Thermo-oxidative aging-resistant and wear-resistant rubber composition and application thereof

Abstract

The invention provides a rubber composition, the raw materials of the rubber composition comprise 100 parts by mass of a diene elastomer, 0.5-5 parts by mass of an anti-aging agent A and 0.5-5 parts by mass of an anti-aging agent S-TMQ, and the anti-aging agent A and the anti-aging agent S-TMQ are described in the specification. The anti-aging agent A and the anti-aging agent S-TMQ are combined to serve as an anti-aging agent system of the rubber composition, and the anti-aging agent system can endow the rubber composition with excellent thermo-oxidative aging resistance and wear resistance, so that the service life of the windscreen wiper rubber strip is remarkably prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of rubber materials, and in particular relates to a heat-oxidation-resistant, aging-resistant and wear-resistant rubber composition and application thereof. Background Art

[0002] The automobile wiper drives the wiper arm and wiper rubber strip to circulate back and forth on the windshield through a motor to remove rain, snow, mud and other debris attached to the windshield, so as to ensure that the windshield has good light transmittance and ensure driving safety. The wiper rubber strip is the part that is in close contact with the windshield, and must have a series of properties such as wear resistance, small deformation, resistance to thermal oxygen aging, resistance to ozone, resistance to low temperature, and good elasticity. Because the wiper rubber strip is in a complex natural environment of sunshine, rain, high and low temperature alternation for a long time, especially in a continuous heat aging environment, the rubber strip ages very quickly. The rapid aging of the rubber strip causes the hardness, flexibility, and scraping characteristics of the rubber strip to change greatly, thereby shortening the service life of the wiper, resulting in the wiper being unable to remove rain and clean well after a short period of use, and it will also jump and produce noise, greatly affecting the wiping quality and driving safety.

[0003] Most wiper rubber strips are made of rubber products. Commonly used rubbers include one or more of natural rubber, EPDM rubber, chloroprene rubber, and silicone rubber. Among them, natural rubber is widely used because of its good mechanical strength and excellent wear resistance, but its ozone resistance, heat resistance, and chemical corrosion resistance are poor. Chloroprene rubber has high tensile strength, elongation, and reversible crystallinity, good adhesion, excellent aging resistance, heat resistance, oil resistance, and chemical corrosion resistance. Its weather resistance and ozone aging resistance are second only to EPDM rubber and butyl rubber, and its heat resistance is equivalent to that of nitrile rubber. People use natural rubber and chloroprene rubber to make wiper rubber strips, and use antioxidants such as N-isopropyl-N'-phenyl-p-phenylenediamine (4010NA) in the formula to improve the anti-aging effect. However, the rubber strips made by mixing natural rubber and chloroprene rubber still have the disadvantages of poor aging performance, poor wear resistance, and short service life. The wiper rubber strips still need to be replaced frequently to ensure good use effects. Summary of the invention

[0004] In view of the problems existing in the prior art, the present invention provides a rubber composition that can be used to prepare a wiper rubber strip. The present invention uses antioxidant A and antioxidant S-TMQ together as an antioxidant system of the rubber composition, and the antioxidant system can give the rubber composition excellent heat-oxidative aging resistance and wear resistance, thereby significantly improving the service life of the wiper rubber strip.

[0005] Specifically, one aspect of the present invention provides a rubber composition, the raw materials of the rubber composition comprising 100 parts by mass of a diene elastomer, 0.5-5 parts by mass of an antioxidant A and 0.5-5 parts by mass of an antioxidant S-TMQ;

[0006] The antioxidant A has a structure shown in Formula I:

[0007]

[0008] The antioxidant S-TMQ is a 2,2,4-trimethyl-1,2-dihydroquinoline polymer with a total mass fraction of dimers, trimers and tetramers of 2,2,4-trimethyl-1,2-dihydroquinoline being ≥80%.

[0009] In one or more embodiments, the raw material of the rubber composition further comprises 40-90 parts by mass of a reinforcing filler.

[0010] In one or more embodiments, the reinforcing filler includes carbon black and white carbon black in a mass ratio of 1:1 to 4:1.

[0011] In one or more embodiments, the diene elastomer comprises natural rubber and chloroprene rubber; preferably, the mass ratio of natural rubber to chloroprene rubber is from 3:7 to 7:3.

[0012] In one or more embodiments, the raw material of the rubber composition further includes 0.5-10 parts by mass of sulfur.

[0013] In one or more embodiments, the raw material of the rubber composition further comprises 1 to 5 parts by mass of a protective wax.

[0014] In one or more embodiments, the raw material of the rubber composition further includes 1 to 10 parts by mass of a softener.

[0015] In one or more embodiments, the softener includes naphthenic oil and stearic acid in a mass ratio of 2:1 to 10:1.

[0016] In one or more embodiments, the content of the antioxidant A in the raw materials of the rubber composition is 1-3 parts by mass.

[0017] In one or more embodiments, the content of the antioxidant S-TMQ in the raw materials of the rubber composition is 1-3 parts by mass, preferably 1-2 parts by mass.

[0018] In one or more embodiments, in the raw materials of the rubber composition, the mass ratio of the antioxidant A to the antioxidant S-TMQ is 1:3 to 3:1, preferably 1:1 to 3:1.

[0019] In one or more embodiments, the raw material of the rubber composition further comprises 5-20 parts by mass of an active agent.

[0020] In one or more embodiments, the active agent includes ZnO and MgO in a mass ratio of 1:1-3:1.

[0021] In one or more embodiments, the raw material of the rubber composition further includes 0.1-2 parts by mass of an accelerator.

[0022] In one or more embodiments, the accelerator is 2,2'-dibenzothiazole disulfide.

[0023] In one or more embodiments, the raw materials of the rubber composition include 100 parts by mass of a diene elastomer, 0.5-5 parts by mass of an antioxidant A, 0.5-5 parts by mass of an antioxidant S-TMQ, 30-60 parts by mass of carbon black, 10-30 parts by mass of white carbon, 0.5-3 parts by mass of sulfur, 2-6 parts by mass of naphthenic oil, 0.5-1.5 parts by mass of stearic acid, 1-5 parts by mass of a protective wax, 3-9 parts by mass of ZnO, 2-5 parts by mass of MgO, and 0.1-2 parts by mass of 2,2'-dithiodibenzothiazole.

[0024] Another aspect of the present invention provides a rubber product, wherein the rubber product comprises the rubber composition described in any embodiment of the present invention.

[0025] In one or more embodiments, the rubber product is a wiper rubber strip.

[0026] Another aspect of the present invention provides the use of a combination of an antioxidant A and an antioxidant S-TMQ in improving the heat-oxidative aging resistance and wear resistance of a rubber composition or a rubber product, wherein the antioxidant A has a structure shown in Formula I:

[0027]

[0028] The antioxidant S-TMQ is a 2,2,4-trimethyl-1,2-dihydroquinoline polymer with a total mass fraction of dimers, trimers and tetramers of 2,2,4-trimethyl-1,2-dihydroquinoline being ≥80%.

[0029] In one or more embodiments, the rubber product is a wiper rubber strip. DETAILED DESCRIPTION

[0030] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0031] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0032] Herein, “comprising”, “including”, “containing” and similar terms encompass the meanings of “consisting essentially of” and “consisting of”. For example, when “A comprises B and C” is disclosed herein, “A consists essentially of B and C” and “A consists of B and C” should be deemed to be disclosed herein.

[0033] Herein, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0034] In this document, unless otherwise specified, percentage refers to mass percentage and ratio refers to mass ratio.

[0035] Herein, when describing embodiments or examples, it should be understood that they are not used to limit the present invention to these embodiments or examples. On the contrary, all substitutes, improvements and equivalents of the methods and materials described in the present invention can be included in the scope limited by the claims.

[0036] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0037] The present invention finds that the use of antioxidant A and antioxidant S-TMQ as an antioxidant system in a rubber composition, especially a rubber composition for wiper rubber strips, can significantly improve the heat oxygen aging resistance and wear resistance of the rubber. Antioxidant A and antioxidant S-TMQ show an unexpected synergistic effect in improving the heat oxygen aging resistance and wear resistance of the rubber.

[0038] In the present invention, antioxidant A refers to a compound represented by formula I:

[0039]

[0040] In the present invention, the antioxidant S-TMQ refers to a 2,2,4-trimethyl-1,2-dihydroquinoline polymer having a total mass fraction of di-, tri- and tetramers of 2,2,4-trimethyl-1,2-dihydroquinoline of ≥ 80%. The 2,2,4-trimethyl-1,2-dihydroquinoline polymer (also known as antioxidant TMQ) has a structure shown in Formula II:

[0041]

[0042] In formula II, n represents the degree of polymerization.

[0043] The raw materials of the rubber composition generally include a diene elastomer, a reinforcing filler, an antioxidant and a crosslinking agent. Herein, the rubber composition includes unvulcanized rubber and vulcanized rubber. The unvulcanized rubber can be vulcanized (cured) to obtain vulcanized rubber.

[0044] The raw materials of the rubber composition of the present invention include a diene elastomer, an antioxidant A and an antioxidant S-TMQ, wherein, based on 100 parts by mass of the diene elastomer, the amount of the antioxidant A is 0.5-5 parts by mass, and the amount of the antioxidant S-TMQ is 0.5-5 parts by mass. Herein, unless otherwise specified, the mass of the diene elastomer in the raw materials of the rubber composition is taken as 100 parts by mass as a basis to calculate the mass parts of other components in the raw materials of the rubber composition.

[0045] Herein, diene elastomer refers to an elastomer whose monomers contain dienes (such as butadiene, isoprene). Suitable diene elastomers for the present invention can be various diene elastomers known in the art, including but not limited to one or more selected from natural rubber (NR), butadiene rubber (BR), isoprene rubber, styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR), isoprene / butadiene copolymer, isoprene / styrene copolymer and isoprene / butadiene / styrene copolymer. In some preferred embodiments, for example, in an embodiment where the rubber composition is a rubber composition for wiper rubber strips, the diene elastomer comprises natural rubber and chloroprene rubber, or is composed of natural rubber and chloroprene rubber. The mass ratio of natural rubber and chloroprene rubber is preferably 3:7 to 7:3, for example 3.5:6.5 to 6.5:3.5, 4:6-6:4, 1:1.

[0046] The antioxidant contained in the rubber composition of the present invention includes antioxidant A and antioxidant S-TMQ. In some embodiments, the rubber composition of the present invention does not contain other antioxidants except antioxidant A and antioxidant S-TMQ. In the raw materials of the rubber composition of the present invention, the amount of antioxidant A can be 0.5-5 mass parts, preferably 1-3 mass parts, such as 1.5 mass parts, 2 mass parts, 2.5 mass parts. In the raw materials of the rubber composition of the present invention, the amount of antioxidant S-TMQ can be 0.5-5 mass parts, preferably 1-3 mass parts, such as 1-2 mass parts, 1.5 mass parts. The mass ratio of antioxidant A and antioxidant S-TMQ can be 1:3 to 3:1, preferably 1:1 to 3:1, such as 1.3:1, 1.5:1, 1.7:1, 2:1.

[0047] The raw materials of the rubber composition of the present invention may include reinforcing fillers. In the raw materials of the rubber composition of the present invention, the amount of reinforcing fillers can be 40-90 parts by mass, such as 50 parts by mass, 55 parts by mass, 60 parts by mass, 65 parts by mass, 70 parts by mass, 75 parts by mass, and 80 parts by mass. The reinforcing filler suitable for the present invention can be a reinforcing filler conventionally used for rubber compositions, including but not limited to one or more selected from carbon black, white carbon black, titanium oxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, clay, and talc. In some preferred embodiments, the reinforcing filler comprises carbon black and white carbon black. The mass ratio of carbon black and white carbon black can be 1:1 to 4:1, such as 2:1, 2.5:1, and 3:1. In some preferred embodiments, in the raw materials of the rubber composition of the present invention, the amount of carbon black is 30-60 parts by mass, such as 35 parts by mass, 40 parts by mass, 45 parts by mass, and 55 parts by mass; the amount of white carbon black is 10-30 parts by mass, such as 15 parts by mass, 20 parts by mass, and 25 parts by mass.

[0048] The raw materials of the rubber composition of the present invention include a crosslinking agent, such as sulfur. The amount of sulfur in the raw materials of the rubber composition of the present invention can be 0.5-10 parts by mass, such as 1 part by mass, 1.5 parts by mass, 2 parts by mass, 2.5 parts by mass, 3 parts by mass, and 5 parts by mass.

[0049] The raw materials of the rubber composition of the present invention may further include other ingredients commonly used in rubber compositions, including but not limited to one or more selected from the group consisting of softeners, protective waxes, activators and accelerators.

[0050] Softener can be used to improve the processing properties of rubber composition. Softener can include petroleum softener, such as naphthenic oil, aromatic oil, process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, vaseline etc., and also can include fatty oil softener, such as stearic acid, castor oil, linseed oil, rapeseed oil, coconut oil, wax (such as beeswax, carnauba wax and lanolin), tall oil, linoleic acid, palmitic acid, lauric acid etc. In the raw material of rubber composition of the present invention, the consumption of softener can be 1-10 mass parts, preferably 2-8 mass parts, such as 3 mass parts, 4 mass parts, 5 mass parts, 6 mass parts, 7 mass parts. In some preferred embodiments, softener includes naphthenic oil and stearic acid. The mass ratio of naphthenic oil and stearic acid can be 2:1 to 10:1, such as 3:1, 4:1, 5:1, 6:1. In some preferred embodiments, in the raw materials of the rubber composition of the present invention, the amount of cyclohexane oil is 2-6 parts by mass, such as 3 parts by mass, 4 parts by mass, and 5 parts by mass; the amount of stearic acid is 0.5-1.5 parts by mass, such as 1 part by mass.

[0051] The protective wax can migrate from the inside of the rubber to the surface to form a wax film, which plays a role in isolating the rubber surface from the external environment. In the raw materials of the rubber composition of the present invention, the amount of the protective wax can be 1-5 parts by mass, such as 1.5 parts by mass, 2 parts by mass, 3 parts by mass, and 4 parts by mass.

[0052] The activator can accelerate the vulcanization speed, improve the thermal conductivity, wear resistance and tear resistance of the rubber. In the raw materials of the rubber composition of the present invention, the amount of the activator can be 5-20 parts by mass, such as 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, 10 parts by mass, 11 parts by mass, 12 parts by mass, and 15 parts by mass. In some preferred embodiments, the activator includes ZnO and MgO. The mass ratio of ZnO to MgO can be 1:1 to 3:1, such as 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.7:1, 1.8:1, 2:1, 2.5:1. In some preferred embodiments, among the raw materials of the rubber composition of the present invention, the amount of ZnO used is 3-9 parts by mass, for example, 4 parts by mass, 5 parts by mass, 6 parts by mass, 7 parts by mass, and 8 parts by mass; the amount of MgO used is 2-5 parts by mass, for example, 2.5 parts by mass, 3 parts by mass, 3.5 parts by mass, 4 parts by mass, and 4.5 parts by mass.

[0053] The accelerator is usually a vulcanization accelerator, which can be selected from sulfonamide vulcanization accelerators, thiazole vulcanization accelerators, thiuram vulcanization accelerators, thiourea vulcanization accelerators, guanidine vulcanization accelerators, dithiocarbamate vulcanization accelerators, aldehyde amine vulcanization accelerators, aldehyde ammonia vulcanization accelerators, imidazoline vulcanization accelerators and xanthate vulcanization accelerators. In the raw materials of the rubber composition of the present invention, the amount of the accelerator can be 0.1-2 mass parts, such as 0.2 mass parts, 0.25 mass parts, 0.5 mass parts, 0.75 mass parts, 1 mass parts, 1.5 mass parts. In some preferred embodiments, the accelerator is accelerator DM (2,2'-dithiodibenzothiazole).

[0054] In addition, when necessary, the rubber composition may also contain plasticizers such as DMP (dimethyl phthalate), DEP (diethyl phthalate), DBP (dibutyl phthalate), DHP (diheptyl phthalate), DOP (dioctyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate), BBP (butyl benzyl phthalate), DWP (dilauryl phthalate), and DCHP (dicyclohexyl phthalate), etc. The amount of the plasticizer may be a conventional amount in the art.

[0055] In some preferred embodiments, the raw materials of the rubber composition of the present invention include: 100 parts by mass of diene elastomer, 0.5-5 parts by mass of antioxidant A, 0.5-5 parts by mass of antioxidant S-TMQ, 30-60 parts by mass of carbon black, 10-30 parts by mass of white carbon black, 0.5-3 parts by mass of sulfur, 2-6 parts by mass of cyclohexane oil, 0.5-1.5 parts by mass of stearic acid, 1-5 parts by mass of protective wax, 3-9 parts by mass of ZnO, 2-5 parts by mass of MgO and 0.1-2 parts by mass of 2,2'-dithiodibenzothiazole, or consist of the above components; wherein the diene elastomer contains natural rubber and chloroprene rubber in a mass ratio of 3:7-7:3.

[0056] The unvulcanized rubber of the present invention can be prepared by a conventional rubber mixing method, for example, by a two-stage mixing method: a first stage of mixing in an internal mixer, mixing the rubber composition raw materials except the crosslinking agent and the accelerator, with the rubber discharge temperature being above 110°C, to obtain a first stage of rubber; a second stage of mixing in an open mixer, mixing the first stage of rubber with the crosslinking agent and the accelerator, to obtain a second stage of rubber, i.e., the unvulcanized rubber.

[0057] Vulcanized rubber can be obtained by vulcanizing the unvulcanized rubber. The vulcanization temperature is usually 130-200°C, such as 140-160°C, 155±5°C; the vulcanization time depends on the vulcanization temperature, the vulcanization system and the vulcanization kinetics, and is usually 5-60 minutes, such as 10±2 minutes. The unvulcanized rubber can be sheeted before vulcanization.

[0058] The rubber composition of the present invention is used in rubber products, especially wiper rubber strips. Compared with the rubber composition using the combination of antioxidant 4010NA and antioxidant S-TMQ, it can not only significantly improve the heat-oxidative aging resistance of the rubber product, but also improve the wear resistance of the rubber product. Therefore, the present invention also provides a rubber product, the rubber product containing the rubber composition described herein. The rubber product is preferably a wiper rubber strip.

[0059] The present invention also provides the use of a combination of antioxidant A and antioxidant S-TMQ in improving the heat-oxidative aging resistance and / or wear resistance of a rubber composition or a rubber product, and a method for improving the heat-oxidative aging resistance and / or wear resistance of a rubber composition or a rubber product. Preferably, the use or method of the present invention comprises: adding 0.5-5 parts by mass of antioxidant A and 0.5-5 parts by mass of antioxidant S-TMQ to the raw materials of the rubber composition relative to 100 parts by mass of diene elastomer. Preferably, the diene elastomer comprises natural rubber and chloroprene rubber in a mass ratio of 3:7-7:3. In the use or method of the present invention, the components and their amounts in the raw materials of the rubber composition can be as described in any embodiment of the present invention.

[0060] The present invention will be described below in the form of specific examples. It should be understood that these examples are merely illustrative and are not intended to limit the scope of the present invention. The methods, reagents and materials used in the examples are, unless otherwise stated, conventional methods, reagents and materials in the art. The raw material compounds in the examples can all be purchased through commercial routes.

[0061] The sources and specifications of the raw materials used in the examples are as follows:

[0062] Natural rubber: Xishuangbanna Sinochem Rubber Co., Ltd., SCR5;

[0063] Neoprene: Nippon Denka Co., Ltd., DCR40A;

[0064] Carbon black: Cabot Corporation, carbon black N330;

[0065] Silica: Rhodia Silica (Qingdao) Co., Ltd., 175GR;

[0066] Naphthenic oil: Maoming Runhua Petrochemical Co., Ltd., naphthenic oil KN4010;

[0067] Protective wax: Bairuimei Special Materials (Suzhou) Co., Ltd., OKERIN 1987;

[0068] Antioxidant A: Shengao Chemical Technology Co., Ltd.;

[0069] Antioxidant 4010NA: Shengao Chemical Technology Co., Ltd.;

[0070] Antioxidant S-TMQ: Shengao Chemical Technology Co., Ltd.;

[0071] ZnO: Shanghai Titan Technology Co., Ltd., general reagent, ZnO (AR);

[0072] MgO: Shanghai Titan Technology Co., Ltd., general reagent, MgO (AR);

[0073] Stearic acid: Shanghai Titan Technology Co., Ltd., general reagent, stearic acid (AR);

[0074] Sulfur: Sinopharm Chemical Reagent Company, sublimated sulfur (AR);

[0075] Accelerator DM: Weilin New Materials Technology Co., Ltd.

[0076] Example

[0077] According to the formulation shown in Table 1, rubber compositions 1-6 were prepared using the following process:

[0078] Add natural rubber and chloroprene rubber into an internal mixer, then add carbon black, white carbon black, antioxidant, ZnO, MgO, cyclopentane oil, stearic acid and protective wax, discharge the rubber when the temperature of the rubber material rises to 130°C to obtain a first-stage rubber, and leave it for 24 hours; knead the first-stage rubber on an open mixer, add accelerator DM and sulfur after the rubber material is rolled, and after the accelerator and sulfur are absorbed, make triangle bags 5-7 times with a thin pass, and then take out the sheet to obtain a second-stage rubber; after the kneaded rubber material is left for 24 hours, determine its positive vulcanization temperature and time with a rotorless vulcanizer, and press-mold it with a wiper rubber strip mold on a flat vulcanizer, and the vulcanization conditions are 155°C*10min to obtain a rubber composition 1-6 used as a wiper rubber strip.

[0079] Table 1: Formulation of rubber composition (unit: parts by mass)

[0080]

[0081]

[0082] Test Example 1

[0083] The vulcanization properties t10 and t90, mechanical properties before aging and mechanical properties after aging of the rubber compositions 1-6 were measured according to the following standards. The results are shown in Table 2:

[0084] Vulcanization characteristics: GB / T 16584-1996 Rubber vulcanizer without rotor for vulcanization characteristics;

[0085] Elongation at break and tensile strength before aging: GB / T 528-2009 Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber;

[0086] Elongation at break and tensile strength after aging at 90℃×72H: GB / T 3512-2014 Hot air accelerated aging and heat resistance test for vulcanized rubber or thermoplastic rubber.

[0087] Change rate of elongation at break after aging = (elongation at break before aging - elongation at break after aging) / elongation at break before aging × 100%

[0088] Tensile strength change rate after aging = (tensile strength before aging - tensile strength after aging) / tensile strength before aging × 100%

[0089] Table 2: Basic physical properties of rubber compositions

[0090]

[0091]

[0092] Test Example 2

[0093] The wear resistance test of rubber compositions 1-6 was conducted on a DIN abrasion tester using GB / T9867-2008 Determination of wear resistance of vulcanized rubber or thermoplastic rubber (rotating roller abrasion machine method), with a roller diameter of 150.0±0.2mm, a rotation speed of 40±1r / min, a wear process of 40.0±0.2m, and the sample was punched into a cylindrical sample with a diameter of 16.0±0.2mm and a height of not less than 6mm. The results are shown in Table 3.

[0094] Table 3: Abrasion test results of rubber compositions

[0095] Rubber composition number 1 2 3 4 5 6 Wear index 125％ 123％ 130％ 136％ 135％ 135％

[0096] According to Table 2, by comparing rubber composition 1 and rubber composition 2, it can be known that when only using antioxidant 4010NA or antioxidant A as antioxidant, antioxidant A shows poor anti-thermal oxidative aging effect, which is suitable with antioxidant 4010NA. By comparing rubber composition 3 and rubber composition 5, it can be known that, compared with the combination of antioxidant 4010NA and antioxidant S-TMQ, the combination of antioxidant A and antioxidant S-TMQ shows the anti-thermal oxidative aging effect of obvious improvement, showing that antioxidant A and antioxidant S-TMQ have unexpected synergy in improving anti-thermal oxidative aging property. By rubber composition 4-6, it can be known that when and using 1.5, 2 or 2.5 parts of antioxidant A and 1.5 parts of antioxidant S-TMQ, rubber composition all has excellent anti-thermal oxidative aging property.

[0097] As shown in Table 3, the wear resistance of rubber composition 2 using antioxidant A alone is not as good as that of rubber composition 1 using antioxidant 4010NA alone, but the wear resistance of rubber composition 5 using antioxidant A and antioxidant S-TMQ together is worse than that of rubber composition 3 using antioxidant 4010NA and antioxidant S-TMQ together, indicating that antioxidant A and antioxidant S-TMQ have unexpected synergistic effects in improving wear resistance. As shown in rubber compositions 4-6, when 1.5, 2 or 2.5 parts of antioxidant A and 1.5 parts of antioxidant S-TMQ are used together, the rubber compositions all have good wear resistance.

Claims

1. A rubber composition, characterized in that: The raw materials of the rubber composition include 100 parts by mass of a diene elastomer, 0.5-5 parts by mass of an antioxidant A and 0.5-5 parts by mass of an antioxidant S-TMQ; The antioxidant A has a structure shown in Formula I: The antioxidant S-TMQ is a 2,2,4-trimethyl-1,2-dihydroquinoline polymer with a total mass fraction of dimers, trimers and tetramers of 2,2,4-trimethyl-1,2-dihydroquinoline being ≥80%.

2. The rubber composition according to claim 1, characterized in that The raw materials of the rubber composition further include 40-90 parts by mass of a reinforcing filler; preferably, the reinforcing filler includes carbon black and white carbon black in a mass ratio of 1:1-4:

1.

3. The rubber composition according to claim 1, characterized in that The rubber composition has one or more of the following characteristics: The diene elastomer comprises natural rubber and chloroprene rubber; preferably, the mass ratio of natural rubber to chloroprene rubber is 3:7-7:3; The raw materials of the rubber composition further include 0.5-10 parts by mass of sulfur; The raw materials of the rubber composition further include 1-5 parts by mass of protective wax.

4. The rubber composition according to claim 1, characterized in that The raw materials of the rubber composition further include 1-10 parts by mass of a softener; preferably, the softener includes cyclohexane oil and stearic acid in a mass ratio of 2:1-10:

1.

5. The rubber composition according to claim 1, characterized in that The rubber composition has one or more of the following characteristics: In the raw materials of the rubber composition, the content of antioxidant A is 1-3 parts by mass; In the raw materials of the rubber composition, the content of the antioxidant S-TMQ is 1-3 parts by mass, preferably 1-2 parts by mass; In the raw materials of the rubber composition, the mass ratio of the antioxidant A to the antioxidant S-TMQ is 1:3 to 3:1, preferably 1:1 to 3:

1.

6. The rubber composition according to claim 1, characterized in that The raw materials of the rubber composition further include 5-20 parts by mass of an active agent; preferably, the active agent includes ZnO and MgO in a mass ratio of 1:1-3:

1.

7. The rubber composition according to claim 1, characterized in that The raw materials of the rubber composition further include 0.1-2 parts by mass of an accelerator; preferably, the accelerator is 2,2'-dibenzothiazole disulfide.

8. The rubber composition according to claim 1, characterized in that The raw materials of the rubber composition include 100 parts by mass of a diene elastomer, 0.5-5 parts by mass of an antioxidant A, 0.5-5 parts by mass of an antioxidant S-TMQ, 30-60 parts by mass of carbon black, 10-30 parts by mass of white carbon black, 0.5-3 parts by mass of sulfur, 2-6 parts by mass of naphthenic oil, 0.5-1.5 parts by mass of stearic acid, 1-5 parts by mass of a protective wax, 3-9 parts by mass of ZnO, 2-5 parts by mass of MgO and 0.1-2 parts by mass of 2,2'-dithiodibenzothiazole.

9. A rubber product, characterized in that: The rubber product contains the rubber composition according to any one of claims 1 to 8; preferably, the rubber product is a wiper rubber strip.

10. Use of a combination of antioxidant A and antioxidant S-TMQ in improving the heat-oxidative aging resistance and wear resistance of a rubber composition or a rubber product, wherein: The antioxidant A has a structure shown in Formula I: The antioxidant S-TMQ is a 2,2,4-trimethyl-1,2-dihydroquinoline polymer with a total mass fraction of di-, tri- and tetramers of 2,2,4-trimethyl-1,2-dihydroquinoline of ≥80%; Preferably, the rubber product is a wiper rubber strip.

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