Environmentally friendly tire brightener and preparation method thereof

Abstract

The invention relates to the technical field of brighteners, and discloses an environmentally friendly tire brightener and a preparation method thereof. The invention provides an environmentally friendly tire brightener by adding water-based silicone oil, polyurethane emulsion, water, nano zinc oxide modified imidazoline, and modified polyurethane into a stirrer and stirring. The aminated zinc oxide and imidazole groups in the nano zinc oxide modified imidazoline have good self-cleaning effects, and can effectively remove oil stains on the tire surface. The polyphenylene sulfide structure itself also has good oil resistance, so that the tire surface does not absorb oil, thereby maintaining good brightness; after the chloromethylated polyphenylene sulfide reacts with the intermediate 1, the substitution degree of the polyphenylene sulfide is increased, and the oil resistance of the tire is further improved. The fluorine element in the modified polyurethane is introduced into the tire brightener and applied to the tire surface, so that a smooth fluorocarbon layer that is not easy to adhere to objects is formed on the surface, so that it has a good self-cleaning effect.

Description

Technical Field

[0001] The invention relates to the technical field of brighteners, in particular to an environmentally friendly tire brightener and a preparation method thereof. Background Art

[0002] During long-term use, dirt and oil will adhere to the surface of the tire, which makes the surface unsightly and becomes a nuisance for car owners. Therefore, how to avoid this phenomenon is the key to solving the problem. For example, patent CN105505232A discloses a tire brightener, which can keep the tire clean for a longer period of time. The protective film formed by the brightener on the tire surface is not easy to fall off and effectively prevents dust, but its oil resistance effect is not improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides an environmentally friendly tire brightener and a preparation method thereof, which has good oil resistance and self-cleaning effects.

[0005] (II) Technical solution

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: an environmentally friendly tire brightener, comprising the following weight components: 4-8 weight parts of aqueous silicone oil, 12-16 weight parts of polyurethane emulsion, 35-50 weight parts of water, 3-5 weight parts of nano zinc oxide modified imidazoline, and 4-8 weight parts of modified polyurethane.

[0007] Preferably, the preparation method of the nano zinc oxide modified imidazoline is:

[0008] (1) Adding 3-aminopropyltriethoxysilane and nano zinc oxide to a toluene solvent for surface modification, reacting at 50-75° C. for 2-3 hours, and obtaining amino zinc oxide after the reaction is completed;

[0009] (2) Add amination zinc oxide to a reactor containing ethylene glycol solvent, stir and mix, slowly dropwise add epichlorohydrin, react at 25-40°C for 4-6 hours, then continue to add oleic acid diethylenetriamine imidazoline, react at 110-130°C for 3-5 hours, and then cool to room temperature to obtain intermediate 1;

[0010] (3) adding 5-10 parts by weight of polyphenylene sulfide to 1-2 parts by weight of chloromethyl ether and 0.5-0.8 parts by weight of tin tetrachloride, stirring and mixing, reacting at 80-95° C., filtering after the reaction, washing and drying to obtain chloromethylated polyphenylene sulfide;

[0011] (4) Add 7-15 parts by weight of chloromethylated polyphenylene sulfide and 8-11 parts by weight of intermediate 1 to N,N-dimethylformamide solvent, stir, add 0.8-1.3 parts by weight of sodium acetate, heat to 60-80° C. and reflux for reaction for 3-4 hours, cool, concentrate, and wash with petroleum ether to obtain nano zinc oxide modified imidazoline.

[0012] Preferably, the mass ratio of 3-aminopropyltriethoxysilane to nano zinc oxide in (1) is 1.2-1.6:1.

[0013] Preferably, in said (2), the content of amination zinc oxide is 5-10 parts by weight, epichlorohydrin is 7-12 parts by weight, and oleic acid diethylenetriamine imidazoline is 4-8 parts by weight.

[0014] Preferably, the reaction time in (3) is 7-13 hours.

[0015] Preferably, the stirring time in (4) is 20-35 min.

[0016] Preferably, the preparation method of the modified polyurethane is:

[0017] S1. Add 4-9 parts by weight of 2-amino-2-hydroxymethyl-1,3-propanediol to N,N-dimethylformamide solvent, stir evenly, continue to add 3-6 parts by weight of perfluorooctanoyl chloride and 0.1-0.2 parts by weight of triethylamine catalyst, react at 65-80° C. for 5-8 hours, and then perform rotary distillation, wash and dry to obtain a fluorine-containing chain extender;

[0018] S2. 10-12 parts by weight of polyether diol are removed from water and mixed evenly with 7-14 parts by weight of hexamethylene diisocyanate, nitrogen is introduced, and then 0.02-0.04 parts by weight of dibutyltin dilaurate catalyst is added dropwise, and the mixture is reacted at 50-85°C for 2-5 hours for prepolymerization, and then 0.6-0.8 parts by weight of fluorine-containing chain extender is added and the chain extension reaction is continued with stirring. After the reaction is completed, the mixture is cooled and discharged to obtain a modified polyurethane.

[0019] Preferably, the preparation method of the environmentally friendly tire brightener is: adding water-based silicone oil, polyurethane emulsion, water, nano zinc oxide modified imidazoline, and modified polyurethane into a stirrer, stirring for 2-4 minutes, and obtaining the environmentally friendly tire brightener.

[0020] 3. Beneficial technical effects

[0021] The invention prepares an environmentally friendly tire brightener by adding water-based silicone oil, polyurethane emulsion, water, nano zinc oxide modified imidazoline and modified polyurethane into a stirrer and stirring.

[0022] The amino zinc oxide and imidazole groups in the nano-zinc oxide modified imidazoline have good self-cleaning effect and can effectively remove oil stains on the tire surface. The polyphenylene sulfide structure itself also has good oil resistance, so that the tire surface does not absorb oil, thereby maintaining good brightness; after the chloromethylated polyphenylene sulfide reacts with the intermediate 1, the substitution degree of polyphenylene sulfide is increased, further improving the oil resistance of the tire. The fluorine element in the modified polyurethane is introduced into the tire brightener and applied to the tire surface, which can form a smooth fluorocarbon layer on the surface that is not easy to adhere to objects, so it has a good self-cleaning effect, and the polyurethane itself has good oil resistance. DETAILED DESCRIPTION Example 1

[0023] (1) adding 12 parts by weight of 3-aminopropyltriethoxysilane and 10 parts by weight of nano zinc oxide to a toluene solvent for surface modification, and reacting at 50° C. for 2 hours. After the reaction is completed, amino zinc oxide is obtained;

[0024] (2) Add 5 parts by weight of amino zinc oxide to a reactor containing ethylene glycol solvent, stir and mix, slowly dropwise add 7 parts by weight of epichlorohydrin, react at 25°C for 4 hours, then continue to add 4 parts by weight of oleic acid diethylenetriamine imidazoline, react at 110°C for 3 hours, and then cool to room temperature to obtain intermediate 1;

[0025] (3) adding 5 parts by weight of polyphenylene sulfide to 1 part by weight of chloromethyl ether and 0.5 parts by weight of tin tetrachloride, stirring and mixing, reacting at 80° C. for 7 hours, filtering after the reaction, washing and drying to obtain chloromethylated polyphenylene sulfide;

[0026] (4) Add 7 parts by weight of chloromethylated polyphenylene sulfide and 8 parts by weight of intermediate 1 to N,N-dimethylformamide solvent, stir for 20 minutes, add 0.8 parts by weight of sodium acetate, heat to 60° C. and reflux for 3 hours, cool, concentrate, and wash with petroleum ether to obtain nano zinc oxide modified imidazoline;

[0027] (5) Add 4 parts by weight of 2-amino-2-hydroxymethyl-1,3-propanediol to N,N-dimethylformamide solvent, stir evenly, continue to add 3 parts by weight of perfluorooctanoyl chloride and 0.1 parts by weight of triethylamine catalyst, react at 65° C. for 5 hours, and then perform rotary distillation, wash and dry to obtain a fluorine-containing chain extender;

[0028] (6) 10 parts by weight of polyether diol after dehydration and 7 parts by weight of hexamethylene diisocyanate were mixed evenly, nitrogen was introduced, and then 0.02 parts by weight of dibutyltin dilaurate catalyst was added dropwise, and the mixture was reacted at 50° C. for 2 hours to carry out prepolymerization, and then 0.6 parts by weight of fluorine-containing chain extender was added, and the chain extension reaction was continued with stirring. After the reaction was completed, the mixture was cooled and discharged to obtain a modified polyurethane;

[0029] (7) Add 4 parts by weight of aqueous silicone oil, 12 parts by weight of polyurethane emulsion, 35 parts by weight of water, 3 parts by weight of nano zinc oxide modified imidazoline, and 4 parts by weight of modified polyurethane into a stirrer and stir for 2 minutes to obtain an environmentally friendly tire brightener. Example 2

[0030] (1) adding 16 parts by weight of 3-aminopropyltriethoxysilane and 10 parts by weight of nano zinc oxide to a toluene solvent for surface modification, and reacting at 75° C. for 3 hours. After the reaction is completed, amino zinc oxide is obtained;

[0031] (2) Add 10 parts by weight of amino zinc oxide to a reactor containing ethylene glycol solvent, stir and mix, slowly dropwise add 12 parts by weight of epichlorohydrin, react at 40°C for 6 hours, then continue to add 8 parts by weight of oleic acid diethylenetriamine imidazoline, react at 130°C for 5 hours, and then cool to room temperature to obtain intermediate 1;

[0032] (3) adding 10 parts by weight of polyphenylene sulfide to 2 parts by weight of chloromethyl ether and 0.8 parts by weight of tin tetrachloride, stirring and mixing, reacting at 95° C. for 13 hours, filtering after the reaction, washing and drying to obtain chloromethylated polyphenylene sulfide;

[0033] (4) Add 15 parts by weight of chloromethylated polyphenylene sulfide and 11 parts by weight of intermediate 1 to N,N-dimethylformamide solvent, stir for 35 minutes, add 1.3 parts by weight of sodium acetate, heat to 80° C. and reflux for 4 hours, cool, concentrate, and wash with petroleum ether to obtain nano zinc oxide modified imidazoline;

[0034] (5) Add 9 parts by weight of 2-amino-2-hydroxymethyl-1,3-propanediol to N,N-dimethylformamide solvent, stir evenly, continue to add 6 parts by weight of perfluorooctanoyl chloride and 0.2 parts by weight of triethylamine catalyst, react at 80° C. for 8 hours, and then perform rotary distillation, wash and dry to obtain a fluorine-containing chain extender;

[0035] (6) 12 parts by weight of polyether diol after dehydration and 14 parts by weight of hexamethylene diisocyanate were mixed evenly, nitrogen was introduced, and then 0.04 parts by weight of dibutyltin dilaurate catalyst was added dropwise, and the mixture was reacted at 85° C. for 5 hours to carry out prepolymerization, and then 0.8 parts by weight of fluorine-containing chain extender was added, and the chain extension reaction was continued with stirring. After the reaction was completed, the mixture was cooled and discharged to obtain a modified polyurethane;

[0036] (7) Add 8 parts by weight of aqueous silicone oil, 16 parts by weight of polyurethane emulsion, 50 parts by weight of water, 5 parts by weight of nano zinc oxide modified imidazoline, and 8 parts by weight of modified polyurethane into a stirrer and stir for 4 minutes to obtain an environmentally friendly tire brightener. Example 3

[0037] (1) adding 14 parts by weight of 3-aminopropyltriethoxysilane and 10 parts by weight of nano zinc oxide to a toluene solvent for surface modification, and reacting at 65° C. for 2 h. After the reaction is completed, amino zinc oxide is obtained;

[0038] (2) Add 8 parts by weight of amino zinc oxide to a reactor containing ethylene glycol solvent, stir and mix, slowly dropwise add 10 parts by weight of epichlorohydrin, react at 35°C for 5 hours, then continue to add 6 parts by weight of oleic acid diethylenetriamine imidazoline, react at 120°C for 4 hours, and then cool to room temperature to obtain intermediate 1;

[0039] (3) adding 8 parts by weight of polyphenylene sulfide to 1 part by weight of chloromethyl ether and 0.7 parts by weight of tin tetrachloride, stirring and mixing, reacting at 85° C. for 10 hours, filtering after the reaction, washing and drying to obtain chloromethylated polyphenylene sulfide;

[0040] (4) Add 12 parts by weight of chloromethylated polyphenylene sulfide and 9 parts by weight of intermediate 1 to N,N-dimethylformamide solvent, stir for 25 minutes, add 1.2 parts by weight of sodium acetate, heat to 70° C. and reflux for 3 hours, cool, concentrate, and wash with petroleum ether to obtain nano zinc oxide modified imidazoline;

[0041] (5) Add 8 parts by weight of 2-amino-2-hydroxymethyl-1,3-propanediol to N,N-dimethylformamide solvent, stir evenly, continue to add 5 parts by weight of perfluorooctanoyl chloride and 0.1 parts by weight of triethylamine catalyst, react at 72° C. for 7 hours, and then perform rotary distillation, wash and dry to obtain a fluorine-containing chain extender;

[0042] (6) 11 parts by weight of polyether diol after dehydration and 12 parts by weight of hexamethylene diisocyanate were mixed evenly, nitrogen was introduced, and then 0.03 parts by weight of dibutyltin dilaurate catalyst was added dropwise, and the mixture was reacted at 65° C. for 3 hours to carry out prepolymerization, and then 0.7 parts by weight of fluorine-containing chain extender was added, and the chain extension reaction was continued with stirring. After the reaction was completed, the mixture was cooled and discharged to obtain a modified polyurethane;

[0043] (7) Add 6 parts by weight of aqueous silicone oil, 14 parts by weight of polyurethane emulsion, 40 parts by weight of water, 4 parts by weight of nano zinc oxide modified imidazoline, and 4-8 parts by weight of modified polyurethane into a stirrer and stir for 3 minutes to obtain an environmentally friendly tire brightener. Example 4

[0044] (1) adding 12 parts by weight of 3-aminopropyltriethoxysilane and 10 parts by weight of nano zinc oxide to a toluene solvent for surface modification, and reacting at 50° C. for 2 hours. After the reaction is completed, amino zinc oxide is obtained;

[0045] (2) Add 5 parts by weight of amino zinc oxide to a reactor containing ethylene glycol solvent, stir and mix, slowly dropwise add 7 parts by weight of epichlorohydrin, react at 25°C for 4 hours, then continue to add 4 parts by weight of oleic acid diethylenetriamine imidazoline, react at 110°C for 3 hours, and then cool to room temperature to obtain intermediate 1;

[0046] (3) adding 10 parts by weight of polyphenylene sulfide to 2 parts by weight of chloromethyl ether and 0.8 parts by weight of tin tetrachloride, stirring and mixing, reacting at 95° C. for 13 hours, filtering after the reaction, washing and drying to obtain chloromethylated polyphenylene sulfide;

[0047] (4) Add 15 parts by weight of chloromethylated polyphenylene sulfide and 11 parts by weight of intermediate 1 to N,N-dimethylformamide solvent, stir for 35 minutes, add 1.3 parts by weight of sodium acetate, heat to 80° C. and reflux for 4 hours, cool, concentrate, and wash with petroleum ether to obtain nano zinc oxide modified imidazoline;

[0048] (5) Add 8 parts by weight of 2-amino-2-hydroxymethyl-1,3-propanediol to N,N-dimethylformamide solvent, stir evenly, continue to add 5 parts by weight of perfluorooctanoyl chloride and 0.1 parts by weight of triethylamine catalyst, react at 72° C. for 7 hours, and then perform rotary distillation, wash and dry to obtain a fluorine-containing chain extender;

[0049] (6) 11 parts by weight of polyether diol after dehydration and 12 parts by weight of hexamethylene diisocyanate were mixed evenly, nitrogen was introduced, and then 0.03 parts by weight of dibutyltin dilaurate catalyst was added dropwise, and the mixture was reacted at 65° C. for 3 hours to carry out prepolymerization, and then 0.7 parts by weight of fluorine-containing chain extender was added, and the chain extension reaction was continued with stirring. After the reaction was completed, the mixture was cooled and discharged to obtain a modified polyurethane;

[0050] (7) Add 6 parts by weight of aqueous silicone oil, 14 parts by weight of polyurethane emulsion, 40 parts by weight of water, 4 parts by weight of nano zinc oxide modified imidazoline, and 4-8 parts by weight of modified polyurethane into a stirrer and stir for 3 minutes to obtain an environmentally friendly tire brightener. Example 5

[0051] (1) adding 16 parts by weight of 3-aminopropyltriethoxysilane and 10 parts by weight of nano zinc oxide to a toluene solvent for surface modification, and reacting at 75° C. for 3 hours. After the reaction is completed, amino zinc oxide is obtained;

[0052] (2) Add 10 parts by weight of amino zinc oxide to a reactor containing ethylene glycol solvent, stir and mix, slowly dropwise add 12 parts by weight of epichlorohydrin, react at 40°C for 6 hours, then continue to add 8 parts by weight of oleic acid diethylenetriamine imidazoline, react at 130°C for 5 hours, and then cool to room temperature to obtain intermediate 1;

[0053] (3) adding 8 parts by weight of polyphenylene sulfide to 1 part by weight of chloromethyl ether and 0.7 parts by weight of tin tetrachloride, stirring and mixing, reacting at 85° C. for 10 hours, filtering after the reaction, washing and drying to obtain chloromethylated polyphenylene sulfide;

[0054] (4) Add 12 parts by weight of chloromethylated polyphenylene sulfide and 9 parts by weight of intermediate 1 to N,N-dimethylformamide solvent, stir for 25 minutes, add 1.2 parts by weight of sodium acetate, heat to 70° C. and reflux for 3 hours, cool, concentrate, and wash with petroleum ether to obtain nano zinc oxide modified imidazoline;

[0055] (5) Add 4 parts by weight of 2-amino-2-hydroxymethyl-1,3-propanediol to N,N-dimethylformamide solvent, stir evenly, continue to add 3 parts by weight of perfluorooctanoyl chloride and 0.1 parts by weight of triethylamine catalyst, react at 65° C. for 5 hours, and then perform rotary distillation, wash and dry to obtain a fluorine-containing chain extender;

[0056] (6) 10 parts by weight of polyether diol after dehydration and 7 parts by weight of hexamethylene diisocyanate were mixed evenly, nitrogen was introduced, and then 0.02 parts by weight of dibutyltin dilaurate catalyst was added dropwise, and the mixture was reacted at 50° C. for 2 hours to carry out prepolymerization, and then 0.6 parts by weight of fluorine-containing chain extender was added, and the chain extension reaction was continued with stirring. After the reaction was completed, the mixture was cooled and discharged to obtain a modified polyurethane;

[0057] (7) Add 4 parts by weight of aqueous silicone oil, 12 parts by weight of polyurethane emulsion, 35 parts by weight of water, 3 parts by weight of nano zinc oxide modified imidazoline, and 4 parts by weight of modified polyurethane into a stirrer and stir for 2 minutes to obtain an environmentally friendly tire brightener.

[0058] Comparative Example 1

[0059] The difference between this comparative example and Example 5 is that nano zinc oxide-modified imidazoline is not added.

[0060] Comparative Example 2

[0061] The difference between this comparative example and Example 5 is that no modified polyurethane is added.

[0062] The examples 1-5 and the comparative examples 1-2 were respectively coated on the tire surface to prepare cubic samples of the tire with a size of 150 mm*150 mm*150 mm.

[0063] The surface wettability of the samples of Examples 1-5 and Comparative Examples 1-2 was characterized according to JC2000D, and the contact angle test was performed.

[0064] Table 1: Contact angle tests.

[0065] project Contact angle Example 1 125.7° Example 2 127.3° Example 3 126.1° Example 4 125.9° Example 5 126.2° Comparative Example 1 90.4 Comparative Example 2 92.6°

[0066] As can be seen from Table 1, compared with Comparative Examples 1-2, the contact angles of Examples 1-5 are larger, resulting in the water droplets being unable to spread and being very easy to slide, indicating that the brightener with self-cleaning function prepared by the present invention has a better self-cleaning function.

[0067] The oil resistance performance is tested according to ASTMD471 standard.

[0068] Table 2: Oil resistance test.

[0069] project Oil resistance (%) Example 1 5.1 Example 2 5.3 Example 3 5.1 Example 4 5.0 Example 5 5.2 Comparative Example 1 6.3 Comparative Example 2 6.5

[0070] It can be seen from Table 2 that Examples 1-5 of the present invention have better oil resistance than Comparative Examples 1-2.

[0071] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An environmentally friendly tire brightener, characterized in that: The invention comprises the following components by weight: 4-8 parts by weight of water-based silicone oil, 12-16 parts by weight of polyurethane emulsion, 35-50 parts by weight of water, 3-5 parts by weight of nano zinc oxide modified imidazoline, and 4-8 parts by weight of modified polyurethane; The preparation method of the nano zinc oxide modified imidazoline is: (1) Adding 3-aminopropyltriethoxysilane and nano zinc oxide to a toluene solvent for surface modification, reacting at 50-75° C. for 2-3 hours, and obtaining amino zinc oxide after the reaction is completed; (2) Add amination zinc oxide to a reactor containing ethylene glycol solvent, stir and mix, slowly dropwise add epichlorohydrin, react at 25-40°C for 4-6 hours, then continue to add oleic acid diethylenetriamine imidazoline, react at 110-130°C for 3-5 hours, and then cool to room temperature to obtain intermediate 1; (3) adding 5-10 parts by weight of polyphenylene sulfide to 1-2 parts by weight of chloromethyl ether and 0.5-0.8 parts by weight of tin tetrachloride, stirring and mixing, reacting at 80-95° C., filtering after the reaction, washing and drying to obtain chloromethylated polyphenylene sulfide; (4) Add 7-15 parts by weight of chloromethylated polyphenylene sulfide and 8-11 parts by weight of intermediate 1 to N,N-dimethylformamide solvent, stir, add 0.8-1.3 parts by weight of sodium acetate, heat to 60-80° C., reflux for reaction for 3-4 hours, cool, concentrate, and wash with petroleum ether to obtain nano zinc oxide modified imidazoline; The preparation method of the modified polyurethane is: S1. Add 4-9 parts by weight of 2-amino-2-hydroxymethyl-1,3-propanediol to N,N-dimethylformamide solvent, stir evenly, continue to add 3-6 parts by weight of perfluorooctanoyl chloride and 0.1-0.2 parts by weight of triethylamine catalyst, react at 65-80° C. for 5-8 hours, and then perform rotary distillation, wash and dry to obtain a fluorine-containing chain extender; S2. 10-12 parts by weight of polyether diol are removed from water and mixed evenly with 7-14 parts by weight of hexamethylene diisocyanate, nitrogen is introduced, and then 0.02-0.04 parts by weight of dibutyltin dilaurate catalyst is added dropwise, and the mixture is reacted at 50-85°C for 2-5 hours for prepolymerization, and then 0.6-0.8 parts by weight of fluorine-containing chain extender is added and the chain extension reaction is continued with stirring. After the reaction is completed, the mixture is cooled and discharged to obtain a modified polyurethane.

2. The environmentally friendly tire brightener according to claim 1, characterized in that: The mass ratio of 3-aminopropyltriethoxysilane to nano zinc oxide in (1) is 1.2-1.6:

1.

3. The environmentally friendly tire brightener according to claim 1, characterized in that: In the above (2), the amount of amination zinc oxide is 5-10 parts by weight, the amount of epichlorohydrin is 7-12 parts by weight, and the amount of diethylenetriamine imidazoline oleate is 4-8 parts by weight.

4. The environmentally friendly tire brightener according to claim 1, characterized in that: The reaction time in (3) is 7-13h.

5. The environmentally friendly tire brightener according to claim 1, characterized in that: The stirring time in (4) is 20-35 minutes.

6. A method for preparing the environmentally friendly tire brightener according to any one of claims 1 to 5, characterized in that: The preparation method of the environmentally friendly tire brightener is as follows: adding water-based silicone oil, polyurethane emulsion, water, nano zinc oxide modified imidazoline and modified polyurethane into a stirrer, stirring for 2-4 minutes, and obtaining the environmentally friendly tire brightener.