阅读说明：本技术 一种高性能轮胎胎侧用橡胶组合物及其制备方法 (High-performance rubber composition for tire side and preparation method thereof ) 是由 季军胜 徐檬 徐宝羚 于 2019-10-28 设计创作，主要内容包括：本发明公开了一种高性能轮胎胎侧用橡胶组合物及其制备方法,其中所述高性能轮胎胎侧用橡胶组合物,以100重量份的橡胶成分为基准,包括以下组分,40-50重量份的N220炭黑、1-2重量份的硫、2-5.5重量份的防老剂、0.5-1重量份的硫磺、1-1.5重量份的促进剂、3-8重量份的活性剂及0.1-0.4重量份的防焦剂；其中橡胶成分为天然橡胶和顺丁橡胶、且所述天然橡胶占30-50wt%；其中,所述顺丁橡胶采用钕系支化末端改性顺丁橡胶或镍系高顺式顺丁橡胶的一种或两种并用；其中,所述硫磺和所述促进剂按1：1.5-3进行配比。本发明所采用的配方可实现高强度、耐撕裂、耐疲劳以及较好的耐老化性能；同时所采用的制备方法能满足加工性能需要,更加效率,更加节能,分散效果更好。(The invention discloses a rubber composition for a high-performance tire side wall and a preparation method thereof, wherein the rubber composition for the high-performance tire side wall comprises 40-50 parts by weight of N220 carbon black, 1-2 parts by weight of sulfur, 2-5.5 parts by weight of an anti-aging agent, 0.5-1 part by weight of sulfur, 1-1.5 parts by weight of an accelerator, 3-8 parts by weight of an active agent and 0.1-0.4 part by weight of a scorch retarder on the basis of 100 parts by weight of a rubber component; wherein the rubber components are natural rubber and butadiene rubber, and the natural rubber accounts for 30-50 wt%; wherein the butadiene rubber is one or two of neodymium branched terminal modified butadiene rubber or nickel high cis-butadiene rubber; wherein the sulfur and the accelerator are mixed according to a ratio of 1: 1.5-3. The formula adopted by the invention can realize high strength, tear resistance, fatigue resistance and better aging resistance; meanwhile, the adopted preparation method can meet the requirements of processability, and is more efficient, more energy-saving and better in dispersing effect.)

1. The rubber composition for the side wall of the high-performance tire is characterized by comprising 40-50 parts by weight of N220 carbon black, 2-5 parts by weight of an anti-aging agent, 0.5-1 part by weight of sulfur, 1-1.5 parts by weight of an accelerator, 3-8 parts by weight of an active agent and 0.1-0.4 part by weight of an anti-scorching agent based on 100 parts by weight of a rubber component;

wherein the rubber components are natural rubber and butadiene rubber, and the natural rubber accounts for 30-50 wt%;

wherein the butadiene rubber is one or two of neodymium branched terminal modified butadiene rubber or nickel high cis-butadiene rubber;

wherein the sulfur and the accelerator are mixed according to a ratio of 1: 1.5-3.

2. The high performance rubber composition for tire sidewalls as in claim 1, wherein said anti-aging agent is microcrystalline wax, N-phenyl-N '- (1, 3-dimethylbutyl) p-phenylenediamine, and N, N' -ditolyl-p-phenylenediamine in a weight ratio of 2: 2: 1, and mixing the components in a ratio of 1.

3. A method for producing the rubber composition for a high performance tire side wall according to claims 1 to 2, characterized by comprising the steps of,

(1) first-stage mixing:

putting natural rubber, butadiene rubber, a dispersing agent, an anti-aging agent and an active agent into a meshing type internal mixer with the rotating speed of 40-50rpm and the pressure of 90-110Bar according to the proportion, and pressurizing for 20-40S to lift a weight;

adding N220 carbon black into the internal mixer, pressurizing for 60-70S, and then pressurizing to 160-170 ℃ to lift and discharge rubber; the lower auxiliary machine discharges the rubber compound into a rubber sheet in a double-screw extrusion tablet press, the rubber sheet is transferred to an open mill unit formed by connecting open mills in parallel for supplementary mixing for 6-8min, the open mill at the terminal discharges the rubber sheet to obtain a section of master rubber, and the master rubber is placed for 4-6h at room temperature;

(2) final mixing:

putting sulfur, an accelerant, a scorch retarder and a section of masterbatch into a shearing type internal mixer with the rotating speed of 20-30rpm and the pressure of 140-160Bar, pressurizing 40-50S weight, pressurizing 30-40S weight, and finally pressurizing to 110-120 ℃ weight and discharging the masterbatch;

and (3) discharging the rubber compound from the double-screw extrusion tablet press by using a lower auxiliary machine, transferring the rubber compound to an open mill unit formed by connecting open mills in parallel, performing supplementary mixing for 3-5min, discharging the rubber compound by using a terminal open mill to obtain final rubber compound, and cooling to room temperature to obtain the high-performance rubber composition.

4. The method for preparing a rubber composition for a high-performance tire side wall according to claim 3, wherein in the step (1), the roll speed of the front roll of each open mill is controlled to be 30-35rpm, the roll speed of the rear roll of each open mill is controlled to be 25-30rpm, the roll temperature is controlled to be below 135 ℃, and the roll gap is controlled to be 2-4 cm.

5. The method for preparing a rubber composition for a high-performance tire side wall according to claim 3, wherein in the step (2), the roll speed of the front roll of each open mill is controlled to be 25-30rpm, the roll speed of the rear roll of each open mill is controlled to be 20-25rpm, the roll temperature is controlled to be below 100 ℃, and the roll gap is controlled to be 2-4 cm.

Technical Field

The invention belongs to the technical field of tires, and particularly relates to a high-performance rubber composition for a tire side and a preparation method thereof.

Background

Along with people's environmental awareness is higher and higher, traditional diesel engine car begins to be gradually replaced by electric automobile, electric drive is also changed into mostly to city public transit, motor drive except cleaner, its starting torque is bigger, initial acceleration is faster, consequently, the performance requirement to the tire is just severer, wherein to tire side strength and tear resistance demand harsher, if side strength is more weak, tear resistance is relatively poor, easily cause the side wall early breach to appear, can not effectively play the effect of protection matrix cord, influence tire security performance, for adapting to electric public transit tire performance demand, promotion tire side strength and tear resistance have become the first objective.

As is well known, the main component of the tire sidewall is rubber, which is divided into natural rubber and synthetic rubber, and because the tire always performs circular rotation motion in the using process and the sidewall correspondingly performs circular reciprocating motion, the sidewall needs certain fatigue resistance besides certain strength and tear resistance, and the prepared sidewall rubber composition is difficult to maintain the fatigue resistance and the aging resistance of the sidewall while improving the strength and the tear resistance of the sidewall in the prior art.

Disclosure of Invention

The invention aims to provide a preparation method of a high-performance rubber composition for a tire side wall, so as to overcome the technical problems.

The technical purpose of the invention is realized by the following technical scheme:

a high-performance rubber composition for tire side walls comprises, based on 100 parts by weight of rubber components, 40-50 parts by weight of N220 carbon black, 1-2 parts by weight of sulfur, 2-5 parts by weight of anti-aging agent, 0.5-1 part by weight of sulfur, 1-1.5 parts by weight of accelerator, 3-8 parts by weight of activator and 0.1-0.4 part by weight of anti-scorching agent; wherein the rubber components are natural rubber and butadiene rubber, and the natural rubber accounts for 30-50 wt%; wherein the butadiene rubber is one or both of neodymium branched terminal modified butadiene rubber or nickel high cis-butadiene rubber; wherein the sulfur and the accelerator are mixed according to a ratio of 1: 1.5-3.

Wherein the anti-aging agent is microcrystalline wax, N-phenyl-N '- (1, 3-dimethylbutyl) p-phenylenediamine and N, N' -xylyl p-phenylenediamine, and the weight ratio of the anti-aging agent to the anti-aging agent is 2: 2: 1, and mixing the components in a ratio of 1.

Another object of the present invention is to provide a method for preparing a rubber composition for a high performance tire sidewall, comprising the steps of,

(1) first-stage mixing:

putting natural rubber, butadiene rubber, a dispersing agent, an anti-aging agent and an active agent into a meshing type internal mixer with the rotating speed of 40-50rpm and the pressure of 90-110Bar according to the proportion, and pressurizing for 20-40S to lift a weight;

adding N220 carbon black into the internal mixer, pressurizing for 60-70S, and then pressurizing to 160-170 ℃ to lift and discharge rubber;

the lower auxiliary machine discharges the rubber compound into a rubber sheet in a double-screw extrusion tablet press, the rubber sheet is transferred to an open mill unit formed by connecting open mills in parallel for supplementary mixing for 6-8min, the open mill at the terminal discharges the rubber sheet to obtain a section of master rubber, and the master rubber is placed for 4-6h at room temperature;

(2) final mixing:

putting sulfur, an accelerant, a scorch retarder and a section of masterbatch into a shearing type internal mixer with the rotating speed of 20-30rpm and the pressure of 140-160Bar, pressurizing 40-50S weight, pressurizing 30-40S weight, and finally pressurizing to 110-120 ℃ weight and discharging the masterbatch;

and (3) discharging the rubber compound from the double-screw extrusion tablet press by using a lower auxiliary machine, transferring the rubber compound to an open mill unit formed by connecting open mills in parallel, performing supplementary mixing for 3-5min, discharging the rubber compound by using a terminal open mill to obtain final rubber compound, and cooling to room temperature to obtain the high-performance rubber composition.

Further, in the step (1), the roll speed of the front roll of each open mill is controlled to be 30-35rpm, the roll speed of the rear roll of each open mill is controlled to be 25-30rpm, the roll temperature is controlled to be below 135 ℃, and the roll spacing is controlled to be 2-4 cm.

Further, in the step (2), the roll speed of the front roll of each open mill is controlled to be 25-30rpm, the roll speed of the rear roll of each open mill is controlled to be 20-25rpm, the roll temperature is controlled to be below 100 ℃, and the roll spacing is controlled to be 2-4 cm.

Has the advantages that: the formula adopted by the invention can realize high strength, tear resistance, fatigue resistance and better aging resistance; meanwhile, the adopted preparation method improves the production process, reduces the number of mixing stages, shortens mixing time, improves dispersion performance, is convenient for large-scale rapid production, can meet the requirement of processability, and is more efficient and energy-saving.

Detailed Description

In the description of the present invention, unless otherwise specified, the terms "upper", "lower", "left", "right", "front", "rear", and the like, indicate orientations or positional relationships only for the purpose of describing the present invention and simplifying the description, but do not indicate or imply that the designated device or structure must have a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

A high-performance rubber composition for tire side walls comprises, based on 100 parts by weight of rubber components, 40-50 parts by weight of N220 carbon black, 2-5 parts by weight of anti-aging agent, 0.5-1 part by weight of sulfur, 1-1.5 parts by weight of accelerator, 3-8 parts by weight of activator and 0.1-0.4 part by weight of anti-scorching agent; wherein the rubber components are natural rubber and butadiene rubber, and the natural rubber accounts for 30-50 wt%; wherein the butadiene rubber is one or both of neodymium branched terminal modified butadiene rubber or nickel high cis-butadiene rubber; wherein the sulfur and the accelerator are mixed according to a ratio of 1: 1.5-3.

Wherein the anti-aging agent is microcrystalline wax, N-phenyl-N '- (1, 3-dimethylbutyl) p-phenylenediamine and N, N' -xylyl p-phenylenediamine, and the weight ratio of the anti-aging agent to the anti-aging agent is 2: 2: 1, and mixing the components in a ratio of 1.

Based on the above formulation design, the following examples are provided to illustrate the present invention and to examine the properties of the rubber compositions prepared in the examples, which are specifically shown in tables 1 and 2 below.

TABLE 1 (examples)

Wherein: the natural rubber is one of SMR10#, STR10#, SIR10#, SMR20#, STR20#, and SIR20 #;

the cis-butadiene rubber is one or both of neodymium branched end modified cis-butadiene rubber or nickel high cis-butadiene rubber;

the anti-aging agent A is microcrystalline wax;

the anti-aging agent B is N-phenyl-N' - (1, 3-dimethylbutyl) p-phenylenediamine;

the anti-aging agent C is N, N' -xylyl p-phenylenediamine;

the accelerant is one or more of N-cyclohexyl-2-benzothiazole sulfonamide, N-dicyclohexyl-2-benzothiazole sulfonamide and N-tertiary butyl-2-benzothiazole sulfonamide.

The active agent consists of zinc oxide and stearic acid;

the scorch retarder is N-cyclohexyl thiophthalimide.

TABLE 2 (Performance test)

As can be seen from the above table, the tensile fatigue and aging retention of examples 1-6 in the formulation range are better than those of comparative examples 1-2, particularly the obvious difference between tensile fatigue of examples 1-6 and aging retention of comparative example 1 and aging retention of examples 1-6 and comparative example 2; in addition, the tensile strength, the tear strength, the aging retention rate and the tensile fatigue data of the embodiments 1 to 6 show that the embodiments of the present application have good sidewall strength, tear resistance, fatigue performance and aging resistance.

Meanwhile, the invention also aims to provide a preparation method of the rubber composition for the side wall of the high-performance tire according to the formula, which comprises the following steps,

(1) first-stage mixing:

putting natural rubber, butadiene rubber, a dispersing agent, an anti-aging agent and an active agent into a meshing type internal mixer with the rotating speed of 40-50rpm and the pressure of 90-110Bar according to the proportion, and pressurizing for 20-40S to lift a weight;

adding N220 carbon black into the internal mixer, pressurizing for 60-70S, and then pressurizing to 160-170 ℃ to lift and discharge rubber;

the lower auxiliary machine discharges the rubber compound into a rubber sheet in a double-screw extrusion tablet press, the rubber sheet is transferred to an open mill unit formed by connecting open mills in parallel for supplementary mixing for 6-8min, and the rubber sheet is gathered to a terminal open mill for discharging, so that a section of master rubber is prepared, and the master rubber is placed for 4-6h at room temperature; wherein, the open mill set takes the glue feeding direction, the roller speed of the front roller of each open mill is controlled at 30-35rpm, the roller speed of the rear roller is controlled at 25-30rpm, the roller temperature is controlled below 135 ℃, and the roller spacing is controlled at 2-4 cm;

(2) final mixing:

putting sulfur, an accelerant, a scorch retarder and a section of masterbatch into a shearing type internal mixer with the rotating speed of 20-30rpm and the pressure of 140-160Bar, pressurizing 40-50S weight, pressurizing 30-40S weight, and finally pressurizing to 110-120 ℃ weight and discharging the masterbatch;

the lower auxiliary machine discharges rubber sheets from the rubber compound in a double-screw extrusion tablet press, the rubber sheets are transferred to an open mill unit formed by connecting open mills in parallel for supplementary mixing for 3-5min, the rubber sheets are gathered to a terminal open mill for lower sheet, and final rubber compound is prepared, and the final rubber compound is cooled to room temperature, so that the high-performance rubber composition is prepared; wherein, the open mill set takes the rubber as the direction, the roller speed of the front roller of each open mill is controlled at 25-30rpm, the roller speed of the rear roller is controlled at 20-25rpm, the roller temperature is controlled below 100 ℃, and the roller spacing is controlled at 2-4 cm.

A rubber composition was prepared according to the formulation of example 3 in the following three ways, and the prepared rubber composition was examined (the rubber composition of example 3 in table 2 was prepared according to the first way).

The first method is as follows: a preparation method of a rubber composition for a high-performance tire side wall comprises the following steps,

(1) first-stage mixing:

putting natural rubber, butadiene rubber, a dispersing agent, an anti-aging agent and an active agent into a meshing type internal mixer with the rotating speed of 45m and the pressure of 108Bar according to the proportion, and pressurizing for 40S to lift a weight;

adding N220 carbon black into the internal mixer, pressurizing 65S weight, and lifting and discharging rubber when the pressure is increased to 165 ℃;

the lower auxiliary machine discharges the rubber compound into a rubber sheet in a double-screw extrusion tablet press, the rubber sheet is transferred to an open mill unit formed by connecting 4 open mills in parallel for supplementary mixing for 6min, and the rubber sheet is gathered to the lower sheet of a terminal open mill to obtain a section of master rubber which is stood for 6h at room temperature; wherein, the open mill set takes the rubber as the entering direction, the roller speed of the front roller of each open mill is controlled at 32rpm, the roller speed of the rear roller is controlled at 28rpm, the roller temperature is controlled below 135 ℃, and the roller spacing is controlled at 2.5 cm;

(2) final mixing:

putting sulfur, an accelerant, a scorch retarder and a section of masterbatch into a shearing type internal mixer with the rotating speed of 25rpm and the pressure of 140Bar, pressurizing 40S weight, then pressurizing 40S weight, and finally pressurizing to 115 ℃ to lift weight and discharge rubber;

the lower auxiliary machine discharges rubber sheets from the rubber compound in a double-screw extrusion tablet press, the rubber sheets are transferred to an open mill unit formed by connecting open mills in parallel for supplementary mixing for 3min, the rubber sheets are gathered to a terminal open mill for lower sheet, and final rubber compound is prepared, and the final rubber compound is cooled to room temperature, so that the high-performance rubber composition is prepared; wherein, the open mill set takes the rubber as the direction, the roller speed of the front roller of each open mill is controlled at 25rpm, the roller speed of the rear roller is controlled at 20rpm, the roller temperature is controlled below 100 ℃, and the roller spacing is controlled at 2-4 cm.

The second method comprises the following steps:

(1) first-stage mixing:

the method is carried out in a shearing type internal mixer, the rotating speed of the internal mixer is 45rpm, the pressure is 108Bar, natural rubber, butadiene rubber, a dispersing agent, an anti-aging agent and an activating agent are added according to the proportion, 40S weight lifting is carried out, carbon black is added into the internal mixer, 65S weight lifting is carried out, the weight lifting is carried out when the pressure is increased to 165 ℃, rubber is lifted and discharged, and a section of master batch is prepared. Standing the primary rubber for 4-6 hours at room temperature, and finally mixing.

(2) Final mixing:

the process is carried out in a shear type internal mixer, the speed of the internal mixer is 25rpm, and the pressure is 140 Bar. Adding a section of masterbatch, sulfur, an accelerator and an anti-scorching agent into an internal mixer, pressurizing 40S weight, and finally pressurizing to 115 ℃ to lift and discharge rubber to obtain the final rubber compound.

Mode III

(1) First-stage mixing: the process was carried out in a shear type internal mixer, at a speed of 45rpm, at a pressure of 108 Bar. Adding natural rubber, butadiene rubber, a dispersing agent, an anti-aging agent and an activating agent according to a proportion, pressurizing 40S weight lifting, adding carbon black into an internal mixer, pressurizing 65S weight lifting, and lifting and discharging rubber when the pressure is increased to 165 ℃. To obtain a primary rubber. Standing the primary masterbatch for 4-6 hours at room temperature, and then performing secondary mixing.

(2) And (3) second-stage mixing: the process was carried out in a shear type internal mixer, at a speed of 45rpm, at a pressure of 108 Bar. Adding a section of master batch, pressurizing for 35S, pressurizing for 60S, and then pressurizing to 165 ℃ to lift and discharge the rubber. To obtain the second-stage masterbatch. Standing the two-stage masterbatch for 4-6 hours at room temperature, and then carrying out three-stage mixing.

(3) Three-stage mixing: the process was carried out in a shear type internal mixer, at a speed of 45rpm, at a pressure of 108 Bar. Adding two-stage masterbatch, pressurizing 35S weight, pressurizing 60S weight, and then lifting and discharging the masterbatch when the pressure is increased to 165 ℃. And obtaining the three-stage masterbatch. Standing the three-stage master batch at room temperature for 4-6 hours, and then carrying out four-stage mixing.

(4) Four-stage mixing: the process was carried out in a shear type internal mixer, at a speed of 45rpm, at a pressure of 108 Bar. Adding three sections of master batch, pressurizing 35S weight, pressurizing 60S weight, and then lifting and discharging the rubber when the pressure is increased to 165 ℃. And preparing the four-section masterbatch. Standing the four-stage masterbatch for 4-6 hours at room temperature, and finally mixing.

(5) Final mixing: the process is carried out in a shear type internal mixer, the speed of the internal mixer is 25rpm, and the pressure is 140 Bar. Adding the four-section masterbatch, sulfur, an accelerant and an anti-scorching agent into an internal mixer, pressurizing 40S weight lifting, and finally lifting and discharging rubber when the pressure is increased to 115 ℃ to obtain the final rubber compound.

The test data for the three mixes prepared at the time above are as follows:

TABLE 3

Scheme(s)	In a first mode	Mode two	Mode III
				Mooney viscosity 100 ℃ ML (1+4)	57	86	60
Rheology 151 deg.C Tc95(min)	13.03	13.56	12.74
				Carbon black dispersion X value	6.7	2.4	6.0
Tensile strength (Mpa)	19.9	21.0	19.7
				Tear Strength (KN/m)	132	121	117
Aging retention ratio of 100 ℃ multiplied by 48H	92％	86％	83％
				Tensile fatigue (times)	210 ten thousand	190 ten thousand	180 ten thousand

From table 3, it can be seen that:

(1) compared with the first mode and the third mode, the Mooney viscosity of the second mode is too high, and although the requirements on tensile strength, tear strength, aging retention rate and tensile fatigue are met due to the formula, the phenomena of pitted surface and edge cracking are easy to occur during the extrusion of the later tire side, and the processability of rubber compound is poor;

(2) the Mooney viscosity of the third mode is equivalent to that of the first mode, and pitted surfaces and cracked edges do not occur during extrusion of the tire side, but the mixing process of 4-section primary mixing and 1-section final mixing adopted for preparation has low production efficiency and higher energy consumption, and the mechanical property of the rubber material is adversely affected by multi-section mixing, wherein the tensile strength and the tearing strength are reduced;

(3) the first mode can achieve the purposes of high strength, tear resistance, fatigue resistance and better aging resistance, and can also meet the requirements of processability, and the preparation method is more efficient, saves more energy and has the best dispersion effect.

In order to make the objects, technical solutions and advantages of the present invention more concise and clear, the present invention is described with the above specific embodiments, which are only used for describing the present invention, and should not be construed as limiting the scope of the present invention. It should be understood that any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.