Tire glazing agent and preparation method thereof

Abstract

The invention discloses a tire glazing agent and a preparation method thereof, and relates to the technical field of glazing agents. When the tire glazing agent is prepared, firstly, methyl ethyl ketoxime terminated polyurethane reacts with diaminothiourea, then reacts with 3-thiophenecarbonyl chloride and then reacts with thiophene to obtain 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 modified silicone oil; finally, the modified polyurethane emulsion, the modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methyl cellulose and sodium dodecyl benzene sulfonate are added. The tire glazing agent prepared by the invention has good antibacterial property and antistatic property.

Description

Technical Field

[0001] The invention relates to the technical field of polishing agents, in particular to a tire polishing agent 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 bred on the tire surface in a humid or dirty environment, affecting the hygiene of the vehicle; at the same time, the static electricity accumulated by the tire during driving is also easy to cause 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-thiodiaminourea, 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 reaction for 2-3 h. After the reaction was completed, the mixture was cooled to room temperature, and methanol with a mass of 3-4 times that of N-methylpyrrolidone was added. The mixture was filtered and dried under vacuum for 8 h to obtain a triazole polyurethane;

[0011] (2) triazole polyurethane, 3-thiophenecarbonyl chloride, p-toluenesulfonic acid, and N,N-dimethylformamide are 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, with a power of 350 W and an irradiation time of 3 minutes. After the irradiation, the mixture is cooled to 0°C, the pH is adjusted to 7 with triethylamine, and methanol with a mass of 3-4 times that of N,N-dimethylformamide is added, 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 of 10-12 times the mass of the pre-modified polyurethane is added dropwise at a dropping rate of 2 mL / min. After the addition is completed, the temperature is raised to 25-30° C. and reacted for 3-4 hours. After the reaction is completed, methanol of 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 with 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% of triethylamine and benzene in a mass ratio of 1:(12-13), add 3-aminopropyl polydimethylsiloxane, and drip carbon disulfide-benzene solution at a drip rate of 2 mL / min. After stirring at room temperature for 5-6 h, drip at a rate of 0.3 mL / min. Add phosphorus oxychloride-benzene solution at a drop rate, heat to 85-90°C and reflux for 3-4h, cool to room temperature, filter and retain the filtrate, add the remaining triethylamine, and then add 4-aminobenzophenone-benzene solution at a drop rate of 2mL / min. After the addition is completed, add pure water 6.5 times the mass of carbon disulfide, react at room temperature for 1-2h, heat to 85-90°C and reflux for 2-3h. 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) The 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 polytetrahydrofuran diol, 2.5 parts of dimethylol 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 weights of polycaprolactone diol and polytetrahydrofuran diol being both 2000; Ester diol, polytetrahydrofuran diol, dihydroxymethyl propionic 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 to react 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.

[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, in step (4), the molar ratio of amino group to carbon disulfide in the 3-aminopropyl polydimethylsiloxane 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 obtained 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: by mass: 25-30 parts of modified polyurethane emulsion, 20-25 parts of modified silicone oil, 20-25 parts of liquid wax, 2-3 parts of solvent oil, 10-12 parts of pure water, 2-3 parts of ethylene glycol, 1-2 parts of methyl cellulose and 5-6 parts of sodium dodecylbenzene sulfonate; the solvent oil is D40 solvent oil.

[0021] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0022] When preparing the tire polish, the present invention comprises the following steps: firstly, reacting a polyurethane terminated with methyl ethyl ketone oxime 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; finally, the modified polyurethane emulsion, the modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methyl cellulose and sodium dodecylbenzene sulfonate are reacted.

[0023] First, methyl ethyl ketone oxime is used to cap the polyurethane during the synthesis process. The capped polyurethane will be more stable during storage. Then it reacts with diaminothiourea to form a ring to generate a triazole structure, which then reacts with 3-thiophenecarbonyl chloride to generate a triazolothiadiazole structure and grafts a thiophene monomer. The triazolothiadiazole ring is a type of structure with broad-spectrum antibacterial activity, which shows antibacterial activity against many types of pathogenic bacteria and can give the polishing agent good antibacterial properties. 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. The cyanoacrylate structure cyanoacrylate type ultraviolet absorber has a good absorption effect on ultraviolet rays, absorbs ultraviolet energy and converts it into heat energy for release, which can give the polishing agent good ultraviolet resistance 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 described embodiments 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 work are within the scope of protection of the present invention.

[0026] The following examples and comparative examples

[0027] The emulsifier used is OP-10; the defoamer used is Surfynol DF-110C; the solvent oil used is D40 solvent oil; the molecular weights of the polycaprolactone diol and polytetrahydrofuran diol used are both 2000;

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

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

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

[0031] The 4-aminobenzophenone-benzene solution used is 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] Embodiment 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 dimethylol 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; mix polycaprolactone diol, polytetrahydrofuran diol, dimethylol propionic acid, and 1,4-butanediol, dehydrate them at 120° C. for 0.5 h under nitrogen protection, add dibutyltin dilaurate and N-methylpyrrolidone, cool to 75° C., add isophorone diisocyanate, and heat for 1 h. Isocyanate and 4,4-dicyclohexylmethane diisocyanate are reacted for 3 hours, cooled 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 1:0.3:20:0.7, heated to 200°C and refluxed for 3 hours, after the reaction is completed, cooled to room temperature, methanol 3 times the mass of N-methylpyrrolidone is 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, the power was 350 W, the irradiation time was 3 minutes, cooled to 0°C after the irradiation, the pH was adjusted to 7 with triethylamine, methanol with a mass of 3 times that of N,N-dimethylformamide was added, 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 drop rate of 2 mL / min. After the addition was completed, the temperature was raised to 30°C for reaction 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 by mass; the modified polyurethane, emulsifier, defoamer and pure water were mixed, and emulsified with 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, wherein 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 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, and after cooling to room temperature, the filtrate was filtered and retained, the remaining triethylamine was added, and then 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 reaction was carried out at room temperature for 2 h, and the temperature was raised to 90°C and refluxed for 3 h. After the reaction was completed, the pre-modified silicone oil was obtained by vacuum rotary evaporation;

[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, and 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, and 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 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.

[0041] Embodiment 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 dimethylol 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; mix polycaprolactone diol, polytetrahydrofuran diol, dimethylol propionic acid, and 1,4-butanediol, dehydrate them at 120° C. for 0.5 h under nitrogen protection, add dibutyltin dilaurate and N-methylpyrrolidone, cool to 75° C., and then add isophorone diisocyanate. Acid 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, it 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 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, the power was 350 W, the irradiation time was 3 minutes, cooled to 0°C after the irradiation, the pH was adjusted to 7 with triethylamine, methanol with a mass of 3.5 times that of N,N-dimethylformamide was added, filtered and dried under vacuum for 8 hours to obtain a 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 of 11 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 27°C for reaction for 3.5 hours. After the reaction was completed, methanol of 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 by mass; the modified polyurethane, emulsifier, defoamer and pure water were mixed, and emulsified with a high-speed homogenizing emulsifier 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, wherein 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 drop 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 h, and 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 reaction was carried out at room temperature for 1.5 h, and the temperature was raised to 87°C and refluxed for 2.5 h. After the reaction was completed, the pre-modified silicone oil was obtained by vacuum rotary evaporation;

[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, and 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, and 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 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.

[0049] Embodiment 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 dimethylol 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; mix polycaprolactone diol, polytetrahydrofuran diol, dimethylol propionic acid, and 1,4-butanediol, dehydrate them at 120° C. for 0.5 h under nitrogen protection, add dibutyltin dilaurate and N-methylpyrrolidone, cool to 75° C., add isophorone diisocyanate, and heat for 1 h. Isocyanate and 4,4-dicyclohexylmethane diisocyanate are reacted for 3 hours, cooled 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 1:0.5:30:0.9, heated to 190°C and refluxed for 2 hours, and after the reaction is completed, cooled to room temperature, methanol 4 times the mass of N-methylpyrrolidone is 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, the power was 350 W, the irradiation time was 3 minutes, cooled to 0°C after the irradiation, the pH was adjusted to 7 with triethylamine, methanol with a mass of 4 times that of N,N-dimethylformamide was added, filtered and dried under vacuum for 8 hours to obtain a 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 of 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°C for reaction for 3 hours. After the reaction was completed, methanol of 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 by mass; the modified polyurethane, emulsifier, defoamer and pure water were mixed, and emulsified at a speed of 16 kr / min using a high-speed homogenizing emulsifier 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, wherein 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 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, and 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 reaction was carried out at room temperature for 1 h, and the temperature was raised to 85°C and refluxed for 2 h. After the reaction was completed, the pre-modified silicone oil was obtained by vacuum rotary evaporation;

[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, and 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, and 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 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.

[0057] Comparative Example 1:

[0058] The preparation method of the tire polish of Comparative Example 1 is different 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 0.5 h, and add dibutyltin dilaurate and N-methylpyrrolidone, cool to 75°C, then add isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate to react for 3h, cool to 55°C, add methyl ethyl ketone oxime and acetone, and continue to react until the isocyanate group content is 0. The test method for the isocyanate group content is the di-n-butylamine method; after the reaction is completed, rotary evaporation is performed at 50°C and -0.1MPa to obtain a modified polyurethane; the following components are 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 are mixed, and emulsified with a high-speed homogenizing emulsifier 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 by mass of 3-aminopropyl polydimethylsiloxane, 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 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 defoamer, and 45 parts of pure water, by mass; mix the modified polyurethane, emulsifier, defoamer, and pure water, and emulsify them with 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: 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, and the bacteria species was 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 process of polyurethane, and then reacts with diaminothiourea to form a ring to generate a triazole structure, and then reacts with 3-thiophenecarbonyl chloride to generate a triazolothiadiazole structure and grafts a thiophene monomer. The triazolothiadiazole ring is a structure with broad-spectrum antibacterial activity, which shows antibacterial activity against many types of pathogenic bacteria and can give the polishing agent good antibacterial properties.

[0069] Test Example 2:

[0070] Antistatic performance test:

[0071] Test method: The tire polish prepared in the embodiment and the comparative example was evenly stirred and coated on the treated tinplate surface, and then 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 synthesis process of polyurethane, and then reacts with diaminothiourea to form a ring to generate a triazole structure, and then reacts with 3-thiophenecarbonyl chloride to generate a triazole thiadiazole structure and grafts 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 absorbing pollutants such as dust due to static electricity during use.

[0076] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A tire polish, characterized in that: The tire polish comprises modified polyurethane emulsion, modified silicone oil, liquid wax, solvent oil, pure water, ethylene glycol, methyl cellulose, and sodium dodecylbenzene sulfonate; The modified polyurethane emulsion is obtained by reacting a polyurethane terminated with methyl ethyl ketone oxime with diaminothiourea, then reacting with 3-thiophenecarbonyl chloride, and then polymerizing with thiophene; The modified silicone oil is obtained by reacting 3-aminopropyl polydimethylsiloxane with carbon disulfide, then with 4-aminobenzophenone, and finally with methyl cyanoacetate.

2. A method for preparing a tire polish, characterized in that: The method comprises the following preparation steps: (1) blocking polyurethane, 1,3-thiodiaminourea, 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 reaction for 2-3 h. After the reaction was completed, the mixture was cooled to room temperature, and methanol with a mass of 3-4 times that of N-methylpyrrolidone was added. The mixture was filtered and dried under vacuum for 8 h to obtain a triazole polyurethane; (2) triazole polyurethane, 3-thiophenecarbonyl chloride, p-toluenesulfonic acid, and N,N-dimethylformamide are 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, with a power of 350 W and an irradiation time of 3 minutes. After the irradiation, the mixture is cooled to 0°C, the pH is adjusted to 7 with triethylamine, and methanol with a mass of 3-4 times that of N,N-dimethylformamide is added, filtered, and dried under vacuum for 8 hours to obtain a pre-modified polyurethane; (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 of 10-12 times the mass of the pre-modified polyurethane is added dropwise at a dropping rate of 2 mL / min. After the addition is completed, the temperature is raised to 25-30° C. and reacted for 3-4 hours. After the reaction is completed, methanol of 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 with 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% of triethylamine and benzene in a mass ratio of 1:(12-13), add 3-aminopropyl polydimethylsiloxane, and drip carbon disulfide-benzene solution at a drip rate of 2 mL / min. After stirring at room temperature for 5-6 h, drip at a rate of 0.3 mL / min. Add phosphorus oxychloride-benzene solution at a drop rate, heat to 85-90°C and reflux for 3-4h, cool to room temperature, filter and retain the filtrate, add the remaining triethylamine, and then add 4-aminobenzophenone-benzene solution at a drop rate of 2mL / min. After the addition is completed, add pure water 6.5 times the mass of carbon disulfide, react at room temperature for 1-2h, heat to 85-90°C and reflux for 2-3h. After the reaction is completed, obtain pre-modified silicone oil by vacuum rotary evaporation; (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; (6) The 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.

3. The method for preparing a tire polish according to claim 2, 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 polytetrahydrofuran diol, 2.5 parts of dimethylol 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 weights of polycaprolactone diol and polytetrahydrofuran diol being both 2000; Alcohol, polytetrahydrofuran diol, 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 to react 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.

4. The method for preparing a tire polish according to claim 2, characterized in that: 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.

5. The method for preparing a tire polish according to claim 2, characterized in that: 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.

6. The method for preparing a tire polish according to claim 2, 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.

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