dispersion for 30 min to obtain a wear-resistant waterborne alkyd resin.

[0047] Preparation of the polymer with a terminal carboxyl polyamide structure in Example 6:

[0048] 1 kg of methyl 3-amino-2-hydroxy-5-methylbenzoate and 0.8 kg of amino-triethylene glycol were added to 12 kg of tetrahydrofuran. After stirring and dissolving, 2 kg of triphenylphosphine and 1.2 kg of diisopropyl azodicarboxylate were added. The reaction was carried out at 30 °C for 8 h. After the reaction ended, the solvent was removed by distillation under reduced pressure. The obtained residue was dissolved in 10 kg of dichloromethane and then filtered by suction. The obtained filtrate was extracted 5 times with 5 kg of water. The organic layers were combined and the solvent was removed by distillation under reduced pressure and then dried to obtain a methyl bis(aminobenzoate) derivative;

[0049] 1 kg of methyl bis(aminobenzoate) derivative and 0.5 kg of trimesic acid were added to 10 kg of dimethylformamide. After stirring and mixing evenly, 0.6 kg of diethyl azodicarboxylate and 0.3 kg of 1-hydroxybenzotriazole were added. The reaction was carried out at 30 °C for 12 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure. The obtained residue was washed 3 times with petroleum ether and then added to 10 kg of methanol. Then 0.4 kg of sodium hydroxide was added, and the reaction was carried out at 30 °C for 10 h. After the reaction ended, 15 kg of water and 15 kg of dichloromethane were added for extraction. The obtained organic phase was distilled under reduced pressure to remove the solvent, and a polymer with a terminal carboxyl polyamide structure was obtained.

[0050] Preparation of Wear-Resistant Waterborne Alkyd Resin

[0051] Add 15 kg of linseed oil, 15 kg of trimethylolpropane, 12 kg of phthalic anhydride, 3 kg of terminal carboxyl polyamide structural polymer and 2 kg of xylene into a reactor, heat to 190 °C under nitrogen protection, hold the reaction for 1 h, raise the temperature to 210 °C and react for 2 h, continue to raise the temperature to 230 °C, react until the acid value reaches 10 mg KOH / g, evacuate to remove xylene, cool down to 180 °C, add 3 kg of trimellitic anhydride, continue to hold the reaction until the acid value reaches 55 mg KOH / g, cool down to 100 °C, add 15 kg of ethylene glycol butyl ether and 0.2 kg of hydroxyl-terminated carbon nanotubes, stir and disperse for 0.5 h, continue to cool down to 60 °C, add 5 kg of dimethylethanolamine for neutralization reaction for 0.5 h, and finally add water for high-speed emulsification and dispersion for 30 min to obtain the wear-resistant waterborne alkyd resin.

[0052] Comparative Example

[0053] Add 15 kg of linseed oil, 13 kg of trimethylolpropane, 12 kg of phthalic anhydride and 1.5 kg of xylene into a reactor, heat to 185 °C under nitrogen protection, hold the reaction for 1.5 h, raise the temperature to 200 °C and react for 1.5 h, continue to raise the temperature to 225 °C, react until the acid value reaches 13 mg KOH / g, evacuate to remove xylene, cool down to 175 °C, add 4 kg of trimellitic anhydride, continue to hold the reaction until the acid value reaches 55 mg KOH / g, cool down to 110 °C, add 13 kg of ethylene glycol butyl ether, stir and disperse for 0.5 h, continue to cool down to 65 °C, add 4.5 kg of triethylamine for neutralization reaction for 0.7 h, and finally add water for high-speed emulsification and dispersion for 30 min to obtain the waterborne alkyd resin.

[0054] Perform performance tests on the wear-resistant waterborne alkyd resins prepared in Examples 1 to 6 respectively. Among them, the appearance is determined according to the method in GB / T1721-1979; the solid content is determined according to the method in GB / T 1725-1979; the storage stability test method is: place the sample in a glass bottle, seal it, and observe whether there are phenomena of caking, stratification and sedimentation after 6 months. The test results are shown in Table 1.

[0055] Table 1 Performance Test Results of Wear-Resistant Waterborne Alkyd Resin

[0056]

[0057]

[0058] The wear-resistant waterborne alkyd resins prepared in Examples 1-6 and the waterborne alkyd resin prepared in the comparative example were respectively made into paint films according to the method in GB / T 1727-1992, and the paint films were tested. Among them, the drying time was tested according to the method in GB / T1728-1979; the glossiness was tested according to the method in GB / T1743-1979; the pencil hardness was tested according to the method in GB / T 6793-1996; the adhesion was tested according to the method in GB / T 1720-1988; the abrasion resistance was tested according to the method in GB / T1768-1989 and expressed by the weight loss rate; the impact resistance was tested according to the method in GB / T1732-1993. The test results are shown in Table 2.

[0059] Table 2 Test Results of Paint Film Properties

[0060]

[0061] It can be seen from the results in Table 2 that the paint film prepared with the wear-resistant waterborne alkyd resin of the present invention has a shorter surface drying time, better glossiness, greater hardness, stronger adhesion, and excellent mechanical properties and abrasion resistance compared with the comparative example.

[0062] Although the specific embodiments of the present invention are described above, it is not a limitation to the protection scope of the present invention. Based on the technical solutions of the present invention, various modifications or deformations that can be made by those skilled in the art without creative labor are still within the protection scope of the present invention.

Claims

1. A wear-resistant water-based alkyd resin, characterized in that: The invention is composed of the following raw materials in parts by weight: 10 to 15 parts of polyol, 10 to 13 parts of phthalic anhydride, 12 to 20 parts of fatty acid, 2 to 3 parts of carboxyl-terminated polyamide structure polymer, 3 to 5 parts of trimellitic anhydride, 1 to 2 parts of xylene, 10 to 15 parts of cosolvent, 4 to 5 parts of neutralizer and 0.1 to 0.3 parts of hydroxylated carbon nanotube; The carboxyl-terminated polyamide structural polymer is prepared according to the following method: 1) 3-amino-2-hydroxy-5-methylbenzoic acid methyl ester and amino-triethylene glycol are added to tetrahydrofuran, and after stirring and dissolving, triphenylphosphine and diisopropyl azodicarboxylate are added, and the reaction is carried out at 30-40° C. for 5-8 hours. After the reaction is completed, the solvent is removed by distillation under reduced pressure, and the obtained residue is dissolved by adding dichloromethane and then filtered. The obtained filtrate is extracted with water for 3-5 times, and the organic layers are combined, and the solvent is removed by distillation under reduced pressure, and dried to obtain a methyl bisaminobenzoate derivative; 2) adding the methyl bisaminobenzoate derivative and trimesic acid obtained in step 1) into an organic solvent, stirring and mixing evenly, then adding diethyl azodicarboxylate and 1-hydroxybenzotriazole, reacting at 30-40° C. for 5-12 hours, after the reaction is completed, removing the solvent by distillation under reduced pressure, washing the obtained residue with petroleum ether for 2-3 times, adding methanol, then adding sodium hydroxide, reacting at 25-30° C. for 5-10 hours, after the reaction is completed, adding water and dichloromethane for extraction, removing the solvent from the obtained organic phase by distillation under reduced pressure, and obtaining a carboxyl-terminated polyamide structure polymer.

2. The wear-resistant waterborne alkyd resin according to claim 1, characterized in that: The mass ratio of methyl 3-amino-2-hydroxy-5-methylbenzoate, amino-triethylene glycol, tetrahydrofuran, triphenylphosphine, diisopropyl azodicarboxylate, dichloromethane and water in step 1) is 1: 0.8-1.2: 10-15: 1.5-2: 1.2-1.5: 5-10: 5-10.

3. The wear-resistant waterborne alkyd resin according to claim 1, characterized in that: The organic solvent in step 2) is dimethyl sulfoxide or dimethylformamide.

4. The wear-resistant waterborne alkyd resin according to claim 1, characterized in that: The mass ratio of the methyl bisaminobenzoate derivative, trimesic acid, organic solvent, diethyl azodicarboxylate, 1-hydroxybenzotriazole, methanol, sodium hydroxide, water and dichloromethane in step 2) is 1: 0.5-0.8: 8-15: 0.4-0.6: 0.3-0.5: 5-10: 0.4-0.8: 10-15: 10-15.

5. The wear-resistant waterborne alkyd resin according to claim 1, characterized in that: The polyol is glycerol, pentaerythritol or trimethylolpropane.

6. The wear-resistant waterborne alkyd resin according to claim 1, characterized in that: The fatty acid is linseed oil or soybean oil acid.

7. The wear-resistant waterborne alkyd resin according to claim 1, characterized in that: The cosolvent is ethylene glycol butyl ether or propylene glycol methyl ether.

8. The wear-resistant waterborne alkyd resin according to claim 1, characterized in that: The neutralizing agent is triethylamine or dimethylethanolamine.

9. The method for preparing the wear-resistant waterborne alkyd resin according to claim 1, characterized in that: The following steps are involved: In parts by weight, 12 to 20 parts of fatty acid, 10 to 15 parts of polyol, 10 to 13 parts of phthalic anhydride, 2 to 3 parts of terminal carboxyl polyamide structure polymer and 1 to 2 parts of xylene are added to a reactor, heated to 180 to 190°C under nitrogen protection, kept warm for 1 to 2 hours, heated to 195 to 210°C for 2 to 3 hours, and continued to heat to 220 to 230°C, reacted until the acid value reached 10 to 15 mgKOH / g, vacuumed to remove xylene, and reduced The mixture was heated to 170-180°C, 3-5 parts of trimellitic anhydride were added, and the reaction was continued to be kept warm until the acid value reached 40-60 mgKOH / g, and the mixture was cooled to 100-120°C, 10-15 parts of co-solvent and 0.1-0.3 parts of hydroxyl-terminated carbon nanotubes were added, and the mixture was stirred and dispersed for 0.5 h, and the mixture was further cooled to 60-70°C, 4-5 parts of neutralizer were added and the reaction was neutralized for 0.5-1 h, and finally water was added and the mixture was emulsified and dispersed at high speed for 30 min to obtain a wear-resistant waterborne alkyd resin.

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