Tire polish and preparation method thereof

Abstract

The invention discloses a tire polish and a preparation method thereof, and relates to the technical field of polishes. When preparing the tire polish, the present invention first reacts a polyurethane terminated with methyl ethyl ketoxime with diaminothiourea, then reacts with 3-thiophenecarbonyl chloride, and then polymerizes with thiophene to obtain a modified polyurethane; secondly, 3-aminopropyl polydimethylsiloxane is reacted with carbon disulfide and phosphorus oxychloride, then reacts with 4-aminobenzophenone, and finally reacts with methyl cyanoacetate to obtain a modified silicone oil; finally, a modified polyurethane emulsion, modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methylcellulose, and sodium dodecylbenzenesulfonate are reacted. The tire polish prepared by the present invention has good antibacterial and antistatic properties.

Description

Technical Field

[0001] The invention relates to the technical field of polishes, in particular to a tire polish and a preparation method thereof. Background Art

[0002] Tire polish, as a chemical agent specially designed for automobile tire maintenance, has the main function of beautifying the appearance of tires by removing dirt, oil stains and attachments, restoring the original deep black color and gloss of the tires, and forming a protective film to resist the erosion of external factors such as ultraviolet rays, ozone, moisture and oil stains, delaying tire aging, cracking, deformation and fading.

[0003] However, although there are many types of existing tire polishes, bacteria are easily grown on the tire surface in humid or dirty environments, affecting vehicle hygiene. At the same time, static electricity accumulated in the tire during driving can easily lead to the adsorption of dust and dirt, affecting the appearance and service life. Therefore, it is particularly important to develop a tire polish that has both antibacterial and antistatic functions to meet the needs of different application scenarios. Summary of the Invention

[0004] The purpose of the present invention is to provide a tire polish and a preparation method thereof to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A tire polish comprising modified polyurethane emulsion, modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methyl cellulose, and sodium dodecylbenzene sulfonate;

[0007] Preferably, the modified polyurethane emulsion is obtained by reacting a polyurethane terminated with methyl ethyl ketoxime with diaminothiourea, then reacting with 3-thiophenecarbonyl chloride, and then polymerizing with thiophene.

[0008] Preferably, the modified silicone oil is obtained by reacting 3-aminopropyl polydimethylsiloxane with carbon disulfide, then with 4-aminobenzophenone, and finally with methyl cyanoacetate.

[0009] A method for preparing a tire polish comprises the following steps:

[0010] (1) blocking polyurethane, 1,3-diaminothiourea, N-methylpyrrolidone, and 98 wt% concentrated sulfuric acid were mixed in a mass ratio of 1:(0.3-0.5):(20-30):(0.7-0.9), heated to 190-200°C and refluxed for 2-3 hours. After the reaction, cooled to room temperature, methanol 3-4 times the mass of N-methylpyrrolidone was added, filtered, and dried under vacuum for 8 hours to obtain triazole-based polyurethane;

[0011] (2) triazole polyurethane, 3-thiophenecarbonyl chloride, p-toluenesulfonic acid, and N,N-dimethylformamide were mixed in a mass ratio of 1:(0.5-0.6):(0.1-0.2):(20-30), irradiated once every 30 seconds in a microwave reactor at a power of 350 W for 3 minutes, cooled to 0°C after irradiation, adjusted to pH 7 with triethylamine, added with methanol 3-4 times the mass of N,N-dimethylformamide, filtered, and dried under vacuum for 8 hours to obtain a pre-modified polyurethane;

[0012] (3) Under nitrogen protection, pre-modified polyurethane, anhydrous ferric chloride, and N,N-dimethylformamide are mixed in a mass ratio of 1:(2-3):(20-30), and a thiophene solution 10-12 times the mass of the pre-modified polyurethane is added dropwise at a drop rate of 2 mL / min. After the addition is completed, the temperature is raised to 25-30°C and the reaction is carried out for 3-4 hours. After the reaction is completed, methanol 3-4 times the mass of N,N-dimethylformamide is added, filtered, and dried under vacuum for 8 hours to obtain a modified polyurethane; the modified polyurethane, emulsifier, defoamer, and pure water are mixed, and emulsified using a high-speed homogenizer at a speed of 16 kr / min to obtain a modified polyurethane emulsion;

[0013] (4) Weigh triethylamine, carbon disulfide, phosphorus oxychloride, and 4-aminobenzophenone in a mass ratio of 1:(0.35-0.4):(0.35-0.4):(0.75-0.8); mix 50% triethylamine and benzene in a mass ratio of 1:(12-13), add 3-aminopropyl polydimethylsiloxane, and dropwise add carbon disulfide-benzene solution at a rate of 2 mL / min. After stirring at room temperature for 5-6 h, add the mixture at a rate of 0.3 mL / min. Add phosphorus oxychloride-benzene solution dropwise at a low rate, heat to 85-90°C and reflux for 3-4 hours. After cooling to room temperature, filter and retain the filtrate, add the remaining triethylamine, and then add 4-aminobenzophenone-benzene solution dropwise at a rate of 2 mL / min. After the addition is completed, add pure water 6.5 times the mass of carbon disulfide, react at room temperature for 1-2 hours, heat to 85-90°C and reflux for 2-3 hours. After the reaction is completed, obtain pre-modified silicone oil by vacuum rotary evaporation;

[0014] (5) Methyl cyanoacetate and the catalyst solution were mixed at a mass ratio of 1:(0.9-1.1) for 0.5 h, and pre-modified silicone oil with a mass of 1.3-1.5 times that of methyl cyanoacetate and n-heptane with a mass of 20-30 times that of methyl cyanoacetate were added, and the mixture was heated to 98-100 ° C and refluxed for 3-4 h, and the catalyst solution with a mass of 0.9-1.1 times that of methyl cyanoacetate was added dropwise at a drop rate of 0.3 mL / min, and the reflux reaction was continued for 5-6 h. After the reaction was completed, the mixture was cooled to room temperature, and pure water with a volume of 3-4 times that of n-heptane was added for filtration and dried under vacuum for 5-6 h to obtain modified silicone oil;

[0015] (6) Modified polyurethane emulsion, modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methyl cellulose, and sodium dodecylbenzene sulfonate are mixed to obtain a tire polish.

[0016] Preferably, the preparation method of the blocked polyurethane in step (1) is as follows: weigh the following components: 9.4 parts of polycaprolactone diol, 28.3 parts of polytetramethylene glycol, 2.5 parts of dihydroxymethyl propionic acid, 2.7 parts of 1,4-butanediol, 0.002 parts of dibutyltin dilaurate, 15.8 parts of N-methylpyrrolidone, 9.8 parts of isophorone diisocyanate, 12.2 parts of 4,4-dicyclohexylmethane diisocyanate, 5 parts of acetone, and 5 parts of methyl ethyl ketone oxime, the molecular weight of each of polycaprolactone diol and polytetramethylene glycol being 2000; Ester diol, polytetramethylene glycol, dihydroxymethylpropionic acid and 1,4-butanediol were mixed and dehydrated at 120°C for 0.5h under nitrogen protection. Dibutyltin dilaurate and N-methylpyrrolidone were added and the temperature was lowered to 75°C. Isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate were added and reacted for 3h. The temperature was lowered to 55°C. Methyl ethyl ketone oxime and acetone were added and the reaction was continued until the isocyanate group content was 0. The isocyanate group content was tested by the di-n-butylamine method. After the reaction, the blocked polyurethane was obtained by rotary evaporation at 50°C and -0.1MPa.

[0017] Preferably, the thiophene solution in step (3) is prepared by mixing thiophene and N,N-dimethylformamide in a mass ratio of 1:8; the amounts of modified polyurethane, emulsifier, defoamer, and pure water are as follows: 100 parts of modified polyurethane, 10-12 parts of emulsifier, 2-3 parts of defoamer, and 40-50 parts of pure water, by mass; the emulsifier is OP-10; and the defoamer is Surfynol DF-110C.

[0018] Preferably, the molar ratio of amino group to carbon disulfide in the 3-aminopropyl polydimethylsiloxane in step (4) is 1:(1.3-1.5); the carbon disulfide-benzene solution is obtained by mixing carbon disulfide and benzene in a mass ratio of 1:3.5; the phosphorus oxychloride-benzene solution is obtained by mixing phosphorus oxychloride and benzene in a mass ratio of 1:3.5; and the 4-aminobenzophenone-benzene solution is obtained by mixing 4-aminobenzophenone and benzene in a mass ratio of 1:2.5.

[0019] Preferably, the catalyst solution in step (5) is prepared from ammonium acetate and glacial acetic acid in a molar ratio of 0.07:0.21.

[0020] Preferably, the amounts of the modified polyurethane emulsion, modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methyl cellulose, and sodium dodecylbenzene sulfonate in step (6) are as follows: 25-30 parts by mass of modified polyurethane emulsion, 20-25 parts by mass of modified silicone oil, 20-25 parts by mass of liquid wax, 2-3 parts by mass of solvent oil, 10-12 parts by mass of pure water, 2-3 parts by mass of ethylene glycol, 1-2 parts by mass of methyl cellulose, and 5-6 parts by mass of sodium dodecylbenzene sulfonate; and the solvent oil is D40 solvent oil.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] When preparing the tire polish, the present invention comprises the following steps: firstly, reacting a polyurethane terminated with methyl ethyl ketoxime with diaminothiourea, then reacting with 3-thiophenecarbonyl chloride, and then polymerizing with thiophene to obtain a modified polyurethane; secondly, reacting 3-aminopropyl polydimethylsiloxane with carbon disulfide and phosphorus oxychloride, then reacting with 4-aminobenzophenone, and finally reacting with methyl cyanoacetate to obtain a modified silicone oil; and finally, reacting the modified polyurethane emulsion, the modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methyl cellulose, and sodium dodecylbenzenesulfonate.

[0023] First, during the polyurethane synthesis process, methyl ethyl ketone oxime is used to end-cap the polyurethane, making it more stable during storage. The end-capped polyurethane then reacts with diaminothiourea to form a ring, generating a triazole structure. This is then reacted with 3-thiophenecarbonyl chloride to form a triazolothiadiazole structure, which is then grafted with a thiophene monomer. The triazolothiadiazole ring has broad-spectrum antimicrobial activity against a wide range of pathogenic bacteria, and can impart good antimicrobial properties to the polish. The thiophene monomer on the polyurethane is then polymerized with thiophene to form polythiophene, which has a good antistatic effect and can prevent the tire from absorbing dust and other pollutants due to static electricity during use.

[0024] Secondly, 3-aminopropyl polydimethylsiloxane is reacted with carbon disulfide and phosphorus oxychloride, and then reacted with 4-aminobenzophenone to generate a thiourea structure, and a benzophenone structure is introduced. Thiourea has good antibacterial and antioxidant properties. Benzophenone reacts with methyl cyanoacetate to obtain a cyanoacrylate structure. Cyanoacrylate structure Cyanoacrylate ultraviolet absorbers have a good absorption effect on ultraviolet rays, absorb ultraviolet energy and convert it into heat energy for release, which can give the polish good resistance to ultraviolet rays and delay tire aging, cracking, deformation and fading. DETAILED DESCRIPTION

[0025] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0026] The following examples and comparative examples

[0027] The emulsifier used was OP-10; the defoamer used was Surfynol DF-110C; the solvent oil used was D40 solvent oil; the molecular weight of the polycaprolactone diol and polytetramethylene glycol used was 2000;

[0028] The thiophene solution used was obtained by mixing thiophene and N,N-dimethylformamide in a mass ratio of 1:8;

[0029] The carbon disulfide-benzene solution used was obtained by mixing carbon disulfide and benzene in a mass ratio of 1:3.5;

[0030] The phosphorus oxychloride-benzene solution used was obtained by mixing phosphorus oxychloride and benzene in a mass ratio of 1:3.5;

[0031] The 4-aminobenzophenone-benzene solution used was obtained by mixing 4-aminobenzophenone and benzene in a mass ratio of 1:2.5;

[0032] The catalyst solution used was prepared from ammonium acetate and glacial acetic acid in a molar ratio of 0.07:0.21.

[0033] Example 1:

[0034] A method for preparing a tire polish, comprising the following steps:

[0035] (1) Weigh the following components: 9.4 parts of polycaprolactone diol, 28.3 parts of polytetrahydrofuran diol, 2.5 parts of dihydroxymethylpropionic acid, 2.7 parts of 1,4-butanediol, 0.002 parts of dibutyltin dilaurate, 15.8 parts of N-methylpyrrolidone, 9.8 parts of isophorone diisocyanate, 12.2 parts of 4,4-dicyclohexylmethane diisocyanate, 5 parts of acetone, and 5 parts of methyl ethyl ketone oxime; mix polycaprolactone diol, polytetrahydrofuran diol, dihydroxymethylpropionic acid, and 1,4-butanediol, dehydrate at 120°C for 0.5h under nitrogen protection, add dibutyltin dilaurate and N-methylpyrrolidone, cool to 75°C, and then add isophorone diisocyanate. Isocyanate and 4,4-dicyclohexylmethane diisocyanate were reacted for 3 hours, the temperature was lowered to 55°C, methyl ethyl ketone oxime and acetone were added, and the reaction was continued until the isocyanate group content was 0. The isocyanate group content was tested by the di-n-butylamine method; after the reaction, the blocked polyurethane was obtained by rotary evaporation at 50°C and -0.1MPa; the blocked polyurethane, 1,3-diaminothiourea, N-methylpyrrolidone, and 98wt% concentrated sulfuric acid were mixed in a mass ratio of 1:0.3:20:0.7, the temperature was raised to 200°C, and the reaction was refluxed for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, and methanol 3 times the mass of N-methylpyrrolidone was added, filtered, and dried under vacuum for 8 hours to obtain a triazole-based polyurethane;

[0036] (2) triazole polyurethane, 3-thiophenecarbonyl chloride, p-toluenesulfonic acid, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.5:0.1:20, irradiated once every 30 seconds in a microwave reactor at a power of 350 W for 3 minutes, cooled to 0°C after irradiation, adjusted to pH 7 with triethylamine, added with methanol 3 times the mass of N,N-dimethylformamide, filtered, and dried under vacuum for 8 hours to obtain a pre-modified polyurethane;

[0037] (3) Under nitrogen protection, pre-modified polyurethane, anhydrous ferric chloride, and N,N-dimethylformamide were mixed in a mass ratio of 1:2:20, and a thiophene solution 10 times the mass of the pre-modified polyurethane was added dropwise at a dripping rate of 2 mL / min. After the addition was completed, the temperature was raised to 30°C and reacted for 4 hours. After the reaction was completed, methanol 3 times the mass of N,N-dimethylformamide was added, filtered, and dried under vacuum for 8 hours to obtain a modified polyurethane; the following components were weighed: 100 parts of modified polyurethane, 10 parts of emulsifier, 2 parts of defoamer, and 40 parts of pure water in parts by mass; the modified polyurethane, emulsifier, defoamer, and pure water were mixed, and emulsified using a high-speed homogenizer at a speed of 16 kr / min to obtain a modified polyurethane emulsion;

[0038] (4) Weigh triethylamine, carbon disulfide, phosphorus oxychloride, and 4-aminobenzophenone in a mass ratio of 1:0.35:0.35:0.75; mix 50% of triethylamine and benzene in a mass ratio of 1:12, and then add 3-aminopropyl polydimethylsiloxane, where the molar ratio of amino group to carbon disulfide in 3-aminopropyl polydimethylsiloxane is 1:1.3; add carbon disulfide-benzene solution dropwise at a drop rate of 2 mL / min, stir at room temperature for 6 h, and then add the mixture. Phosphorus oxychloride-benzene solution was added dropwise at a rate of 0.3 mL / min, the temperature was raised to 90°C and refluxed for 4 h. After cooling to room temperature, the filtrate was filtered and retained, the remaining triethylamine was added, and 4-aminobenzophenone-benzene solution was added dropwise at a rate of 2 mL / min. After the addition was completed, pure water (6.5 times the mass of carbon disulfide) was added, and the mixture was reacted at room temperature for 2 h. The mixture was heated to 90°C and refluxed for 3 h. After the reaction was completed, the pre-modified silicone oil was obtained by rotary evaporation under reduced pressure.

[0039] (5) Methyl cyanoacetate and the catalyst solution were mixed at a mass ratio of 1:0.9 for 0.5 h, and pre-modified silicone oil with a mass of 1.3 times that of methyl cyanoacetate and n-heptane with a mass of 20 times that of methyl cyanoacetate were added. The mixture was heated to 100° C. and refluxed for 4 h. The catalyst solution with a mass of 0.9 times that of methyl cyanoacetate was added dropwise at a drop rate of 0.3 mL / min. The reflux reaction was continued for 6 h. After the reaction was completed, the mixture was cooled to room temperature, and pure water with a volume of 3 times that of n-heptane was added for filtration and dried under vacuum for 6 h to obtain modified silicone oil.

[0040] (6) Weigh the following components: 25 parts by mass of modified polyurethane emulsion, 20 parts by mass of modified silicone oil, 20 parts by mass of liquid wax, 2 parts by mass of solvent oil, 10 parts by mass of pure water, 2 parts by mass of ethylene glycol, 1 part by mass of methyl cellulose, and 5 parts by mass of sodium dodecylbenzenesulfonate; mix the modified polyurethane emulsion, modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methyl cellulose, and sodium dodecylbenzenesulfonate to obtain a tire polish.

[0041] Example 2:

[0042] A method for preparing a tire polish, comprising the following steps:

[0043] (1) Weigh the following components: 9.4 parts of polycaprolactone diol, 28.3 parts of polytetrahydrofuran diol, 2.5 parts of dihydroxymethylpropionic acid, 2.7 parts of 1,4-butanediol, 0.002 parts of dibutyltin dilaurate, 15.8 parts of N-methylpyrrolidone, 9.8 parts of isophorone diisocyanate, 12.2 parts of 4,4-dicyclohexylmethane diisocyanate, 5 parts of acetone, and 5 parts of methyl ethyl ketone oxime; mix polycaprolactone diol, polytetrahydrofuran diol, dihydroxymethylpropionic acid, and 1,4-butanediol, dehydrate at 120°C for 0.5h under nitrogen protection, add dibutyltin dilaurate and N-methylpyrrolidone, cool to 75°C, and then add isophorone diisocyanate. Ester and 4,4-dicyclohexylmethane diisocyanate are reacted for 3 hours, the temperature is lowered to 55°C, methyl ethyl ketone oxime and acetone are added, and the reaction is continued until the isocyanate group content is 0. The isocyanate group content is tested by the di-n-butylamine method; after the reaction is completed, the blocked polyurethane is obtained by rotary evaporation at 50°C and -0.1MPa; the blocked polyurethane, 1,3-diaminothiourea, N-methylpyrrolidone, and 98wt% concentrated sulfuric acid are mixed in a mass ratio of 1:0.4:25:0.8, the temperature is raised to 195°C and refluxed for 2.5 hours. After the reaction is completed, the mixture is cooled to room temperature, methanol 3.5 times the mass of N-methylpyrrolidone is added, filtered, and dried under vacuum for 8 hours to obtain a triazole-based polyurethane;

[0044] (2) triazole polyurethane, 3-thiophenecarbonyl chloride, p-toluenesulfonic acid, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.55:0.15:25, irradiated once every 30 seconds in a microwave reactor at a power of 350 W for 3 minutes, cooled to 0°C after irradiation, adjusted to pH 7 with triethylamine, added with methanol 3.5 times the mass of N,N-dimethylformamide, filtered, and dried under vacuum for 8 hours to obtain pre-modified polyurethane;

[0045] (3) Under nitrogen protection, pre-modified polyurethane, anhydrous ferric chloride, and N,N-dimethylformamide were mixed in a mass ratio of 1:2.5:25, and a thiophene solution 11 times the mass of the pre-modified polyurethane was added dropwise at a dripping rate of 2 mL / min. After the addition was completed, the temperature was raised to 27°C and reacted for 3.5 hours. After the reaction was completed, methanol 3.5 times the mass of N,N-dimethylformamide was added, filtered, and dried under vacuum for 8 hours to obtain a modified polyurethane; the following components were weighed: 100 parts of modified polyurethane, 11 parts of emulsifier, 2.5 parts of defoamer, and 45 parts of pure water in parts by mass; the modified polyurethane, emulsifier, defoamer, and pure water were mixed, and emulsified using a high-speed homogenizer at a speed of 16 kr / min to obtain a modified polyurethane emulsion;

[0046] (4) Weigh triethylamine, carbon disulfide, phosphorus oxychloride, and 4-aminobenzophenone in a mass ratio of 1:0.37:0.8:0.77; mix 50% of triethylamine and benzene in a mass ratio of 1:12.5, and then add 3-aminopropyl polydimethylsiloxane, where the molar ratio of amino group to carbon disulfide in 3-aminopropyl polydimethylsiloxane is 1:1.4; add carbon disulfide-benzene solution dropwise at a rate of 2 mL / min, stir at room temperature for 5.5 h, and then at 0. Phosphorus oxychloride-benzene solution was added dropwise at a rate of 3 mL / min, the temperature was raised to 87°C and refluxed for 3.5 hours. After cooling to room temperature, the filtrate was filtered and retained, the remaining triethylamine was added, and 4-aminobenzophenone-benzene solution was added dropwise at a rate of 2 mL / min. After the addition was completed, pure water (6.5 times the mass of carbon disulfide) was added, and the mixture was reacted at room temperature for 1.5 hours. The mixture was heated to 87°C and refluxed for 2.5 hours. After the reaction was completed, the pre-modified silicone oil was obtained by rotary evaporation under reduced pressure.

[0047] (5) Methyl cyanoacetate and the catalyst solution were mixed at a mass ratio of 1:1.0 for 0.5 h, and pre-modified silicone oil with a mass of 1.4 times that of methyl cyanoacetate and n-heptane with a mass of 25 times that of methyl cyanoacetate were added. The mixture was heated to 99° C. and refluxed for 3.5 h. The catalyst solution with a mass of 1.0 times that of methyl cyanoacetate was added dropwise at a drop rate of 0.3 mL / min. The reflux reaction was continued for 5.5 h. After the reaction was completed, the mixture was cooled to room temperature, and pure water with a volume of 3.5 times that of n-heptane was added for filtration and dried under vacuum for 5.5 h to obtain modified silicone oil.

[0048] (6) Weigh the following components: 27 parts by mass of modified polyurethane emulsion, 23 parts by mass of modified silicone oil, 22 parts by mass of liquid wax, 2.5 parts by mass of solvent oil, 11 parts by mass of pure water, 2.5 parts by mass of ethylene glycol, 1.5 parts by mass of methyl cellulose, and 5.5 parts by mass of sodium dodecylbenzenesulfonate; mix the modified polyurethane emulsion, modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methyl cellulose, and sodium dodecylbenzenesulfonate to obtain a tire polish.

[0049] Example 3:

[0050] A method for preparing a tire polish, comprising the following steps:

[0051] (1) Weigh the following components: 9.4 parts of polycaprolactone diol, 28.3 parts of polytetrahydrofuran diol, 2.5 parts of dihydroxymethylpropionic acid, 2.7 parts of 1,4-butanediol, 0.002 parts of dibutyltin dilaurate, 15.8 parts of N-methylpyrrolidone, 9.8 parts of isophorone diisocyanate, 12.2 parts of 4,4-dicyclohexylmethane diisocyanate, 5 parts of acetone, and 5 parts of methyl ethyl ketone oxime; mix polycaprolactone diol, polytetrahydrofuran diol, dihydroxymethylpropionic acid, and 1,4-butanediol, dehydrate at 120°C for 0.5h under nitrogen protection, add dibutyltin dilaurate and N-methylpyrrolidone, cool to 75°C, and then add isophorone diisocyanate. Isocyanate and 4,4-dicyclohexylmethane diisocyanate were reacted for 3 hours, the temperature was lowered to 55°C, methyl ethyl ketone oxime and acetone were added, and the reaction was continued until the isocyanate group content was 0. The isocyanate group content was tested by the di-n-butylamine method; after the reaction, the blocked polyurethane was obtained by rotary evaporation at 50°C and -0.1MPa; the blocked polyurethane, 1,3-diaminothiourea, N-methylpyrrolidone, and 98wt% concentrated sulfuric acid were mixed in a mass ratio of 1:0.5:30:0.9, the temperature was raised to 190°C and refluxed for 2 hours, and after the reaction was completed, the mixture was cooled to room temperature, methanol 4 times the mass of N-methylpyrrolidone was added, filtered, and dried under vacuum for 8 hours to obtain a triazole-based polyurethane;

[0052] (2) triazole polyurethane, 3-thiophenecarbonyl chloride, p-toluenesulfonic acid, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.6:0.2:30, irradiated once every 30 seconds in a microwave reactor at a power of 350 W for 3 minutes, cooled to 0°C after irradiation, adjusted to pH 7 with triethylamine, added with methanol 4 times the mass of N,N-dimethylformamide, filtered, and dried under vacuum for 8 hours to obtain pre-modified polyurethane;

[0053] (3) Under nitrogen protection, pre-modified polyurethane, anhydrous ferric chloride, and N,N-dimethylformamide were mixed in a mass ratio of 1:3:30, and a thiophene solution 12 times the mass of the pre-modified polyurethane was added dropwise at a dripping rate of 2 mL / min. After the addition was completed, the temperature was raised to 25°C and reacted for 3 hours. After the reaction was completed, methanol 4 times the mass of N,N-dimethylformamide was added, filtered, and dried under vacuum for 8 hours to obtain a modified polyurethane; the following components were weighed: 100 parts of modified polyurethane, 12 parts of emulsifier, 3 parts of defoamer, and 50 parts of pure water in parts by mass; the modified polyurethane, emulsifier, defoamer, and pure water were mixed, and emulsified using a high-speed homogenizer at a speed of 16 kr / min to obtain a modified polyurethane emulsion;

[0054] (4) Weigh triethylamine, carbon disulfide, phosphorus oxychloride, and 4-aminobenzophenone in a mass ratio of 1:0.35:0.35:0.75; mix 50% of triethylamine and benzene in a mass ratio of 1:13, and then add 3-aminopropyl polydimethylsiloxane, where the molar ratio of amino group to carbon disulfide in 3-aminopropyl polydimethylsiloxane is 1:1.5; add carbon disulfide-benzene solution dropwise at a drop rate of 2 mL / min, stir at room temperature for 5 h, and then add the mixture. Phosphorus oxychloride-benzene solution was added dropwise at a rate of 0.3 mL / min, the temperature was raised to 85°C and refluxed for 3 h. After cooling to room temperature, the filtrate was filtered and retained, the remaining triethylamine was added, and 4-aminobenzophenone-benzene solution was added dropwise at a rate of 2 mL / min. After the addition was completed, pure water (6.5 times the mass of carbon disulfide) was added, and the mixture was reacted at room temperature for 1 h. The mixture was heated to 85°C and refluxed for 2 h. After the reaction was completed, the pre-modified silicone oil was obtained by rotary evaporation under reduced pressure.

[0055] (5) Methyl cyanoacetate and the catalyst solution were mixed at a mass ratio of 1:1.1 for 0.5 h, and pre-modified silicone oil with a mass of 1.5 times that of methyl cyanoacetate and n-heptane with a mass of 30 times that of methyl cyanoacetate were added. The mixture was heated to 98°C and refluxed for 3 h. The catalyst solution with a mass of 1.1 times that of methyl cyanoacetate was added dropwise at a drop rate of 0.3 mL / min. The reflux reaction was continued for 5 h. After the reaction was completed, the mixture was cooled to room temperature, and pure water with a volume of 4 times that of n-heptane was added for filtration and dried under vacuum for 5 h to obtain modified silicone oil.

[0056] (6) Weigh the following components: 30 parts by mass of modified polyurethane emulsion, 25 parts by mass of modified silicone oil, 25 parts by mass of liquid wax, 3 parts by mass of solvent oil, 12 parts by mass of pure water, 3 parts by mass of ethylene glycol, 2 parts by mass of methyl cellulose, and 6 parts by mass of sodium dodecylbenzenesulfonate; mix the modified polyurethane emulsion, modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methyl cellulose, and sodium dodecylbenzenesulfonate to obtain a tire polish.

[0057] Comparative Example 1:

[0058] The preparation method of the tire polish of Comparative Example 1 differs from that of Example 2 in that it does not contain steps (2) to (5), and step (1) is modified as follows: weigh the following components: 9.4 parts of polycaprolactone diol, 28.3 parts of polytetrahydrofuran diol, 2.5 parts of dihydroxymethylpropionic acid, 2.7 parts of 1,4-butanediol, 0.002 parts of dibutyltin dilaurate, 15.8 parts of N-methylpyrrolidone, 9.8 parts of isophorone diisocyanate, 12.2 parts of 4,4-dicyclohexylmethane diisocyanate, 5 parts of acetone, and 5 parts of methyl ethyl ketone oxime; mix polycaprolactone diol, polytetrahydrofuran diol, dihydroxymethylpropionic acid, and 1,4-butanediol, dehydrate them under nitrogen protection at 120°C for 0.5h, and add dibutyltin dilaurate and N-methylpyrrolidone were added, cooled to 75°C, and isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate were added to react for 3 hours, then cooled to 55°C, methyl ethyl ketone oxime and acetone were added, and the reaction was continued until the isocyanate group content was 0. The isocyanate group content was tested by the di-n-butylamine method. After the reaction was completed, the modified polyurethane was obtained by rotary evaporation at 50°C and -0.1MPa. The following components were weighed: 100 parts of modified polyurethane, 11 parts of emulsifier, 2.5 parts of defoamer, and 45 parts of pure water, by mass. The modified polyurethane, emulsifier, defoamer, and pure water were mixed and emulsified using a high-speed homogenizer at a speed of 16kr / min to obtain a modified polyurethane emulsion.

[0059] Modify step (6) as follows: weigh the following components: 27 parts by mass of modified polyurethane emulsion, 23 parts of 3-aminopropyl polydimethylsiloxane, 22 parts of liquid wax, 2.5 parts of solvent oil, 11 parts of pure water, 2.5 parts of ethylene glycol, 1.5 parts of methyl cellulose, and 5.5 parts of sodium dodecylbenzene sulfonate; mix the modified polyurethane emulsion, modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methyl cellulose, and sodium dodecylbenzene sulfonate to obtain a tire polish.

[0060] Comparative Example 2:

[0061] The difference between the preparation method of the tire polish of Comparative Example 2 and Example 2 is that step (3) is modified as follows: weigh the following components: 100 parts of pre-modified polyurethane, 11 parts of emulsifier, 2.5 parts of defoaming agent, and 45 parts of pure water, in parts by mass; mix the modified polyurethane, emulsifier, defoaming agent, and pure water, and emulsify them using a high-speed homogenizer at a speed of 16 kr / min to obtain a modified polyurethane emulsion.

[0062] Test Example 1:

[0063] Antibacterial performance test:

[0064] Test method: The antibacterial rate of the anti-skid and wear-resistant coatings prepared in the examples and comparative examples was determined according to the standard GB / T21866-2008, with the bacterial species being Escherichia coli. The results are shown in Table 1.

[0065] Table 1 Antibacterial performance test results

[0066] Antibacterial rate (%) Antibacterial rate (%) Example 1 98.14 Comparative Example 1 13.4 Example 2 98.21 Comparative Example 2 97.65 Example 3 98.26

[0067] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 2 in Table 1, it can be found that the tire polish prepared by the present invention has good antibacterial properties.

[0068] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 1, indicating that methyl ethyl ketone oxime is used for end-capping in the synthesis of polyurethane, which is then reacted with diaminothiourea to form a ring to generate a triazole structure, which is then reacted with 3-thiophenecarbonyl chloride to generate a triazolothiadiazole structure and grafted with a thiophene monomer. The triazolothiadiazole ring is a structure with broad-spectrum antibacterial activity, exhibiting antibacterial activity against multiple types of pathogenic bacteria, and can impart good antibacterial properties to the polishing agent.

[0069] Test Example 2:

[0070] Antistatic performance test:

[0071] Test method: The tire polish prepared in the examples and comparative examples was stirred evenly and then coated on the treated tinplate surface. The film was dried and cured at 60°C for 30 minutes to form a film. The volume resistivity was measured according to the standard GB / T 3048. The results are shown in Table 2.

[0072] Table 2 Antistatic performance test results

[0073] Volume resistivity (Ω / cm) Volume resistivity (Ω / cm) Example 1 <![CDATA[5.2*10 7 ]]> Comparative Example 1 <![CDATA[1.19*10 13 ]]> Example 2 <![CDATA[5.4*10 7 ]]> Comparative Example 2 <![CDATA[1.12*10 13 ]]> Example 3 <![CDATA[5.5*10 7 ]]>

[0074] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 2 in Table 2, it can be found that the tire polish prepared by the present invention has good antistatic performance.

[0075] By comparison, the volume resistivity of Examples 1 to 3 is greater than that of Comparative Examples 1 to 2, indicating that methyl ethyl ketone oxime is used for end-capping in the polyurethane synthesis process, which is then reacted with diaminothiourea to form a ring to generate a triazole structure, which is then reacted with 3-thiophenecarbonyl chloride to generate a triazolothiadiazole structure and grafted with a thiophene monomer. The thiophene monomer on the polyurethane is then polymerized with thiophene to form polythiophene, which has a good antistatic effect and can prevent the tire from adsorbing pollutants such as dust due to static electricity during use.

[0076] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.

Claims

1. A method for preparing a tire polish, characterized in that: The method comprises the following preparation steps: (1) Blocked polyurethane, 1,3-diaminothiourea, N-methylpyrrolidone, and 98wt% concentrated sulfuric acid were mixed in a mass ratio of 1:(0.3-0.5):(20-30):(0.7-0.9), heated to 190-200°C and refluxed for 2-3h. After the reaction, cooled to room temperature, added methanol 3-4 times the mass of N-methylpyrrolidone, filtered, and dried under vacuum for 8h to obtain triazole polyurethane; (2) Triazole polyurethane, 3-thiophenecarbonyl chloride, p-toluenesulfonic acid, and N,N-dimethylformamide were mixed in a mass ratio of 1:(0.5-0.6):(0.1-0.2):(20-30), and irradiated once every 30 seconds in a microwave reactor at a power of 350 W for 3 minutes. After irradiation, the mixture was cooled to 0°C, the pH was adjusted to 7 with triethylamine, and methanol (3-4 times the mass of N,N-dimethylformamide) was added. The mixture was filtered and dried under vacuum for 8 hours to obtain pre-modified polyurethane. (3) Under nitrogen protection, pre-modified polyurethane, anhydrous ferric chloride, and N,N-dimethylformamide were mixed in a mass ratio of 1:(2-3):(20-30), and a thiophene solution 10-12 times the mass of the pre-modified polyurethane was added dropwise at a drop rate of 2 mL / min. After the addition was completed, the temperature was raised to 25-30°C and the reaction was carried out for 3-4 hours. After the reaction was completed, methanol 3-4 times the mass of N,N-dimethylformamide was added, filtered, and dried under vacuum for 8 hours to obtain a modified polyurethane; the modified polyurethane, emulsifier, defoamer, and pure water were mixed, and emulsified using a high-speed homogenizer at a speed of 16 kr / min to obtain a modified polyurethane emulsion; (4) Weigh triethylamine, carbon disulfide, phosphorus oxychloride, and 4-aminobenzophenone in a mass ratio of 1:(0.35-0.4):(0.35-0.4):(0.75-0.8); mix 50% triethylamine and benzene in a mass ratio of 1:(12-13), add 3-aminopropyl polydimethylsiloxane, and dropwise add carbon disulfide-benzene solution at a rate of 2 mL / min. After stirring at room temperature for 5-6 h, stir at a rate of 0.3 mL / min. Add phosphorus oxychloride-benzene solution dropwise at a low rate, heat to 85-90°C and reflux for 3-4 hours. After cooling to room temperature, filter and retain the filtrate, add the remaining triethylamine, and then add 4-aminobenzophenone-benzene solution dropwise at a rate of 2 mL / min. After the addition is completed, add pure water 6.5 times the mass of carbon disulfide, react at room temperature for 1-2 hours, heat to 85-90°C and reflux for 2-3 hours. After the reaction is completed, obtain pre-modified silicone oil by vacuum rotary evaporation; (5) Methyl cyanoacetate and catalyst solution were mixed at a mass ratio of 1:(0.9-1.1) for 0.5 h, pre-modified silicone oil with a mass of 1.3-1.5 times that of methyl cyanoacetate and n-heptane with a mass of 20-30 times that of methyl cyanoacetate were added, and the mixture was heated to 98-100 ° C and refluxed for 3-4 h. The catalyst solution with a mass of 0.9-1.1 times that of methyl cyanoacetate was added dropwise at a drop rate of 0.3 mL / min, and the reflux reaction was continued for 5-6 h. After the reaction was completed, the mixture was cooled to room temperature, pure water with a volume of 3-4 times that of n-heptane was added, filtered, and dried under vacuum for 5-6 h to obtain modified silicone oil; (6) Modified polyurethane emulsion, modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methyl cellulose, and sodium dodecylbenzene sulfonate are mixed to obtain a tire polish.

2. The method for preparing a tire polish according to claim 1, characterized in that: The preparation method of the blocked polyurethane in step (1) is as follows: weigh the following components: 9.4 parts of polycaprolactone diol, 28.3 parts of polytetramethylene glycol, 2.5 parts of dihydroxymethyl propionic acid, 2.7 parts of 1,4-butanediol, 0.002 parts of dibutyltin dilaurate, 15.8 parts of N-methylpyrrolidone, 9.8 parts of isophorone diisocyanate, 12.2 parts of 4,4-dicyclohexylmethane diisocyanate, 5 parts of acetone, and 5 parts of methyl ethyl ketone oxime, the molecular weight of polycaprolactone diol and polytetramethylene glycol being 2000; Alcohol, polytetramethylene glycol, dihydroxymethylpropionic acid and 1,4-butanediol are mixed, dehydrated at 120°C for 0.5h under nitrogen protection, dibutyltin dilaurate and N-methylpyrrolidone are added, the temperature is lowered to 75°C, isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate are added and the reaction is continued for 3h, the temperature is lowered to 55°C, methyl ethyl ketone oxime and acetone are added, and the reaction is continued until the isocyanate group content is 0. The isocyanate group content is tested by the di-n-butylamine method; after the reaction is completed, the blocked polyurethane is obtained by rotary evaporation at 50°C and -0.1MPa.

3. The method for preparing a tire polish according to claim 1, wherein: The thiophene solution in step (3) is prepared by mixing thiophene and N,N-dimethylformamide in a mass ratio of 1:8; the amounts of modified polyurethane, emulsifier, defoamer, and pure water are as follows: 100 parts by mass of modified polyurethane, 10-12 parts by mass of emulsifier, 2-3 parts by mass of defoamer, and 40-50 parts by mass of pure water; the emulsifier is OP-10; and the defoamer is Surfynol DF-110C.

4. The method for preparing a tire polish according to claim 1, wherein: The molar ratio of amino group to carbon disulfide in the 3-aminopropyl polydimethylsiloxane in step (4) is 1:(1.3-1.5); the carbon disulfide-benzene solution is obtained by mixing carbon disulfide and benzene in a mass ratio of 1:3.5; the phosphorus oxychloride-benzene solution is obtained by mixing phosphorus oxychloride and benzene in a mass ratio of 1:3.5; and the 4-aminobenzophenone-benzene solution is obtained by mixing 4-aminobenzophenone and benzene in a mass ratio of 1:2.

5.

5. The method for preparing a tire polish according to claim 1, characterized in that: The catalyst solution in step (5) is prepared from ammonium acetate and glacial acetic acid in a molar ratio of 0.07:0.

21.

6. The method for preparing a tire polish according to claim 1, characterized in that: The amounts of the modified polyurethane emulsion, modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methyl cellulose, and sodium dodecylbenzene sulfonate used in step (6) are as follows: 25-30 parts by mass of modified polyurethane emulsion, 20-25 parts by mass of modified silicone oil, 20-25 parts by mass of liquid wax, 2-3 parts by mass of solvent oil, 10-12 parts by mass of pure water, 2-3 parts by mass of ethylene glycol, 1-2 parts by mass of methyl cellulose, and 5-6 parts by mass of sodium dodecylbenzene sulfonate; the solvent oil is D40 solvent oil.

7. A tire polish prepared according to the method for preparing a tire polish according to any one of claims 1 to 6.