Electric bicycle snowfield tire capable of being used in extremely cold area and preparation method of electric bicycle snowfield tire

Abstract

The invention discloses an electric bicycle snow tire capable of being used in extremely cold areas and a preparation method of the electric bicycle snow tire, and relates to the field of rubber materials. The electric bicycle snow tire capable of being used in the extremely cold region comprises the following components in parts by mass: 50-70 parts of natural rubber; 10-20 parts by mass of butadiene rubber; 10-20 parts by mass of modified styrene-butadiene rubber; 40-60 parts by mass of carbon black; 10 to 20 parts by mass of white carbon black; 0.6-1 part by mass of an accelerant; 1-2 parts by mass of a modified triazine compound; and 1-2 parts by mass of a vulcanizing agent. The prepared electric bicycle snow tire capable of being used in the extremely cold area has good anti-aging performance, flame retardant performance and wear-resisting performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of rubber materials, in particular to a snow tire for electric bicycles in extremely cold regions and a preparation method thereof. BACKGROUND

[0002] As a viscoelastic material, rubber itself has high elasticity and certain viscosity, so a single rubber matrix cannot bear a large load when used in tire tread rubber and various other tread rubbers, and the mechanical properties of the tread rubber material need to be reinforced to meet the requirements of various tread rubbers. Ordinary rubber also has the disadvantages of easy wear and tear and easy aging, which limits its application.

[0003] Carbon black has a large number of active sites on its surface, so that it can be firmly combined with rubber macromolecular chains when used as a reinforcing filler, forming a skeletal structure and thus imparting certain strength and hardness to the rubber material. Carbon black and white carbon black, as two traditional nanometer reinforced rubber reinforcing fillers, play an irreplaceable role. The snow tire for electric bicycles in extremely cold regions prepared by the present application has good anti-aging performance, flame retardance and wear resistance, and has a broad market prospect. SUMMARY

[0004] The present application aims to provide a preparation method of a snow tire for electric bicycles in extremely cold regions to solve the problems in the prior art.

[0005] To solve the above technical problems, the present application provides the following technical solutions:

[0006] A snow tire for electric bicycles in extremely cold regions comprises the following components:

[0007] 50-70 parts by mass of natural rubber;

[0008] 10-20 parts by mass of butadiene rubber;

[0009] 10-20 parts by mass of modified butadiene rubber;

[0010] 40-60 parts by mass of carbon black;

[0011] 10-20 parts by mass of white carbon black;

[0012] 0.6-1 parts by mass of an accelerator;

[0013] 1-2 parts by mass of a modified triazine compound;

[0014] 1-2 parts by mass of a vulcanizing agent.

[0015] Preferably, the accelerator is N-cyclohexyl-2-benzothiazole sulfenamide.

[0016] Preferably, the vulcanizing agent is sulfur.

[0017] Preferably, the preparation step of the modified styrene-butadiene rubber is as follows:

[0018] The styrene solution, 2,2-bis (tetrahydrofuran) propane are mixed, heated at 50℃ for 8-12 min, then n-butyllithium is added to kill impurities, and then an appropriate amount of n-butyllithium is added, and the reaction is continued for 35-45 min, then allyltrimethoxysilane is added and the reaction is continued for 1-2 h, isopropyl alcohol is added to terminate the reaction, and then the precipitate is separated and dried in anhydrous ethanol at 50℃ for 5-7 h.

[0019] Preferably, the preparation method of the styrene solution is as follows: cyclohexane and n-hexane are mixed in a volume ratio of 1:1, and then 0.4 times the mass of cyclohexane of styrene is added and mixed to obtain the styrene solution.

[0020] Preferably, the molar ratio of n-butyllithium to 2,2-bis (tetrahydrofuran) propane is 1:1.2.

[0021] Preferably, the preparation method of the modified triazine compound is as follows:

[0022] The 2-chloro-4,6-diamino-1,3,5-triazine, resorcinol, aluminum chloride and chlorobenzene are mixed and reacted at 70℃ for 5-7 h to obtain the triazine compound; the triazine compound, acrolein and 1,4-dioxane are mixed in a mass ratio of 1:(0.6-0.8):(8-12), heated to reflux at 40-50℃ for 12 h, then 2-4 times the mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide of 2-chloro-4,6-diamino-1,3,5-triazine is added, and the reaction is continued to reflux for 12 h, then the product is poured into anhydrous ethanol, and the precipitate is washed with anhydrous ethanol and dried in vacuum for 10-14 h.

[0023] Preferably, the mass ratio of 2-chloro-4,6-diamino-1,3,5-triazine, resorcinol, aluminum chloride and chlorobenzene is 1:(0.8-0.9):(1-1.1):(8-12).

[0024] Compared with the prior art, the present application has the following beneficial effects:

[0025] The application is used for the preparation of electric bicycle snow tire capable of being used in extremely cold regions, 2-chloro-4, 6-diamino-1, 3, 5-triazine is reacted with resorcinol, acrolein and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to prepare a modified triazine compound, the triazine structure has abundant nitrogen, the Schiff base structure generated after the reaction of 2-chloro-4, 6-diamino-1, 3, 5-triazine and acrolein is reacted with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus is introduced, and the phosphorus and nitrogen synergistically flame-retard, thereby improving the flame-retardant performance of the electric bicycle snow tire; 2-chloro-4, 6-diamino-1, 3, 5-triazine is reacted with resorcinol to generate an enolic structure, after absorbing ultraviolet light energy, the enolic structure undergoes tautomerism, converts the ultraviolet energy into heat energy and dissipates, effectively improving the anti-aging performance of the electric vehicle tire; the acrolein introduces a double bond on the modified triazine compound, can react with a vulcanizing agent in the vulcanization process to form a complex crosslinking network, improving the crosslinking density of the electric vehicle tire, thereby effectively improving the wear resistance of the electric vehicle tire.

[0026] The modified styrene butadiene rubber prepared by the reaction of styrene and allyl trimethoxysilane introduces a siloxane structure, the siloxane can react with the hydroxyl group on the surface of carbon black or white carbon black, effectively improving the crosslinking degree of carbon black or white carbon black and rubber, thereby improving the wear resistance of the electric vehicle tire. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0028] The preparation method of the electric bicycle snow tire capable of being used in extremely cold regions according to the embodiments of the application specifically comprises the following steps: natural rubber, cis-butadiene rubber, modified styrene butadiene rubber, carbon black, white carbon black, an accelerator, a modified triazine compound and a vulcanizing agent are sequentially added into a banbury mixer, and after mixing, the mixture is placed into a mold and vulcanized at 160 DEG C for 30 minutes on a flat plate vulcanization instrument to obtain the electric bicycle snow tire.

[0029] The accelerator used in the following examples and comparative examples is N-cyclohexyl-2-benzothiazole sulfenamide, and the vulcanizing agent is sulfur.

[0030] Example 1

[0031] An electric bicycle snow tire capable of being used in extremely cold regions comprises the following components:

[0032] 50 parts of natural rubber by mass;

[0033] 10 parts by mass of butadiene rubber;

[0034] 10 parts by mass of modified styrene-butadiene rubber;

[0035] 40 parts by mass of carbon black;

[0036] 10 parts by mass of white carbon black;

[0037] 0.6 parts by mass of accelerator;

[0038] 1 part by mass of modified triazine compound;

[0039] 1 part by mass of vulcanizing agent.

[0040] The preparation step of the modified styrene-butadiene rubber is as follows:

[0041] Cyclohexane and n-hexane are mixed in a volume ratio of 1:1, 0.4 times the mass of cyclohexane of styrene is added, and the styrene solution is prepared by mixing. The styrene solution and 2,2-di(tetrahydrofuran) propane are mixed, heated at 50°C for 8 min, and then n-butyllithium is added to remove impurities. Then, an appropriate amount of n-butyllithium is added, and the reaction is continued for 35 min. Then, allyltrimethoxysilane is added and the reaction is continued for 1 h. Isopropyl alcohol is added to terminate the reaction. The precipitate is separated and dried in a vacuum at 50°C for 5 h to obtain the modified styrene-butadiene rubber.

[0042] The preparation method of the modified triazine compound is as follows:

[0043] 2-chloro-4,6-diamino-1,3,5-triazine, resorcinol, aluminum chloride, and chlorobenzene are mixed in a mass ratio of 1:0.8:1:8, and reacted at 70°C for 5 h to obtain the triazine compound. The triazine compound, acrolein, and 1,4-dioxane are mixed in a mass ratio of 1:0.6:8, heated at 40°C and refluxed for 12 h. Then, 2-chloro-4,6-diamino-1,3,5-triazine is added in an amount of 2 times the mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the reaction is continued for 12 h. The product is poured into anhydrous ethanol, and the precipitate is washed with anhydrous ethanol and dried in a vacuum for 10 h to obtain the modified triazine compound.

[0044] Example 2:

[0045] An electric bicycle snow tire capable of being used in extremely cold regions, comprising the following components:

[0046] 60 parts by mass of natural rubber;

[0047] 15 parts by mass of butadiene rubber;

[0048] 15 parts by mass of modified styrene-butadiene rubber;

[0049] 50 parts by mass of carbon black;

[0050] 15 parts by mass of white carbon black;

[0051] 0.8 parts by mass of an accelerator;

[0052] 1.5 parts by mass of a modified triazine compound;

[0053] 1.5 parts by mass of a vulcanizing agent.

[0054] The preparation step of the modified butadiene styrene rubber is as follows:

[0055] The cyclohexane and n-hexane are mixed in a volume ratio of 1:1, 0.4 times the mass of the cyclohexane of styrene is added, and the styrene solution is prepared by mixing. The styrene solution and 2,2-di(tetrahydrofuran) propane are mixed, heated at 50°C for 10 min, and then n-butyllithium is added to remove impurities. Then, an appropriate amount of n-butyllithium is added, and the reaction is continued for 40 min. Then, allyltrimethoxysilane is added and the reaction is continued for 1.5 h. Isopropyl alcohol is added to terminate the reaction, and the precipitate is separated and dried in anhydrous ethanol at 50°C for 6 h.

[0056] The preparation method of the modified triazine compound is as follows:

[0057] The 2-chloro-4,6-diamino-1,3,5-triazine, resorcinol, aluminum chloride, and chlorobenzene are mixed in a mass ratio of 1:0.85:1.05:10, and the mixture is reacted at 70°C for 6 h to obtain the triazine compound. The triazine compound, propylene aldehyde, and 1,4-dioxane are mixed in a mass ratio of 1:0.7:10, heated at 45°C and refluxed for 12 h. Then, 3 times the mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added, and the mixture is heated and refluxed for another 12 h. The precipitate is washed with anhydrous ethanol and dried in a vacuum oven for 12 h to obtain the modified triazine compound.

[0058] Example 3:

[0059] An electric bicycle snow tire capable of being used in extremely cold regions, comprising the following components:

[0060] 70 parts by mass of natural rubber;

[0061] 20 parts by mass of butadiene rubber;

[0062] 20 parts by mass of modified butadiene styrene rubber;

[0063] 60 parts by mass of carbon black;

[0064] 20 parts by mass of white carbon black;

[0065] 1 part by mass of an accelerator;

[0066] 2 parts by mass of a modified triazine compound;

[0067] 2 parts by mass of a vulcanizing agent.

[0068] The modified butadiene styrene rubber is prepared by the following steps:

[0069] The cyclohexane and n-hexane are mixed in a volume ratio of 1:1, 0.4 times the mass of the cyclohexane of styrene is added, and the mixture is uniformly prepared into a styrene solution. The styrene solution and 2,2-bis(tetrahydrofuran) propane are mixed and heated at 50°C for 12 min. After adding n-butyllithium to remove impurities, an appropriate amount of n-butyllithium is added, and the reaction is continued for 45 min. Allyltrimethoxysilane is added and the reaction is continued for 2 h. Isopropyl alcohol is added to terminate the reaction. The precipitate is separated and dried in a vacuum at 50°C for 7 h to obtain the modified butadiene styrene rubber.

[0070] The modified triazine compound is prepared by the following method:

[0071] The 2-chloro-4,6-diamino-1,3,5-triazine, resorcinol, aluminum chloride, and chlorobenzene are mixed in a mass ratio of 1:0.9:1.1:12 and reacted at 70°C for 7 h to obtain the triazine compound. The triazine compound, acrolein, and 1,4-dioxane are mixed in a mass ratio of 1:0.8:12, heated at 50°C for 12 h, and then 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added in an amount of 4 times the mass of the 2-chloro-4,6-diamino-1,3,5-triazine. The mixture is heated and refluxed for another 12 h. The precipitate is washed with anhydrous ethanol and dried in a vacuum for 14 h to obtain the modified triazine compound.

[0072] Comparative Example 1:

[0073] An electric bicycle snow tire capable of being used in extremely cold regions, comprising the following components:

[0074] 60 parts by mass of natural rubber;

[0075] 15 parts by mass of butadiene rubber;

[0076] 15 parts by mass of modified butadiene styrene rubber;

[0077] 50 parts by mass of carbon black;

[0078] 15 parts by mass of white carbon black;

[0079] 0.8 parts by mass of an accelerator;

[0080] 1.5 parts by mass of a vulcanizing agent.

[0081] The modified butadiene styrene rubber is prepared by the following steps:

[0082] Mix cyclohexane and n-hexane in a volume ratio of 1:1, add styrene with a mass of 0.4 times that of cyclohexane, mix to prepare a styrene solution, mix the styrene solution and 2,2-bis(tetrahydrofuran) propane, heat at 50℃ for 10 min, add n-butyllithium to remove impurities, then add an appropriate amount of n-butyllithium, continue to react for 40 min, then add allyltrimethoxysilane and continue to react for 1.5 h, add isopropyl alcohol to terminate the reaction, precipitate in anhydrous ethanol, separate the precipitate, and vacuum dry at 50℃ for 6 h to prepare.

[0083] Comparative Example 2:

[0084] A kind of electric bicycle snow tire capable of being used in extremely cold regions, comprising the following components:

[0085] 60 parts by mass of natural rubber;

[0086] 15 parts by mass of butadiene rubber;

[0087] 15 parts by mass of butadiene rubber;

[0088] 50 parts by mass of carbon black;

[0089] 15 parts by mass of white carbon black;

[0090] 0.8 parts by mass of accelerator;

[0091] 1.5 parts by mass of modified triazine compound;

[0092] 1.5 parts by mass of vulcanizing agent.

[0093] The preparation method of the modified triazine compound is:

[0094] Mix 2-chloro-4,6-diamino-1,3,5-triazine, resorcinol, aluminum chloride and chlorobenzene in a mass ratio of 1:0.85:1.05:10, react at 70℃ for 6 h to prepare a triazine compound; mix the triazine compound, propylene aldehyde and 1,4-dioxane in a mass ratio of 1:0.7:10, heat at 45℃ to reflux for 12 h, then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with a mass of 3 times that of 2-chloro-4,6-diamino-1,3,5-triazine, continue to heat to reflux for 12 h, pour into anhydrous ethanol, wash the precipitate with anhydrous ethanol and vacuum dry for 12 h to prepare.

[0095] Test Example 1:

[0096] Flame retardant performance test: according to GB / T 10707—2008, the sample length is 120 mm, the width is 6.5 mm, and the thickness is 3 mm. The results are shown in Table 1.

[0097] Table 1 Statistics of flame retardant performance test

[0098]

[0099] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1 and 2 in Table 1, it can be found that the snow tire for electric bicycles used in extremely cold regions prepared by the present application has good flame retardant performance.

[0100] The difference between Comparative Example 1 and Example 2 is that no modified triazine compound is added. Through comparison, the limiting oxygen index of Examples 1-3 is greater than that of Comparative Example 1, indicating that the modified triazine compound prepared by reacting 2-chloro-4,6-diamino-1,3,5-triazine with resorcinol, acrolein and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide has a rich nitrogen in the triazine structure, and the Schiff base structure generated after the reaction of 2-chloro-4,6-diamino-1,3,5-triazine with acrolein reacts with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, introducing phosphorus, which synergistically retards flame, thereby improving the flame retardant performance of the snow tire for electric bicycles.

[0101] Test Example 2:

[0102] Anti-aging performance test: According to GB / T 528-2009, dumbbell-shaped samples with a thickness of 2 mm and a tensile rate of 500 mm / min were used to test the original tensile strength of each example and comparative example. The samples prepared in each example and comparative example were aged in an aging simulation box under simulated sunlight for 72 h, and the tensile strength after aging was tested. The tensile strength loss rate was calculated according to the formula: (original tensile strength - tensile strength after aging) / original tensile strength x 100%. The results are shown in Table 2.

[0103] Table 2 Statistics of anti-aging performance test

[0104]

[0105] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1 and 2 in Table 2, it can be found that the snow tire for electric bicycles used in extremely cold regions prepared by the present application has good anti-aging performance.

[0106] The difference between Comparative Example 1 and Example 2 is that no modified triazine compound is added. Through comparison, the tensile strength loss rate of Examples 1-3 is less than that of Comparative Example 1, indicating that the enolic structure is generated by the reaction of 2-chloro-4,6-diamino-1,3,5-triazine with resorcinol. After absorbing ultraviolet energy, the enolic structure undergoes tautomerism, converting the ultraviolet energy into heat energy, effectively improving the anti-aging performance of the electric vehicle tire.

[0107] Test Example 3:

[0108] Wear resistance test: the tires prepared from each example and the comparative example were tested for wear rate under the conditions of 20℃, constant load 60N, constant speed 800r / min, running distance 25m, friction time 9min, and the wear rate was calculated according to wear rate = volume loss / (constant load x total friction distance). The results are shown in Table 3.

[0109] Table 3 Wear resistance test statistics

[0110]

[0111] From the experimental data of Examples 1-3 and Comparative Examples 1 and 2 in Table 3, it can be found that the snow tire for electric bicycles prepared by the application has good wear resistance.

[0112] The difference between Comparative Example 1 and Example 2 is that no modified triazine compound is added. By comparison, the wear rate of Examples 1-3 is less than that of Comparative Example 1, which shows that the modified triazine compound prepared by reacting 2-chloro-4,6-diamino-1,3,5-triazine with resorcinol, acrolein and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide introduces a double bond on the modified triazine compound, which can react with the vulcanizing agent during the vulcanization process to form a complex crosslinking network, thereby increasing the crosslinking density of the electric vehicle tire and effectively improving the wear resistance of the electric vehicle tire.

[0113] The difference between Comparative Example 2 and Example 2 is that no modified butadiene-styrene rubber is added. By comparison, the wear rate of Examples 1-3 is less than that of Comparative Example 2, which shows that the modified butadiene-styrene rubber prepared by reacting styrene with allyltrimethoxysilane introduces a siloxane structure, which can react with the hydroxyl groups on the surface of carbon black or white carbon black, effectively increasing the crosslinking degree of carbon black or white carbon black and rubber, thereby improving the wear resistance of the electric vehicle tire.

[0114] The above specific embodiments further illustrate the purpose, technical solutions and advantages of the application. It should be understood that the above description is only a specific embodiment of the application and is not intended to limit the protection scope of the application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the application shall be included in the protection scope of the application.

Claims

1. An electric bicycle snow tire capable of being used in extremely cold regions, characterized in that, It comprises the following components: 50-70 parts by mass of natural rubber; 10-20 parts by mass of butadiene rubber; 10-20 parts by mass of modified butadiene rubber; 40-60 parts by mass of carbon black; 10-20 parts by mass of white carbon black; 0.6-1 parts by mass of accelerator; 1-2 parts by mass of modified triazine compound; 1-2 parts by mass of vulcanizing agent.

2. The snow tire for electric bicycle capable of being used in extremely cold regions according to claim 1, characterized in that, The accelerator is N-cyclohexyl-2-benzothiazole sulfenamide.

3. The snow tire for electric bicycle capable of being used in extremely cold regions as claimed in claim 1 wherein, The vulcanizing agent is sulfur.

4. The snow tire for electric bicycle capable of being used in extremely cold regions as claimed in claim 1 wherein, The preparation steps of the modified butadiene rubber are as follows: The styrene solution, 2,2-di (tetrahydrofuran) propane are mixed, heated at 50℃ for 8-12 min, then butyl lithium is added to remove impurities, and then an appropriate amount of butyl lithium is added, and the reaction is continued for 35-45 min, then allyl trimethoxysilane is added and the reaction is continued for 1-2 h, isopropyl alcohol is added to terminate the reaction, and then the sediment is separated and dried in vacuum at 50℃ for 5-7 h.

5. The snow tire for electric bicycle capable of being used in extremely cold regions as claimed in claim 4 wherein, The preparation method of the styrene solution is as follows: cyclohexane and n-hexane are mixed in a volume ratio of 1:1, and then styrene is added in an amount of 0.4 times the mass of cyclohexane, and then mixed to obtain the styrene solution.

6. The snow tire for electric bicycle capable of being used in extremely cold regions as claimed in claim 4 wherein, The molar ratio of butyl lithium to 2,2-di (tetrahydrofuran) propane is 1:1.

2.

7. The snow tire for electric bicycle capable of being used in extremely cold regions as claimed in claim 1 wherein, The preparation method of the modified triazine compound is as follows: The 2-chloro-4,6-diamino-1,3,5-triazine, resorcinol, aluminum chloride and chlorobenzene are mixed and reacted at 70℃ for 5-7 h to obtain the triazine compound; the triazine compound, acrolein and 1,4-dioxane are mixed in a mass ratio of 1: (0.6-0.8): (8-12), heated to reflux at 40-50℃ for 12 h, then 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added in an amount of 2-4 times the mass of 2-chloro-4,6-diamino-1,3,5-triazine, and the reaction is continued to reflux for 12 h, then the product is poured into anhydrous ethanol, and the precipitate is washed with anhydrous ethanol and dried in vacuum for 10-14 h.

8. The snow tire for electric bicycle capable of being used in extremely cold regions as claimed in claim 7 wherein, The mass ratio of 2-chloro-4,6-diamino-1,3,5-triazine, resorcinol, aluminum chloride and chlorobenzene is 1: (0.8-0.9): (1-1.1): (8-12).

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