CN116265517A - Rubber composition for tire sidewall, vulcanized rubber, and preparation method and application thereof - Google Patents

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

Info

Publication number
CN116265517A
CN116265517A CN202111543601.3A CN202111543601A CN116265517A CN 116265517 A CN116265517 A CN 116265517A CN 202111543601 A CN202111543601 A CN 202111543601A CN 116265517 A CN116265517 A CN 116265517A
Authority
CN
China
Prior art keywords
rubber
agent
weight
parts
contained
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111543601.3A
Other languages
Chinese (zh)
Inventor
孙攀
刘苹
段海东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Chemical Research Institute Co ltd, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Chemical Research Institute Co ltd
Priority to CN202111543601.3A priority Critical patent/CN116265517A/en
Publication of CN116265517A publication Critical patent/CN116265517A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • B60C1/0025—Compositions of the sidewalls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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 

Abstract

The invention relates to the field of rubber, and discloses a rubber composition for a tire sidewall, vulcanized rubber, a preparation method and application thereof. The rubber composition contains one or more of a rubber matrix, white carbon black, kaolin, a surface treatment agent, an activator, an anti-aging agent, a softener, an anti-cracking agent, a tackifier, a vulcanizing agent, an accelerator and carbon blackSeed; wherein the rubber matrix contains butadiene rubber and/or natural rubber, the surface treating agent is silane-terminated polybutadiene, the number average molecular weight Mn of the silane-terminated polybutadiene is 3000-4000, and the glass transition temperature T g The temperature is less than or equal to-80 ℃; the vulcanized rubber can further improve the heat aging resistance and the ultraviolet aging resistance on the premise of basic mechanical properties and appearance.

Description

Rubber composition for tire sidewall, vulcanized rubber, and preparation method and application thereof
Technical Field
The invention relates to the field of rubber, in particular to a rubber composition for a tire sidewall, vulcanized rubber, a preparation method and application thereof.
Background
The sidewall is the part of the tire with the largest lateral deformation, is subjected to frequent flexural deformation, is also directly contacted with the atmosphere and is corroded by light, heat, oxygen and ozone, so the radial tire requires the sidewall rubber to have excellent flex crack resistance and ozone, hot oxygen and atmospheric aging resistance. The anti-aging agent can improve the cracking and aging phenomena of the surface of the tire side, but the surface of the tire side is easy to be colored along with the migration of the auxiliary agents such as the anti-aging agent and the like to the surface of the tire side, so that the appearance and the quality of the tire are affected.
With the development of scientific technology, tires are also developed in the directions of environmental protection, energy saving, new technology, new materials, new design and the like, and particularly with the proposal of a green tire concept, the requirements on the quality of the tires are higher and higher, and the anti-aging performance of sidewall rubber is also receiving attention. If the ageing resistance of the radial tire sidewall rubber needs to be further improved, the dosage of the anti-ageing agent cannot be improved at the same time; there is a need to find a tire sidewall rubber that is excellent in combination properties and good in aging resistance.
Disclosure of Invention
The invention aims to overcome the defect of relatively poor ageing resistance of side rubber in the prior art, and provides a rubber composition for a tire side, vulcanized rubber, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a rubber composition for a tire sidewall, wherein the rubber composition contains one or more of a rubber matrix, white carbon black, kaolin, a surface treatment agent, an activator, an anti-aging agent, a softener, an anti-cracking agent, a tackifier, a vulcanizing agent, an accelerator, and carbon black; wherein the rubber matrix contains butadiene rubber and/or natural rubber, the surface treating agent is silane-terminated polybutadiene, the number average molecular weight Mn of the silane-terminated polybutadiene is 3000-4000, and the glass transition temperature Tg is less than or equal to-80 ℃.
In a second aspect, the present invention provides a process for producing a vulcanized rubber using the rubber composition described above, wherein the process comprises:
(1) The method comprises the steps of (1) carrying out first mixing on a component A containing a rubber matrix, white carbon black, kaolin, a surface treatment agent and an anti-cracking agent to obtain a section of master batch;
(2) The first-stage masterbatch is subjected to second mixing with a component B containing carbon black, an activating agent, an anti-aging agent, a tackifier and a softener to obtain a second-stage masterbatch;
(3) Thirdly, mixing the two-stage masterbatch with a component C containing a vulcanizing agent and an accelerator to obtain final rubber;
(4) And vulcanizing the final rubber mixture to obtain vulcanized rubber.
In a third aspect, the present invention provides a vulcanized rubber prepared by the method described above.
In a fourth aspect, the present invention provides the use of the aforesaid vulcanizate in a tire sidewall.
Through the technical scheme, the technical scheme provided by the invention has the following advantages:
(1) The invention adopts the surface treating agent silane to end the polybutadiene, has the dispersion of Li Bai carbon black and kaolin in the rubber matrix, can better play the physical shielding effect of the kaolin on the hot oxygen and the ultraviolet rays, and can also better play the role of the rubber matrix;
(2) The vulcanized rubber prepared by the invention can further improve the heat aging resistance and the ultraviolet aging resistance on the premise of having basic mechanical properties and appearance;
(3) The vulcanized rubber is obtained by a novel mixing method, the chemical combination of the white carbon black and the rubber can be better improved, the advantages of each filler are exerted, the rolling resistance and the heat generation of the vulcanized rubber are further reduced, and the flexure resistance and the ageing resistance of the vulcanized rubber compound are improved. And simultaneously, the basic mechanical property requirement and the appearance quality requirement of the sidewall rubber are ensured.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a rubber composition for a tire sidewall, wherein the rubber composition contains one or more of a rubber matrix, white carbon black, kaolin, a surface treatment agent, an activator, an anti-aging agent, a softener, an anti-cracking agent, a tackifier, a vulcanizing agent, an accelerator, and carbon black; wherein the rubber matrix contains butadiene rubber and/or natural rubber, the surface treating agent is silane-terminated polybutadiene, the number average molecular weight Mn of the silane-terminated polybutadiene is 3000-4000, and the glass transition temperature T g ≤-80℃。
The inventors of the present invention found that: the surface treating agent silane-terminated polybutadiene is adopted, the silane end group can react with the white carbon black and the hydroxyl on the surface of the kaolin, and the dispersion of Li Bai carbon black and the kaolin in the rubber matrix can better play the physical shielding effect of the kaolin on the thermal oxygen and the ultraviolet rays and also can better play the role of the rubber matrix; in addition, the vulcanized rubber of the present invention is obtained by a novel kneading method in which a rubber matrix is first mixed with white carbon black, kaolin, a surface treating agent and a crack-resistant agent to prepare a master batch (matrix master batch); then adding carbon black, an activating agent, an anti-aging agent, a softening agent, a tackifier and the like into the primary master batch to prepare a secondary master batch; then adding a vulcanizing agent and an accelerator into the second-stage masterbatch to prepare final rubber, and finally vulcanizing the final rubber to prepare vulcanized rubber. In the processing technology of the invention, the chemical combination of the white carbon black and the rubber can be better improved, the advantages of each filler are exerted, the rolling resistance and heat generation of the vulcanized rubber are further reduced, and the flexure resistance and ageing resistance of the vulcanized rubber material are improved. And simultaneously, the basic mechanical property requirement and the appearance quality requirement of the sidewall rubber are ensured.
According to the invention, the silane-terminated polybutadiene has a number-average molecular weight Mn of 3000 to 3500 and a glass transition temperature T g Is at-100 ℃ to-80 ℃; preferably, the silane-terminated polybutadiene has a number average molecular weight Mn of 3200 to 3300 and a glass transition temperature T g Is-80 ℃.
According to the invention, the silane-terminated polybutadiene is preferably selected from silane-terminated polybutadiene
Figure BDA0003415039900000041
EP ST-E60 having a number average molecular weight of 3200, T g Is at-80 ℃; and/or, silane-terminated polybutadiene
Figure BDA0003415039900000042
EP ST-E100, number average molecular weight 3300, T g Is-80 ℃.
According to the invention, the rubber matrix is a mixture of butadiene rubber and natural rubber.
According to the present invention, the content of the natural rubber is 40 to 60 parts by weight and the content of the butadiene rubber is 40 to 60 parts by weight with respect to 100 parts by weight of the rubber base; preferably, the content of the natural rubber is 40 to 58 parts by weight and the content of the butadiene rubber is 42 to 60 parts by weight with respect to 100 parts by weight of the rubber base.
According to the invention, the cis structure content in the butadiene rubber is 95-99 wt%, and the Mooney viscosity ML (1+4) The temperature of 100 ℃ is 40-65; preferably, the cis structure content in the butadiene rubber is 97 to 98 weight percent, and the Mooney viscosity ML (1+4) The temperature of 100 ℃ is 42-46.
According to the invention, the natural rubber is SMR-20.
According to the invention, the butadiene rubber is BR9000.
According to the present invention, the white carbon black is contained in an amount of 30 to 60 parts by weight, the kaolin is contained in an amount of 2 to 15 parts by weight, the surface treating agent is contained in an amount of 0.5 to 8 parts by weight, the activating agent is contained in an amount of 2 to 10 parts by weight, the anti-aging agent is contained in an amount of 2 to 8 parts by weight, the softening agent is contained in an amount of 10 to 30 parts by weight, the anti-cracking agent is contained in an amount of 1 to 5 parts by weight, the tackifier is contained in an amount of 1 to 5 parts by weight, the accelerator is contained in an amount of 0.5 to 3 parts by weight, the vulcanizing agent is contained in an amount of 0.5 to 5 parts by weight, and the carbon black is contained in an amount of 0 to 10 parts by weight, relative to 100 parts by weight of the rubber substrate.
According to the present invention, preferably, the white carbon black is contained in an amount of 36 to 48 parts by weight, the kaolin is contained in an amount of 3 to 14 parts by weight, the surface treating agent is contained in an amount of 2 to 3.5 parts by weight, the activating agent is contained in an amount of 4 to 5 parts by weight, the age resistor is contained in an amount of 4 to 7 parts by weight, the softening agent is contained in an amount of 15 to 25 parts by weight, the crack inhibitor is contained in an amount of 2 to 3 parts by weight, the tackifier is contained in an amount of 1.5 to 3 parts by weight, the accelerator is contained in an amount of 1.5 to 2 parts by weight, the vulcanizing agent is contained in an amount of 2 to 3 parts by weight, and the carbon black is contained in an amount of 4 to 5 parts by weight, relative to 100 parts by weight of the rubber substrate.
According to the invention, the nitrogen adsorption specific surface area of the white carbon black is 10-200m 2 Preferably 150-170m 2 /g; in the invention, the white carbon black is 165GR.
According to the invention, the kaolin has a nitrogen adsorption specific surface area of 10-100m 2 /g, average diameter of 0.1-2 μm; preferably, the kaolin has a nitrogen adsorption specific surface area of 12-21m 2 And/g, average diameter of 0.2-1.22 μm. The kaolin mineral belongs to 1:1 layered silicate, and the crystal chemical formula is 2SiO 2 ·Al 2 O 3 ·2H 2 O, its theoretical chemical composition is 46.54% of SiO 2 39.5% Al 2 O 3 13.96% H 2 O; in the present invention, the kaolin is HG90 and/orDLX。
According to the invention, the carbon black has a CTAB adsorption specific surface area of 10-600m 2 Preferably 73-85m 2 /g; in the present invention, the carbon black is N330.
According to the invention, the activator is a mixture of metal oxide and fatty acid and/or fatty acid metal soap salt; preferably, the activator is a mixture of a metal oxide and a fatty acid or is a fatty acid metal soap salt; preferably, the metal oxide is preferably zinc oxide and/or magnesium oxide; the fatty acid is preferably stearic acid; the fatty acid metal soap salt is preferably zinc stearate and/or zinc borate; more preferably, the activator is zinc oxide and/or stearic acid.
According to the invention, the anti-aging agent is selected from one or more of amine anti-aging agents, quinoline anti-aging agents, benzimidazole anti-aging agents and physical protective agents; preferably, the anti-aging agent is N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (anti-aging agent 4020) and/or a 2, 4-trimethyl-1, 2-dihydroquinoline polymer (anti-aging agent RD); more preferably, the content weight ratio of the antioxidant 4020 and the antioxidant RD in the mixture is (1-3): 1.
according to the present invention, the softener is selected from one or more of naphthenic oil, aromatic oil, paraffin oil, pine tar, tall oil, coumarone resin and polyethylene wax; preferably, the softener is naphthenic oil ASTM 103#.
According to the invention, the anti-cracking agent is a mixture of microcrystalline wax and paraffin wax; as a protective auxiliary agent, the anti-cracking agent has good effects of inhibiting the cracking and ageing of rubber and improving the anti-flexing performance and heat-resistant ageing of rubber; preferably, the anti-cracking agent is LSB20 and/or H2122H.
According to the invention, the tackifier is selected from one or more of phenolic resin, alkyl modified phenolic resin, cashew modified phenolic resin and tall modified phenolic resin; preferably, the tackifier is tert-butylphenol formaldehyde resin (SL-1401) and/or octylphenol formaldehyde resin (SL-1801).
According to the invention, the vulcanizing agent is a sulfur donor; the sulfur donor is a substance capable of providing sulfur. Preferably, the vulcanizing agent IS ordinary sulfur S and/or oil-filled insoluble sulfur IS.
According to the present invention, the accelerator is selected from one or more of sulfenamide accelerators, thiazole accelerators, thiuram accelerators and guanidine accelerators; preferably, the accelerator is N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and/or N-tert-butyl-2-benzothiazole sulfenamide (TBBS).
In the present invention, it is noted that each component may be stored independently or in a mixture.
In order to make the components of the obtained rubber compound more uniform and to have better performance after vulcanization, the invention provides a method for preparing vulcanized rubber by using the rubber composition, wherein the method comprises the following steps:
(1) The method comprises the steps of (1) carrying out first mixing on a component A containing a rubber matrix, white carbon black, kaolin, a surface treatment agent and an anti-cracking agent to obtain a section of master batch;
(2) The first-stage masterbatch is subjected to second mixing with a component B containing carbon black, an activating agent, an anti-aging agent, a tackifier and a softener to obtain a second-stage masterbatch;
(3) Thirdly, mixing the two-stage masterbatch with a component C containing a vulcanizing agent and an accelerator to obtain final rubber;
(4) And vulcanizing the final rubber mixture to obtain vulcanized rubber.
The invention adopts the method that the component A containing the rubber matrix, the white carbon black, the kaolin, the surface treatment agent and the anti-cracking agent is firstly mixed to obtain a section of master batch, and then the subsequent process steps of the invention are carried out, so that the obtained vulcanized rubber has more excellent performances such as strength, fatigue resistance, rolling resistance and the like.
According to the present invention, the conditions of the first kneading include: the temperature is 80-130 ℃ and the time is 3-12min; preferably, the conditions of the first mixing include: the temperature is 90-130 ℃ and the time is 3-10min; more preferably, the conditions of the first kneading include: the temperature is 100-110deg.C, and the time is 5-8min.
According to the present invention, the conditions for the second kneading include: the temperature is 90-145 ℃ and the time is 3-12min; preferably, the conditions of the second kneading include: the temperature is 100-130 ℃ and the time is 3-7min; more preferably, the conditions of the second kneading include: the temperature is 115-125 ℃ and the time is 5-6min.
According to the present invention, the conditions for the third kneading include: the temperature is not more than 130 ℃ and the time is 4-7min; preferably, the conditions of the third mixing include: the temperature is 100-105 ℃ and the time is 5-6min.
Preferably according to the present invention, the vulcanization conditions include: the temperature is 145-165 ℃, the pressure is 10-20MPa, and the time is 25-50min; preferably, the temperature is 150-155 ℃, the pressure is 15-20MPa, and the time is 28-35min.
In a second aspect of the present invention, according to a preferred embodiment, the conditions of the first mixing include: the temperature is 100-110 ℃ and the time is 5-8min; the conditions for the second mixing include: the temperature is 115-125 ℃ and the time is 5-6min; the conditions for the third kneading include: the temperature is 100-105 ℃ and the time is 5-5min; the vulcanization conditions include: the temperature is 150-155 ℃, the pressure is 15-20MPa, and the time is 28-35min. The vulcanized rubber prepared by adopting the preferred embodiment has better mechanical properties (strength is improved, ageing resistance and heat generation is reduced), and the service life of the vulcanized rubber is longer (heat generation is reduced, ultraviolet ageing resistance and fatigue resistance are better).
In order to specifically explain the method for producing a vulcanized rubber of the present invention, the following provides a preferred embodiment for explanation:
(1) Placing the rubber matrix in an internal mixer, and plasticating under the conditions that the rotating speed is 40-90rpm, the initial mixing temperature is 70-100 ℃ and the raw rubber plasticating time is 0.3-2 min; then, introducing the component A containing white carbon black, kaolin, a surface treatment agent and an anti-cracking agent into the internal mixer for first mixing to obtain a section of master batch;
(2) Adding the second-stage masterbatch and a component B containing carbon black, an activating agent, an anti-aging agent, a softening agent and a tackifier into an internal mixer for third mixing, discharging and standing for 3-10 hours to obtain the second-stage masterbatch;
(3) Setting the rotating speed of an internal mixer to be 50-100rpm, setting the initial mixing temperature to be 25-50 ℃, plasticating the three-section masterbatch for 0.5-1.5min, and adding a component C containing an accelerator and a vulcanizing agent for third mixing to obtain final mixing;
(4) Tabletting and cutting the final rubber mixing open mill, and then putting the final rubber mixing open mill into a flat vulcanizing machine for vulcanization;
the surface treating agent is silane-terminated polybutadiene, and the rubber matrix contains a mixture of butadiene rubber and natural rubber.
The preparation method for preparing the vulcanized rubber is simple and reliable and is easy to popularize and apply.
The pressures used in the present invention are gauge pressure.
As previously described, a third aspect of the present invention provides a vulcanized rubber prepared by the method of the foregoing second aspect.
As previously mentioned, a fourth aspect of the present invention provides the use of the vulcanized rubber of the foregoing third aspect in a tire sidewall.
The invention will be described in detail below by way of examples.
Unless otherwise specified, various commercial products used below are commercially available.
The equipment conditions for preparing vulcanized rubber in the following examples and comparative examples are shown in Table 1.
The test instruments and test conditions of the vulcanized rubbers obtained in examples and comparative examples are shown in Table 2 and Table 3.
The chemical reagents used in the examples and comparative examples are commercially available, and are specifically as follows:
natural rubber: SMR-20, qingdao Sirait International Logistics Co., ltd;
butadiene rubber: BR9000, a Yanshan petrochemical product (wherein the cis content is 97.1%, mooney viscosity 43);
white carbon black: 165GR, french Rodiola, nitrogen adsorption specific surface area 170m 2 /g；
Kaolin:
Figure BDA0003415039900000091
HG90, kaMin Co., U.S.A., average particle diameter of 0.2 μm, nitrogen adsorption specific surface area of 21m 2 /g；/>
Figure BDA0003415039900000092
DLX, kaMin Co., U.S.A., average particle diameter of 1.2 μm, nitrogen adsorption specific surface area of 12m 2 /g；
Carbon black: n330, CTAB adsorption specific surface area of 73-85m 2 Per g, jiangxi black cat carbon black Co., ltd;
surface treating agent: silane-terminated polybutadiene, EVONIK Co
Figure BDA0003415039900000093
EP ST-E60 having a number average molecular weight of 3200 and a Tg of-80 ℃; silane-terminated polybutadiene, company EVONIK (-)>
Figure BDA0003415039900000094
EP ST-E100, number average molecular weight 3300, tg-80 ℃);
an activating agent: zinc oxide, stearic acid, weifang Hengfeng chemical Co., ltd;
anti-aging agent: n- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (anti-aging agent 4020), a company of Jiangsu san chemical technology, inc.; 2, 4-trimethyl-1, 2-dihydroquinoline polymer (antioxidant RD), shandong Shun chemical Co., ltd;
softening agent: naphthenic oil ASTM 103#, ningbo co-evolution company limited;
anti-cracking agent: LSB20, guangzhou Jinchangsheng technology Co., ltd, freezing point 60-67 ℃; H2122H, freezing point of shandong yang valley Huatai chemical company limited: 63-68 ℃;
tackifier: tert-butylphenol formaldehyde resin (SL-1401), hua Ji (China) chemical industry Co., ltd; octyl phenol formaldehyde resin (SL-1801), hua Ji (China) chemical industry Co., ltd;
vulcanizing agent: sulfur, a constant chemical company in Weifang;
and (3) an accelerator: n-cyclohexyl-2-benzothiazole sulfenamide (CBS), shandong Yangguhua Talcum chemical Co., ltd; n-tert-butyl-2-benzothiazole sulfenamide (TBBS), shanghai Yongyangxiao chemical technology Co.
The amounts of the components used in the following examples and comparative examples were all by weight, and the total amounts of the rubber compositions involved were the same and were 1200g.
Examples are provided to illustrate the rubber compositions, vulcanizates, and methods of making the same of the present invention.
TABLE 1
Figure BDA0003415039900000101
TABLE 2
Figure BDA0003415039900000102
TABLE 3 Table 3
Figure BDA0003415039900000103
Example 1
The rubber composition formulation is shown in Table 4.
The preparation process of the vulcanized rubber comprises the following steps:
(1) Carrying out first mixing on a rubber matrix, white carbon black, kaolin, a surface treating agent and an anti-cracking agent to obtain a section of master batch; specifically, natural rubber and rare earth butadiene rubber are added into an internal mixer, the rotating speed is set to be 77rpm, the initial mixing temperature is 85 ℃, and the raw rubber plasticating time is 1min; adding white carbon black, kaolin, a surface treatment agent and an anti-cracking agent into the internal mixer for mixing, wherein the mixing temperature is 110 ℃, and the mixing time is 6min, so as to obtain a section of master batch;
(2) Carrying out second mixing on the primary master batch, carbon black, an activating agent, a softening agent and an anti-aging agent to obtain a secondary master batch; specifically, adding the ingredients into an internal mixer, carrying out second mixing with the first-stage master batch for 5min at the mixing temperature of 120 ℃, discharging and standing for 5 hours to obtain a second-stage master batch;
(3) Thirdly, mixing the two-stage masterbatch, an accelerator and a vulcanizing agent to obtain final rubber; specifically, setting the rotation speed of an internal mixer at 70rpm, carrying out plasticating on the two-stage master batch for 0.5min at the initial mixing temperature of 40 ℃, adding a vulcanizing agent and an accelerator for carrying out third mixing, carrying out mixing at 105 ℃ for 5min, and discharging to obtain final rubber;
(4) And tabletting and cutting the final rubber mixing mill, and then putting the final rubber mixing mill into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 155 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 30min, so that the vulcanized rubber sample S1 is prepared.
The vulcanized rubber sample S1 was subjected to a performance test, and the results are shown in Table 5.
Examples 2 to 4
A vulcanized rubber was prepared in the same manner as in example 1 except that: the rubber compositions employed were of different formulations and process parameters, see in particular Table 4.
The prepared vulcanized rubber samples S2-S4 were subjected to performance test, and the results are shown in Table 5.
Example 5
The rubber composition formulation of this example was the same as in example 1, and a vulcanized rubber was prepared by a method similar to that of example 1, except that:
in the process of preparing the primary master batch, the temperature of the first mixing is 125 ℃ and the time is 3.5min;
in the process of preparing the two-stage master batch, the temperature of the second mixing is 100 ℃ and the time is 9min;
in the process of preparing the final rubber, the time of the third rubber mixing is 5min, and the rubber discharging temperature is 130 ℃.
A vulcanized rubber sample S5 was obtained.
The vulcanized rubber sample S5 was subjected to a performance test, and the results are shown in Table 5.
Comparative examples 1 to 4
A vulcanized rubber was prepared in the same manner as in example 1 except that: the rubber compositions employed were of different formulations and process parameters, see in particular Table 4.
The prepared vulcanized rubber samples CS1-CS4 were subjected to performance test, and the results are shown in Table 5.
TABLE 4 Table 4
Figure BDA0003415039900000121
Figure BDA0003415039900000131
Test case
The rubber compositions corresponding to the examples and the comparative examples are rolled on an open mill to prepare 3-5mm rubber compound sheets, then vulcanized rubber sheets with the thickness of 2.0mm and 1.0mm are prepared on a flat vulcanizing machine, and the 2.0mm rubber sheets are subjected to cutting test on mechanical properties. The dynamic mechanical property test uses 1.0mm film, and cuts according to the size of 40mm multiplied by 5mm multiplied by 1mm, and the temperature scanning range is-80 ℃ to 80 ℃. The results obtained are shown in Table 5.
Wherein, the wet skid resistance of the vulcanized rubber is represented by a loss factor at 0 ℃, and the higher the value is, the better the wet skid resistance of the vulcanized rubber is represented; the rolling resistance of the vulcanized rubber was characterized by a loss factor of 60℃and the smaller the value thereof, the smaller the rolling resistance of the vulcanized rubber was represented.
The thermal oxidative aging property of the vulcanized rubber is the change of the physical and mechanical properties of the vulcanized rubber before and after aging at a certain aging temperature and time, and the change of the tensile strength (hereinafter referred to as tensile change rate) is the change of the tensile strength before and after thermal oxidative aging, and the change of the elongation is the change of the elongation value of the vulcanized rubber before and after thermal oxidative aging, which is measured according to the method of GB/T3512-2001 sample.
GT-7017-EL1 type thermo-oxidative aging experimental box manufactured by Taiwan high-speed rail instrument detection Co., ltd., test conditions: aging temperature 100 ℃ and time 24 hours.
TABLE 5
Figure BDA0003415039900000141
From the above results, it can be seen that the combination of the kaolin, the anti-cracking agent and the surface treatment agent with other rubber additives in the rubber composition of the present invention can make the vulcanized rubber made of natural rubber/butadiene rubber have excellent comprehensive properties of improving strength, reducing rolling resistance and heat generation, improving dynamic fatigue, heat aging, ultraviolet aging and the like, thereby having a prospect of being applicable to tire sidewalls.
The silane-terminated polybutadiene of comparative example 1, which has no surface treatment agent added, has a good steric hindrance isolation effect on the filler surface due to the fact that the silane end can be successfully grafted on the surfaces of the white carbon black and the kaolin, and the combination property of the results is poorer than that of examples 1-5.
In comparative example 2, the kaolin as a filler and the anti-cracking agent are not added, and the kaolin deflects or stops cracks in the aspect of resisting crack propagation, and can be matched with the anti-cracking agent to better play roles in resisting ultraviolet rays, crack propagation and the like, so that the overall performance is poorer than that of examples 1-5.
Comparative example 3 was free of the addition of the surface treatment agent silane-terminated polybutadiene and the anti-cracking agent, and the filler was unevenly dispersed in the size due to the lack of the silane-terminated polybutadiene, the mechanical properties were poor, and the overall properties were poor as compared to examples 1-5 without the anti-cracking agent.
Comparative example 4 was not added with an anti-cracking agent and was not subjected to the second mixing, but the first-stage master batch, the component B containing carbon black, an activator, an anti-aging agent, a tackifier and a softener, and the component C containing a vulcanizing agent and an accelerator were subjected to the third mixing; because the softener, the tackifier and the like are directly mixed with one section of material, frictional heat generated in the mixing process can be reduced, the uniform dispersion of the material is not facilitated, and the carbon black is slightly poorer in one-step full-addition mixing effect than step-by-step addition, so that the overall performance of the result is poorer than that of examples 1-5.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (10)

1. A rubber composition for a tire sidewall, characterized in that the rubber composition contains one or more of a rubber matrix, white carbon black, kaolin, a surface treatment agent, an activator, an anti-aging agent, a softener, an anti-cracking agent, a tackifier, a vulcanizing agent, an accelerator and carbon black; wherein the rubber matrix contains butadiene rubber and/or natural rubber, the surface treating agent is silane-terminated polybutadiene, the number average molecular weight Mn of the silane-terminated polybutadiene is 3000-4000, and the glass transition temperature T g ≤-80℃。
2. The composition of claim 1, wherein the silane-terminated polybutadiene has a number average molecular weight Mn of 3000-3500 and a glass transition temperature T g Is at-100 ℃ to-80 ℃;
preferably, the silane-terminated polybutadiene has a number average molecular weight Mn of 3200 to 3300 and a glass transition temperature T g Is-80 ℃.
3. The composition of claim 1 or 2, wherein the silane-terminated polybutadiene is selected from silane-terminated polybutadiene
Figure FDA0003415039890000011
EP ST-E60 having a number average molecular weight of 3200, T g Is at-80 ℃;
and/or the number of the groups of groups,
silane-terminated polybutadiene
Figure FDA0003415039890000012
EP ST-E100, number average molecular weight 3300, T g Is-80℃。
4. The composition of claim 1, wherein the rubber matrix is a mixture of butadiene rubber and natural rubber;
preferably, the content of the natural rubber is 40 to 60 parts by weight and the content of the butadiene rubber is 40 to 60 parts by weight with respect to 100 parts by weight of the rubber base;
and/or the cis structure content in the butadiene rubber is 95-99 wt%, and the Mooney viscosity ML (1+4) The temperature of 100 ℃ is 40-65 ℃.
5. The composition according to any one of claims 1 to 4, wherein the white carbon black is contained in an amount of 30 to 60 parts by weight, the kaolin is contained in an amount of 2 to 15 parts by weight, the surface treating agent is contained in an amount of 0.5 to 8 parts by weight, the activator is contained in an amount of 2 to 10 parts by weight, the anti-aging agent is contained in an amount of 2 to 8 parts by weight, the softening agent is contained in an amount of 10 to 30 parts by weight, the anti-cracking agent is contained in an amount of 1 to 5 parts by weight, the tackifier is contained in an amount of 1 to 5 parts by weight, the accelerator is contained in an amount of 0.5 to 3 parts by weight, the vulcanizing agent is contained in an amount of 0.5 to 5 parts by weight, and the carbon black is contained in an amount of 0 to 10 parts by weight, relative to 100 parts by weight of the rubber substrate.
6. The composition according to claim 1 or 5, wherein the white carbon black has a nitrogen adsorption specific surface area of 10 to 200m 2 /g；
And/or the kaolin has a nitrogen adsorption specific surface area of 10-100m 2 /g, average diameter of 0.1-2 μm;
and/or the CTAB adsorption specific surface area of the carbon black is 10-600m 2 /g；
And/or the activator is a mixture of metal oxide and fatty acid and/or fatty acid metal soap salt;
and/or the anti-aging agent is selected from one or more of amine anti-aging agents, quinoline anti-aging agents, benzimidazole anti-aging agents and physical protective agents;
and/or the softener is selected from one or more of naphthenic oil, aromatic oil, paraffin oil, pine tar, tall oil, coumarone resin and polyethylene wax;
and/or the anti-cracking agent is a mixture of microcrystalline wax and paraffin wax;
and/or the tackifier is selected from one or more of phenolic resin, alkyl modified phenolic resin, cashew modified phenolic resin and tall modified phenolic resin;
and/or, the vulcanizing agent is a sulfur donor;
and/or the accelerator is selected from one or more of sulfenamide accelerators, thiuram accelerators, thiazole accelerators and guanidine accelerators.
7. A process for preparing a vulcanized rubber using the rubber composition as defined in any one of claims 1 to 6, said process comprising:
(1) The method comprises the steps of (1) carrying out first mixing on a component A containing a rubber matrix, white carbon black, kaolin, a surface treatment agent and an anti-cracking agent to obtain a section of master batch;
(2) The first-stage masterbatch is subjected to second mixing with a component B containing carbon black, an activating agent, an anti-aging agent, a tackifier and a softener to obtain a second-stage masterbatch;
(3) Thirdly, mixing the two-stage masterbatch with a component C containing a vulcanizing agent and an accelerator to obtain final rubber;
(4) And vulcanizing the final rubber mixture to obtain vulcanized rubber.
8. The method of claim 7, wherein the conditions of the first mixing comprise: the temperature is 80-130 ℃ and the time is 3-12min;
and/or, the conditions of the second mixing include: the temperature is 90-145 ℃ and the time is 3-12min;
and/or, the conditions of the third mixing include: the temperature is not higher than 130 ℃ and the time is 5-7min;
and/or, the vulcanization conditions include: the temperature is 145-165 ℃, the pressure is 10-20MPa, and the time is 25-50min.
9. A vulcanized rubber prepared by the process of claim 7 or 8.
10. Use of the vulcanized rubber of claim 9 in a tire sidewall.
CN202111543601.3A 2021-12-16 2021-12-16 Rubber composition for tire sidewall, vulcanized rubber, and preparation method and application thereof Pending CN116265517A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111543601.3A CN116265517A (en) 2021-12-16 2021-12-16 Rubber composition for tire sidewall, vulcanized rubber, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111543601.3A CN116265517A (en) 2021-12-16 2021-12-16 Rubber composition for tire sidewall, vulcanized rubber, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116265517A true CN116265517A (en) 2023-06-20

Family

ID=86743167

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111543601.3A Pending CN116265517A (en) 2021-12-16 2021-12-16 Rubber composition for tire sidewall, vulcanized rubber, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116265517A (en)

Similar Documents

Publication Publication Date Title
CN109942910A (en) A kind of high flexing fatigue service life aviation sidewall rubber, preparation method and application
JP5715609B2 (en) Steel cord coating, breaker edge strip, rubber composition for breaker cushion or cord adjacent strip, and pneumatic tire
JP2020045408A (en) Rubber composition for tire inner layer and process for producing the same
EP3323841B1 (en) White carbon black/poly(itaconate-isoprene-glycidyl methacrylate) bio-based elastomer composite material free of silane coupling agent, and preparation method therefor
CN108178846A (en) High performance tire sidewall rubber composition
CN113004586B (en) Tire side wall rubber composition with low hysteresis loss and improved appearance and preparation method thereof
CN109762219A (en) A kind of high wet-sliding resistant tear-proof tire tread rubber material and preparation method thereof
CN109400980B (en) Rubber composition, vulcanized rubber, and preparation method and application thereof
CN116265517A (en) Rubber composition for tire sidewall, vulcanized rubber, and preparation method and application thereof
EP2746064B1 (en) Antiozonant for polymers
CN113480859B (en) Rubber protective wax, and preparation method and application thereof
CN108424560A (en) A kind of Tire tread rubber composition and its preparation method and application
CN109694506B (en) Low-zinc high-wear-resistance rubber composition and application thereof
KR101165374B1 (en) Rubber composition for run flat tire and tire manufactured by using the same
KR20110079125A (en) Rubber composition for tire and method of manufacturing the same
KR100360938B1 (en) Rubber composition for sidewall of radial tire for truck and bus
CN116265518A (en) Rubber composition for tire sidewall, vulcanized rubber, preparation method and application thereof
JP5912935B2 (en) Rubber composition for tire and pneumatic tire
CN114213714B (en) Porous silicon-loaded anti-aging agent-silver ion compound, and preparation method and application thereof
KR102457813B1 (en) Tread compound composition for tire and tire comprising the same
CN114149627B (en) Rubber composition for light tire tread, application of rubber composition, vulcanized rubber, preparation method of vulcanized rubber and application of vulcanized rubber
KR100481455B1 (en) Rubber composition for bladder with self-release character
CN116265520A (en) Acetic acid resistant rubber composition, vulcanized rubber, preparation method and application thereof
JPH05112674A (en) Rubber composition with excellent rolling resistance
US11499038B2 (en) Tread composition and tire produced by using the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination