A rubber material for automobile tires and its preparation method

Abstract

The present invention provides a rubber material for automobile tires and a preparation method thereof. The rubber material comprises 60 to 100 parts by mass of solution-polymerized styrene-butadiene rubber, 0 to 40 parts by mass of natural rubber, 1 to 30 parts by weight of modified petroleum resin, 1 to 3 parts by weight of sulfur, 4 to 9 parts by weight of activator, 50 to 175 parts by weight of reinforcing filler, and 5 to 25 parts by weight of plasticizer. Among them, the modified petroleum resin is a hydrogenated epoxide of petroleum resin, which enhances the interaction with the reinforcing filler, promotes the dispersion of the reinforcing filler among the fillers, improves the viscoelasticity of the rubber, and enables the rubber to have better stability and mechanical properties when applied to tires.

Description

Technical Field

[0001] The present invention belongs to the technical field of tires. Further, it relates to a rubber material for automobile tires and a preparation method thereof. Background Art

[0002] Rubber is widely used in various aspects, such as the field of automobile tires. With the development of the automobile industry, the performance requirements for automobile tires are getting higher and higher. Especially in the field of high-performance tires, there are high requirements for the wear resistance, wet skid resistance and rolling resistance performance of tires. If rubber products do not have good wear resistance, anti-wet skid performance and low rolling resistance, it will cause the tires to be easily worn, the service life to be reduced, seriously pollute the environment, and affect the safety during the driving of the automobile, etc.

[0003] As is well known, the anti-wet skid performance, rolling resistance and wear resistance are the three major driving performance indicators of tires, which are regarded as the "magic triangle" of tires. At present, it is difficult to balance the high wear resistance, high anti-wet skid and low rolling resistance of automobile tire rubber materials. With the increasing requirements for tire performance by people, developing high-performance tires is the future development direction.

[0004] Resins are usually used as plasticizers in the rubber industry. In recent years, the use of resins as functional fillers to regulate the "magic triangle" performance of tires has been widely studied at home and abroad. Among them, certain achievements have been made in regulating the "magic triangle" performance of tires by using styrene resins, C9 resins and C5 / C9 resins, etc. For example, researchers obtained hydrogenated resins by hydrogenating the unsaturated bonds in the resins. After hydrogenation, the compatibility between the resins and rubber is enhanced and the stability of the hydrogenated resins themselves is enhanced, and they are not prone to oxidation reactions. However, the interaction between the hydrogenated resins and fillers is weak and still cannot meet the existing requirements. Therefore, the research on the application of hydrogenated resins in tires still needs to be further explored and improved. Summary of the Invention

[0005] To solve the above problems, the present invention provides a rubber material for automobile tires and a preparation method thereof. By adding epoxy groups to hydrogenated petroleum resins through epoxidation reaction, the interaction with reinforcing fillers is enhanced, the dispersion of reinforcing fillers among the fillers is promoted, and the viscoelasticity of rubber is improved, so that the rubber has better stability and mechanical properties when applied to tires.

[0006] First, one of the purposes of the present invention is to provide a rubber material for automobile tires.

[0007] Specifically, the rubber is prepared from raw materials including the following components: solution styrene-butadiene rubber, natural rubber, modified petroleum resin, sulfur, activator, reinforcing filler, plasticizer. Among them, based on the total weight of solution styrene-butadiene rubber and natural rubber being 100 parts by weight, the components are as follows by parts by weight:

[0008]

[0009] Preferably, each component is by weight parts:

[0010]

[0011] Among them, the modified petroleum resin is a hydrogenated epoxide of petroleum resin. In the present invention, the petroleum resin is preferably one or a combination of C9 resin, C5 / C9 copolymer resin, DCPD resin, and terpene resin. The present invention modifies the petroleum resin by hydrogenation reaction and epoxidation reaction, so that the epoxy degree of the modified petroleum resin is 5-90%, the hydrogenation degree is 10-95%, the glass transition temperature is 30-100 °C, and the aromaticity is 10-70%; more preferably, the glass transition temperature is 30-60 °C, and the aromaticity is 20-30%.

[0012] Furthermore, in a preferred embodiment of the present invention, the activator is preferably zinc oxide and stearic acid.

[0013] In another preferred embodiment of the present invention, the reinforcing filler is silica or a combination of silica and carbon black.

[0014] In another preferred embodiment of the present invention, the plasticizer is aromatic oil.

[0015] Even further, in the present invention, the raw materials for preparing the rubber material further include an antioxidant, an accelerator, and a silane coupling agent. Each component is by weight parts,

[0016] Antioxidant 2-8 weight parts;

[0017] Accelerator 2-7 weight parts;

[0018] Silane coupling agent 3-10 weight parts.

[0019] Preferably, the antioxidant can be a commonly used antioxidant in the art, such as: antioxidant RD, antioxidant 4020, and paraffin wax;

[0020] The accelerator can be a commonly used accelerator in the art, such as: accelerator NS, accelerator D;

[0021] The silane coupling agent can be a commonly used silane coupling agent in the art, such as: one of Si69, Si75, or Si747.

[0022] Other commonly used additives in the art, such as: naphthenic oil, paraffin oil, carbon nanotubes, etc., can also be added to the rubber material of the present application. Those skilled in the art can add them according to the actual situation, and their dosages are also the usual dosages.

[0023] Furthermore, the present invention also discloses a preparation method of the modified petroleum resin in the above rubber material, comprising the following steps:

[0024] (1) Dissolve the petroleum resin in an organic solvent, and under the action of a catalyst, carry out a hydrogenation reaction to obtain a hydrogenated petroleum resin solution in which part of the carbon-carbon double bonds are hydrogenated;

[0025] (2) Add an epoxidizing reagent to the hydrogenated petroleum resin solution to carry out an epoxidation reaction to obtain a modified petroleum resin in which part of the carbon-carbon double bonds are epoxidized.

[0026] Among them, in step (1), the organic solvent is one of tetrahydrofuran, toluene, and cyclohexane; the hydrogenation reaction mode is one of autoclave hydrogenation reaction, fixed bed hydrogenation reaction, and spray tower hydrogenation reaction. The hydrogen pressure of the hydrogenation reaction is 10-15 Mpa, the reaction temperature is 220-300 °C, and the reaction time is 1-6 h; the catalyst for the hydrogenation reaction is preferably a nickel catalyst, and the catalyst dosage is 0.5-1.5% of the mass of the petroleum resin; in step (2), the epoxidizing reagent is preferably m-chloroperbenzoic acid, and the molar ratio of m-chloroperbenzoic acid to the double bonds in the hydrogenated petroleum resin is 1:0.5-1:1.5; the temperature of the epoxidation reaction is 20-60 °C, and the reaction time is 2-5 h.

[0027] Further, to purify and obtain the modified petroleum resin, after the epoxidation reaction is completed, add methanol to the reaction solution to precipitate the product, and collect the precipitate and dry it to constant weight to obtain the modified petroleum resin.

[0028] Secondly, the second object of the present invention is to provide a preparation method of the rubber material for automobile tires of the first object of the present invention.

[0029] Specifically, the components are mixed and vulcanized according to the required amounts to prepare a rubber material for automobile tires, wherein the vulcanization temperature is 140-160 °C; the vulcanization time for tensile and tear products is t90 + 2 min, and the vulcanization time for compression heat generation and Akron abrasion products is 2t90 + 4 min.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0031] The rubber material for automobile tires provided by the present invention is non-toxic and harmless, has good weather resistance, has good stability and mechanical properties, has the characteristics of low rolling resistance, high anti-wet skid, and high wear resistance, breaks through the defect that the interaction between the resin and the filler in traditional synthetic rubber is weak, and has strong practical value. Detailed Embodiments

[0032] The present invention will be specifically described below in conjunction with specific embodiments. It is necessary to point out here that the following embodiments are only used for further illustration of the present invention and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art to the present invention based on the content of the present invention still fall within the protection scope of the present invention.

[0033] In the following embodiments, the raw materials or reagents used are all commercially available without special instructions.

[0034] Example 1

[0035] 150 g of C5 / C9 resin was added to 800 ml of tetrahydrofuran solution and stirred until completely dissolved, then transferred to a high-pressure reactor. 1.2 g of nickel catalyst was added, hydrogen was charged to exhaust air, the hydrogen pressure was increased to 11 MPa, and the temperature was raised to 235 °C for reaction for 1.5 hours. The supernatant was taken out to obtain partially hydrogenated C5 / C9 hydrogenated resin, and the hydrogenation degree was measured to be 45-55%. The supernatant was transferred to a flask, 20 g of m-chloroperoxybenzoic acid was dissolved in 80 ml of tetrahydrofuran solution, added to the supernatant, and then the temperature was raised to 30 °C for reaction for 3 hours. After the reaction, methanol was added to the solution, and the product precipitated out. Then the precipitate was dried to constant weight to obtain modified C5 / C9 resin. The epoxy degree of the modified petroleum resin was 45-55%, Tg = 45-55 °C, and the aromaticity was 25-30%.

[0036] Example 2

[0037] 150 g of C5 / C9 resin was added to 800 mL of tetrahydrofuran solution and stirred until completely dissolved, then transferred to a high-pressure reactor. 1 g of nickel catalyst was added, hydrogen was charged to exhaust air, the hydrogen pressure was increased to 10 MPa, and the temperature was raised to 220 °C for reaction for 1 hour. The supernatant was taken out to obtain partially hydrogenated C5 / C9 hydrogenated resin, and the hydrogenation degree was measured to be 10-15%. The supernatant was transferred to a flask, 40 g of m-chloroperoxybenzoic acid was dissolved in 160 mL of tetrahydrofuran solution, added to the supernatant, and then the temperature was raised to 50 °C for reaction for 3.5 hours. After the reaction, methanol was added to the solution, and the product precipitated out. Then the precipitate was dried to constant weight to obtain modified C5 / C9 resin. The epoxy degree of the modified petroleum resin was 75-85%, Tg = 45-55 °C, and the aromaticity was 25-30%.

[0038] Example 3

[0039] 150 g of C5 / C9 resin was added to 800 mL of tetrahydrofuran solution and stirred until completely dissolved, then transferred to a high-pressure reactor. 1.2 g of nickel catalyst was added, hydrogen was charged to purge the air, the hydrogen pressure was raised to 10 MPa, and the temperature was raised to 240 °C for reaction for 2.5 hours. The supernatant was taken out to obtain partially hydrogenated C5 / C9 hydrogenated resin, and the hydrogenation degree was measured to be 65-75%. The supernatant was transferred to a flask, 11 g of m-chloroperoxybenzoic acid was dissolved in 44 mL of tetrahydrofuran solution, added to the supernatant, and then the temperature was raised to 30 °C for reaction for 3 hours. After the reaction, methanol was added to the solution, and the product precipitated out. Then the precipitate was dried to constant weight to obtain modified C5 / C9 resin. The epoxy degree of the modified petroleum resin was 25-35%, Tg = 45-55 °C, and the aromaticity was 25-30%.

[0040] Example 4

[0041] 150 g of C5 / C9 resin was added to 800 mL of tetrahydrofuran solution and stirred until completely dissolved, then transferred to a high-pressure reactor. 1.5 g of nickel catalyst was added, hydrogen was charged to purge the air, the hydrogen pressure was raised to 10 MPa, and the temperature was raised to 240 °C for reaction for 4 hours. The supernatant was taken out to obtain partially hydrogenated C5 / C9 hydrogenated resin, and the hydrogenation degree was measured to be 85-95%. The supernatant was transferred to a flask, 3.5 g of m-chloroperoxybenzoic acid was dissolved in 14 mL of tetrahydrofuran solution, added to the supernatant, and then the temperature was raised to 30 °C for reaction for 3 hours. After the reaction, methanol was added to the solution, and the product precipitated out. Then the precipitate was dried to constant weight to obtain modified C5 / C9 resin. The epoxy degree of the modified petroleum resin was 5-10%, Tg = 40-50 °C, and the aromaticity was 25-30%.

[0042] Example 5

[0043] 150 g of C9 resin was added to 800 mL of tetrahydrofuran solution and stirred until completely dissolved, then transferred to a high-pressure reactor. 1.2 g of nickel catalyst was added, hydrogen was charged to purge the air, the hydrogen pressure was raised to 10 MPa, and the temperature was raised to 240 °C for reaction for 2.5 hours. The supernatant was taken out to obtain partially hydrogenated C9 hydrogenated resin, and the hydrogenation degree was measured to be 65-75%. The supernatant was transferred to a flask, 10 g of m-chloroperoxybenzoic acid was dissolved in 40 mL of tetrahydrofuran solution, added to the supernatant, and then the temperature was raised to 30 °C for reaction for 3 hours. After the reaction, methanol was added to the solution, and the product precipitated out. Then the precipitate was dried to constant weight to obtain modified C9 resin. The epoxy degree of the modified petroleum resin was 25-35%, Tg = 45-55 °C, and the aromaticity was 55-65%.

[0044] Example 6

[0045] 150 g of DCPD resin was added to 800 mL of tetrahydrofuran solution and stirred until completely dissolved, then transferred to a high-pressure reactor. 1.2 g of nickel catalyst was added, hydrogen was charged to displace air, the hydrogen pressure was raised to 10 MPa, the temperature was raised to 240 °C and reacted for 2.5 hours. The supernatant was taken out to obtain partially hydrogenated hydrogenated DCPD resin, and the hydrogenation degree was measured to be 65 - 75%. The supernatant was transferred to a flask. 16 g of m-chloroperoxybenzoic acid was dissolved in 64 mL of tetrahydrofuran solution and added to the supernatant, then the temperature was raised to 30 °C and reacted for 3 hours. After the reaction, methanol was added to the solution, and the product precipitated out. Then the precipitate was dried to constant weight to obtain modified DCPD resin. The epoxy degree of the modified petroleum resin was 25 - 35%, Tg = 45 - 55 °C, and the aromaticity was 10 - 15%.

[0046] Example 7

[0047] 150 g of terpene resin was added to 800 mL of tetrahydrofuran solution and stirred until completely dissolved, then transferred to a high-pressure reactor. 1.2 g of nickel catalyst was added, hydrogen was charged to displace air, the hydrogen pressure was raised to 10 MPa, the temperature was raised to 240 °C and reacted for 2.5 hours. The supernatant was taken out to obtain partially hydrogenated hydrogenated terpene resin, and the hydrogenation degree was measured to be 65 - 75%. The supernatant was transferred to a flask. 30 g of m-chloroperoxybenzoic acid was dissolved in 120 mL of tetrahydrofuran solution and added to the supernatant, then the temperature was raised to 30 °C and reacted for 3 hours. After the reaction, methanol was added to the solution, and the product precipitated out. Then the precipitate was dried to constant weight to obtain modified terpene resin. The epoxy degree of the modified petroleum resin was 25 - 35%, Tg = 45 - 55 °C, and the aromaticity was 60 - 70%.

[0048] Example 8

[0049] This example is used to illustrate that the rubber material for automobile tires is prepared by mixing and vulcanization, and the specific mass parts of the components in the rubber material of this example are as follows:

[0050]

[0051] Among them, the modified C5 / C9 resin was prepared in Example 2, with a hydrogenation degree of 15%, an epoxy degree of 85%, and an aromaticity of 28%.

[0052] The specific preparation process is as follows:

[0053] Set the temperature of the HAAKE mixer to 60 °C and the rotational speed to 60 revolutions per minute. Add solution styrene-butadiene rubber and natural rubber. After plasticizing for 1 min, add the modified C5 / C9 resin. After the torque increases, add zinc oxide and stearic acid and mix for 1 min. Then add the antioxidant and paraffin wax and mix for 2 min. After that, add the reinforcing filler, plasticizer, and coupling agent in two portions. Then raise the temperature of the mixer to 150 °C and heat-treat the mixed rubber for 5 min. After heat treatment, wait for the blend sample to cool, place it on a two-roll mill, pass the blend through the rolls and mix three times, then add sulfur and accelerator, make three triangular bales and three rolls respectively to disperse the vulcanizing agent and accelerator evenly, and finally sheet out.

[0054] The performance test data of the rubber material prepared in this example are shown in Table 1 in detail.

[0055] Example 9

[0056] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanization. The specific mass parts of each component in the rubber material prepared in this example are as follows:

[0057]

[0058] Among them, the modified C5 / C9 resin is prepared from Example 1, with a hydrogenation degree of 50%, an epoxy degree of 50%, and an aromaticity of 28%.

[0059] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 1 in detail.

[0060] Example 10

[0061] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanization. The specific mass parts of each component in the rubber material prepared in this example are as follows:

[0062]

[0063]

[0064] Among them, the modified C5 / C9 resin is prepared from Example 3, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity of 28%.

[0065] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 1 in detail.

[0066] Example 11

[0067] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanization. The specific mass parts of each component in the rubber material prepared in this example are as follows:

[0068]

[0069]

[0070] Among them, the modified C5 / C9 resin is prepared in Example 4, with a hydrogenation degree of 90%, an epoxy degree of 10%, and an aromaticity of 28%.

[0071] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 1 for details.

[0072] Comparative Example 1

[0073] In this comparative example, the modified petroleum resin is not added to the components for preparing the rubber material. The specific mass parts of other components are as follows:

[0074]

[0075]

[0076] The preparation process of the rubber material in this comparative example is the same as that in Example 8. The performance test data of the rubber material prepared in this comparative example are shown in Table 1 for details.

[0077] Comparative Example 2

[0078] In this comparative example, the petroleum resin is added to the components for preparing the rubber material. The specific mass parts of other components are as follows:

[0079]

[0080] The preparation process of the rubber material in this comparative example is the same as that in Example 8. The performance test data of the rubber material prepared in this comparative example are shown in Table 1 for details.

[0081] Comparative Example 3

[0082] In this comparative example, the hydrogenated petroleum resin is added to the components for preparing the rubber material. The specific mass parts of other components are as follows:

[0083]

[0084] The preparation process of the rubber material in this comparative example is the same as that in Example 8. The performance test data of the rubber material prepared in this comparative example are shown in Table 1 for details.

[0085] Example 12

[0086] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanizing, and the specific mass parts of the components in preparing the rubber material in this example are as follows:

[0087]

[0088]

[0089] Among them, the modified C9 resin is prepared in Example 5, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity degree of 60%

[0090] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 2 for details.

[0091] Example 13

[0092] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanization. The specific mass parts of each component in the rubber material prepared in this example are as follows:

[0093]

[0094]

[0095] Among them, the modified DCPD resin is prepared in Example 6, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity degree of 12%.

[0096] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 2 for details.

[0097] Example 14

[0098] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanization. The specific mass parts of each component in the rubber material prepared in this example are as follows:

[0099]

[0100]

[0101] Among them, the modified terpene resin is prepared in Example 7, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity degree of 65%

[0102] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 2 for details.

[0103] Example 15

[0104] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanization. The specific mass parts of each component in the rubber material prepared in this example are as follows:

[0105]

[0106] Among them, the modified C5 / C9 resin is prepared in Example 3, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity of 28%.

[0107] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 2 for details.

[0108] Example 16

[0109] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanizing, and the mass parts of the components in the rubber material prepared in this example are specifically as follows:

[0110]

[0111] Among them, the modified C5 / C9 resin is prepared in Example 3, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity of 28%

[0112] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 2 for details.

[0113] Example 17

[0114] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanizing, and the mass parts of the components in the rubber material prepared in this example are specifically as follows:

[0115]

[0116] Among them, the modified C5 / C9 resin is prepared in Example 3, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity of 28%; the modified C9 resin is prepared in Example 5, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity of 60%;

[0117] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 2 for details.

[0118] Example 18

[0119] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanizing, and the mass parts of the components in the rubber material prepared in this example are specifically as follows:

[0120]

[0121] Among them, the modified C5 / C9 resin is prepared in Example 3, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity of 28%. The modified DCPD resin is prepared in Example 6, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity of 12%.

[0122] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 2 for details.

[0123] Example 19

[0124] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanization. The specific mass parts of each component in the preparation of the rubber material in this example are as follows:

[0125]

[0126]

[0127] Among them, the modified C5 / C9 resin is prepared in Example 3, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity of 28%. The modified terpene resin is prepared in Example 7, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity of 65%.

[0128] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 2 for details.

[0129] Example 20

[0130] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanization. The specific mass parts of each component in the preparation of the rubber material in this example are as follows:

[0131]

[0132]

[0133] Among them, the modified C5 / C9 resin is prepared in Example 3, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity of 28%.

[0134] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 2 for details.

[0135] Example 21

[0136] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanization. The specific mass parts of each component in the preparation of the rubber material in this example are as follows:

[0137]

[0138]

[0139] Among them, the modified C5 / C9 resin is prepared in Example 3, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity of 28%.

[0140] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 2 for details.

[0141] Example 22

[0142] This example is used to illustrate that the rubber material for automobile tires is obtained by mixing and vulcanization. The specific mass parts of each component in the preparation of the rubber material in this example are as follows:

[0143]

[0144]

[0145] Among them, the modified C5 / C9 resin is prepared in Example 3, with a hydrogenation degree of 70%, an epoxy degree of 30%, and an aromaticity of 28%.

[0146] The preparation process of the rubber material in this example is the same as that in Example 8. The performance test data of the rubber material prepared in this example are shown in Table 2 for details.

[0147] Table 1 and Table 2 are the performance test data of the prepared rubber materials. Among them, the tensile property and tear strength of the vulcanizate are tested according to ASTM D412 and ASTM D624 respectively. The Akron abrasion is tested according to the national standard GB / T1689 - 1998.

[0148] Specifically, the performance test data of the rubber materials prepared in Comparative Examples 1 - 3 and Examples 8 - 11 are shown in Table 1 below.

[0149] Table 1

[0150]

[0151] The performance test data of the rubber materials prepared in Examples 12 - 22 are shown in Table 2 below.

[0152] Table 2

[0153]

[0154] Based on the above analysis, the resin has a relatively small molecular weight (the molecular weight of the resin in the present invention is approximately 500 - 1500), which can play a plasticizing role in rubber and can play a role similar to that of rubber processing oil. However, compared with rubber processing oil, the resin can improve rubber vulcanization, increase the crosslinking density of rubber, and improve the mechanical properties of rubber; in addition, the molecular weight of the resin is higher than that of rubber, and adding it to rubber can increase the glass transition temperature of rubber and regulate the dynamic properties of rubber.

[0155] Specifically, from Comparative Examples 1 and 2, it can be seen that after adding resin to replace aromatic oil, the mechanical properties increase, and the 100% and 300% modulus increase, indicating an increase in the degree of vulcanization; at the same time, it can also increase the glass transition temperature of rubber, physical and mechanical properties, and wet skid resistance; from Comparative Examples 2 and 3, it can be seen that hydrogenated resin can improve the compatibility with rubber, and the mechanical strength, wet skid resistance, and rolling resistance of rubber are further improved compared to the added resin.

[0156] From Comparative Example 3 and Examples 8 - 11, it can be seen that when the modified resin of the present invention is used, the properties of the rubber compound can be further improved. And when the Tanδ at 60°C changes little, the Tanδ at 0°C is further increased, indicating that under the condition of little change in rolling resistance, the wet skid resistance is further improved. This is attributed to the fact that the hydrogenated epoxide of the resin can increase the interaction between the resin and silica, improve the dispersion of silica in rubber, and further improve the mechanical properties and dynamic properties of the rubber compound.

[0157] Furthermore, from Examples 8 - 11, it can be seen that the introduction of epoxy groups needs to be maintained at an appropriate ratio. If too many epoxy groups are introduced (Example 8), it will lead to poor compatibility between the resin and rubber, which is not conducive to improving the properties of rubber; if too few epoxy groups are introduced (Example 11), the effect will not be obvious and it cannot play a role in improving the dispersion of silica; from Example 10, it can be seen that when the hydrogenation degree of the modified resin is 70% and the epoxy degree is 30%, the compatibility and the role of dispersing silica can be better balanced, and the physical and mechanical properties and dynamic properties of the rubber compound are more excellent.

[0158] Furthermore, from Example 10 and Examples 15 and 16, it can be seen that the dosage of the modified resin also affects the properties of rubber. As the dosage of the added modified resin increases, the Tanδ at 0°C increases significantly when the Tanδ at 60°C changes little, which indicates that under the condition of little change in rolling resistance, the wet skid resistance can be improved significantly; however, the increase in the dosage of the modified resin will lead to a decrease in the mechanical properties of rubber, indicating that the modified resin plays a plasticizing role, and as the plasticizing fraction increases, the mechanical properties of rubber decrease. Under the action of the same plasticizing fraction, the mechanical properties of the rubber compound added with resin are better than those added with rubber processing oil.

[0159] Example 10 and Examples 20 to 22 reflect the influence of the rubber compound ratio and the amount of silica on the properties of rubber. After the amount of silica increases, the mechanical properties of the rubber increase, while the dynamic properties decrease to a certain extent. As the amount of natural rubber increases, the mechanical properties of the rubber are less affected, and the wet skid resistance in terms of dynamic properties is significantly affected. As the amount of natural rubber increases, the Tanδ at 0°C shows a downward trend. This is mainly because the wet skid resistance of natural rubber itself is poorer than that of solution-polymerized styrene-butadiene rubber, but the addition of natural rubber can improve the processing performance of the rubber. During the processing of pure styrene-butadiene rubber, problems such as fragmentation and difficulty in feeding easily occur.

[0160] It can be seen from Examples 12 to 14 and Examples 17 to 19 that different resins have different tendencies to adjust the properties of rubber, and the properties of the rubber compound can be adjusted within a wider range by using a blending method to meet the actual requirements.

Claims

1. A rubber material for automobile tires, characterized in that, the rubber material is prepared from raw materials including the following components: solution-polymerized styrene-butadiene rubber, natural rubber, modified petroleum resin, sulfur, activator, reinforcing filler, plasticizer; Based on the total weight of solution-polymerized styrene-butadiene rubber and natural rubber being 100 parts by weight, the weight parts of each component are, solution-polymerized styrene-butadiene rubber 60 - 100 parts by weight; natural rubber 0 - 40 parts by weight; modified petroleum resin 1 - 30 parts by weight; sulfur 1 - 3 parts by weight; activator 4 - 9 parts by weight; reinforcing filler 50 - 175 parts by weight; plasticizer 5 - 25 parts by weight; wherein, the modified petroleum resin is a hydrogenated epoxy compound of petroleum resin.

2. The rubber material for automobile tires according to claim 1, characterized in that, the epoxy degree of the modified petroleum resin is 5 - 90%, and the hydrogenation degree is 10 - 95%.

3. The rubber material for automobile tires according to claim 1, characterized in that, the glass transition temperature of the modified petroleum resin is 30 - 100 °C, and the aromaticity is 10 - 70%.

4. The rubber material for automobile tires according to claim 3, characterized in that, the glass transition temperature of the modified petroleum resin is 30 - 60 °C, and the aromaticity is 20 - 30%.

5. The rubber material for automobile tires according to claim 1, characterized in that, the petroleum resin includes one or a combination of C9 resin, C5 / C9 copolymer resin, DCPD resin, and terpene resin.

6. The rubber material for automobile tires according to claim 1, characterized in that, Based on the total weight of solution-polymerized styrene-butadiene rubber and natural rubber being 100 parts by weight, the weight parts of each component are, solution-polymerized styrene-butadiene rubber 80 - 100 parts by weight; natural rubber 0 - 20 parts by weight; modified petroleum resin 10 - 20 parts by weight; sulfur 1 - 2 parts by weight; activator 4 - 7 parts by weight; reinforcing filler 60 - 100 parts by weight; plasticizer 5 - 15 parts by weight.

7. The rubber material for automobile tires according to claim 1, characterized in that, the activator is zinc oxide and stearic acid; and / or, the reinforcing filler is silica, or silica and carbon black; and / or the plasticizer is aromatic oil.

8. The rubber material for automobile tires according to claim 1, characterized in that, the rubber material further includes anti-aging agent, accelerator, and silane coupling agent; the weight parts of each component are, anti-aging agent 2 - 8 parts by weight; accelerator 2 - 7 parts by weight; silane coupling agent 3 - 10 parts by weight.

9. The rubber material for automobile tires according to any one of claims 1 - 8, characterized in that, the preparation method of the modified petroleum resin includes the following steps: (1) Dissolve the petroleum resin in an organic solvent, and under the action of a catalyst, carry out a hydrogenation reaction to obtain a hydrogenated petroleum resin solution in which some carbon-carbon double bonds are hydrogenated; (2) Add an epoxidizing reagent to the hydrogenated petroleum resin solution, and carry out an epoxidation reaction to obtain a modified petroleum resin in which some carbon-carbon double bonds are epoxidized.

10. The rubber material for automobile tires according to claim 9, characterized in that, in the step (1), The catalyst for the hydrogenation reaction is a nickel catalyst, and the dosage of the nickel catalyst is 0.5% to 1.5% of the mass of the petroleum resin; The hydrogen pressure for the hydrogenation reaction is 10 to 15 Mpa, the hydrogenation reaction temperature is 220 to 300 °C, and the hydrogenation reaction time is 1 to 6 h; In the step (2), The epoxidizing agent is m-chloroperoxybenzoic acid, and the molar ratio of m-chloroperoxybenzoic acid to the double bond in the hydrogenated petroleum resin is 1:0.5 to 1:1.5; The temperature for the epoxidation reaction is 20 to 60 °C, and the epoxidation reaction time is 2 to 5 h.

11. A preparation method of a rubber material for automobile tires according to any one of claims 1 to 10, characterized in that the method comprises: The components are mixed and vulcanized according to the dosages to obtain the rubber material for automobile tires.

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