阅读说明：本技术 一种胎面橡胶组合物及其制备方法、载重子午线轮胎 (Tread rubber composition, preparation method thereof and truck radial tire ) 是由 高绪风 刘立杰 张进生 刘连波 丛守青 张晨 李慧 张�杰 王洋 于 2021-10-25 设计创作，主要内容包括：本发明提出一种胎面橡胶组合物及其制备方法、载重子午线轮胎,属于轮胎加工领域,能够解决全钢载重子午线轮胎在耐磨性、低滞后损失等相关性能方面不佳的问题。本发明胎面橡胶组合物,按照质量份计包括下列组分：基体橡胶100份,炭黑20-30份,白炭黑20-30份,硅烷偶联剂2-4份,防老剂3-5份,活性剂4-7份,硫化剂1-3份,促进剂3-5份。本发明胎面橡胶组合物具有更高的耐磨性能、低的滞后损失,较低的生热,能够应用于载重子午线轮胎,使其具有高耐磨低滞后性能。(The invention provides a tread rubber composition, a preparation method thereof and a truck radial tire, belongs to the field of tire processing, and can solve the problem that an all-steel truck radial tire is poor in relevant performances such as wear resistance and low hysteresis loss. The tread rubber composition comprises the following components in parts by mass: 100 parts of matrix rubber, 20-30 parts of carbon black, 20-30 parts of white carbon black, 2-4 parts of silane coupling agent, 3-5 parts of anti-aging agent, 4-7 parts of active agent, 1-3 parts of vulcanizing agent and 3-5 parts of accelerator. The tread rubber composition has higher wear resistance, low hysteresis loss and lower heat generation, and can be applied to a heavy-duty radial tire to ensure that the tread rubber composition has high wear resistance and low hysteresis performance.)

1. The tread rubber composition is characterized by comprising the following components in parts by mass: 100 parts of matrix rubber, 20-30 parts of carbon black, 20-30 parts of white carbon black, 2-4 parts of silane coupling agent, 3-5 parts of anti-aging agent, 4-7 parts of active agent, 1-3 parts of vulcanizing agent and 3-5 parts of accelerator.

2. The tread rubber composition of claim 1, wherein the base rubber comprises 40-55 parts of smoked sheet rubber, 15-25 parts of rare earth butadiene rubber and 25-35 parts of trans poly cyclopentene rubber, and the rare earth butadiene rubber is high-linearity neodymium butadiene rubber CB 22.

3. The tread rubber composition of claim 2, wherein the mass part ratio of the smoked sheet rubber, the rare earth butadiene rubber and the trans-form polycyclopentene rubber is 5: 2: 3.

4. the tread rubber composition of claim 1, wherein the carbon black is MH169 carbon black and the white carbon black is microbead white carbon black.

5. The tread rubber composition according to claim 1, wherein the silane coupling agent is a novel silane coupling agent IMLV; the accelerator is sulfenamide accelerator TBBS and guanidine accelerator DPG; the anti-aging agent is a mixture of p-phenylenediamine antiozonant, quinoline anti-aging agent and bimodal protective wax; the active agent is zinc oxide and stearic acid, and the mass part of the zinc oxide is 2-4 parts; the vulcanizing agent is common sulfur and a multifunctional crosslinking agent, and the multifunctional crosslinking agent is 1, 6 bis (N, N-dibenzyl thiocarbamoyl disulfide) hexane.

6. A method for producing the tread rubber composition according to any one of claims 1 to 5, comprising the steps of:

1) respectively preparing the raw materials according to the mass parts of the raw materials;

2) adding smoked sheet rubber and trans-form poly cyclopentene rubber into a first internal mixer, mixing and then discharging rubber to obtain a plasticated rubber material;

3) placing the plasticated rubber material for 2 hours, putting the plasticated rubber material and rare earth butadiene rubber into a series internal mixer system for mixing, and discharging rubber to obtain a section of master batch;

4) and standing the primary rubber for 8 hours, adding the primary rubber, a vulcanizing agent and an accelerator into a first internal mixer, mixing, and discharging rubber to finish the preparation of final rubber so as to obtain the tread rubber composition.

7. The method for producing a tread rubber composition according to claim 6, wherein the kneading time in the step 2) is 90 to 120 seconds, and the temperature for rubber removal is 155-165 ℃.

8. The method for preparing the tread rubber composition according to claim 6, wherein the series internal mixer system in the step 3) comprises a second internal mixer and a third internal mixer, the plasticated rubber material, the rare earth butadiene rubber, the carbon black, the white carbon black, the silane coupling agent, the anti-aging agent and the activator are firstly added into the second internal mixer, the mixture is mixed for 1.5 to 2.5min at a constant temperature of 135 ℃ and 150 ℃ for 10 to 20 seconds, the rubber is discharged into the third internal mixer for mixing again for 1 to 2min, and then the rubber is discharged into a lower auxiliary machine for supplementary mixing, and the rubber is discharged at a temperature of 155 ℃.

9. The method for producing the tread rubber composition according to claim 6, wherein the kneading time in the step 4) is 2 to 3min, and the temperature for rubber removal is 100-110 ℃.

10. A tire comprising a tread for contact with the ground during driving, characterized in that: the tread is prepared from the tread rubber composition of any of claims 1 to 9 and has a DIN abrasion index of > 250.

Technical Field

The invention belongs to the field of tire processing, and particularly relates to a tread rubber composition, a preparation method thereof and a truck radial tire.

Background

In recent years, with the construction of highways and the rapid development of the automobile industry in China, the requirements of people on the performance of tires are higher and higher, and particularly the demand proportion of high-performance radial tires and ultrahigh-performance radial tires is obviously improved. Since 2012, the european union and the united states have issued specific requirements that tires must comply with, such as high wet skid resistance, low rolling resistance, low noise, low abrasion and low hysteresis loss, which also pose great challenges to the development of domestic high-performance all-steel truck radial tires.

At present, all-steel radial truck tires are widely applied, but the existing all-steel radial truck tires on the market are poor in relevant performances such as wear resistance, low hysteresis loss and the like, and various domestic main engine plants also propose to reduce the rolling resistance of the tires on the basis of ensuring wear resistance and cutting resistance, so that the problem that the technical personnel in the field attach importance to the provision of a high-performance tire with high wear resistance and low hysteresis loss is solved.

Disclosure of Invention

The invention provides a tread rubber composition with high wear resistance and low hysteresis loss, a preparation method thereof and a truck radial tire aiming at the problems in the prior art.

In order to achieve the above object, one aspect of the present invention provides a tread rubber composition, which adopts the following technical scheme:

a tread rubber composition comprises the following components in parts by weight: 100 parts of matrix rubber, 20-30 parts of carbon black, 20-30 parts of white carbon black, 2-4 parts of silane coupling agent, 3-5 parts of anti-aging agent, 4-7 parts of active agent, 1-3 parts of vulcanizing agent and 3-5 parts of accelerator.

Further, the matrix rubber comprises 40-55 parts of smoked sheet rubber, 15-25 parts of rare earth butadiene rubber and 25-35 parts of trans-form poly cyclopentene rubber, and the rare earth butadiene rubber is neodymium butadiene rubber CB22 with high linearity.

And further, the mass part ratio of the smoked sheet rubber, the rare earth butadiene rubber and the trans-form polycyclopentene rubber is 5: 2: 3.

further, the carbon black is MH169 carbon black, and the white carbon black is microbead white carbon black.

Further, the silane coupling agent is a novel silane coupling agent IMLV; the accelerator is sulfenamide accelerator TBBS and guanidine accelerator DPG; the anti-aging agent is a mixture of p-phenylenediamine antiozonant, quinoline anti-aging agent and bimodal protective wax; the active agents are zinc oxide and stearic acid, and the zinc oxide accounts for 2-4 parts; the vulcanizing agent is common sulfur and a multifunctional crosslinking agent, and the multifunctional crosslinking agent is 1, 6 bis (N, N-dibenzyl thiocarbamoyl disulfide) hexane.

The invention also provides a preparation method of the tread rubber composition, which comprises the following steps:

1) respectively preparing the raw materials according to the mass parts of the raw materials;

2) adding smoked sheet rubber and trans-form poly cyclopentene rubber into a first internal mixer, mixing and then discharging rubber to obtain a plasticated rubber material;

3) placing the plasticated rubber material for 2 hours, putting the plasticated rubber material and rare earth butadiene rubber into a series internal mixer system for mixing, and discharging rubber to obtain a section of master batch;

4) and standing the primary rubber for 8 hours, adding the primary rubber, a vulcanizing agent and an accelerator into a first internal mixer, mixing, and discharging rubber to finish the preparation of final rubber so as to obtain the tread rubber composition.

Further, the mixing time in the step 2) is 90-120 seconds, and the glue discharging temperature is 155-165 ℃.

Further, the series internal mixer system in the step 3) comprises a second internal mixer and a third internal mixer, plasticated rubber materials, rare earth butadiene rubber, carbon black, white carbon black, a silane coupling agent, an anti-aging agent and an active agent are firstly added into the second internal mixer, the mixture is mixed for 1.5 to 2.5min, then the mixture is mixed for 10 to 20 seconds at a constant temperature of 135 ℃ plus 150 ℃, the rubber is discharged into the third internal mixer for mixing again for 1 to 2min, then the rubber is discharged into a lower auxiliary machine for supplementary mixing, and the rubber is discharged, wherein the rubber discharging temperature is 155 ℃.

Further, the mixing time in the step 4) is 2-3min, and the glue discharging temperature is 100-.

Accordingly, the present invention also provides a tire comprising a tread for contact with the ground during running, the tread being prepared from the above-described tread rubber composition and having a DIN abrasion index of > 250.

Compared with the prior art, the invention has the advantages and positive effects that:

(1) the invention provides a tread rubber composition and a preparation method thereof, and the tread rubber composition has higher wear resistance, low hysteresis loss and lower heat generation.

(2) The base rubber in the raw materials of the tread rubber composition adopts a wear-resistant crude rubber system which comprises smoked sheet rubber, rare earth butadiene rubber and trans-form polycyclopentene rubber (TPR), and the smoked sheet rubber, the high-linearity rare earth butadiene rubber CB22 and the trans-form polycyclopentene rubber (TPR) are used together, so that the wear resistance of the composition is improved, the hysteresis loss of the rubber composition is greatly reduced, and the rolling resistance is reduced.

(3) The carbon black in the tread rubber composition adopts the carbon black MH169 with high wear resistance and low hysteresis, and the nitrogen adsorption value is 135, so that the wear resistance can be improved; the white carbon black adopts novel white carbon black microbead white carbon black which has high dispersibility and developed pore structure, can greatly increase the contact area with the filler, and can achieve the reinforcing effect by using a smaller using amount.

(4) The silane coupling agent in the tread rubber composition is a novel silane coupling agent IMLV, and the ethoxy group of the traditional silane coupling agent 1/3 is replaced by chemical reaction, so that the rolling resistance is reduced, the VOC emission is reduced, and the hysteresis loss is reduced and the emission reduction is realized.

(5) In the preparation method of the tread rubber composition, the masterbatch is prepared in a series internal mixer system in the preparation of the first section, the constant-temperature mixing is carried out in the second internal mixer, and the constant-temperature mixing is finished and then the mixture enters the third internal mixer for supplementary mixing, so that the raw materials are further dispersed, the parking time and the parking place are saved, the adverse factors of rubber material mixing engineering increase due to high Mooney viscosity of the used rubber material are avoided, the process is simple and feasible, and the industrial production is facilitated.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The embodiment of the invention provides a tread rubber composition, in particular to a tread rubber composition with high wear resistance and low hysteresis loss, which comprises the following components in parts by mass: 100 parts of matrix rubber, 20-30 parts of carbon black, 20-30 parts of white carbon black, 2-4 parts of silane coupling agent, 3-5 parts of anti-aging agent, 4-7 parts of active agent, 1-3 parts of vulcanizing agent and 3-5 parts of accelerator.

The matrix rubber in the embodiment of the invention adopts a wear-resistant crude rubber system, and comprises smoked sheet rubber, rare earth cis-butadiene rubber and trans-polycyclopentene rubber. Wherein, the natural rubber is 40-55 parts, the adopted smoked sheet rubber has good flexibility, rebound resilience and wear resistance, the natural rubber molecule is composed of 1-4-polyisoprene, the molecule is extremely regular, the natural rubber is crystalline rubber and has self-reinforcement, so the smoked sheet rubber has very high mechanical strength; 15-25 parts of rare earth butadiene rubber, adopts high-linearity neodymium butadiene rubber CB22, has low glass transition temperature of-96 ℃, good low-temperature performance, fatigue resistance, low heat generation of compression fatigue, excellent wear resistance and low hysteresis performance; the trans-form polycyclopentene rubber (TPR) is 25-35 parts, cyclopentene in the carbon five fraction is used as a monomer, the glass transition temperature (Tg) of the trans-form polycyclopentene rubber is low and is below minus 90 ℃, the green rubber strength is high, and the trans-form polycyclopentene rubber has high resilience, fatigue resistance, low hysteresis, low rolling resistance and excellent wear resistance.

According to the technical scheme, the smoked sheet rubber, the high-linearity rare earth butadiene rubber CB22 and the trans-form poly cyclopentene rubber (TPR) are used together, so that the wear resistance of the rubber composition is improved, the hysteresis loss of the rubber composition is greatly reduced, and the rolling resistance is reduced.

In a preferred embodiment, the mass part ratio of the smoked sheet rubber, the rare earth butadiene rubber and the trans-form poly cyclopentene rubber is 5: 2: 3.

the carbon black adopted in the embodiment of the invention is the carbon black MH169 carbon black with high wear resistance and low hysteresis, the wear resistance of the carbon black is close to N134, the hysteresis loss is close to N234, and the nitrogen adsorption value of the MH169 carbon black is 135, so that the rolling resistance can be reduced while the wear resistance is improved; white carbon black is novel white carbon black microballon white carbon black, has the characteristics of high dispersibility, can improve the dispersion of white carbon black in the mixture greatly, simultaneously because novel white carbon black microballon white carbon black's pore structure is flourishing, can also increase by a wide margin with the area of contact of filler, adopt less quantity just can reach the effect of reinforcement, greatly reduced carbon black and white carbon black quantity, reduced hysteresis loss.

The silane coupling agent adopted in the embodiment of the invention is a novel silane coupling agent IMLV, and replaces an ethoxy group of the traditional silane coupling agent 1/3 through a chemical reaction, so that the rolling resistance is reduced, the VOC emission is reduced, and the hysteresis loss is reduced and the emission reduction is realized; the accelerator is a sulfenamide accelerator TBBS and a guanidine accelerator DPG which are used together, and the vulcanization activity of the TBBS is improved and the vulcanization speed is accelerated by using the accelerator DPG.

The anti-aging agent adopted in the embodiment of the invention is the combination of p-phenylenediamine antiozonant, quinoline anti-aging agent and bimodal protective wax; the used active agents comprise indirect zinc oxide and stearic acid, wherein the indirect zinc oxide accounts for 2-4 parts, and the rest is stearic acid; the vulcanizing agent is a mixture of common sulfur and a multifunctional crosslinking agent, wherein the multifunctional crosslinking agent is WY9188, namely 1, 6 bis (N, N-dibenzylthiocarbamoyldisulfide) hexane.

According to the embodiment of the invention, by adding the raw materials such as smoked sheet rubber, rare earth cis-polybutadiene rubber and trans-polycyclopentene rubber, MH169 carbon black, microbead white carbon black and a novel silane coupling agent IMLV, the tread has respective performance advantage effects on the basis of the original material, so that the tread formula is more wear-resistant, the hysteresis loss is lower, the heat generation is lower, and the rolling resistance is lower.

The preparation method of the tread rubber composition with high wear resistance and low hysteresis loss of the embodiment comprises the following steps:

1) respectively preparing the raw materials according to the mass parts of the raw materials;

2) adding smoked sheet rubber and trans-form poly cyclopentene rubber into a first internal mixer, mixing and then discharging rubber to obtain a plasticated rubber material;

3) placing the plasticated rubber material for 2 hours, putting the plasticated rubber material and rare earth butadiene rubber into a series internal mixer system for mixing, and discharging rubber to obtain a section of master batch;

4) and standing the primary rubber for 8 hours, adding the primary rubber, a vulcanizing agent and an accelerator into a first internal mixer, mixing, and discharging rubber to finish the preparation of final rubber so as to obtain the tread rubber composition.

The mixing time in the step 2) of the preparation method is 90-120 seconds, the glue discharging temperature is 155-165 ℃, and the optimal temperature is 160 ℃.

The series internal mixer system in the step 3) of the preparation method comprises a second internal mixer and a third internal mixer, plasticated rubber materials, rare earth butadiene rubber, carbon black, white carbon black, a silane coupling agent, an anti-aging agent and an active agent are firstly added into the second internal mixer, the mixture is mixed for 1.5 to 2.5min, then the mixture is mixed for 10 to 20 seconds at a constant temperature of 135 ℃ plus 150 ℃, the rubber is discharged into the third internal mixer for mixing again for 1 to 2min, and then the rubber is discharged into a lower auxiliary machine for supplementary mixing and rubber discharge, wherein the rubber discharge temperature is 155 ℃.

The preparation of the masterbatch in the first section in the steps adopts a series internal mixer system, the masterbatch is mixed in a second internal mixer at constant temperature, and then enters a third internal mixer for supplementary mixing after the constant-temperature mixing is finished, so that the dispersion of raw materials is improved, the parking time and the parking place are saved, the adverse factors of rubber mixing engineering increase due to high Mooney viscosity of the used rubber are avoided, the process is simple and feasible, and the industrial production is facilitated.

The mixing time in the step 4) of the preparation method is 2-3min, the glue discharging temperature is 100-.

The tread rubber composition has high wear resistance and low hysteresis loss, and the DIN abrasion index of the tread of the truck radial tire prepared from the tread rubber composition is more than 250, so that the abrasion performance is greatly improved, the driving mileage of the tire is increased, and the withdrawal rate is reduced; the hysteresis loss is reduced by 16%, and the heat generation is reduced by 5.7%.

In order to more clearly describe the preparation method of the tread rubber composition with high wear resistance and low hysteresis loss provided by the embodiment of the invention, the following description is provided with reference to the specific embodiment.

Table 1 shows the raw material formulations of examples 1 to 3 and comparative examples 1 to 4

Example 1

The preparation method of the tread rubber composition with high wear resistance and low hysteresis loss performance provided by the invention comprises the following steps:

1) respectively preparing the raw materials according to the mass parts in the table 1;

2) adding smoked sheet rubber and trans-poly cyclopentene rubber into a first closed rubber mixing mill, mixing, and discharging rubber when the temperature reaches 160 ℃ to obtain a plasticated rubber material;

3) placing plasticated rubber for 2 hours, putting the plasticated rubber and rare earth butadiene rubber into a series internal mixer system together for mixing, firstly adding the plasticated rubber, the rare earth butadiene rubber, carbon black, white carbon black, a silane coupling agent, an anti-aging agent and an active agent into a second internal mixer, mixing for 1.5-2.5min, then mixing for 20 seconds at the constant temperature of 148 ℃, discharging the rubber to a third closed rubber mixing machine for mixing again for 1.5min, then discharging the rubber to a lower auxiliary machine for supplementary mixing, and discharging the rubber when the temperature reaches 155 ℃ to obtain a section of master batch;

4) standing the primary rubber for 8h, adding the primary rubber, a vulcanizing agent and an accelerator into a first internal mixer, mixing for 2-3min, and finishing the preparation of final rubber at the rubber discharge temperature of 105 ℃ to obtain the tread rubber composition.

Example 2

The difference from the example 1 is that the rare earth butadiene rubber in the example 2 is 30 parts, and the trans-poly cyclopentene rubber (TPR) is 20 parts.

The preparation method is the same as example 1.

Example 3

The difference from the example 1 is that the rare earth butadiene rubber in the example 2 is 10 parts, and the trans-poly cyclopentene rubber (TPR) is 40 parts.

The preparation method is the same as example 1.

Comparative example 1

The difference from example 1 is that carbon black N234 was used in comparative example 1.

The preparation method is the same as example 1.

Comparative example 2

The difference from example 1 is that in comparative example 2, ordinary white carbon black was used.

The preparation method is the same as example 1.

Comparative example 3

The difference from example 1 is that in comparative example 3, liquid silane coupling agent Si-69 was used. The preparation method is the same as example 1.

Comparative example 4

The difference from example 1 is that in comparative example 4, trans-polycyclopentene rubber (TPR) was not used as the base rubber, and only smoked sheet rubber and rare earth butadiene rubber were used.

The preparation method is the same as example 1.

And (3) performance testing:

the tread rubber compositions prepared in examples 1 to 3 and comparative examples 1 to 4 were pressed into rubber sheets of 2.0mm thickness by means of an open mill, and left for 6 hours to prepare respective test specimens.

According to the corresponding national standard GB/T16584-1996 rotor-free vulcanization instrument for rubber determination vulcanization characteristics and GB/T531.1-2008 compression hardness test method for vulcanized rubber or thermoplastic rubber part 1: shore durometer method (Shore hardness), GB/T533-2008 & lt & gt determination of density of vulcanized rubber or thermoplastic rubber, GB/T528-2009 & lt & gt determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber, GB/T529-2008 & lt & gt determination of tear strength of vulcanized rubber and thermoplastic rubber, GB/T1-2009 & lt & gt determination of resilience of vulcanized rubber, GB/T9867-2008 & lt & gt determination of wear resistance of vulcanized rubber or thermoplastic rubber (rotating drum type wearing machine method) & lt & gt, were subjected to various performance tests, and specific performance test results are shown in tables 2-5.

Table 2 shows a comparison of the physical properties of the tread rubber compositions obtained in examples 1 to 3 and comparative examples 1 to 4.

Table 3 shows the results of comparison of the respective performance indexes of tread rubber compositions obtained in examples 1 to 3 and comparative examples 1 to 4, which were vulcanized at 151 ℃ for 30 minutes by a steam press vulcanizer.

Table 4 shows the performance indexes of tread rubber compositions obtained in examples 1 to 3 and comparative examples 1 to 4 after aging at 100 ℃ for 48 hours.

Table 5 shows DMA measurements of the tread rubber compositions obtained in examples 1 to 3 and comparative examples 1 to 4 at a temperature of-20 ℃ to 80 ℃. The hysteresis loss factor obtained using DMA scanning can be used to characterize the rolling resistance and heat build-up of a tire, with lower rolling resistance and lower heat build-up for smaller hysteresis loss factors.

Test parameters	Example 1	Example 2	Example 3	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
								0℃Tanδ	0.1339	0.1387	0.1412	0.1505	0.1445	0.1431	0.1451
60℃Tanδ	0.0715	0.0734	0.0728	0.0739	0.0802	0.0865	0.0889

As can be seen from tables 2 to 5, the tread rubber composition prepared in example 1 exhibited the best abrasion resistance before and after aging, the lowest heat generation and the lowest hysteresis loss (tg. delta. at 60 ℃); the DIN abrasion indexes of the tread rubber compositions prepared in examples 1-3 are greater than 250, and the DIN abrasion indexes of the tread rubber compositions prepared in comparative examples 1-4 are all greater. The proportion of trans-polycyclopentene rubber (TPR) in example 1 is most suitable as compared with examples 2 and 3, and the wear resistance of the obtained tread rubber composition is the best.

In comparison with comparative example 1, example 1 used carbon black MH169, and the tread rubber composition obtained therefrom was significantly superior in abrasion resistance to that of the tread rubber composition obtained in comparative example 1; compared with the comparative example 2, the novel white carbon black microbead white carbon black is adopted in the example 1, and the hysteresis loss of the obtained tread rubber composition is obviously lower than that of the tread rubber composition obtained in the comparative example 2; in comparison with comparative example 3, example 1 employed a novel silane coupling agent IMLV, which gave a tread rubber composition having a hysteresis loss significantly lower than that of the tread rubber composition obtained in comparative example 3; compared with the comparative example 4, the base rubber adopted in the example 1 comprises trans-poly cyclopentene rubber (TPR), the DIN abrasion index of the obtained tread rubber composition is larger than that of the tread rubber composition obtained in the comparative example 4, the DIN abrasion index of the obtained tread rubber composition is still larger than that of the tread rubber composition obtained in the comparative example 4 after aging for 48 hours at 100 ℃, and the abrasion resistance of the obtained tread rubber composition is obviously better than that of the obtained tread rubber composition in the comparative example 4.