CN107955277B - Rubber product and preparation method thereof - Google Patents
Rubber product and preparation method thereof Download PDFInfo
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- CN107955277B CN107955277B CN201610899865.5A CN201610899865A CN107955277B CN 107955277 B CN107955277 B CN 107955277B CN 201610899865 A CN201610899865 A CN 201610899865A CN 107955277 B CN107955277 B CN 107955277B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/04—Oxygen-containing compounds
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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Abstract
The invention relates to the field of polymer synthetic materials, in particular to a rubber product which contains a rubber antioxidant composition, butyl rubber, a vulcanizing agent and auxiliary materials; the anti-aging agent composition contains compounds shown in formulas (1) and (2) and compounds shown in formulas (3) and/or (4); r1‑R9、R1’‑R8’、R1”‑R4"each independently is a branched or straight chain hydrocarbyl group selected from C1-C6; n is an integer of 1 to 10. A method of making the rubber article is also disclosed. The rubber antioxidant provided by the invention is applied to the preparation of butyl rubber, and can play a synergistic role among substances, so that excellent heat-resistant oxidation anti-aging performance is endowed to rubber products, and the rubber antioxidant has high environmental protection property.
Description
Technical Field
The invention belongs to the field of polymer synthetic materials, and particularly relates to a rubber product and a preparation method of the rubber product.
Background
Rubber, one of the three major synthetic polymeric materials, is also inevitably subject to aging during storage, transportation, processing and use. For example, although butyl rubber is a low unsaturation rubber, which has far better heat and aging resistance than other general purpose rubbers, it also becomes gradually softer and more tacky with continued thermal oxygen aging, resulting in aging. In order to further improve the aging resistance of polymer materials such as butyl rubber and the like and slow or delay the aging speed of the polymer materials such as rubber and the like, the most important method is to add an anti-aging agent in the material processing so as to reduce the aging fracture and crosslinking speed of the rubber and prolong the reaction induction period, thereby achieving the purpose of improving the aging resistance of the rubber materials.
At present, the common rubber anti-aging agents mainly comprise amines and phenols. However, when these two antioxidants are used in the preparation of butyl rubber products, their anti-aging effect is still to be further improved.
Because the requirement on the anti-aging agent is higher and higher in the process of preventing rubber from aging, finding a high-efficiency anti-aging agent suitable for butyl rubber for preparing butyl rubber products is very critical to the anti-aging work of the butyl rubber products.
Disclosure of Invention
The invention aims to overcome the defects and provide a butyl rubber product with high-efficiency anti-aging performance and a preparation method of the butyl rubber product.
In order to achieve the purpose, the invention provides a rubber product, wherein the rubber product contains a rubber antioxidant composition, butyl rubber, a vulcanizing agent and auxiliary materials;
the rubber antioxidant composition comprises a component A, a component B and a component C, wherein the component A is a compound shown as a formula (1), the component B is a compound shown as a formula (2), and the component C is a compound shown as a formula (3) and/or a compound shown as a formula (4);
wherein, in the formula (1), R1、R2、R3、R4、R5、R6、R7、R8And R9Each independently selected from C1-C6 branched or straight chain hydrocarbon groups; in the formula (2), n is an integer of 1 to 10; in the formula (3), R1’、R2’、R3’、R4’、R5’、R6’、R7' and R8' each independently is a branched or straight chain hydrocarbyl group selected from C1-C6; in the formula (4), R1”、R2”、R3"and R4"each independently selected from C1-C6 branched or straight chain hydrocarbon group.
In a second aspect, the present invention also provides a method for producing the above rubber article, which comprises: mixing and vulcanizing the butyl rubber, a vulcanizing agent, auxiliary materials and the rubber antioxidant composition.
By applying the composition containing the component A, the component B and the component C as the rubber antioxidant composition to the preparation of butyl rubber products, the synergistic effect can be achieved among all the substances, and the prepared vulcanized butyl rubber products are endowed with excellent thermal oxidation resistance and aging resistance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In a first aspect, the invention provides a rubber product, wherein the rubber product contains a rubber antioxidant composition, butyl rubber, a vulcanizing agent and auxiliary materials;
the rubber antioxidant composition comprises a component A, a component B and a component C, wherein the component A is a compound shown as a formula (1), the component B is a compound shown as a formula (2), and the component C is a compound shown as a formula (3) and/or a compound shown as a formula (4);
wherein, in the formula (1), R1、R2、R3、R4、R5、R6、R7、R8And R9Each independently selected from C1-C6 branched or straight chain hydrocarbon groups; in the formula (2), n is an integer of 1 to 10; in the formula (3), R1’、R2’、R3’、R4’、R5’、R6’、R7' and R8' each independently is a branched or straight chain hydrocarbyl group selected from C1-C6; in the formula (4), R1”、R2”、R3"and R4"each independently selected from C1-C6 branched or straight chain hydrocarbon group.
The inventors of the present invention found in the course of research that when the above combination of component a, component B and component C is used as a butyl rubber antioxidant, the components thereof can provide good synergistic effect, thereby providing butyl rubber products with more excellent performance, and thus completed the present invention.
According to the present invention, it is preferred that in formula (1), R1、R2、R3、R4、R5、R6、R7、R8And R9Each independently selected from C1-C4 branched or straight chain hydrocarbon groups; in the formula (2), n is 1-5; in the formula (3), R1’、R2’、R3’、R4’、R5’、R6’、R7' and R8' each is independently selected fromC1-C4 branched or straight chain hydrocarbon group; in the formula (4), R1”、R2”、R3"and R4"each independently selected from C1-C4 branched or straight chain hydrocarbon group.
Wherein, without any indication to the contrary, the term "C1-C4 branched or straight chain hydrocarbyl" denotes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
According to the invention, R1、R2、R3、R4、R5、R6、R1’、R2’、R3’、R4’、R5’、R6’、R7’、R8’、R1”、R2”、R3"and R4"are both preferably butyl, most preferably tert-butyl; r7、R8And R9Both are preferably methyl.
Accordingly, when R is1、R4、R3、R4、R5And R6Is tert-butyl, and R7、R8And R9When the component A is methyl, the component A is 1,3, 5-trimethyl-2, 4, 6-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene; in the component B, n is preferably an integer of 1 to 5, and is preferably a mixture of p-methylphenol-dicyclopentadiene-tert-butylated resin represented by the following formula (5), and the average molecular weight thereof is preferably 460-1420, more preferably 460-700; when R is1’、R2’、R3’、R4’、R5’、R6’、R7' and R8When both are tert-butyl groups, the compound represented by the formula (3) is tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol esters; when R is1”、R2”、R3"and R4When both are tertiary butyl groups, the compound represented by the formula (4) is bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
According to the present invention, the object of the present invention can be achieved by using the above components in combination, but the content of the components in the rubber antioxidant composition is not excessively limited, and they can be varied within a wide range. However, in a preferred case, the component B is contained in an amount of 4 to 800 parts by weight, preferably 50 to 800 parts by weight, more preferably 50 to 300 parts by weight, and the component C is contained in an amount of 15 to 1100 parts by weight, preferably 50 to 640 parts by weight, more preferably 90 to 400 parts by weight, relative to 100 parts by weight of the component A.
It is to be noted herein that, in the rubber antioxidant composition of the present invention, when component C is selected from two compounds, the term "content of component C" refers to the total content of the two compounds, and when component C is selected from one compound, the term "content of component C" refers to the content of the compound from which it is selected.
According to one embodiment of the present invention, the component C is bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, i.e., the antioxidant composition contains 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, p-methylphenol-dicyclopentadiene-tert-butylated resin and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
According to a preferred embodiment of the present invention, the component C is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], i.e. the antioxidant composition contains 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, p-methylphenol-dicyclopentadiene-tert-butylated resin and pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
According to another preferred embodiment of the present invention, component C is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, i.e., the antioxidant composition contains 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, p-methylphenol-dicyclopentadiene-tert-butylated resin, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
Wherein, although the synergistic effect between the components can be further enhanced in the case where the rubber antioxidant composition of the present invention contains the above 4 compounds, the present inventors have found that the synergistic effect can be further enhanced in the case where the weight ratio of pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] to bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite is 1:0.25 to 10, more preferably 1:1 to 10.
According to the rubber product of the present invention, the method for preparing the rubber antioxidant composition is preferably: mixing the component A, the component B and the component C.
According to the present invention, the mixing conditions of the above components are not limited too much, so long as the components are mixed sufficiently. For example, the mixing temperature may be 30-70 ℃, the stirring speed may be 100-2000rpm, and the time may be 10-30 min.
The amount of each component can be referred to the above description, and the description is not repeated here.
The amount of the rubber antioxidant composition contained in the butyl rubber product is not particularly limited in the present invention, as long as it can impart the anti-aging property to the rubber product produced. Preferably, the antioxidant composition is contained in an amount of 1 to 5 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the butyl rubber raw material.
According to the present invention, the inventors of the present invention have found that the rubber antioxidant composition as described above is particularly suitable for butyl rubber, which is capable of effectively improving the tensile strength change rate and the elongation change rate at break of butyl rubber, and effectively increasing the anti-aging coefficient of butyl rubber. Among them, the term "butyl rubber" is a kind of synthetic rubber, which is synthesized from isobutylene and a small amount of isoprene.
The butyl rubber may be ordinary butyl rubber (non-halogenated butyl rubber) or halogenated butyl rubber, and may be, for example, chlorinated butyl rubber and/or brominated butyl rubber, preferably brominated butyl rubber.
In addition, the present invention is also not particularly limited in kind and content of the vulcanizing agent and the auxiliary materials, and may be performed according to the conventional selection in the art, for example, the vulcanizing agent may be used in an amount of 1 to 5 parts by weight, preferably 1 to 2.5 parts by weight, with respect to 100 parts by weight of the butyl rubber.
In the present invention, the selection of the vulcanizing agent is not particularly limited, and may be a selection conventionally used in the art. Preferably, the vulcanizing agent is selected from one or more of insoluble sulfur, dithiomorphine and dithiomorphine tetrasulfide.
The rubber article according to the present invention may be an auxiliary conventionally used in the art for preparing rubber articles, and may be, for example, carbon black, an activator and an accelerator. Preferably, the carbon black may be used in an amount of 10 to 70 parts by weight, preferably 30 to 50 parts by weight, relative to 100 parts by weight of the butyl rubber; the amount of the activator may be 2 to 10 parts by weight, preferably 2 to 8 parts by weight; the accelerator may be used in an amount of 0.2 to 2 parts by weight, preferably 0.5 to 1 part by weight.
Wherein the carbon black, activator and accelerator may be various carbon blacks, activators and accelerators conventionally used in the art, for example, the carbon black may be one or more of carbon black N550, carbon black N774 and carbon black N330; the activator may be zinc oxide and/or stearic acid; the accelerator may be one or more of a guanidine type accelerator, a thiazole type accelerator, a sulfenamide type accelerator, a thiuram type accelerator, a dithiocarbamate type accelerator, and a thiophosphate type accelerator; preferably, the accelerator is tetramethylthiuram dithiolate (TMTD).
In a second aspect, the present invention further provides a method for preparing a rubber article as described above, the method comprising: the butyl rubber as described above, the vulcanizing agent as described above, the auxiliary material as described above, and the rubber antioxidant composition as described above are kneaded and vulcanized.
The mixing and vulcanization processes according to the invention may also be conventional in the art and are not described in detail herein.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
according to the provisions of GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber, an I-type dumbbell cutter is selected to cut the rubber Y1-Y10 obtained in the examples and the rubber D1-D4 obtained in the comparative examples into I-type dumbbell standard samples, and the tensile strength and the elongation at break before aging are tested under the conditions of 23 +/-2 ℃ and the moving speed of a gripper of a tensile machine (Beijing Yongshen electronic instruments Co., Ltd., T2000E) of 500 +/-50 mm/min.
According to the specification in GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber, an I-type dumbbell-shaped cutter is selected to cut the rubber Y1-Y10 obtained in the examples and the rubber D1-D4 obtained in the comparative examples into I-type dumbbell-shaped standard samples, then according to the specification in GB/T3512-2014 Hot air accelerated ageing and Heat resistance test of vulcanized rubber or thermoplastic rubber, the standard samples are hung in a free state in a hot air ageing oven (Chongqing Huidao laboratory instrument factory, L R-1) under the condition of 145 ℃, the samples are taken out after being aged for 72 hours by thermal oxidation, the samples are adjusted for 16 hours under the laboratory environment of 23 ℃ +/-2 ℃ and the relative humidity of 50% +/-10%, then according to the specification in GB/T-2009, the tensile strength and the tensile strength after being aged and the tensile elongation coefficient of tensile strength and the elongation coefficient of the samples after being aged are determined under the conditions of 23 ℃ +/-2 ℃ and the moving speed of a tensile machine holder of 500mm/min +/-50 mm/min, and the final elongation coefficient of 528 and elongation coefficient of elongation after being calculated.
The tensile strength change rate, the elongation at break change rate and the aging factor were calculated according to the following formulas.
The tensile strength change rate is 100% × (tensile strength after aging-tensile strength before aging)/tensile strength before aging, and the smaller the absolute value, the better.
The change in tensile elongation at break is 100% × (tensile elongation after aging-tensile elongation before aging)/tensile elongation before aging, and the smaller the absolute value, the better.
The aging factor (tensile strength after aging × tensile elongation after aging)/(tensile strength before aging × tensile elongation before aging), and the larger the absolute value, the better.
Preparation examples 1 to 9 and comparative preparation examples 1 to 4
Explanation of preparation of rubber antioxidant composition
The respective components and amounts shown in Table 1 in the preparation examples and comparative preparation examples were mixed uniformly at room temperature (25 ℃ C.) to obtain antioxidants F1-F9 corresponding to preparation examples 1-9 and antioxidants DF1-DF4 corresponding to comparative preparation examples 1-4, respectively.
TABLE 1
Note that 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene was obtained from Beijing very chemical Co., Ltd, p-methylphenol-dicyclopentadiene-tert-butylated resin was obtained from Nantong new Long chemical Co., Ltd, which is a mixture of a homopolymer (N ═ 1) and a dimer (N ═ 2), and its average molecular weight was 650, tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester was obtained from Tianjin Chenguang chemical Co., Ltd, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite was obtained from Beijing very chemical Co., Ltd, 2, 6-di-tert-butyl-4-methylphenol was obtained from Taiwan Oji rubber auxiliary Co., Ltd, and N-isopropyl-N' -phenyl-p-phenylenediamine was obtained from Guangzhou Yu chemical Co., Ltd.
Examples 1 to 9
Preparation and testing of rubber articles
100 parts by weight of non-halogenated butyl rubber (product of Beijing Yanshan division, China petrochemical, IIR1751), 50 parts by weight of carbon black N330 (Shanghai Kabau, N330), 1 part by weight of stearic acid (Shanghai Bingspeciality chemical Co., Ltd.), 3 parts by weight of a rubber antioxidant (antioxidant F1-F9 of preparation examples 1-9, respectively), 3 parts by weight of zinc oxide (Zibohai cis-Zinc Co., Ltd.), 1.75 parts by weight of insoluble sulfur (Iseman USA) and 1 part by weight of accelerator TMTD (Tianjin chemical Co., Ltd.) were added to an open mill (Shanghai rubber machinery plant, XK-160A), mixed at 45 ℃ and 500rpm for 18 minutes, the rubber compound was prepared into a sheet having a thickness of about 2.2mm, after 24 hours of parking the rubber compound after mixing, the rubber compound was parked in a flat plate vulcanizer (Hongyo rubber machinery Co., Ltd., X L X × X-D600) at 150 ℃ for 24 hours, the rubber sheet was taken out of the flat plate vulcanizer (Mercury Macroqiao rubber machinery Co., X L X × X-D ×) at 150 ℃ and then the butyl rubber was prepared into a dry mold at 25 ℃ for 25 minutes, and Y5923 mm, and then the butyl rubber was taken out of Y4623 mm, and the butyl rubber was prepared into a test sheet, and then.
The tensile strength change rate, the elongation at break change rate and the aging coefficient of the butyl rubber products Y1-Y9 before and after thermal oxidative aging were measured, and the results are shown in Table 2.
Example 10
Butyl rubber product preparation and performance testing were carried out in the same manner as in example 1 (using rubber antioxidant F1 of example 1) except that 100 parts by weight of brominated butyl rubber (BIIR 2046, a product of Yanshan division, Beijing, petrochemical, China) was used in this example in place of the butyl rubber of example 1 to obtain butyl rubber product Y10, and the change in tensile strength, the change in elongation at break and the aging coefficient before and after thermo-oxidative aging of butyl rubber product Y10 were measured, and the results are shown in Table 2.
Comparative examples 1 to 4
Butyl rubber products D1-D4 using the rubber antioxidants of comparative preparation examples 1-4 were prepared in the same manner as in example 1, except that 3 parts by weight of the rubber antioxidant were used as antioxidants DF1-DF4 of comparative preparation examples 1-4, respectively, and the other components and amounts and the preparation conditions were not changed.
The tensile strength change rate, the elongation at break change rate and the aging coefficient before and after the thermo-oxidative aging of the rubber articles D1-D4 were measured, and the results are shown in Table 2.
TABLE 2
| Numbering | Percent change in tensile Strength% | Elongation at break/%) | Aging factor |
| Example 1(Y1) | -27 | -20 | 0.58 |
| Example 2(Y2) | -30 | -20 | 0.56 |
| Example 3(Y3) | -30 | -22 | 0.55 |
| Example 4(Y4) | -34 | -24 | 0.50 |
| Example 5(Y5) | -33 | -24 | 0.51 |
| Example 6(Y6) | -36 | -26 | 0.47 |
| Example 7(Y7) | -33 | -22 | 0.52 |
| Example 8(Y8) | -34 | -20 | 0.53 |
| Example 9(Y9) | -37 | -24 | 0.48 |
| Example 10(Y10) | -24 | -18 | 0.63 |
| COMPARATIVE EXAMPLE 1(D1) | -44 | -33 | 0.38 |
| COMPARATIVE EXAMPLE 2(D2) | -46 | -33 | 0.36 |
| COMPARATIVE EXAMPLE 3(D3) | -68 | -44 | 0.18 |
| COMPARATIVE EXAMPLE 4(D4) | -33 | -21 | 0.53 |
As can be seen from the above Table 2, compared with comparative examples 1-4, the rubber antioxidant composition provided by the present invention has excellent thermo-oxidative aging resistance when applied to the preparation of butyl rubber products. Moreover, comparing examples 1-3 of the present invention with examples 4-9, it can be seen that the performance of butyl rubber products obtained by applying the antioxidant composition of the present invention to the preparation of butyl rubber products can be further improved with the preferred component ratios, and the performance of rubber products prepared by using brominated butyl rubber can be further improved as seen from the comparison of example 1 with example 10.
In addition, all the components for preparing the rubber antioxidant composition are nontoxic or low-toxicity components, and no toxic substance is generated in the process of mixing or vulcanizing rubber, so the rubber antioxidant composition belongs to an environment-friendly rubber antioxidant. Although the rubber antioxidant of comparative preparation example 4 has satisfactory anti-aging performance, the antioxidant used therein causes a certain pollution to the environment, and is a non-environment-friendly rubber antioxidant.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (11)
1. A rubber product is characterized by comprising a rubber antioxidant composition, butyl rubber, a vulcanizing agent and auxiliary materials;
the rubber antioxidant composition comprises a component A, a component B and a component C, wherein the component A is a compound shown as a formula (1), the component B is a compound shown as a formula (2), and the component C is a compound shown as a formula (3) and/or a compound shown as a formula (4);
wherein, in the formula (1), R1、R2、R3、R4、R5、R6、R7、R8And R9Each independently selected from C1-C4 branched or straight chain hydrocarbon groups; in the formula (2), n is an integer of 1-5; in the formula (3), R1’、R2’、R3’、R4’、R5’、R6’、R7' and R8' each independently is a branched or straight chain hydrocarbyl group selected from C1-C4; in the formula (4), R1”、R2”、R3"and R4"each independently is a branched or straight chain hydrocarbyl group selected from C1-C4;
wherein, in the rubber antioxidant composition, the content of the component B is 4 to 800 parts by weight and the content of the component C is 15 to 1100 parts by weight relative to 100 parts by weight of the component A.
2. The rubber article of claim 1, wherein R1、R2、R3、R4、R5、R6、R1’、R2’、R3’、R4’、R5’、R6’、R7’、R8’、R1”、R2”、R3"and R4"are both butyl; r7、R8And R9Are all methyl.
3. The rubber article according to claim 1 or 2, wherein the content of the component B is 50 to 800 parts by weight and the content of the component C is 50 to 640 parts by weight with respect to 100 parts by weight of the component a.
4. The rubber article according to claim 1 or 2, wherein in the rubber antioxidant composition, the component C is a compound represented by formula (3) and a compound represented by formula (4).
5. The rubber article according to claim 4, wherein the weight ratio of the compound represented by the formula (3) to the compound represented by the formula (4) is 1: 0.25-10.
6. The rubber article of claim 5, wherein the weight ratio of the compound represented by formula (3) to the compound represented by formula (4) is 1: 1-10.
7. The rubber article according to any one of claims 1 to 2 and 5 to 6, wherein the method for producing the rubber antioxidant composition comprises: mixing the component A, the component B and the component C.
8. The rubber article of claim 7, wherein the mixing conditions comprise: the temperature is 30-70 ℃, the stirring speed is 100-2000rpm, and the time is 10-30 min.
9. The rubber article of claim 1 wherein the butyl rubber is a non-halogenated butyl rubber and/or a halogenated butyl rubber.
10. The rubber article of claim 9 wherein the halogenated butyl rubber is chlorinated butyl rubber and/or brominated butyl rubber.
11. A method of making the rubber article of any of claims 1-10, comprising: mixing and vulcanizing the butyl rubber, the vulcanizing agent, the auxiliary material and the rubber antioxidant composition.
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