A high-cutting-resistant rubber composite material and its preparation method and application

Abstract

A highly cut-resistant rubber composite material and its preparation method and application. The present invention belongs to the field of rubber materials and their preparation. The purpose of the present invention is to solve the technical problem that the existing modified composite rubber has low cut resistance. The material of the present invention is prepared from olefin rubber, reinforcing filler, zinc oxide, stearic acid, plasticizer, coupling agent, sulfur, accelerator and antioxidant. The olefin rubber is a mixture of butadiene rubber, styrene-butadiene rubber and iron-based butadiene-elastomer rubber. The molecular weight of the iron-based butadiene-elastomer rubber is 60 to 200w, and the sum of the vinyl and propylene side group contents is 10 to 40%. The material of the present invention is used as tire tread rubber. The present invention effectively improves the cut resistance of the rubber material by introducing iron-based butadiene-elastomer rubber with ultra-high molecular weight and specific side group ratio into the rubber system.

Description

Technical Field

[0001] The invention belongs to the field of rubber materials and preparation thereof, and particularly relates to a high-cutting-resistant rubber composite material and a preparation method and application thereof. Background Art

[0002] In recent years, my country's rubber consumption has been the largest in the world, resulting in a shortage of natural rubber resources. Therefore, vigorously developing synthetic rubber has become a better choice to solve the problem of insufficient supply of natural rubber in my country. With the large-scale development of ethylene engineering, a large amount of C5 fractions have been accumulated. In order to make full use of these C5 resources, using them to synthesize polyisoprene synthetic rubber has become a better choice. It not only effectively utilizes C5 resources, but also provides the necessary conditions for synthesizing polyisoprene synthetic rubber.

[0003] Butadiene rubber has good flexibility and good processing performance, but its cut resistance is relatively poor. Butadiene rubber can be used as a rubber modifier to improve the compression heat generation, mechanical properties and anti-slip properties of rubber materials. However, the cut resistance of existing composite rubbers is still poor. Therefore, it is of great significance to design a rubber composite material with high cut resistance and excellent comprehensive performance. Summary of the invention

[0004] The purpose of the present invention is to solve the technical problem that the existing modified composite rubber has low cutting resistance, and to provide a high-cutting-resistant rubber composite material and a preparation method and application thereof.

[0005] The high-cutting-resistant rubber composite material of the present invention is prepared from the following components in parts by weight:

[0006] 100 parts of olefin rubber;

[0007] 20 to 90 parts of reinforcing filler;

[0008] 1-5 parts of zinc oxide;

[0009] 0.5-5 parts of stearic acid;

[0010] 5-70 parts of plasticizer;

[0011] 1-5 parts of sulfur;

[0012] 1 to 5 parts of accelerator;

[0013] 1 to 5 parts of antioxidant;

[0014] The olefin rubber is mixed by weight of 0-30 parts of cis-1,4-butadiene rubber, 0-70 parts of styrene-butadiene rubber, and 5-30 parts of ferro-1,4-butadiene rubber, wherein the parts of cis-1,4-butadiene rubber and styrene-butadiene rubber cannot be 0 at the same time, the molecular weight of the ferro-1,4-butadiene rubber is 60-200w, and the sum of the contents of vinyl and propylene side groups is 10-40%.

[0015] It is further defined that the iron-based butadiene-pentadiene rubber is composed of butadiene structural units and isoprene structural units, wherein the molar content of the isoprene structural units is 20-50%, and the molar content of the butadiene structural units is 50-80%.

[0016] It is further defined that the molar content of 1,2-butadiene in the butadiene structural unit is 10-40%, the molar content of 1,4-butadiene is 60-90%, and the molar content of 3,4-isoprene in the isoprene structural unit is 10-40%, the molar content of 1,4-isoprene is 60-90%.

[0017] It is further defined that the glass transition temperature of the iron-based butadiene-pentadiene rubber is -45 to -15°C.

[0018] It is further defined that the reinforcing filler is one of carbon black and white carbon black or a mixture of the two in any ratio.

[0019] It is further defined that the carbon black is one or a mixture of any proportions of contact carbon black, furnace carbon black, thermal carbon black and new process carbon black.

[0020] It is further defined that the plasticizer is one or a mixture of any ratio of aromatic oil, cyclohexane oil, paraffin oil, coal tar and naphtha.

[0021] It is further defined that the accelerator is one or a mixture of any ratio of sulfonamide, thiazole, thiuram, thiourea, dithiocarbamate, aldehyde amine, guanidine and xanthate accelerators.

[0022] It is further defined that the antioxidant is one or a mixture of any proportion of quinolines, p-phenylenediamines, naphthylamines, aromatic amines, amines, phenols, and aromatic amines.

[0023] The preparation method of a high-cutting-resistant rubber composite material of the present invention is carried out according to the following steps:

[0024] Step 1: Add olefin rubber to an internal mixer for mixing, mix at 120-135° C. for 180-240 seconds, let stand for more than 4 hours, then add reinforcing filler, zinc oxide, stearic acid, plasticizer, coupling agent and antioxidant, mix at 135-150° C. for 240-300 seconds to obtain a mixed rubber;

[0025] Step 2: Add sulfur and accelerator to the mixed rubber and continue mixing to obtain a high-cutting-resistant rubber composite material.

[0026] The high-cutting-resistant rubber composite material of the invention is used for preparing tire treads.

[0027] Compared with the prior art, the present invention has the following significant effects:

[0028] 1) The present invention introduces iron-based butadiene-vinyl rubber into the rubber composite material to replace part of the styrene-butadiene rubber. The ultra-high molecular weight iron-based butadiene-vinyl rubber has a large intermolecular force and can form physical entanglements with other synthetic rubber molecular chains. At the same time, the design of the 10-40% side group content of the present invention makes it difficult for the molecular chains to slip, has a good ability to resist deformation due to external forces, and effectively improves the tensile tearing performance and wear resistance of the rubber material and the cutting resistance of the rubber.

[0029] 2) The present invention improves the rigidity of the molecular chain by utilizing a large number of side methyl groups in the iron-based butadiene-pentadiene rubber with a high 1,4-isoprene molar content in the rubber composite material, and the high steric hindrance can limit the movement of the molecular chain, thereby further improving the hardness and rigidity of the material, thereby further improving the anti-cutting performance of the rubber.

[0030] 3) The molecular chain of iron-based butyl rubber also contains a part of 1,4-butadiene chain segments, which have a high structural similarity with the butadiene structural unit in cis-1,4-butadiene rubber. This makes the surface energy of iron-based catalyzed butyl rubber closer to that of other synthetic rubbers. Therefore, during the mixing process, it has good compatibility with other synthetic rubbers and is easy to mix and process with other synthetic rubbers, with obvious synergistic effect. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0032] The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and instruments used are conventional materials, reagents, methods and instruments in the art unless otherwise specified, and can be obtained through commercial channels by those skilled in the art.

[0033] The terms "comprising," "including," "having," "containing," or any other variations thereof, as used in the following examples, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus comprising the listed elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.

[0034] The "one embodiment" or "embodiment" referred to in the following embodiments refers to a specific feature, structure or characteristic that can be included in at least one implementation of the present invention. The "in one embodiment" that appears in different places in this specification does not refer to the same embodiment, nor is it a separate or selective embodiment that is mutually exclusive with other embodiments.

[0035] When equivalent, concentration or other value or parameter is represented by the range limited by range, preferred range or a series of upper preferred value and lower preferred value, this should be understood as specifically disclosing all ranges formed by any pairing of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether the scope is disclosed separately. For example, when disclosing range "1 to 5", described range should be interpreted as including range "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5" etc. When numerical range is described in this article, unless otherwise stated, the scope is intended to include its end value and all integers and fractions within the scope. In the present application specification and claims, range limitation can be combined and / or interchanged, if these ranges are not otherwise stated, include all sub-ranges contained therein.

[0036] The indefinite articles "a" and "an" before the elements or components of the present invention have no limitation on the quantity requirements (i.e. the number of occurrences) of the elements or components. Therefore, "a" or "an" should be interpreted as including one or at least one, and the elements or components in the singular form also include the plural form, unless the quantity obviously refers to the singular form only.

[0037] Example 1: The formula of the high-cutting-resistant rubber composite material of this example is shown in Table 1, and the performance test results are shown in Table 2;

[0038] Among them, the molecular weight of iron-based butyl-pentyl rubber is 81w, the glass transition temperature is -21°C, and the sum of the vinyl and propylene side group contents is 30%;

[0039] During the preparation process, the molar ratio of monomers butadiene to isoprene is 6:4, the molar content of 1,2-butadiene in the butadiene structural unit is 30%, the sum of the molar contents of cis-1,4-butadiene and trans-1,4-butadiene is 70%, the molar content of 3,4-isoprene in the isoprene structural unit is 30%, and the sum of the molar contents of cis-1,4-isoprene and trans-1,4-isoprene is 70%.

[0040] The preparation method of the highly cut-resistant rubber composite material is carried out according to the following steps:

[0041] Step 1, adding butadiene rubber 9000, styrene butadiene rubber SSBR4630, and iron-based butadiene rubber to an internal mixer, with a filling factor of 0.7, mixing at 130° C. for 190 seconds, standing for more than 4 hours, and then adding carbon black N234, zinc oxide, stearic acid, antioxidant TMQ and naphthenic oil, with a filling factor of 0.7, mixing at 135° C. for 240 seconds to obtain a mixed rubber;

[0042] Step 2: Add sulfur and accelerator CZ to the mixed rubber and continue mixing to obtain a high-cutting-resistant rubber composite material.

[0043] Example 2: The formula of the high-cutting-resistant rubber composite material of this example is shown in Table 1, and the performance test results are shown in Table 2;

[0044] Among them, the molecular weight of the iron-based butyl-pentane rubber is 85w, the glass transition temperature is -20°C, and the sum of the vinyl and propylene side group contents is 30%;

[0045] During the preparation process, the molar ratio of monomers butadiene to isoprene is 7:3, the molar content of 1,2-butadiene in the butadiene structural unit is 30%, the sum of the molar contents of cis-1,4-butadiene and trans-1,4-butadiene is 70%, the molar content of 3,4-isoprene in the isoprene structural unit is 30%, and the sum of the molar contents of cis-1,4-isoprene and trans-1,4-isoprene is 70%.

[0046] The preparation method of the highly cut-resistant rubber composite material is carried out according to the following steps:

[0047] Step 1, adding butadiene rubber 9000, styrene butadiene rubber SSBR4630, and iron-based butadiene rubber to an internal mixer, with a filling factor of 0.7, mixing at 130° C. for 190 seconds, standing for more than 4 hours, and then adding carbon black N234, zinc oxide, stearic acid, antioxidant TMQ and naphthenic oil, with a filling factor of 0.7, mixing at 135° C. for 240 seconds to obtain a mixed rubber;

[0048] Step 2: Add sulfur and accelerator CZ to the mixed rubber and continue mixing to obtain a high-cutting-resistant rubber composite material.

[0049] Example 3: The formula of the high-cutting-resistant rubber composite material of this example is shown in Table 1, and the performance test results are shown in Table 2;

[0050] Among them, the molecular weight of iron-based butyl-pentane rubber is 88w, the glass transition temperature is -16°C, and the sum of the vinyl and propylene side group contents is 35%;

[0051] During the preparation process, the molar ratio of monomers butadiene to isoprene is 1:1, the molar content of 1,2-butadiene in the butadiene structural unit is 40%, the sum of the molar contents of cis-1,4-butadiene and trans-1,4-butadiene is 60%, the molar content of 3,4-isoprene in the isoprene structural unit is 30%, and the sum of the molar contents of cis-1,4-isoprene and trans-1,4-isoprene is 70%.

[0052] The preparation method of the highly cut-resistant rubber composite material is carried out according to the following steps:

[0053] Step 1, adding butadiene rubber 9000, styrene butadiene rubber SSBR4630, and iron-based butadiene rubber to an internal mixer, with a filling factor of 0.7, mixing at 130° C. for 190 seconds, standing for more than 4 hours, and then adding carbon black N234, zinc oxide, stearic acid, antioxidant TMQ and naphthenic oil, with a filling factor of 0.7, mixing at 135° C. for 240 seconds to obtain a mixed rubber;

[0054] Step 2: Add sulfur and accelerator CZ to the mixed rubber and continue mixing to obtain a high-cutting-resistant rubber composite material.

[0055] Example 4: The formula of the high-cutting-resistant rubber composite material of this example is shown in Table 1, and the performance test results are shown in Table 2;

[0056] Among them, the molecular weight of the iron-based butyl-pentyl rubber is: 98w, the glass transition temperature is -19°C, and the sum of the vinyl and propylene side group contents is 30%;

[0057] During the preparation process, the molar ratio of monomers butadiene to isoprene is 8:2, the molar content of 1,2-butadiene in the butadiene structural unit is 30%, the sum of the molar contents of cis-1,4-butadiene and trans-1,4-butadiene is 70%, the molar content of 3,4-isoprene in the isoprene structural unit is 30%, and the sum of the molar contents of cis-1,4-isoprene and trans-1,4-isoprene is 70%.

[0058] The preparation method of the highly cut-resistant rubber composite material is carried out according to the following steps:

[0059] Step 1, adding butadiene rubber 9000, styrene butadiene rubber SSBR4630, and iron-based butadiene rubber to an internal mixer, with a filling factor of 0.7, mixing at 130° C. for 190 seconds, standing for more than 4 hours, and then adding carbon black N234, zinc oxide, stearic acid, antioxidant TMQ and naphthenic oil, with a filling factor of 0.7, mixing at 135° C. for 240 seconds to obtain a mixed rubber;

[0060] Step 2: Add sulfur and accelerator CZ to the mixed rubber and continue mixing to obtain a high-cutting-resistant rubber composite material.

[0061] Comparative Example 1: The difference between this comparative example and Example 1 is that no iron-based butyl-pentene rubber is added. Other materials and preparation methods are the same as those of Example 1, and the specific formula is shown in Table 1.

[0062] Comparative Example 2: The difference between this comparative example and Example 2 is that the molecular weight of the iron-based butadiene-vinyl rubber is 98w, and the molar ratio of the monomers butadiene and isoprene in the preparation process is 3:7. Other parameters and preparation methods are the same as those in Example 2, and the specific formula is shown in Table 1.

[0063] Comparative Example 3: The difference between this comparative example and Example 2 is that the molecular weight of the iron-based butadiene-vinyl rubber is 25w, the glass transition temperature is -16°C, and the sum of the vinyl and propylene side group contents is 40%; the molar ratio of the monomers butadiene and isoprene during the preparation process is 8 / 2, the molar content of 1,2-butadiene in the butadiene structural unit is 40%, the sum of the molar contents of cis-1,4-butadiene and trans-1,4-butadiene is 60%, the molar content of 3,4-isoprene in the isoprene structural unit is 40%, and the sum of the molar contents of cis-1,4-isoprene and trans-1,4-isoprene is 60%. Other parameters and preparation methods are the same as those in Example 2, and the specific formula is shown in Table 1.

[0064] Table 1 Formulation of rubber composite materials

[0065] formula Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Butadiene rubber 9000 30 30 30 30 30 30 30 Styrene butadiene rubber SSBR4630 65 60 55 45 70 60 60 Iron-based NBR 5 10 15 20 0 10 10 Carbon Black N234 50 50 50 50 50 50 50 sulfur 1.3 1.3 1.3 1.3 1.3 1.3 1.3 Accelerator TBBS 1.35 1.35 1.35 1.35 1.35 1.35 1.35 Zinc Oxide 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Stearic acid 2 2 2 2 2 2 2 Antioxidant TMQ 1 1 1 1 1 1 1 Naphthenic Oil 10 10 10 10 10 10 10

[0066] Table 2 Properties of rubber composite materials

[0067]

[0068]

[0069] It can be seen from Examples 1 to 4 that as the content of iron-based catalyzed butadiene-pentadiene rubber in the formula increases, the tensile strength and tear strength are improved, and the wear resistance and cut resistance are improved. After adding 20 parts of ultra-high molecular weight iron-based catalyzed butadiene-pentadiene rubber, the Mooney viscosity increases to 82.3.

[0070] By comparing Comparative Example 2 with Example 2, the ratio of butadiene and isoprene monomers is changed, so that the compatibility of the butyl-pentene rubber in the system of Comparative Example 2 with the butadiene rubber and the styrene-butadiene rubber is poor, which reduces the mechanical properties and cut resistance of the material.

[0071] By comparing Comparative Example 3 with Example 2, the reasonable structural design of the iron-based butadiene-pentadiene rubber of the present invention can effectively improve the tensile strength, tear strength, wear resistance and cut resistance of the rubber composite material.

[0072] The above are only preferred specific embodiments of the present invention, which are all different implementations based on the overall concept of the present invention, and the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A highly cut-resistant rubber composite material, characterized in that: It is prepared from the following components by weight: 100 parts of olefin rubber; 20 to 90 parts of reinforcing filler; 1-5 parts of zinc oxide; 0.5-5 parts of stearic acid; 5-70 parts of plasticizer; 1-5 parts of sulfur; 1 to 5 parts of accelerator; 1 to 5 parts of antioxidant; The olefin rubber is mixed by weight of 0-30 parts of cis-1,4-butadiene rubber, 0-70 parts of styrene-butadiene rubber, and 5-30 parts of ferro-1,4-butadiene rubber, wherein the parts of cis-1,4-butadiene rubber and styrene-butadiene rubber cannot be 0 at the same time, the molecular weight of the ferro-1,4-butadiene rubber is 60-200w, and the sum of the ethylene and propylene side group contents is 10-40%; The iron-based butadiene-vinyl rubber is composed of butadiene structural units and isoprene structural units, wherein the molar content of the isoprene structural units is 20-50%, the molar content of the butadiene structural units is 50-80%, the molar content of 1,2-butadiene in the butadiene structural units is 10-40%, the molar content of 1,4-butadiene is 60-90%, the molar content of 3,4-isoprene in the isoprene structural units is 10-40%, and the molar content of 1,4-isoprene is 60-90%.

2. The highly cut-resistant rubber composite material according to claim 1, characterized in that: The glass transition temperature of iron-based butadiene-pentadiene rubber is -45 to -15°C.

3. The highly cut-resistant rubber composite material according to claim 1, characterized in that: The reinforcing filler is carbon black, white carbon black or a mixture of the two.

4. The highly cut-resistant rubber composite material according to claim 3, characterized in that: The carbon black is one or a mixture of contact carbon black, furnace carbon black, thermal carbon black and new process carbon black.

5. The highly cut-resistant rubber composite material according to claim 3, characterized in that: White carbon black is one or a mixture of fumed white carbon black and precipitated white carbon black.

6. The highly cut-resistant rubber composite material according to claim 1, characterized in that: The plasticizer is one or a mixture of aromatic oil, cyclohexane oil, paraffin oil, coal tar and naphtha; the accelerator is one or a mixture of sulfonamide, thiazole, thiuram, thiourea, dithiocarbamate, aldehyde amine, guanidine and xanthate accelerators; the antioxidant is one or a mixture of quinoline, p-phenylenediamine, naphthylamine and phenol.

7. The method for preparing the highly cut-resistant rubber composite material according to any one of claims 1 to 6, characterized in that: The method proceeds as follows: Step 1: Add olefin rubber to an internal mixer for mixing, mix at 120-135° C. for 180-240 seconds, let stand for more than 4 hours, then add reinforcing filler, zinc oxide, stearic acid, plasticizer, coupling agent and antioxidant, mix at 135-150° C. for 240-300 seconds to obtain a mixed rubber; Step 2: Add sulfur and accelerator to the mixed rubber and continue mixing to obtain a high-cutting-resistant rubber composite material.

8. The highly cut-resistant rubber composite material according to any one of claims 1 to 6 is used for preparing tire treads.

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