CN112778590A - Rubber composition, preparation method and application thereof, rubber composition for tire treads and preparation method thereof - Google Patents

Rubber composition, preparation method and application thereof, rubber composition for tire treads and preparation method thereof Download PDF

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Publication number
CN112778590A
CN112778590A CN201911059264.3A CN201911059264A CN112778590A CN 112778590 A CN112778590 A CN 112778590A CN 201911059264 A CN201911059264 A CN 201911059264A CN 112778590 A CN112778590 A CN 112778590A
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parts
carbon black
rubber
rubber composition
mixing
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CN112778590B (en
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王雷雷
刘苹
解希铭
李绍宁
段海东
乔勋昌
刘翠云
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the field of rubber and discloses a rubber composition, wherein the rubber composition comprises 50-100 parts by mass of solution polymerized styrene-butadiene rubber (SBR) in 100 parts by mass of the total amount of rubber; 0-50 parts of butadiene rubber; 50-77 parts of white carbon black; 2-10 parts by mass of carbon black; 5-25 parts of calcium sulfate whisker; 4-10 parts of a surface modifier; 5-15 parts by mass of a softener; 2-8 parts of an activating agent; 0.3-2 parts by mass of a vulcanizing agent; 2-6 parts of an accelerator; 1-5 parts of anti-aging agent, and 77-87 parts of white carbon black, carbon black and calcium sulfate whisker. The rubber composition has low rolling resistance on the premise of not reducing the wet skid resistance and the wear resistance, obviously reduces the fuel consumption of tires, and is suitable for preparing green and energy-saving tire tread rubber.

Description

Rubber composition, preparation method and application thereof, rubber composition for tire treads and preparation method thereof
Technical Field
The invention relates to the field of rubber, in particular to a rubber composition, a preparation method and application thereof, and a rubber composition for tire treads and a preparation method thereof.
Background
The green environmental protection is the development direction of the future society, and in recent years, green tires are paid attention to due to the characteristics of low rolling resistance, oil saving and environmental protection. The united states passed regulations including tire label regulations as early as 2007; japan implemented a voluntary tire labeling system from 2010; and the european union and korea have implemented a mandatory tire label regulation from 11/1/2012. These regulations put higher level requirements on tire rolling resistance and wet skid resistance, so the research on how to reduce tire rolling resistance and improve wet skid resistance is of great significance to the green upgrade of the Chinese tire industry.
At present, research is focused on how to improve the dispersion of the white carbon black in the rubber matrix, including wet mixing, improving the mixing equipment capability, and the like. The application of calcium sulfate whiskers in rubber has been studied, and CN102134339A discloses a calcium sulfate whisker modified styrene-butadiene rubber composite material and a preparation process thereof.
CN102234387A discloses a calcium sulfate whisker modified rubber and a preparation process thereof, and the provided calcium sulfate whisker modified rubber is used as a tire side rubber material for manufacturing a tire, so that the environmental stress resistance of the tire can be effectively improved, and the tire is not easy to crack. The rubber is particularly suitable for being used as sidewall rubber of high-performance large and medium heavy duty tires.
In the above patents, the calcium sulfate whisker is modified and then added to the rubber to improve the performance of the rubber. The preparation process is complicated and the process cost is increased. Meanwhile, in the prior art, no relevant report of using the calcium sulfate whiskers for preparing green tire tread rubber exists.
Disclosure of Invention
The invention aims to overcome the problem of high rolling resistance existing when a rubber composition is used for a tire tread in the prior art, and provides a rubber composition, a preparation method and application thereof, and a rubber composition for a tire tread and a preparation method thereof.
In order to achieve the above object, the first aspect of the present invention provides a rubber composition comprising, based on 100 parts by mass of the total amount of rubber, 50 to 100 parts by mass of a solution-polymerized styrene-butadiene rubber; 0-50 parts of butadiene rubber; 50-77 parts of white carbon black; 2-10 parts by mass of carbon black; 5-25 parts of calcium sulfate whisker; 4-10 parts of a surface modifier; 5-15 parts by mass of a softener; 2-8 parts of an activating agent; 0.3-2 parts by mass of a vulcanizing agent; 2-6 parts of an accelerator; 1-5 parts of an anti-aging agent;
the total amount of the white carbon black, the carbon black and the calcium sulfate whisker is 77-87 parts by mass.
In a second aspect, the present invention provides a method for preparing the rubber composition of the present invention.
In a third aspect, the invention provides a use of the rubber composition of the invention, wherein the use is a tire, preferably a tire tread.
The fourth aspect of the present invention provides a rubber composition for a tire tread, wherein the rubber composition is the rubber composition of the present invention.
In a fifth aspect, the present invention provides a method for producing the rubber composition for a tire tread of the present invention, the method comprising vulcanizing the rubber composition for a tire tread.
Through the technical scheme, the rubber composition, the preparation method and the application thereof, the rubber composition for the tire tread and the preparation method thereof provided by the invention have the following beneficial effects:
the rubber composition containing the calcium sulfate whiskers provided by the invention has low rolling resistance, the fuel consumption of a tire containing the rubber composition is obviously reduced, and a green and energy-saving tire is obtained.
In the preparation method of the rubber composition provided by the invention, the calcium sulfate whisker does not need to be modified in advance, so that the preparation process of the rubber composition is greatly simplified, and the process cost is reduced.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a rubber composition comprising, based on 100 parts by mass of the total amount of rubber, 50 to 100 parts by mass of a solution-polymerized styrene-butadiene rubber; 0-50 parts of butadiene rubber; 50-77 parts of white carbon black; 2-10 parts by mass of carbon black; 5-25 parts of calcium sulfate whisker; 4-10 parts of a surface modifier; 5-15 parts by mass of a softener; 2-8 parts of an activating agent; 0.3-2 parts by mass of a vulcanizing agent; 2-6 parts of an accelerator; 1-5 parts of an anti-aging agent;
the total amount of the white carbon black, the carbon black and the calcium sulfate whisker is 77-87 parts by mass.
In the invention, the inventor researches and discovers that the calcium sulfate whisker, the carbon black and the white carbon black are matched with each other and are added into the rubber composition together as a filler, so that the rolling resistance of the rubber composition can be obviously improved on the premise of not reducing the wear resistance and the wet skid resistance of the rubber composition, and the provided rubber composition containing the calcium sulfate whisker has the characteristic of low rolling resistance.
Meanwhile, the inventors have studied and found that, when the amounts of the respective components in the rubber composition satisfy the above requirements, the obtained rubber composition exhibits more excellent overall properties, in particular, lower rolling resistance without affecting the abrasion resistance and wet skid resistance of the rubber composition.
Further, in the present invention, the total amount of the rubber is 60 to 80 parts by mass per 100 parts by mass of the solution-polymerized styrene-butadiene rubber; 20-40 parts of butadiene rubber; 60-80 parts of white carbon black; 4-8 parts of carbon black; 10-20 parts of calcium sulfate whisker; 5-7 parts of a surface modifier; 8-13 parts by mass of a softener; 3-6 parts of an activating agent; 0.5-1.5 parts by mass of a vulcanizing agent; 3-5 parts of an accelerator; 2-4 parts of an anti-aging agent; the total amount of the white carbon black, the carbon black and the calcium sulfate whisker is 80-85 parts by mass.
According to the invention, the white carbon black is selected from fumed white carbon black and/or precipitated white carbon black, preferably precipitated white carbon black.
According to the invention, the nitrogen adsorption specific surface area of the white carbon black is 60-230m2Per g, preferably from 100 to 190m2(ii) in terms of/g. For example, the white carbon black may be 115GR and 165GR of Rodiya, France, and the nitrogen adsorption specific surface areas thereof are 115m2G and 165m2/g。
According to the invention, the carbon black has a CTAB adsorption specific surface area of 10 to 300m2A/g, preferably from 20 to 140m2(ii) in terms of/g. For example, the carbon black may be N330 and N220 of Zideli chemical technology Co., Ltd, Dongguan, and the CTAB adsorption specific surface areas thereof are 82m each2G and 111m2/g。
The length-diameter ratio of the calcium sulfate whisker is (30-80): 1, preferably (30-60): 1.
according to the invention, the calcium sulphate whiskers have an average diameter of 1 to 6 μm, preferably 2 to 5 μm. For example, the calcium sulfate whiskers are available from shenyang dongdong mineral materials research and development ltd, and have an aspect ratio of 45:1 and an average diameter of 4 μm.
According to the invention, the surface modifier is at least one selected from silane coupling agent, zirconate coupling agent, phthalate coupling agent and alcohol compound, preferably silane coupling agent, for example, the surface modifier is bis- [ gamma- (triethoxy silicon) propyl ] -tetrasulfide (Si 69).
According to the invention, the antioxidant is selected from a physical antioxidant and/or a chemical antioxidant.
According to the invention, the chemical anti-aging agent is at least one selected from amine anti-aging agents, quinoline anti-aging agents and benzimidazole anti-aging agents. The physical anti-aging agent is selected from paraffin and/or microcrystalline wax. For example, the chemical antioxidant is N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (4020), and the physical antioxidant is microcrystalline wax.
According to the present invention, the softening agent is at least one selected from the group consisting of aromatic oil, paraffin oil, naphthenic oil, petroleum resin, and low molecular weight polyethylene glycol. For example, the softener is environment-friendly aromatic oil TDAE and PEG 4000.
According to the invention, the active agent is selected from the group consisting of a combination of metal oxides and fatty acids and/or fatty acid metal soap salts.
According to the invention, the metal oxide is selected from zinc oxide and/or magnesium oxide.
According to the invention, the fatty acid is chosen from stearic acid.
According to the invention, the fatty acid metal soap salt is selected from zinc stearate.
According to the present invention, the accelerator is selected from at least one of sulfenamide accelerators, thiazole accelerators, thiuram accelerators and guanidine accelerators. For example, the accelerator is N-tert-butyl-2-benzothiazolesulfenamide (TBBS) and/or diphenylguanidine (D).
According to the invention, the vulcanizing agent is selected from at least one of sulfur, insoluble sulfur, oil-extended sulfur and sulfur donors. For example, the vulcanizing agent IS ordinary sulfur S, oil-extended insoluble sulfur IS, or the like.
The composition provided by the invention can be used for preparing rubber compositions by adopting various methods in the prior art, and the prepared rubber compositions have better performances, such as lower rolling resistance and the like, compared with the rubber compositions provided by the prior art.
However, through a large amount of experimental studies, the inventors of the present invention found that the rubber composition is prepared by using the composition provided by the present invention in a manner of staged mixing and stepwise feeding, and particularly, the solution-polymerized styrene-butadiene rubber, the white carbon black and the surface modifier in the composition of the present invention are firstly mixed to obtain the white carbon black masterbatch, and the obtained white carbon black masterbatch is mixed with other components in the composition of the present invention, and particularly, the white carbon black masterbatch is mixed with other components except the vulcanizing agent and the accelerator to obtain the second-stage masterbatch, and then the vulcanizing agent is mixed with the second-stage masterbatch to obtain the rubber composition of the present invention. The rubber composition thus obtained is capable of significantly improving the rolling resistance of the rubber composition relative to prior art processes.
Specifically, the second aspect of the present invention provides a method for preparing the rubber composition of the present invention, comprising the steps of:
(1) white carbon black masterbatch process: carrying out first mixing on solution polymerized styrene butadiene rubber, white carbon black and a surface modifier to prepare white carbon black master batch;
(2) the two-stage masterbatch process comprises the following steps: carrying out second mixing on carbon black, calcium sulfate whisker, an activating agent, an anti-aging agent, a softening agent and white carbon black master batch to obtain second-stage master batch;
(3) and (3) final rubber mixing process: and carrying out third mixing on a vulcanizing agent, an accelerant and the second-stage masterbatch to obtain final rubber.
According to the present invention, the method further comprises masticating the solution-polymerized styrene-butadiene rubber and the butadiene rubber.
Specifically, the plastication temperature is 60-90 ℃, and the plastication time is 0.5-1 min.
According to the invention, the mixing temperature of the first mixing is 80 to 160 ℃, preferably 130 to 155 ℃.
According to the invention, the mixing time of the first mixing is 2-8min, preferably 4-6 min.
According to the invention, the mixing temperature of the second mixing is 120 to 170 ℃, preferably 145 to 165 ℃.
According to the invention, the mixing time of the second mixing is 2-8min, preferably 4-6 min.
According to the invention, the mixing temperature of the third mixing is not more than 120 ℃, preferably 90-110 ℃.
According to the present invention, the mixing time of the third mixing is 4 to 6min, preferably 4 to 5 min.
In a third aspect, the invention provides a use of the rubber composition of the invention, wherein the use is a tire, preferably a tire tread.
The fourth aspect of the present invention provides a rubber composition for a tire tread, wherein the rubber composition is the rubber composition of the present invention.
In a fifth aspect, the present invention provides a method for producing the rubber composition for a tire tread of the present invention, the method comprising vulcanizing the rubber composition for a tire tread.
According to the invention, the conditions of the vulcanization include: the vulcanizing time is 20-45min, preferably 25-40 min; the vulcanization temperature is 145-180 ℃, and the preferable temperature is 150-170 ℃; the vulcanization pressure is 3.5-40MPa, preferably 10-20 MPa.
In the present invention, the pressure used is a gauge pressure unless otherwise specified.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used below were commercially available unless otherwise specified.
The following examples and comparative examples the equipment for the preparation of vulcanizates are shown in Table 1.
The apparatus for testing the vulcanized rubbers obtained in the examples and comparative examples is shown in Table 2, and the test conditions are shown in Table 3.
The chemicals used in the examples and comparative examples are commercially available and are specified below:
solution polymerized styrene-butadiene rubber: 2636, Yanshan petrochemicals;
butadiene rubber: BR9000, a yanshan petrochemical;
white carbon black: 115GR, Rodiya, France, nitrogen adsorption specific surface area 115m2/g；
White carbon black: 165GR, Rodiya, France, nitrogen adsorption specific surface area 165m2/g；
Carbon black: n330, Zideli chemical technology Co., Ltd, Dongguan, CTAB adsorption specific surface area of 82m2/g；
Carbon black: n220, Zideli chemical technology Co., Ltd, Dongguan, CTAB adsorption specific surface area of 111m2/g；
Calcium sulfate whisker: shenyangdong Dafulong mineral materials research and development Co., Ltd, the length-diameter ratio is 45:1, and the diameter is 4 μm;
surface modifier: bis- [ gamma- (triethoxysilyl) propyl ] -tetrasulfide (Si69), Nanjing eosin chemical Co., Ltd;
softening agent: environmental aromatic oil TDAEV500, new dayan (ningbo) limited;
activating agent: zinc oxide, stearic acid, Weifang Heng Feng chemical Limited;
PEG 4000: huaihean petrochemical plant;
anti-aging agent 4020: n- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, san Ox chemical science and technology, Jiangsu;
sulfur, Heicheng Hechenghuai chemical Limited;
accelerator TBBS: n-tert-butyl-2-benzothiazolesulfenamide;
accelerant D diphenylguanidine, Shanghai Yongyan chemical science and technology Co., Ltd.
The amounts of the components used in the following examples and comparative examples are all parts by mass, each representing 1 g.
TABLE 1
Serial number Device name Model number Manufacturer of the product
1 Internal mixer BR1600 Farrel America Ltd
2 Open mill XK-160 Qingdao Xincheng Yiming mechanical Co Ltd
3 Flat vulcanizing machine XLB-D400*400*2 Shanghai first rubber machinery plant
4 High-speed heating mixer HRK-10 Making a JinzhouPlant of industrial and equipment
TABLE 2
Figure BDA0002257434110000081
TABLE 3
Figure BDA0002257434110000082
Example 1
The formula is as follows: solution polymerized styrene-butadiene rubber 80; 20 parts of butadiene rubber; white carbon black 115GR 70; carbon black N2204; 10 parts of calcium sulfate whiskers; silane coupling agent Si 697; TDAE 12; zinc oxide 4; 2 parts of stearic acid; PEG 40001; 1.5 of a vulcanizing agent; TBBS 2; d2; 40203; microcrystalline wax 1.
Setting the rotating speed of an internal mixer to be 80rpm, setting the initial plastication temperature to be 80 ℃, and plasticating the crude rubber for 0.5 min; adding white carbon black and Si69, heating to 130-155 ℃ at the initial temperature of about 60 ℃, and mixing for 5 min; adding all the fillers except the vulcanizing agent and the accelerant, heating to the initial temperature of about 120 ℃, mixing for 5min when the temperature is raised to 145-165 ℃, discharging, and standing for 4h to obtain master batch; setting the rotating speed of an internal mixer at 80rpm, setting the initial plastication temperature at 40 ℃, plasticating the master batch in the previous step for 1min, adding a vulcanizing agent and an accelerant, mixing for 4min, setting the initial temperature to be about 60 ℃, mixing the maximum temperature to be 105-110 ℃, and discharging.
And vulcanizing the mixed sample for 35min at 160 ℃ under the pressure of 15MPa to prepare samples with different experimental specifications for performance test. The sample of example 1 was labeled S-1. The sample S-1 was subjected to the performance test, and the results are shown in Table 4.
Example 2
The formula is as follows: solution polymerized styrene-butadiene rubber 60; butadiene rubber 40; white carbon black 165GR 60; carbon black N3304; calcium sulfate whiskers 20; a silane coupling agent Si 695; TDAE 8; 2 parts of zinc oxide; stearic acid 1; PEG 40003; 0.5 of vulcanizing agent; TBBS 2; d1; 40201; microcrystalline wax 1.
Setting the rotating speed of an internal mixer to be 80rpm, setting the initial plastication temperature to be 80 ℃, and plasticating the crude rubber for 0.5 min; adding white carbon black and Si69, heating to 130-155 ℃ at the initial temperature of about 60 ℃, and mixing for 5 min; adding all the fillers except the vulcanizing agent and the accelerant, heating to the initial temperature of about 120 ℃, mixing for 5min when the temperature is raised to 145-165 ℃, discharging, and standing for 4h to obtain master batch; setting the rotating speed of an internal mixer at 80rpm, setting the initial plastication temperature at 40 ℃, plasticating the master batch in the previous step for 1min, adding a vulcanizing agent and an accelerant, mixing for 4min, setting the initial temperature to be about 60 ℃, mixing the maximum temperature to be 105-110 ℃, and discharging.
And vulcanizing the mixed sample for 35min at 160 ℃ under the pressure of 15MPa to prepare samples with different experimental specifications for performance test. The sample of example 2 was labeled S-2. The sample S-2 was subjected to the performance test, and the results are shown in Table 4.
Example 3
The formula is as follows: solution polymerized styrene-butadiene rubber 70; 30 parts of butadiene rubber; white carbon black 165GR 61; carbon black N3308; 15 parts of calcium sulfate whiskers; silane coupling agent Si 696; TDAE 6; zinc oxide 3; stearic acid 1; PEG 40002; 1.0 parts of vulcanizing agent; TBBS 2.5; d2.5; 40202; microcrystalline wax 1.
Setting the rotating speed of an internal mixer to be 80rpm, setting the initial plastication temperature to be 80 ℃, and plasticating the crude rubber for 0.5 min; adding white carbon black and Si69, heating to 130-155 ℃ at the initial temperature of about 60 ℃, and mixing for 5 min; adding all the fillers except the vulcanizing agent and the accelerant, heating to the initial temperature of about 120 ℃, mixing for 5min when the temperature is raised to 145-165 ℃, discharging, and standing for 4h to obtain master batch; setting the rotating speed of an internal mixer at 80rpm, setting the initial plastication temperature at 40 ℃, plasticating the master batch in the previous step for 1min, adding a vulcanizing agent and an accelerant, mixing for 4min, setting the initial temperature to be about 60 ℃, mixing the maximum temperature to be 105-110 ℃, and discharging.
And vulcanizing the mixed sample for 35min at 160 ℃ under the pressure of 15MPa to prepare samples with different experimental specifications for performance test. The sample of example 3 was labeled S-3. The sample S-3 was subjected to the performance test, and the results are shown in Table 4.
Example 4
Vulcanized rubber samples were prepared according to the method of example 1, except that: the amount of the solution polymerized styrene-butadiene rubber is 50, and the amount of the butadiene rubber is 50.
The sample produced is labeled S-4.
The sample S-4 was subjected to the performance test, and the results are shown in Table 4.
Example 5
Vulcanized rubber samples were prepared according to the method of example 2, except that: the using amount of the white carbon black is 50, the using amount of the carbon black is 9, and the using amount of the calcium sulfate whisker is 25.
The sample produced is labeled S-5.
The sample S-5 was subjected to the performance test, and the results are shown in Table 4.
Example 6
Vulcanized rubber samples were prepared according to the method of example 3, except that: the amount of white carbon black is 77, the amount of carbon black is 2, and the amount of calcium sulfate whisker is 5.
The sample produced is labeled S-6.
The sample S-6 was subjected to the performance test, and the results are shown in Table 4.
Example 7
Vulcanized rubber samples were prepared according to the method of example 2, except that: the amount of TDAE is 15.
The sample produced is labeled S-7.
The sample S-7 was subjected to the performance test, and the results are shown in Table 4.
Example 8
Vulcanized rubber samples were prepared according to the method of example 3, except that: the sulfur dosage is 0.3.
The sample produced is labeled S-8.
The sample S-8 was subjected to the performance test, and the results are shown in Table 4.
Example 9
Vulcanized rubber samples were prepared according to the method of example 3, except that: the method is characterized in that a silane coupling agent Si69 is adopted to modify calcium sulfate whiskers in advance, and the modification method comprises the following steps: modification of calcium sulfate whiskers: adding the calcium sulfate whisker into a high-speed mixer, heating and stirring, adding a silane coupling agent Si69 accounting for 10 wt% of the dosage of the calcium sulfate whisker when the temperature reaches 120 ℃, and stirring and reacting for 10min to obtain the modified calcium sulfate whisker. The rubber composition was prepared without adding the silane coupling agent Si 69.
The sample produced is labeled S-9.
The sample S-9 was subjected to the performance test, and the results are shown in Table 4.
Example 10
Vulcanized rubber samples were prepared according to the method of example 3, except that: the method is characterized in that a silane coupling agent Si69 is adopted to modify calcium sulfate whiskers in advance, and the modification method comprises the following steps: adding the calcium sulfate whisker into a high-speed mixer, heating and stirring, adding a silane coupling agent Si69 accounting for 10 wt% of the dosage of the calcium sulfate whisker when the temperature reaches 120 ℃, and stirring and reacting for 10min to obtain the modified calcium sulfate whisker. When the rubber composition was prepared, 6 parts by mass of a silane coupling agent Si69 was added.
The sample prepared was labeled S-10.
The sample S-10 was subjected to the performance test, and the results are shown in Table 4.
Example 11
A vulcanized rubber article was prepared as in example 3, except that: in the preparation of the rubber composition, the raw materials other than the vulcanizing agent and the accelerator are simultaneously kneaded.
The sample produced is labeled S-11.
The sample S-11 was subjected to the performance test, and the results are shown in Table 4.
Example 12
A vulcanized rubber article was prepared as in example 3, except that: the solution polymerized styrene butadiene rubber and butadiene rubber are not masticated in preparing the rubber composition.
The sample produced is labeled S-12.
The sample S-12 was subjected to the performance test, and the results are shown in Table 4.
Comparative example 1
Vulcanized rubber samples were prepared according to the method of example 1, except that: and replacing the calcium sulfate whiskers with white carbon black in equal parts by weight.
The sample produced is labeled D-1.
The sample D-1 was subjected to the performance test, and the results are shown in Table 4.
Comparative example 2
Vulcanized rubber samples were prepared according to the method of example 2, except that: and replacing the calcium sulfate whiskers with white carbon black in equal parts by weight.
The sample produced is labeled D-2.
The sample D-2 was subjected to the performance test, and the results are shown in Table 4.
Comparative example 3
Vulcanized rubber samples were prepared according to the method of example 3, except that: and replacing the calcium sulfate whiskers with white carbon black in equal parts by weight.
The sample produced is labeled D-3.
The sample D-3 was subjected to the performance test, and the results are shown in Table 4.
Comparative example 4
A vulcanized rubber article was prepared as in example 3, except that: and replacing the calcium sulfate whiskers with carbon black with equal mass.
The sample produced is labeled D-4.
The sample D-4 was subjected to the performance test, and the results are shown in Table 4.
Comparative example 5
A vulcanized rubber article was prepared as in example 3, except that: and replacing the carbon black with calcium sulfate whiskers with equal mass.
The sample produced is labeled D-5.
The performance test was performed on sample D-5, and the results are shown in Table 4.
Comparative example 6
A vulcanized rubber article was prepared as in example 3, except that: and replacing the white carbon black with calcium sulfate whisker with equal mass.
The sample produced is labeled D-6.
The performance test was performed on sample D-6, and the results are shown in Table 4.
TABLE 4
Figure BDA0002257434110000141
From the results, the vulcanized rubber prepared by using the rubber composition disclosed by the invention has the advantages that the rolling resistance is greatly reduced, the wet skid resistance is slightly improved, and the fuel economy of an automobile can be remarkably improved when the vulcanized rubber is applied to the tread of the automobile tire.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (11)

1. A rubber composition comprising, based on 100 parts by mass of the total amount of rubber, 50 to 100 parts by mass of a solution-polymerized styrene-butadiene rubber; 0-50 parts of butadiene rubber; 50-77 parts of white carbon black; 2-10 parts by mass of carbon black; 5-25 parts of calcium sulfate whisker; 4-10 parts of a surface modifier; 5-15 parts by mass of a softener; 2-8 parts of an activating agent; 0.3-2 parts by mass of a vulcanizing agent; 2-6 parts of an accelerator; 1-5 parts of an anti-aging agent;
the total amount of the white carbon black, the carbon black and the calcium sulfate whisker is 77-87 parts by mass.
2. The rubber composition according to claim 1, wherein the total amount of the rubber is 60 to 80 parts by mass per 100 parts by mass of the solution-polymerized styrene-butadiene rubber; 20-40 parts of butadiene rubber; 60-70 parts of white carbon black; 4-8 parts of carbon black; 10-20 parts of calcium sulfate whisker; 5-7 parts of a surface modifier; 8-13 parts by mass of a softener; 3-6 parts of an activating agent; 0.5-1.5 parts by mass of a vulcanizing agent; 3-5 parts of an accelerator; 2-4 parts of an anti-aging agent;
the total amount of the white carbon black, the carbon black and the calcium sulfate whisker is 80-85 parts by mass.
3. The rubber composition according to claim 1 or 2, wherein the white carbon is selected from fumed white carbon and/or precipitated white carbon, preferably precipitated white carbon;
preferably, the nitrogen adsorption specific surface area of the white carbon black is 60-230m2Per g, preferably from 100 to 190m2/g；
Preferably, the carbon black has a CTAB adsorption specific surface area of 10 to 300m2A/g, preferably from 20 to 140m2/g。
4. The rubber composition according to any one of claims 1 to 3, wherein the aspect ratio of the calcium sulfate whiskers is (30-80): 1, preferably (30-60): 1;
preferably, the calcium sulfate whiskers have an average diameter of 1 to 6 μm, preferably 2 to 5 μm.
5. The rubber composition according to any one of claims 1 to 4, wherein the surface modifier is at least one selected from the group consisting of a silane coupling agent, a zirconate coupling agent, a phthalate coupling agent, and an alcohol compound, preferably a silane coupling agent;
preferably, the antioxidant is selected from physical antioxidants and/or chemical antioxidants;
preferably, the physical anti-aging agent is selected from paraffin and/or microcrystalline wax;
preferably, the chemical anti-aging agent is selected from at least one of amine anti-aging agents, quinoline anti-aging agents and benzimidazole anti-aging agents;
preferably, the softening agent is selected from at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin and low molecular weight polyethylene glycol;
preferably, the active agent is selected from the group consisting of a combination of a metal oxide and a fatty acid and/or a fatty acid metal soap salt;
preferably, the metal oxide is selected from zinc oxide and/or magnesium oxide;
preferably, the fatty acid is selected from stearic acid;
preferably, the fatty acid metal soap salt is selected from zinc stearate;
preferably, the accelerator is selected from at least one of sulfenamide accelerators, thiazole accelerators, thiuram accelerators and guanidine accelerators;
preferably, the vulcanizing agent is selected from at least one of sulfur, insoluble sulfur, oil-extended sulfur, and sulfur donors.
6. A method for preparing the rubber composition of any one of claims 1 to 5, comprising the steps of:
(1) white carbon black masterbatch process: carrying out first mixing on solution polymerized styrene butadiene rubber, white carbon black and a surface modifier to prepare white carbon black master batch;
(2) the two-stage masterbatch process comprises the following steps: carrying out second mixing on carbon black, calcium sulfate whisker, an activating agent, an anti-aging agent, a softening agent and white carbon black master batch to obtain second-stage master batch;
(3) and (3) final rubber mixing process: and carrying out third mixing on a vulcanizing agent, an accelerant and the second-stage masterbatch to obtain final rubber.
7. The method of claim 6, wherein the method further comprises masticating the solution-polymerized styrene-butadiene rubber and the butadiene rubber;
preferably, the plastication temperature is 60-90 ℃; the plasticating time is 0.5-1 min.
8. The production method according to claim 6 or 7, wherein the mixing temperature of the first mixing is 80 to 160 ℃, preferably 130 to 155 ℃;
preferably, the mixing time of the first mixing is 2-8min, preferably 4-6 min;
preferably, the mixing temperature of the second mixing is 120-170 ℃, preferably 145-165 ℃;
preferably, the mixing time of the second mixing is 2-8min, preferably 4-6 min;
preferably, the mixing temperature of the third mixing is not more than 120 ℃, and preferably 90-110 ℃;
preferably, the mixing time of the third mixing is 4 to 6min, preferably 4 to 5 min.
9. Use of a rubber composition according to any one of claims 1 to 5, wherein the use is a tire, preferably a tire tread.
10. A rubber composition for a tire tread, wherein the rubber composition is the rubber composition according to any one of claims 1 to 5.
11. A method for producing the rubber composition for a tire tread according to claim 10, the method comprising vulcanizing the rubber composition for a tire tread;
preferably, the conditions of the vulcanization include: the vulcanizing time is 20-45min, preferably 25-40 min; the vulcanization temperature is 145-180 ℃, and the preferable temperature is 150-170 ℃; the vulcanization pressure is 3.5-40MPa, preferably 10-20 MPa.
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