阅读说明：本技术 一种用于制备高性能全钢子午线轮胎胎面胶组合物及其混炼方法和轮胎 (High-performance all-steel radial tire tread rubber composition, mixing method thereof and tire ) 是由 彭俊彪 张春生 戴华平 胡善军 陈家辉 戴仲娟 刘乐 范泽华 于 2020-06-01 设计创作，主要内容包括：本发明属于橡胶轮胎技术领域,具体涉及一种用于制备高性能全钢子午线轮胎胎面胶组合物及其混炼方法和轮胎。该胎面胶组合物由以下重量份的组分原料混炼制得：天然橡胶100份,硬脂酸1～3份,氧化锌2.5～7份,促进剂0.8～1.6份,硫磺0.8～1.5份,防老剂1.5～4份,防护蜡0.5～1.5份,炭黑45～57份,间苯二甲酰肼0.2～1.2,1,6-双(N,N′-二苯并噻唑氨基甲酰二硫)-己烷0.2～1.2防焦剂CTP 0.05～0.20份。本发明有效地的降低胶料的Payne效应和损耗因子tanδ,同时进一步降低损耗因子tanδ的同时提升胎面胶的耐磨性,有效地解决了降低滚阻的同时耐磨性下降的缺陷等技术问题。(The invention belongs to the technical field of rubber tires, and particularly relates to a high-performance all-steel radial tire tread rubber composition, a mixing method thereof and a tire. The tread rubber composition is prepared by mixing the following raw materials in parts by weight: 100 parts of natural rubber, 1-3 parts of stearic acid, 2.5-7 parts of zinc oxide, 0.8-1.6 parts of accelerator, 0.8-1.5 parts of sulfur, 1.5-4 parts of anti-aging agent, 0.5-1.5 parts of protective wax, 45-57 parts of carbon black, 0.2-1.2 parts of isophthaloyl hydrazine, 0.2-1.2 parts of 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane and 0.05-0.20 parts of anti-scorching agent CTP. The invention effectively reduces the Payne effect and the loss factor tan of the rubber material, further reduces the loss factor tan, improves the wear resistance of the tread rubber, and effectively solves the technical problems of reducing rolling resistance and simultaneously reducing the wear resistance.)

1. The tread rubber composition for preparing the high-performance all-steel radial tire is characterized by being prepared by mixing the following raw materials in parts by weight:

100 parts of natural rubber, namely 100 parts of natural rubber,

1-3 parts of stearic acid,

2.5 to 7 parts of zinc oxide,

0.8 to 1.6 parts of an accelerator,

0.8 to 1.5 parts of sulfur,

1.5-4 parts of an anti-aging agent,

0.5 to 1.5 parts of protective wax,

45-57 parts of carbon black,

0.2 to 1.2 parts of isophthaloyl hydrazine,

0.2 to 1.2 parts of 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane,

0.05-0.20 part of anti-scorching agent CTP.

2. The tread rubber composition for preparing the high-performance all-steel radial tire of claim 1, which is prepared by mixing the following raw materials in parts by weight:

100 parts of natural rubber, namely 100 parts of natural rubber,

1-3 parts of stearic acid,

2.5 to 7 parts of zinc oxide,

0.8 to 1.6 parts of an accelerator,

0.8 to 1.5 parts of sulfur,

1.5-4 parts of an anti-aging agent,

0.5 to 1.5 parts of protective wax,

45-55 parts of carbon black,

0.5 to 1.0 part of isophthaloyl hydrazine,

0.5 to 1.0 portion of 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane,

0.05-0.20 part of anti-scorching agent CTP.

3. The tread rubber composition for preparing all-steel radial tires with high performance according to claim 1 or 2, wherein the natural rubber is smoked sheet rubber RSS3^#、STR20^#、SMR20^#One or two of them are used in combination.

4. The tread rubber composition for preparing all-steel radial tires with high performance according to claim 1 or 2, wherein the carbon black is one or two of N134, N234 and N375.

5. The tread rubber composition for preparing the high-performance all-steel radial tires according to claim 1 or 2, wherein the anti-aging agent is one or more of anti-aging agent 4020, anti-aging agent DTPD and anti-aging agent RD.

6. The tread rubber composition for preparing the high-performance all-steel radial tires according to claim 1 or 2, wherein the total amount of the accelerator and the 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane in the tread rubber is 1.0-2.8 parts by weight.

7. The tread rubber composition for preparing all-steel radial tires with high performance according to claim 1 or 2, wherein the accelerator is one or two of NS and CBS.

8. A method of mixing a tread rubber composition according to any of claims 1 to 7, wherein both isophthaloyl hydrazine and 1, 6-bis (N, N '-dibenzothiazyl carbamoyl disulfide) -hexane are used as compounds participating in the rubber reaction, and wherein isophthaloyl hydrazine is added in the second stage of the masterbatch after pre-dispersion of carbon black in the natural rubber, and 1, 6-bis (N, N' -dibenzothiazyl carbamoyl disulfide) -hexane is added after reaction of isophthaloyl hydrazine with the natural rubber.

9. The method of mixing the tread rubber composition of any one of claim 8, comprising the steps of:

1) starting an internal mixer, setting the rotating speed of a rotor of the internal mixer to be 40-55 rmp, mixing pressure to be 10-15 MPa, cooling water temperature to be 30-40 ℃, rotor temperature to be 30-40 ℃, adding natural rubber, carbon black, zinc oxide, an anti-aging agent and protective wax, mixing for 20-40 seconds, lifting a top bolt, staying for 10-15 seconds, pressing the top bolt, mixing until the temperature is 135-145 ℃, lifting the top bolt, staying for 10-15 seconds, pressing the top bolt, and discharging rubber when the temperature is 145-165 ℃, wherein the rubber is a first-section rubber;

2) the method comprises the steps of mixing two-stage masterbatch, starting an internal mixer, setting the rotor speed of the internal mixer to be 45-55 rmp, mixing pressure to be 10-15 MPa, cooling water temperature to be 30-40 ℃, rotor temperature to be 30-40 ℃, adding first-stage rubber and isophthaloyl hydrazine, mixing for 20-40 seconds, lifting a top plug, staying for 5-12 seconds, pressing the top plug, mixing until the temperature is 135-145 ℃, lifting the top plug, reducing the rotation speed to be 20-35 rmp, staying for 10-15 seconds, pressing the top plug, mixing until the temperature is 145-155 ℃, and discharging rubber, wherein the rubber is the two-stage masterbatch;

3) and (3) a step of refining final rubber, which is to start the internal mixer, set the rotor speed of the internal mixer to be 20-35 rmp, the mixing pressure to be 10-15 MPa, the cooling water temperature to be 30-40 ℃ and the rotor temperature to be 30-45 ℃, put the secondary master batch, sulfur, an accelerator, 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane and an anti-scorching agent CTP into a mixing chamber, lift the top plug for 40-60 seconds, stay the mixture for 10-15 seconds for pressing the plug, lift the plug when the temperature of the rubber material is 100-113 ℃ for rubber removal, and cool the lower piece to room temperature to obtain the tread rubber for preparing the high-performance all-steel radial tire.

10. A high-performance all-steel radial tire is characterized in that the tread of the tire is vulcanized by adopting the tread rubber composition of any one of claims 1 to 7.

Technical Field

The application belongs to the technical field of rubber tires, and particularly relates to a tread rubber composition for preparing a high-performance all-steel radial tire, a mixing method of the tread rubber composition and a tire.

Background

As the economic development and the road driving condition become better, the truck and passenger cars begin to pay more attention to the oil consumption and mileage of the tires, and higher requirements on rolling resistance and wear resistance of the tires are made. According to the research, the rolling resistance of the heavy-duty tire is reduced by 3%, the oil is saved by 1%, and the tire has great economic value in reducing the rolling resistance of the tire. With the implementation of the tire labeling law of various countries, higher requirements are put on the rolling resistance of the heavy-duty radial tire.

At present, one of the effective means for reducing the rolling resistance of tires is to adopt biphase carbon black, white carbon black and a silane coupling agent to achieve the effect of reducing the rolling resistance. In general, wear resistance of the tread rubber is reduced by using the carbon black and the carbon black together with the two-phase carbon black, so that mileage is reduced while oil is saved, service life of the tire is reduced, and tire cost is not substantially reduced. In the tire industry, magic triangle rolling resistance, wear resistance and wet gripping are permanent subjects, and a means is hoped to be found to break the balance, so that the rolling resistance is reduced, and meanwhile, the wear resistance of the tread rubber is improved. Therefore, the requirement of improving the wear resistance of the heavy-duty radial tire and reducing the rolling resistance becomes an important subject of tire developers.

At present, Chinese patent application (publication No. CN110283364A) reports that one or more other hydrazides of the same type as isophthaloyl hydrazine can reduce heat generation in a tire side formula, but does not consider the synergistic effect of 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane on other performances such as abrasion, and the preparation method of the composition has the defect that Mooney is rapidly increased by adding hydrazide into a butadiene-containing rubber composition, so that the dispersion of a filler in natural rubber and butadiene rubber is influenced.

The Chinese patent application (publication No. CN109251375A) reports that isophthaloyl hydrazine can reduce heat generation and improve fatigue performance in engineering tire treads, and only the effect of isophthaloyl hydrazine is considered, but the synergistic effect with 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane is not considered. The adopted 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane participates in the reaction to form thermodynamically stable monothio bond, disulfide bond and mixed crosslinking bond with similar polysulfide bond flexibility, so as to ensure that the tread has good wear resistance and low hysteresis.

The Chinese patent application (publication number: CN106832448B) reports that 1, 6-bis (N, N '-dibenzothiazyl carbamyl disulfide) -hexane used in a tread has the characteristics of low heat generation and good wear resistance, and the synergistic effect of isophthaloyl hydrazine is not considered, so that the heat generation reduction and the wear resistance improvement of the method are not obvious in the synergistic effect of isophthaloyl hydrazine and 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane. The technical problem that the abrasion resistance of the tire is reduced while the rolling resistance of the tire is reduced is effectively solved by utilizing the synergistic effect of isophthaloyl hydrazine and 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane.

Disclosure of Invention

In order to solve the above technical problems, a first object of the present application is to provide a tread rubber for preparing a high performance all steel radial tire, which simultaneously adopts two compounds of isophthaloyl hydrazine and 1, 6-bis (N, N' -dibenzothiazyl carbamoyl disulfide) -hexane participating in rubber reaction, and the adopted isophthaloyl hydrazine reacts with aldehyde groups at the ends of natural rubber, so as to improve the dispersibility of carbon black and effectively reduce the Payne effect of a filler and the loss factor tan of a rubber compound.

In order to achieve the above object, the present application adopts the following technical solutions:

the tread rubber composition for preparing the high-performance all-steel radial tire is prepared by mixing the following raw materials in parts by weight:

preferably, the tread rubber composition is prepared by mixing the following raw materials in parts by weight:

preferably, the natural gum is tobacco sheet gum RSS3^#、STR20^#、SMR20^#One or two of them are used in combination.

Preferably, the carbon black is one or two of N134, N234 and N375.

The tread rubber composition for preparing the high-performance all-steel radial tires according to claim 1 or 2, wherein the anti-aging agent is one or more of anti-aging agent 4020, anti-aging agent DTPD and anti-aging agent RD.

Preferably, the total amount of the accelerator and the 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane in the tread rubber is 1.0-2.8 parts by weight.

Preferably, one or two of the promoters NS and CBS are used together as the promoter.

The application further discloses a mixing method of the tread rubber composition, the method simultaneously adopts two compounds of isophthaloyl hydrazine and 1, 6-bis (N, N '-dibenzothiazyl carbamoyl disulfide) -hexane which participate in rubber reaction, the isophthaloyl hydrazine is added into a second rubber section after carbon black is pre-dispersed in natural rubber, and the 1, 6-bis (N, N' -dibenzothiazyl carbamoyl disulfide) -hexane is added after the isophthaloyl hydrazine reacts with the natural rubber.

As a preferred mode, the method of the present application comprises the steps of:

1) starting an internal mixer, setting the rotating speed of a rotor of the internal mixer to be 40-55 rmp, mixing pressure to be 10-15 MPa, cooling water temperature to be 30-40 ℃, rotor temperature to be 30-40 ℃, adding natural rubber, carbon black, zinc oxide, an anti-aging agent and protective wax, mixing for 20-40 seconds, lifting a top bolt, staying for 10-15 seconds, pressing the top bolt, mixing until the temperature is 135-145 ℃, lifting the top bolt, staying for 10-15 seconds, pressing the top bolt, and discharging rubber when the temperature is 145-165 ℃, wherein the rubber is a first-section rubber;

2) the method comprises the steps of firstly, smelting two-stage masterbatch, starting an internal mixer, setting the rotor speed of the internal mixer to be 45-55 rmp, the mixing pressure to be 10-15 MPa, the cooling water temperature to be 30-40 ℃, the rotor temperature to be 30-40 ℃, adding a first-stage rubber and isophthaloyl hydrazine, mixing for 20-40 seconds, lifting a top plug, staying for 5-12 seconds, pressing the top plug, mixing until the temperature is 135-145 ℃, lifting the top plug, reducing the rotation speed to be 20-35 rmp, staying for 10-15 seconds, pressing the top plug, mixing until the temperature is 145-155 ℃, and discharging rubber, wherein the rubber is the two-stage masterbatch;

3) and a step of refining final rubber, which is to start the internal mixer, set the rotor speed of the internal mixer to be 20-35 rmp, the mixing pressure to be 10-15 MPa, the cooling water temperature to be 30-40 ℃ and the rotor temperature to be 30-45 ℃, put the secondary master batch, sulfur, an accelerator, 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane and an anti-scorching agent CTP into a mixing chamber together, lift the top plug for 40-60 seconds, stay for 10-15 seconds for pressing the plug, lift the top plug when the mixing temperature is 80-85 ℃, stay for 10-15 seconds for pressing the top plug, lift the plug and discharge the rubber when the temperature of the rubber material is 100-113 ℃, and cool the lower piece to room temperature to obtain the tread rubber for preparing the high-performance all-steel radial tires.

Further, the application also discloses a high-performance all-steel radial tire, and the tread of the tire is prepared by vulcanizing the tread rubber composition.

The application adopts two compounds of isophthaloyl hydrazine and 1, 6-bis (N, N '-dibenzothiazyl carbamoyl disulfide) -hexane which participate in the reaction with rubber, wherein isophthaloyl hydrazine is added in a second masterbatch section after carbon black is pre-dispersed in natural rubber, and 1, 6-bis (N, N' -dibenzothiazyl carbamoyl disulfide) -hexane is added after isophthaloyl hydrazine reacts with the natural rubber. The mutual promotion and synergy effects can be realized through the added phenylhydrazine and 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane, and the adopted phenylhydrazine reacts with aldehyde groups at the tail ends of natural rubber, so that the dispersibility of carbon black is improved, and the Payne effect of the filler and the loss factor tan of the rubber compound are effectively reduced; the adopted 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane participates in the reaction to form thermodynamically stable monothio bond, disulfide bond and mixed crosslinking bond with similar polysulfide bond flexibility, so as to ensure that the tread has good wear resistance and low hysteresis.

Compared with the prior art, the application has the advantages that the progress is positive and obvious, the technical problems of the defects of reducing heat generation and simultaneously reducing wear resistance in the formula of the all-natural rubber adopting carbon black are effectively solved, the prepared tire can effectively reduce the heat generation of the tire in the use process and simultaneously keep the wear resistance of the tire, so that the rolling resistance and oil consumption of the tire are reduced, and the service life of the tire is prolonged.

Detailed Description

The present application is further illustrated by the following specific examples.

In the present application:

carbon blacks N134, N234, N375: manufactured by cabot chemical (tianjin) limited.

Anti-aging agent 4020: the product is an anti-aging agent 4020 and the chemical name is N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine.

Anti-aging agent RD: manufactured by Tianjin chemical company Limited, and is sold under the name of antioxidant RD and the chemical name of 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer.

Anti-aging agent DTPD: the product is DTPD and the chemical name is N, N' -xylyl p-phenylenediamine.

And (2) an accelerator NS: produced by Shandong Turkish New Material Co., Ltd, under the trade name NS and under the chemical name N-tert-butyl-2-benzene

And (d) a thiazole sulfenamide.

Antiscorching agent CTP: the product is manufactured by Yanggu Huatai chemical company Limited, the product is an anti-scorching agent CTP, and the chemical name is N-cyclohexyl thio-collar phthalimide.

Isophthaloyl hydrazine: tsukamur materials science and technology (shanghai) ltd, under the trade name IDH, and under the chemical name isophthaloyl hydrazine.

1, 6-bis (N, N' -dibenzothiazyl carbamoyldisulfide) -hexane: the product name of Jiangsu Qi Xiang high-tech materials Co., Ltd is WY988, and the chemical name is 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane.