阅读说明：本技术 包含新型长效橡胶防老剂的轮胎用橡胶组合物 (Rubber composition for tire comprising novel long-acting rubber antioxidant ) 是由 高杨 邹飚 于 2018-06-12 设计创作，主要内容包括：本发明涉及包含新型长效橡胶防老剂的轮胎用橡胶组合物。本发明的防老剂至少含有两种选自(1)下式I、(2)下式II和(3)下式III-a和/或下式III-b的化合物。使用本发明的防老剂能为橡胶组合物提供更好的长期抗热氧老化和抗臭氧老化性能。<Image he="965" wi="700" file="DDA0001693146540000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to a rubber composition for a tire comprising a novel long-acting rubber antioxidant. The antioxidant of the present invention comprises at least two compounds selected from the group consisting of (1) the following formula I, (2) the following formula II and (3) the following formula III-a and/or the following formula III-b. The anti-aging agent can provide better long-term thermal-oxidative aging resistance and ozone aging resistance for the rubber composition.)

1. Compounds of the following formulae II, III-a and III-b:

wherein the content of the first and second substances,

R₁is C1-C12 alkyl or C3-C8 cycloalkyl; and

R₂and R₃The same or different, are independently selected from C1-C12 alkyl and C3-C8 cycloalkyl;

with the proviso that the compound of formula II does not include R₁Compounds which are ortho-substituted methyl, the compounds of formula III-a not including R₂And R₃And at the same time, ortho-substituted methyl.

2. The compound of claim 1,

in the compound of formula II, R₁Is para-substituted C3-C8 cycloalkyl or C1-C12 alkyl, or ortho-substituted C2-C4 alkyl;

in the compound of formula III-a, R₂Is ortho-substituted C1-C4 alkyl, R₃Is a meta-substituted C1-C4 alkyl group;

in the compound of formula III-b, R₂Is ortho-substituted C1-C4 alkyl, R₃Is meta-substituted C1-C6 alkyl or para-substituted C1-C4 alkyl.

3. An antioxidant agent, characterized by comprising at least two compounds selected from the group consisting of (1) the following formula I, (2) the following formula II and (3) the following formula III-a and/or the following formula III-b:

wherein the content of the first and second substances,

R₁is C1-C12 alkyl or C3-C8 cycloalkyl; and

R₂and R₃The same or different, each independently selected from C1-C12 alkyl and C3-C8 cycloalkyl.

4. The antioxidant according to claim 3,

in the compound of formula II, R₁Is ortho-substituted C1-C6 alkyl, para-substituted C1-C12 alkyl or para-substituted C3-C8 cycloalkyl;

in the compounds of the formulae III-a and III-b, R₂And R₃Each independently is a C1-C6 alkyl group; preferably, in the compounds of formula III-a, R₂Is ortho-substituted C1-C4 alkyl, R₃Is a meta-substituted C1-C4 alkyl group; preferably, in the compounds of formula III-b, R₂Is ortho-substituted C1-C4 alkyl, R₃Is meta-or para-substituted C1-C6 alkyl.

5. The antioxidant according to claim 3,

in the compound of formula II, R₁Is ortho-substituted methyl, para-substituted cyclohexyl, para-substituted methyl, para-substituted 2,4, 6-trimethyloctyl or ortho-substituted butyl; and/or

In the compound of formula III-a, R₂Is ortho-substituted methyl, R₃Is a meta-substituted methyl or ethyl group; and/or

In the compound of formula III-b, R₂Is ortho-substituted methyl, R₃Is a para-substituted isobutyl group; or R₂Is ortho-substituted methyl, R₃Is meta-substituted 1, 3-dimethylbutyl; or R₂Being ortho-substituted ethyl radicals, R₃Is a para-substituted ethyl group.

6. The antioxidant according to any one of claims 3-5,

the anti-aging agent contains a compound shown in a formula I and a compound shown in a formula II; preferably, in the antioxidant, the mass ratio of the compound of formula I to the compound of formula II is 1: 3 to 3: 1, preferably 1:2 to 2: 1;

the antioxidant contains (a) a compound shown in a formula II, and (b) any one or both of a compound shown in a formula III-a and a compound shown in a formula III-b; preferably, the mass ratio of (a) the compound to (b) the compound is 3: 1 to 1: 3, preferably 2: 1 to 1: 2; or

The anti-aging agent contains (a) a compound shown in formula I, (b) a compound shown in formula II, and (c) any one or both of a compound shown in formula III-a and a compound shown in formula III-b; preferably, the anti-aging agent comprises a compound of formula I, a compound of formula II and a compound of formula III-b; preferably, in the antioxidant, the mass percent of (a) is 5-20%, preferably 8-18%, more preferably 10-17%, the mass percent of (b) is 45-85%, preferably 48-82%, more preferably 50-80%, and the mass percent of (c) is 5-45%, preferably 8-42%, more preferably 10-40%, based on the total weight of the compounds (a), (b) and (c); or

The antioxidant comprises (a) a compound of formula I, and (b) a compound of formula III-a; preferably, the mass ratio of (a) the compound to (b) the compound is 3: 1 to 1: 3, preferably 2: 1 to 1: 2.

7. the antioxidant according to claim 6, wherein the antioxidant comprises a compound of formula I, a compound of formula II, and a compound of formula III-b, wherein,

in the compound of formula II, R₁Is an ortho-substituted methyl group; in the compound of formula III-b, R₂Is ortho-substituted methyl, R₃Is a para-substituted isobutyl group; and based on the total weight of the compound of the formula I, the compound of the formula II and the compound of the formula III-b, the mass percent of the compound of the formula I is 8-12%, the mass percent of the compound of the formula II is 78-82%, and the mass percent of the compound of the formula III-b is 8-12%;

in the compound of formula II, R₁Is para-substituted methyl; in the compound of formula III-b, R₂Is ortho-substituted methyl, R₃Is meta-substituted 1, 3-dimethylbutyl; and the mass of the compound of formula I based on the total weight of the compound of formula I, the compound of formula II and the compound of formula III-bThe percentage is 15-18%, the mass percentage of the compound in the formula II is 64-68%, and the mass percentage of the compound in the formula III-b is 15-18%; or

In the compound of formula II, R₁Is ortho-substituted butyl; in the compound of formula III-b, R₂Being ortho-substituted ethyl radicals, R₃Is para-substituted ethyl; and based on the total weight of the compound of the formula I, the compound of the formula II and the compound of the formula III-b, the mass percent of the compound of the formula I is 8-12%, the mass percent of the compound of the formula II is 48-52%, and the mass percent of the compound of the formula III-b is 38-42%.

8. A rubber composition containing the antioxidant agent according to any one of claims 3 to 7;

preferably, the antioxidant is contained in an amount of 0.1 to 5 parts by mass per 100 parts by mass of the diene elastomer contained in the rubber composition;

more preferably, the content of the antioxidant is 0.1 to 2.0 parts by mass, or 1.2 to 5.0 parts by mass.

9. A rubber article produced using the rubber composition according to claim 8 as a rubber component;

preferably, the rubber article is a tire, or a belt or sidewall of a tire.

10. Use of the compound according to any one of claims 1 to 2 or the antioxidant according to any one of claims 3 to 7 for improving the resistance of rubber to thermo-oxidative aging and ozone aging.

11. Use of the rubber composition of claim 8 in the manufacture or retreading of a tire.

Technical Field

The present invention relates to a rubber composition for a tire comprising a novel long-acting rubber antioxidant.

Background

The tire is an important part of modern automobiles, is often used under complicated and severe conditions, bears various deformation, load, force and high and low temperature effects during running, and the quality of the performance directly influences the economical efficiency and safety of driving.

The belt and the sidewall of the tire are two important parts of the tire, and are required to have excellent high durability. The belt layer is composed of the rubber composition and the reinforcing material, and the tire is compressed at a certain frequency in the belt layer part in the running process, so that the belt layer rubber composition is required to have extremely high crack propagation resistance and thermal-oxidative aging resistance, and particularly, an effective long-acting thermal-oxidative aging resistance anti-aging agent is required to be used to ensure high durability. Sidewalls are another critical part in determining tire performance, particularly in radial tires. The tire sidewall is subjected to damages caused by illumination, rain, high temperature, ozone and the like for a long time, and the tire is subjected to periodic deflection during the driving process. In order to ensure the long-term service performance of the tire, the tire side wall rubber composition is required to have excellent bending resistance, thermal oxidation resistance and ozone aging resistance, and a high-performance long-acting anti-aging agent is selected in the rubber composition.

In rubber compositions for tires, particularly belt and sidewall rubber compositions, p-phenylenediamine antioxidants such as N, N ' -bis- (1, 4-dimethylpentyl) p-phenylenediamine (77PD), N-isopropyl-N ' -phenyl-p-phenylenediamine (IPPD), N-1, 3-dimethylbutyl-N ' -phenyl-p-phenylenediamine (6PPD) and mixtures of diphenyl-ditolyl-and phenyl-tolyl-p-phenylenediamine (3100) have long been selected.

The p-phenylenediamine anti-aging agent has better protection to the thermal oxygen and ozone of the rubber composition, but has poor long-acting performance.

Disclosure of Invention

The invention discloses an anti-aging agent and a rubber composition containing the same, wherein the rubber composition has better long-term thermal-oxidative aging resistance and ozone aging resistance, and can be particularly applied to all or part of a rubber substrate of a tire.

The antioxidant of the present invention comprises at least two compounds selected from the group consisting of (1) the following formula I, (2) the following formula II and (3) the following formula III-a or the following formula III-b:

in the formula (I), the compound is shown in the specification,

R₁is C1-C12 alkyl or C3-C8 cycloalkyl;

R₂and R₃The same or different, each independently selected from C1-C12 alkyl and C3-C8 cycloalkyl.

In one or more embodiments, R₁In the ortho or para position.

In one or more embodiments, R₁In para position, is C3-C8 cycloalkyl or C1-C12 alkyl.

In one or more embodiments, R₁In the ortho position, is a C1-C12 alkyl group.

In one or more embodiments, R₁Is ortho-substituted methyl or butyl, or para-substituted methyl, cyclohexyl or 2,4, 6-trimethyloctyl.

In one or more embodiments, R₂In the ortho position, R3 is in the meta or para position.

In one or more embodiments, R₂Is C1-C6 alkyl.

In one or more embodiments, R₃Is C1-C6 alkyl.

In one or more embodiments, in formula III-a, R₂Is ortho-substituted C1-C4 alkyl, R₃Is meta-substituted C1-C4 alkyl.

In one or more embodiments, in formula III-a, R₂Is ortho-substituted methyl, R₃Is a meta-substituted methyl or ethyl group.

In one or more embodiments, in formula III-b, R₂Is ortho-substituted C1-C4 alkyl, R₃Is a para-substituted C1-C6 alkyl group.

In one or more embodiments, in formula III-b, R₂Is ortho-substituted methyl or ethyl, R₃Is para-substituted ethyl, isobutyl or 1, 3-dimethylbutyl.

In one or more embodiments, the antioxidant agent comprises a compound of formula I and formula II, wherein the mass ratio of the compound of formula I to the compound of formula II is 1: 3 to 3: 1, preferably 1:2 to 2: 1.

in one or more embodiments, the antioxidant comprises a compound of formula II and a compound of formula III-a or formula III-b, wherein the mass ratio of the compound of formula II to the compound of formula III-a or formula III-b is 3: 1 to 1: 3, preferably 2: 1 to 1: 2.

in one or more embodiments, the antioxidant agent comprises a compound of formula I and a compound of formula III-a; preferably, the mass ratio of the compound of formula I to the compound of formula III-a is 3: 1 to 1: 3, preferably 2: 1 to 1: 2.

in one or more embodiments, the anti-aging agent contains a compound of formula I, a compound of formula II and a compound of formula III-a or formula III-b, wherein the mass percent of the compound of formula I is 5-20%, the mass percent of the compound of formula II is 45-85%, and the mass percent of the compound of formula III-a or formula III-b is 5-45% based on the total weight of the compound of formula I, the compound of formula II and the compound of formula III-a or formula III-b.

In one or more embodiments, the anti-aging agent contains a compound of formula I, a compound of formula II and a compound of formula III-a or formula III-b, wherein the mass percent of the compound of formula I is 8-18%, the mass percent of the compound of formula II is 48-82%, and the mass percent of the compound of formula III-a or formula III-b is 8-42% based on the total weight of the compound of formula I, the compound of formula II and the compound of formula III-a or formula III-b.

In one or more embodiments, the anti-aging agent contains a compound of formula I, a compound of formula II and a compound of formula III-b, wherein the mass percent of the compound of formula I is 10-17%, the mass percent of the compound of formula II is 50-80%, and the mass percent of the compound of formula III-b is 10-40% based on the total weight of the compound of formula I, the compound of formula II and the compound of formula III-b.

In one or more embodiments, the antioxidant comprises a compound of formula I, a compound of formula II, and a compound of formula III-b, wherein in the compound of formula II, R₁Is ortho-or para-substituted C1-C4 alkyl; r₃Is meta-or para-substituted C1-C6 alkyl.

In one or more embodiments, the antioxidant comprises a compound of formula I, a compound of formula II, and a compound of formula III-b, wherein in the compound of formula II, R₁Is ortho-substituted methyl, or para-substituted methyl or butyl; r₃Is para-substituted ethyl or isobutyl or meta-substituted 1, 3-dimethylbutyl.

In one or more embodiments, the antioxidant also contains other antioxidants, such as para-phenylenediamine antioxidants, for example, N ' -bis- (1, 4-dimethylpentyl) para-phenylenediamine (77PD), N-isopropyl-N ' -phenyl-para-phenylenediamine (IPPD), N-1, 3-dimethylbutyl-N ' -phenyl-para-phenylenediamine (6PPD), and mixtures of diphenyl-xylyl-and phenyl-tolyl-para-phenylenediamine (3100).

The present invention also provides a rubber composition comprising the antioxidant described herein.

In one or more embodiments, the rubber composition further contains a diene elastomer, a reinforcing filler, and a crosslinking agent.

In one or more embodiments, the antioxidant is used in an amount of 0.1 to 5 parts by mass in the rubber composition, based on 100 parts by mass of the diene elastomer.

The present invention also provides a rubber article prepared using the rubber composition described herein as a rubber component.

In one or more embodiments, the rubber article is a tire.

In one or more embodiments, the rubber article is a belt and sidewall of a tire.

The invention also provides application of the anti-aging agent in improving the thermal-oxidative aging resistance and ozone aging resistance of rubber.

Detailed Description

It is to be understood that within the scope of the present invention, the above-described technical features of the present invention and the technical features described in detail below (e.g., the embodiments) may be combined with each other to constitute a preferred embodiment.

The present invention relates to diene elastomer compositions and also to anti-ageing agents for the anti-ageing protection of such compositions. More particularly, the present invention relates to diene elastomer compositions used to make all or part of the rubber matrix of a tire, and in particular to these tire sidewall rubber compositions and belt rubber compositions.

The antioxidant used in the present invention comprises at least two compounds selected from the group consisting of (1) the following formula I, (2) the following formula II and (3) the following formula III-a or the following formula III-b:

in the formula, R₁、R₂And R₃Identical or different, R₁，R₂And R₃Each of which isIndependently selected from C1-C12 alkyl and C3-C8 cycloalkyl.

Herein, the alkyl group may be a linear or branched alkyl group. The alkyl group may be 1 to 12 carbon atoms in length; in certain embodiments, alkyl is C1-C6 straight or branched chain alkyl. For example, the alkyl group may be methyl, ethyl, n-butyl, isobutyl, 1, 3-dimethylbutyl, and 2,4, 6-trimethyloctyl. Herein, exemplary cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, and the like.

In the compound of formula II, R₁May be located in adjacent, intermediate or para positions. Suitable R₁May be C1-C12 alkyl, or C3-C8 cycloalkyl. For example, in certain embodiments, R₁Is methyl, butyl, 2,4, 6-trimethyl octyl or cyclohexyl. In certain embodiments, R₁Is ortho-substituted C1-C6 alkyl (preferably C1-C4 alkyl) or para-substituted C1-C12 alkyl or C3-C8 cycloalkyl. In certain embodiments, the compound of formula II is R₁A compound which is an ortho-substituted methyl group, a para-substituted cyclohexyl group, a para-substituted methyl group, a para-substituted 2,4, 6-trimethyloctyl group or an ortho-substituted butyl group.

In the compounds of the formulae III-a and III-b, R₂And R₃Each may be in the ortho, meta or para position. In certain embodiments, R₂And R₃Each independently is a C1-C6 alkyl group. It is understood that in formula III-b, R₂And R₃Attached to different carbon atoms. In certain embodiments, R₂Is C1-C4 alkyl. In certain embodiments, R₃Is C1-C6 alkyl. In certain embodiments, R₂In ortho position, R₃In the meta or para position.

In certain embodiments, in the compounds of formula III-a, R₂Is ortho-substituted C1-C4 alkyl, R₃Is meta-substituted C1-C4 alkyl. In certain embodiments, in the compounds of formula III-a, R₂Is ortho-substituted methyl, R₃Is a meta-substituted methyl or ethyl group.

In certain embodiments, in the compounds of formula III-b, R₂Is ortho-substituted C1-C4 alkyl, R₃Is meta or paraA C1-C6 alkyl group substituted at the position. In certain embodiments, in the compounds of formula III-b, R₂Is ortho-substituted methyl, R₃Is a para-substituted isobutyl group; or R₂Is ortho-substituted methyl, R₃Is meta-substituted 1, 3-dimethylbutyl; or R₂Being ortho-substituted ethyl radicals, R₃Is a para-substituted ethyl group.

In certain embodiments, the anti-aging agents herein comprise a compound of formula I and a compound of formula II. Preferably, R in the compound of formula II₁Is C3-C8 cycloalkyl, more preferably cyclohexyl. Preferably, in the anti-aging agent, the mass ratio of the compound of the formula I to the compound of the formula II is 1: 3 to 3: 1, preferably 1:2 to 2: 1.

in certain embodiments, the anti-aging agents herein comprise a compound of formula I and a compound of formula III-a. Preferably, in the antioxidant, the mass ratio of the compound shown in the formula I to the compound shown in the formula III-a is 3: 1 to 1: 3, preferably 2: 1 to 1: 2.

in certain embodiments, the antioxidants herein comprise (1) a compound of formula II, and (2) either or both of a compound of formula III-a and a compound of formula III-b. In certain embodiments, the anti-aging agents herein comprise a compound of formula II and a compound of formula III-b. Preferably, in the compounds of formula II, R₁Is C1-C12 alkyl, such as 2,4, 6-trimethyloctyl; in the compound of formula III-a, R2 is ortho-substituted C1-C4 alkyl, such as methyl, R3 is meta-substituted C1-C4 alkyl, such as ethyl; in the compound of formula III-b, R₂Is ortho-substituted C1-C4 alkyl, R₃Is meta-or para-substituted C1-C6 alkyl. Preferably, in the antioxidant, in the compound of formula II, R₁Is para-substituted 2,4, 6-trimethyloctyl; in the compound of formula III-b, R₂Is ortho-substituted methyl, R₃Is para-substituted isobutyl, or R₂Is ortho-substituted methyl, R₃Is meta-substituted 1, 3-dimethylbutyl, or R₂Is an ortho-substituted ethyl radical, R₃Is an ortho-substituted ethyl group. In a preferred embodiment, the mass ratio of the compound of formula II to the compound of formula III-a or the compound of formula III-b is 3: 1 to 1: 3, preferably 2: 1 to 1: 2.

in certain embodiments, the antioxidants herein comprise (1) a compound of formula I, (2) a compound of formula II, and (3) either or both of a compound of formula III-a and a compound of formula III-b. Preferably, in the compounds of formula II, R₁Is ortho-substituted C1-C4 alkyl, such as methyl; in the compound of formula III-a, R₂Is ortho-substituted C1-C4 alkyl (e.g. methyl), R₃Is a meta-substituted C1-C4 alkyl group (e.g., ethyl); in the compound of formula III-b, R₂Is ortho-substituted C1-C4 alkyl, R₃Is meta-or para-substituted C1-C6 alkyl. In certain embodiments, the anti-aging agents herein comprise a compound of formula I, a compound of formula II, and a compound of formula III-b. In certain embodiments, the anti-aging agents herein comprise a compound of formula I, a compound of formula II, and a compound of formula III-b; wherein in the compound of formula II, R₁Is an ortho-substituted methyl group; in the compound of formula III-b, R₂Is ortho-substituted methyl, R₃Is para-substituted isobutyl, or R₂Is ortho-substituted methyl, R₃Is meta-substituted 1, 3-dimethylbutyl, or R₂Is an ortho-substituted ethyl radical, R₃Is an ortho-substituted ethyl group. In a preferred embodiment, in the anti-aging agent, the mass percent of the compound of formula I is 5-20%, the mass percent of the compound of formula II is 45-85%, and the mass percent of the compound of formula III-a and/or III-b (when both are contained, the sum of the mass percent of the compound of formula I and the compound of formula II) is 5-45% based on the total weight of the compound of formula I, the compound of formula II and the compound of formula III-a and/or III-b; preferably, the mass percent of the compound of the formula I is 8-18%, the mass percent of the compound of the formula II is 48-82%, and the mass percent of the compound of the formula III-a or III-b is 8-42%. Preferably, the anti-aging agent contains a compound of formula I, a compound of formula II and a compound of formula III-b, wherein the mass percent of the compound of formula I is 10-17%, the mass percent of the compound of formula II is 50-80%, and the mass percent of the compound of formula III-b is 10-40% based on the total weight of the compound of formula I, the compound of formula II and the compound of formula III-b.

It is to be understood that the antioxidant described herein is not antioxidant 3100 known in the art, but that the antioxidants of the invention may also contain other known antioxidants, such as para-phenylenediamine antioxidants, for example N, N ' -bis- (1, 4-dimethylpentyl) para-phenylenediamine (77PD), N-isopropyl-N ' -phenyl-para-phenylenediamine (IPPD), N-1, 3-dimethylbutyl-N ' -phenyl-para-phenylenediamine (6PPD) and mixtures of diphenyl-ditolyl-and phenyl-tolyl-para-phenylenediamine (3100). These known antioxidants may be added to the antioxidant of the present invention in their conventional amounts. Specifically, the amount added thereof usually satisfies the following requirements: when the antioxidant of the present invention containing the known antioxidant is added to the rubber composition, the other known antioxidant is present in an amount of 0.1 to 1.5 parts by mass per 100 parts by mass of the diene elastomer.

The anti-aging agent can provide better long-term thermal-oxidative aging resistance and ozone aging resistance for the rubber composition. Accordingly, the present invention also provides a rubber composition comprising the antioxidant as described herein. Generally, the rubber composition also contains a diene elastomer, a reinforcing filler and a crosslinking agent. The amount of the antioxidant to be used in the rubber composition is usually 0.1 to 5 parts by mass, for example 0.1 to 2.0 parts by mass, or 1.2 to 5.0 parts by mass, based on 100 parts by mass of the diene elastomer.

The rubber composition may also contain other conventional ingredients including, but not limited to, fillers, processing aids, microcrystalline waxes, sulfur, accelerators, and the like.

The filler may be titanium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, clay, talc, or the like. Generally, the filler is used in an amount of 40 to 60 parts by weight per 100 parts by weight of the raw rubber.

The processing aid may be, for example, a softener used for improving processability. The softening agent may be petroleum type softening agent such as processing oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt and vaseline; fatty oil softeners such as castor oil, linseed oil, rapeseed oil and coconut oil, waxes such as beeswax, carnauba wax and lanolin, and tall oil, linoleic acid, palmitic acid, stearic acid and lauric acid, and the like. Generally, the processing aid is used in an amount of 10 to 18 parts by weight per 100 parts by weight of raw rubber.

Generally, 1 to 3 parts by weight of sulfur is used per 100 parts by weight of raw rubber.

The accelerator is usually a vulcanization accelerator, and may be at least one of sulfonamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamate, aldehyde amine, imidazoline and xanthate vulcanization accelerators. Generally, the accelerator is used in an amount of 0.5 to 1.3 parts by weight per 100 parts by weight of raw rubber.

In addition, if necessary, 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), DCHP (dicyclohexyl phthalate), and the like may also be used in the polluting rubber. The amount of plasticizer used is that amount conventionally used in the art.

The contaminating rubber articles of the present invention can be prepared by conventional methods. For example, the preparation is carried out by a two-stage kneading method. Mixing in a first banbury mixer, mixing raw rubber, stuffing, processing assistant and antiager at rubber discharging temperature over 130 deg.c. Mixing the mixture in a two-stage open mill, mixing the first-stage rubber compound with sulfur and an accelerant, and discharging at the temperature of 70 ℃. Vulcanization conditions are as follows: 30min at 145 ℃.

The present invention also provides a rubber article prepared using the rubber composition described herein as a rubber component. For example, the rubber article may be a tire, such as all or part of a tire. In certain embodiments, the rubber article is a belt and sidewall of a tire. As the belt layer of the tire, the rubber article may contain, in addition to the rubber composition described herein, a reinforcing material conventionally used in the art.

The invention also provides application of the anti-aging agent in improving the thermal-oxidative aging resistance and ozone aging resistance of rubber. The invention also provides the use of the rubber composition described herein in the manufacture or retreading of a tire.

In certain embodiments, compounds of formulae II, III-a, and III-b provided herein and their use in the preparation of anti-aging agents are also included within the scope herein. Specifically, included herein are compounds of the following formulas II, III-a and III-b:

wherein R is₁、R₂And R₃As described in any one of the preceding embodiments.

Preferably, the compound of formula II does not include R₁A compound which is an ortho-substituted methyl group. For example, in certain embodiments, in the compounds of formula II, R₁Is para-substituted C3-C8 cycloalkyl or C1-C12 alkyl, or ortho-substituted C2-C4 alkyl.

Preferably, in the compound of formula III-a, R₂And R₃Not simultaneously ortho-substituted methyl. For example, in certain embodiments, in the compounds of formula III-a, R₂Is ortho-substituted C1-C4 alkyl, and R₃Then is a meta-substituted C1-C4 alkyl group.

Preferably, in the compounds of formula III-b, R₂And R₃Are attached to different carbon atoms, and R₂Is ortho-substituted C1-C4 alkyl, R₃Is meta-substituted C1-C6 alkyl or para-substituted C1-C4 alkyl.

Also included herein are compositions, such as anti-aging agents, comprising compounds of formula II, formula III-a, and/or formula III-b.

The compounds of formula I, formula II, formula III-a and formula III-b of the present invention may be prepared by reference to the procedures disclosed in CN 106608827A, the entire contents of which are incorporated herein by reference. For example, R' -NHC can be reacted in the presence of a hydrogen acceptor and a catalyst₆H₄NH₂With cyclohexanone and/or alkyl or cycloalkyl substituted cyclohexanone. For example, the compounds of formula I of the present invention can be prepared by the method described in example 1 of this document; the procedure of example 6 of this document can be used to prepare N-phenyl-N' -tolyl-p-phenylenediamine. When R in the compounds of formula I, formula II, formula III-a and formula III-b₁、R₂And R₃When different substituents are present, the corresponding starting materials and hydrogen may be usedThe receptor is reacted under the same or similar conditions to produce the compounds of the invention.

The present invention will be illustrated below by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the present invention. The methods and materials used in the examples are, unless otherwise indicated, conventional in the art.