CN109929149B - Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof - Google Patents
Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof Download PDFInfo
- Publication number
- CN109929149B CN109929149B CN201711353811.XA CN201711353811A CN109929149B CN 109929149 B CN109929149 B CN 109929149B CN 201711353811 A CN201711353811 A CN 201711353811A CN 109929149 B CN109929149 B CN 109929149B
- Authority
- CN
- China
- Prior art keywords
- rubber
- parts
- mixing
- accelerator
- carbon black
- 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.)
- Active
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract 13
- 239000005060 rubber Substances 0.000 title claims abstract 13
- 239000000203 mixture Substances 0.000 title claims abstract 6
- 239000004636 vulcanized rubber Substances 0.000 title claims abstract 5
- 238000002360 preparation method Methods 0.000 title abstract 2
- 239000011159 matrix material Substances 0.000 claims abstract 5
- 239000007822 coupling agent Substances 0.000 claims abstract 4
- 150000001282 organosilanes Chemical class 0.000 claims abstract 4
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract 3
- 239000005062 Polybutadiene Substances 0.000 claims abstract 3
- 229920003052 natural elastomer Polymers 0.000 claims abstract 3
- 229920001194 natural rubber Polymers 0.000 claims abstract 3
- 229920002857 polybutadiene Polymers 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims 15
- 239000003795 chemical substances by application Substances 0.000 claims 6
- 239000004594 Masterbatch (MB) Substances 0.000 claims 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 4
- 239000003963 antioxidant agent Substances 0.000 claims 4
- 230000003078 antioxidant effect Effects 0.000 claims 4
- 239000006229 carbon black Substances 0.000 claims 4
- 239000003999 initiator Substances 0.000 claims 3
- 239000003607 modifier Substances 0.000 claims 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 2
- 239000004902 Softening Agent Substances 0.000 claims 2
- 239000012190 activator Substances 0.000 claims 2
- 230000003712 anti-aging effect Effects 0.000 claims 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 claims 2
- 238000001179 sorption measurement Methods 0.000 claims 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 claims 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 claims 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 claims 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims 1
- 239000005662 Paraffin oil Substances 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000010692 aromatic oil Substances 0.000 claims 1
- 235000019400 benzoyl peroxide Nutrition 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 150000004665 fatty acids Chemical class 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- -1 methoxy, ethoxy Chemical group 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000003921 oil Substances 0.000 claims 1
- 239000003208 petroleum Substances 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims 1
- 229960002447 thiram Drugs 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 abstract 1
Classifications
-
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of rubber, and discloses a rubber composition and vulcanized rubber for tire side walls of tires, and a preparation method and application thereof3SiCH2CH2CH2OCH2-an organosilane coupling agent represented by X, said rubber matrix being a mixture of butadiene rubber and natural rubber. The rubber composition has the advantages of high strength, low rolling resistance and good dynamic bending flexibility, and the vulcanized rubber formed by the composition can be used for the tire side wall.
Description
Technical Field
The invention relates to the field of rubber, in particular to a rubber composition for a tire side wall, a method for preparing vulcanized rubber, the vulcanized rubber prepared by the method and application of the vulcanized rubber in the tire side wall.
Background
In recent years, in order to adapt to the development trend of safety, environmental protection and green of automobile tires, non-petroleum resources such as white carbon black are more and more emphasized in the field of tires due to the characteristics of reducing the rolling resistance of tires, saving the fuel consumption of automobiles and the like, but the dispersion of white carbon black in a rubber matrix becomes extremely difficult due to the strong surface polarity of white carbon black, so that the application of white carbon black is limited to a certain extent.
CN104530501A discloses a rubber composition for color tire sidewall discoloration resistance, which has bright colors and better discoloration resistance, wherein a dark color sidewall tire does not have discoloration phenomenon within one year under the environment of strong illumination and damp heat, and the formula has higher tearing resistance and excellent discoloration resistance under the severe use conditions of strong illumination and damp heat. CN104311918A discloses a rubber composition for the sidewall of a run-flat tire for a passenger car, which can improve the safety performance of the vehicle during running and reduce or eliminate traffic accidents caused by puncture and explosion of the tire.
However, in the above prior art, it is disclosed that the silica white is added with silane coupling agent Si75, etc. to improve the dispersibility, while Si75, etc. is a sulfur-containing compound, and during the high-temperature mixing process, the requirement for process control is high, and improper control thereof may cause scorching, which may further affect the overall performance of the composite material. Si75 and the like are easy to generate ethanol in the processing process, and the existence of the ethanol brings hidden danger to the safety of the tire.
Therefore, the above prior art cannot fully satisfy the requirements of high strength, low rolling resistance, and good dynamic bending flexibility required for the tire sidewall rubber containing the white carbon black formulation, and there is a need for providing a rubber composition with improved properties.
Disclosure of Invention
The invention aims to solve the problems of improving the strength, reducing the rolling resistance and dynamic bending flexibility of rubber used for a tire side wall containing white carbon black formula, and provides a rubber composition with the advantages of high strength, low rolling resistance and good dynamic bending flexibility and vulcanized rubber formed by the composition and capable of being used for the tire side wall.
In order to achieve the above object, the present invention provides, in a first aspect, a rubber composition for a sidewall of a tire, the composition comprising a rubber base, an initiator, a rubber modifier, white carbon, carbon black, an activator, an antioxidant, a softener, an accelerator and a vulcanizing agent, wherein the rubber base is based on a rubber-based rubberThe rubber body is a mixture of butadiene rubber and natural rubber; the rubber modifier is shown as a general formula (RO)3SiCH2CH2CH2OCH2An organosilane coupling agent represented by X, RO being a hydrolyzable group, X being an epoxy group
R1And R2Each independently is H, C1-5Linear or branched alkyl groups of (a).
In a second aspect, the present invention provides a process for preparing a vulcanizate, the process comprising:
(1) carrying out first mixing on a component A containing a rubber matrix, an initiator and a rubber modifier to obtain a section of master batch;
(2) carrying out second mixing on the first-stage masterbatch and a component B containing white carbon black, an activating agent, an anti-aging agent and a softening agent to obtain a second-stage masterbatch;
(3) performing third mixing on the second-stage masterbatch and a component C containing an accelerator and a vulcanizing agent to obtain a final rubber compound;
(4) vulcanizing the final rubber;
the rubber matrix is a mixture of butadiene rubber and natural rubber; the rubber modifier is shown as a general formula (RO)3SiCH2CH2CH2OCH2An organosilane coupling agent represented by X, RO being a hydrolyzable group, X being an epoxy group
R1And R2Each independently is H, C1-5Linear or branched alkyl groups of (a).
The vulcanized rubber is obtained by a novel mixing method, wherein a rubber matrix, an initiator and a rubber modifier are mixed to prepare a matrix master batch; then adding the white carbon black, the activator, the anti-aging agent, the softener and other components into the matrix masterbatch to mix to prepare second-stage masterbatch; and then adding a vulcanizing agent and an accelerator into the secondary masterbatch to prepare final rubber, and finally vulcanizing the final rubber to prepare the vulcanized rubber. In the processing technology, the bridge function of the rubber modifier in the rubber matrix and the white carbon black can be better exerted, the dispersion of the white carbon black in the rubber matrix is facilitated, the strength of vulcanized rubber prepared by further vulcanization can be better improved, the rolling resistance of the vulcanized rubber is reduced, and the bending resistance and flexibility of the vulcanized rubber material are improved.
In a third aspect, the present invention provides a vulcanizate prepared by the method of the second aspect described above.
In a fourth aspect, the present invention provides the use of the vulcanizate of the third aspect described above in a tire sidewall.
The rubber composition has the advantages of high strength, low rolling resistance and good dynamic bending flexibility, and the vulcanized rubber formed by the composition can be used for the tire side wall.
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.
As described above, the first aspect of the present invention provides a rubber composition for a sidewall of a tire, which contains a rubber matrix, an initiator, a rubber modifier, white carbon black, an activator, an antioxidant, a softener, an accelerator and a vulcanizing agent, wherein the rubber matrix is a mixture of butadiene rubber and natural rubber; the rubber modifier is shown as a general formula (RO)3SiCH2CH2CH2OCH2An organosilane coupling agent represented by X, RO being a hydrolyzable group, X being an epoxy group
R1And R2Each independently is H, C1-5Linear or branched alkyl groups ofAn alkyl group.
The rubber modifier can modify a rubber matrix, is beneficial to the interaction between the rubber matrix and white carbon black, is beneficial to the dispersion of the white carbon black in the rubber matrix, can better improve the strength of vulcanized rubber prepared by further vulcanization, reduces the rolling resistance of the vulcanized rubber, and improves the bending resistance and flexibility of a vulcanized rubber material.
Preferably, in the organosilane coupling agent, RO is methoxy, ethoxy or acetoxy.
Preferably, in the organosilane coupling agent, R1And R2Each independently is H, methyl or ethyl.
Preferably, the natural rubber is contained in the rubber matrix in an amount of 40 to 60 parts by weight and the butadiene rubber is contained in an amount of 40 to 60 parts by weight, relative to 100 parts by weight of the rubber matrix.
Preferably, the natural rubber is SMR-20.
Preferably, the cis content in the butadiene rubber is 90 to 99 wt%.
Preferably, the content of the initiator is 0.1 to 0.8 part by weight, the content of the rubber modifier is 3 to 8 parts by weight, the content of the white carbon black is 20 to 50 parts by weight, the content of the carbon black is 30 to 50 parts by weight, the content of the activator is 5 to 10 parts by weight, the content of the anti-aging agent is 1 to 3 parts by weight, the content of the softener is 5 to 15 parts by weight, the content of the accelerator is 1 to 5 parts by weight, and the content of the vulcanizing agent is 0.5 to 4 parts by weight, relative to 100 parts by weight of the rubber matrix.
According to the present invention, it is preferable that the initiator is selected from at least one of dicumyl peroxide, dibenzoyl peroxide, bis (2, 4-dichlorobenzoyl) peroxide, diacetyl peroxide and dilauroyl peroxide.
According to the present invention, preferably, the white carbon black is silica; more preferably, the nitrogen adsorption specific surface area of the white carbon black is 10-200m2(ii) in terms of/g. For example, the white carbon black is 115GR (Rodiya, France) and/or 165GR (Rodiya, France).
Preferably, the carbon black has a CTAB adsorption specific surface area of 10 to 600m2(ii) in terms of/g. For example, the carbon black is N330 (Zideli chemical technologies, Inc. of Dongguan) and/or N550 (Zideli chemical technologies, Inc. of Dongguan).
Preferably, the activator is a mixture of a metal oxide and a fatty acid. The metal oxide is preferably zinc oxide and/or magnesium oxide; the fatty acid is preferably stearic acid.
Preferably, the antioxidant is at least one of an amine antioxidant, a quinoline antioxidant and a benzimidazole antioxidant. For example, the antioxidant is antioxidant 4020.
Preferably, the softening agent is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin, and polyethylene glycol. The aromatic oil may be, for example, aromatic oil TDAE V500. Preferably, the polyethylene glycol has a weight average molecular weight in the range of 3000-.
Preferably, the accelerator is at least one of a sulfenamide accelerator, a thiazole accelerator, a thiuram accelerator and a guanidine accelerator. Preferably, the accelerator is at least one of N-tert-butyl-2-benzothiazolesulfenamide (TBBS), diphenylguanidine (accelerator D), and tetramethylthiuram disulfide (TMTD).
Preferably, the vulcanizing agent is a sulfur donor. The sulfur donor is a substance capable of providing sulfur. The sulfur comprises at least one of insoluble sulfur, soluble sulfur and oil-extended sulfur. For example, the vulcanizing agent IS ordinary sulfur S, oil-extended insoluble sulfur IS, or the like.
As previously mentioned, a second aspect of the present invention provides a process for preparing a vulcanized rubber, the process comprising:
(1) carrying out first mixing on a component A containing a rubber matrix, an initiator and a rubber modifier to obtain a section of master batch;
(2) carrying out second mixing on the first-stage masterbatch and a component B containing white carbon black, an activating agent, an anti-aging agent and a softening agent to obtain a second-stage masterbatch;
(3) performing third mixing on the second-stage masterbatch and a component C containing an accelerator and a vulcanizing agent to obtain a final rubber compound;
(4) vulcanizing the final rubber;
the rubber matrix is a mixture of butadiene rubber and natural rubber; the rubber modifier is shown as a general formula (RO)3SiCH2CH2CH2OCH2An organosilane coupling agent represented by X, RO being a hydrolyzable group, X being an epoxy group
R1And R2Each independently is H, C1-5Linear or branched alkyl groups of (a).
The component a, the component B and the component C referred to in the second aspect of the present invention together form the rubber composition for a tire side wall described in the first aspect of the present invention, and therefore, each of the substances referred to in the second aspect of the present invention has the corresponding same properties as the same substances in the first aspect of the present invention, and in order to avoid repetition, the present invention does not repeat certain features of the substances (such as optional kinds of substances, etc.) in the second aspect, and those skilled in the art should not be construed as limiting the second aspect of the present invention.
The component A containing the rubber matrix, the initiator and the rubber modifier is firstly mixed to obtain a section of master batch, and then the subsequent process steps are carried out, so that the obtained vulcanized rubber has more excellent properties such as strength, rolling resistance and the like.
Preferably, in the second aspect, in the organosilane coupling agent, RO is a methoxy group, an ethoxy group or an acetoxy group.
Preferably, in the second aspect, in the organosilane coupling agent, R1And R2Each independently is H, methyl or ethyl.
Preferably, in the second aspect, the natural rubber is used in an amount of 40 to 60 parts by weight and the butadiene rubber is used in an amount of 40 to 60 parts by weight, relative to 100 parts by weight of the rubber matrix.
Preferably, in the second aspect, the natural rubber is SMR-20.
Preferably, in the second aspect, the cis content in the cis-butadiene rubber is 90 to 99% by weight.
Preferably, in the second aspect, the initiator is used in an amount of 0.1 to 0.8 parts by weight, the rubber modifier is used in an amount of 3 to 8 parts by weight, the white carbon black is used in an amount of 20 to 50 parts by weight, the carbon black is used in an amount of 30 to 50 parts by weight, the activator is used in an amount of 5 to 10 parts by weight, the antioxidant is used in an amount of 1 to 3 parts by weight, the softener is used in an amount of 5 to 15 parts by weight, the accelerator is used in an amount of 1 to 5 parts by weight, and the vulcanizing agent is used in an amount of 0.5 to 4 parts by weight, based on 100 parts by weight of the rubber matrix.
Preferably, in the second aspect, the conditions for the first mixing include: the temperature is 100 ℃ and 150 ℃, and the time is 3-7 min. More preferably, the conditions of the first mixing include: the temperature is 110 ℃ and 130 ℃, and the time is 4-6 min.
Preferably, in the second aspect, the conditions for the second mixing include: the temperature is 100 ℃ and 170 ℃, and the time is 3-10 min. More preferably, the conditions of the second mixing include: the temperature is 140 ℃ and 160 ℃, and the time is 5-7 min.
Preferably, in the second aspect, the third mixing conditions include: the temperature is not more than 130 deg.C, and the time is 5-7 min.
Preferably, in the second aspect, the vulcanization conditions include: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 30-50 min.
In a second aspect of the present invention, according to a preferred embodiment, the conditions of the first mixing include: the temperature is 110-; the conditions of the second mixing include: the temperature is 140 ℃ and 160 ℃, and the time is 5-7 min; the conditions of the third mixing include: the temperature is not more than 130 ℃, and the time is 5-7 min; and the conditions of the vulcanization include: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 30-50 min. The vulcanized rubber prepared by the preferred embodiment has better mechanical properties (improved strength and reduced heat generation), and the service life of the vulcanized rubber is longer.
To specifically illustrate the process of the present invention for preparing a vulcanizate, a preferred embodiment is provided below for illustration:
(1) placing the rubber matrix in an internal mixer, plasticating at the rotation speed of 50-120 rpm, the initial mixing temperature of 70-90 ℃ and the raw rubber plasticating time of 0.1-1 min; then introducing the component A containing an initiator and a rubber modifier into the internal mixer for first mixing to obtain a section of master batch;
(2) adding the first-stage masterbatch and a component B containing white carbon black, an activating agent, an anti-aging agent and a softening agent into an internal mixer for second mixing, discharging and standing for 3-5 hours to obtain second-stage masterbatch;
(3) setting the rotation speed of an internal mixer to be 50-100 rpm, setting the initial mixing temperature to be 25-50 ℃, plasticating the two-stage masterbatch for 0.5-1.5 min, and adding a component C containing an accelerator and a vulcanizing agent to carry out third mixing to obtain final rubber;
(4) putting the final rubber compound into a vulcanizing press for vulcanization;
the rubber matrix is a mixture of butadiene rubber and natural rubber; the rubber modifier is shown as a general formula (RO)3SiCH2CH2CH2OCH2An organosilane coupling agent represented by X, RO being a hydrolyzable group, X being an epoxy group
R1And R2Each independently is H, C1-5Linear or branched alkyl groups of (a).
The pressures used in the present invention are gage pressures.
As previously mentioned, a third aspect of the present invention provides a vulcanizate prepared by the method of the second aspect described above.
As previously mentioned, a fourth aspect of the present invention provides the use of the vulcanizate of the third aspect described above in a sidewall for a tire.
The present invention will be described in detail below by way of examples.
Unless otherwise specified, various commercial products used below are commercially available.
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:
natural rubber: SMR-20, Qingdao Seritet International Logistics, Inc.;
butadiene rubber: BR9000, a yanshan petrochemical (wherein, the cis content is 97.8 mass%);
white carbon black: 165GR, Rodiya, France, nitrogen adsorption specific surface area 170m2/g；
Carbon black: n330, CTAB adsorption specific surface area of 75m2Per kg; n550, CTAB adsorption specific surface area of 103m2Kg, Zideli chemical technology Co., Ltd, Dongguan;
initiator: dicumyl peroxide (DCP), dibenzoyl peroxide (BPO) Haiyin chemical Co., Ltd, analytically pure;
rubber modifier: gamma- (2, 3-epoxypropoxy) propyltriethoxysilane (wherein RO is CH)3CH2O-，R1And R2All H) (Chishiai (Shanghai) Kasei Industrial development Co., Ltd.), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (wherein RO is CH)3O-，R1And R2All H) (Chishiai (Shanghai) Kasei Industrial development Co., Ltd.), gamma- (2, 3-glycidoxy) propyltriacetoxysilane (wherein RO is CH)3COO-，R1And R2Both H) (Dike chemical Co., Ltd.) and bis- [ gamma- (triethoxysilyl) propyl]Tetrasulfide (Si69) (hangzhou jericaka chemical ltd);
softening agent: environmental aromatic oil TDAE V500 (TDAE for short), xindayang (ningbo) limited;
activating agent: zinc oxide, stearic acid, Weifang Heng Feng chemical Limited;
an anti-aging agent: n- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (antioxidant 4020) Jiangsu san ao chemical technology, Inc.;
vulcanizing agent: sulfur, Heicheng Hechenghuai chemical Limited;
accelerator (b): n-tert-butyl-2-benzothiazolesulfenamide (TBBS), diphenylguanidine (accelerator D), tetramethylthiuram disulfide (TMTD), Shanghai Yongyan chemical science and technology Co., Ltd.
The components in the following examples and comparative examples were used in parts by weight, each representing 1 g.
The examples are intended to illustrate the rubber compositions, vulcanizates, and methods of making the same of the present invention.
TABLE 1
| Serial number | Device name | Model number | Manufacturer of the product |
| 1 | Internal mixer | BR1600 | Farrel America Ltd |
| 2 | Flat vulcanizing machine | XLB-D400*400*2 | Shanghai first rubber machinery plant |
TABLE 2
TABLE 3
Example 1
The rubber composition formula comprises: 60 parts of natural rubber, 40 parts of butadiene rubber, 3 parts of gamma- (2, 3-epoxypropoxy) propyltriethoxysilane (rubber modifier), 0.1 part of DCP (initiator), 20 parts of white carbon black, 20 parts of carbon black N55020 parts, 30 parts of carbon black N33030 parts, 15 parts of TDAE (softener), 4 parts of zinc oxide (activator), 1 part of stearic acid (activator), 0.5 part of sulfur (vulcanizing agent), 4 parts of TBBS (accelerator), 1 part of accelerator D (accelerator) and 1 part of antioxidant 4020 (antioxidant).
The preparation process of the vulcanized rubber comprises the following steps:
(1) carrying out first mixing on a rubber matrix, an initiator and a rubber modifier to obtain a section of master batch; concretely, adding natural rubber and butadiene rubber into an internal mixer, setting the rotating speed to be 80rpm, setting the initial mixing temperature to be 80 ℃, and setting the raw rubber plasticating time to be 0.5 min; adding an initiator and a rubber modifier into the internal mixer for mixing at the mixing temperature of 110 ℃ for 6min to obtain a section of master batch;
(2) carrying out second mixing on the first-stage masterbatch, the white carbon black, the activating agent, the anti-aging agent, the softening agent and the carbon black to obtain second-stage masterbatch; specifically, adding white carbon black, TDAE, zinc oxide, stearic acid and an anti-aging agent 4020 into an internal mixer, and carrying out second mixing with the first-stage masterbatch, wherein the mixing time is 7min, the rubber discharge temperature is 140 ℃, discharging and standing for 4 hours to obtain a second-stage masterbatch;
(3) carrying out third mixing on the second-stage masterbatch, an accelerant and a vulcanizing agent to obtain final rubber; specifically, setting the rotation speed of an internal mixer to be 80rpm, setting the initial mixing temperature to be 40 ℃, plasticating the two-stage masterbatch for 1min, adding a vulcanizing agent and an accelerator to perform third mixing, setting the mixing temperature to be 105 ℃, mixing for 5min, and discharging to obtain final mixed rubber;
(4) and (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 150 ℃, the vulcanization pressure is 20MPa, and the vulcanization time is 50min, so that a vulcanized rubber sample S1 is obtained.
The cured rubber sample S1 was subjected to the performance test, and the results are shown in Table 4.
Example 2
The rubber composition formula comprises: 40 parts of natural rubber, 60 parts of butadiene rubber, 8 parts of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (rubber modifier), 0.8 part of BPO (initiator), 50 parts of white carbon black, 30 parts of carbon black N55030 parts, 5 parts of TDAE (softening agent), 4 parts of zinc oxide (activator), 3 parts of stearic acid (activator), 4 parts of sulfur (vulcanizing agent), 1 part of TMTD (accelerator) and 2 parts of anti-aging agent 4020 (anti-aging agent).
The preparation process of the vulcanized rubber comprises the following steps:
(1) carrying out first mixing on a rubber matrix, an initiator and a rubber modifier to obtain a section of master batch; concretely, adding natural rubber and butadiene rubber into an internal mixer, setting the rotating speed to be 80rpm, setting the initial mixing temperature to be 80 ℃, and setting the raw rubber plasticating time to be 0.5 min; adding an initiator and a rubber modifier into the internal mixer for mixing at 120 ℃ for 5min to obtain a section of master batch;
(2) carrying out second mixing on the first-stage masterbatch, the white carbon black, the activating agent, the anti-aging agent, the softening agent and the carbon black to obtain second-stage masterbatch; specifically, adding white carbon black, TDAE, zinc oxide, stearic acid and an anti-aging agent 4020 into an internal mixer, carrying out second mixing with the first-stage masterbatch, wherein the mixing time is 6min, the rubber discharge temperature is 150 ℃, discharging and standing for 4 hours to obtain a second-stage masterbatch;
(3) carrying out third mixing on the second-stage masterbatch, an accelerant and a vulcanizing agent to obtain final rubber; specifically, setting the rotation speed of an internal mixer to be 80rpm, setting the initial mixing temperature to be 40 ℃, plasticating the two-stage masterbatch for 1min, adding a vulcanizing agent and an accelerator to perform third mixing, setting the mixing temperature to be 110 ℃, mixing for 7min, and discharging to obtain final mixed rubber;
(4) and (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 30min, so that a vulcanized rubber sample S2 is obtained.
The cured rubber sample S2 was subjected to the performance test, and the results are shown in Table 4.
Example 3
The rubber composition formula comprises: 50 parts of natural rubber, 50 parts of butadiene rubber, 5 parts of gamma- (2, 3-epoxypropoxy) propyltriacetoxysilane (rubber modifier), 0.5 part of DCP (initiator), 35 parts of white carbon black, 40 parts of carbon black N33040, 10 parts of TDAE (softener), 3 parts of zinc oxide (activator), 7 parts of stearic acid (activator), 2 parts of sulfur (vulcanizing agent), 1 part of TBBS (accelerator), 2 parts of accelerator D (accelerator) and 3 parts of antioxidant 4020 (antioxidant).
The preparation process of the vulcanized rubber comprises the following steps:
(1) carrying out first mixing on a rubber matrix, an initiator and a rubber modifier to obtain a section of master batch; concretely, adding natural rubber and butadiene rubber into an internal mixer, setting the rotating speed to be 80rpm, setting the initial mixing temperature to be 80 ℃, and setting the raw rubber plasticating time to be 0.5 min; adding an initiator and a rubber modifier into the internal mixer for mixing at the mixing temperature of 130 ℃ for 4min to obtain a section of master batch;
(2) carrying out second mixing on the first-stage masterbatch, the white carbon black, the activating agent, the anti-aging agent, the softening agent and the carbon black to obtain second-stage masterbatch; specifically, adding white carbon black, TDAE, zinc oxide, stearic acid and an anti-aging agent 4020 into an internal mixer, carrying out second mixing with the first-stage masterbatch, wherein the mixing time is 5min, the rubber discharge temperature is 160 ℃, discharging and standing for 4 hours to obtain a second-stage masterbatch;
(3) carrying out third mixing on the second-stage masterbatch, an accelerant and a vulcanizing agent to obtain final rubber; specifically, setting the rotation speed of an internal mixer to be 80rpm, setting the initial mixing temperature to be 40 ℃, plasticating the two-stage master batch for 1min, adding a vulcanizing agent and an accelerator to perform third mixing, setting the mixing temperature to be 120 ℃, mixing for 6min, and discharging to obtain final mixed rubber;
(4) and (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 160 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 40min, so that a vulcanized rubber sample S3 is prepared.
The cured rubber sample S3 was subjected to the performance test, and the results are shown in Table 4.
Example 4
This example uses a rubber composition formulation similar to that of example 3, except that the amount of gamma- (2, 3-glycidoxy) propyltriacetoxysilane used in this example was 10 parts by weight.
The procedure for the preparation of the vulcanizates was the same as in example 3.
A vulcanized rubber sample S4 was obtained.
The cured rubber sample S4 was subjected to the performance test, and the results are shown in Table 4.
Example 5
The rubber composition formulation of this example was the same as in example 3 and a vulcanized rubber was prepared in a similar manner to example 3, the vulcanized rubber being prepared in a similar manner to example 3 except that:
in the process of preparing the first-stage masterbatch, the temperature of first mixing is 140 ℃ and the time is 3 min;
in the process of preparing the second-stage masterbatch, the temperature of second mixing is 100 ℃ and the time is 8 min;
in the process of preparing the final rubber compound, the time of the third mixing is 6min, and the rubber discharging temperature is 120 ℃.
A vulcanized rubber sample S5 was obtained.
The cured rubber sample S5 was subjected to the performance test, and the results are shown in Table 4.
Comparative example 1
The formulation of the rubber composition of this comparative example was similar to that of example 3, except that the rubber modifier of example 3 was replaced with the same weight of Si69 in this comparative example, specifically:
the rubber composition formula comprises: 50 parts of natural rubber, 50 parts of butadiene rubber, 5 parts of Si69 (rubber modifier), 0.5 part of DCP (initiator), 35 parts of white carbon black, 40 parts of carbon black N33040, 10 parts of TDAE (softener), 3 parts of zinc oxide (activator), 7 parts of stearic acid (activator), 2 parts of sulfur (vulcanizing agent), 1 part of TBBS (accelerator), 2 parts of accelerator D (accelerator) and 3 parts of anti-aging agent 4020 (anti-aging agent).
The procedure for the preparation of the vulcanizates was the same as in example 3. A vulcanizate sample DS1 was prepared.
The cured rubber sample DS1 was subjected to performance testing and the results are shown in Table 4.
TABLE 4
| Sample numbering | S1 | S2 | S3 | S4 | S5 | DS1 |
| Tear Strength (MPa) | 21.2 | 21.4 | 21.3 | 20.1 | 18.6 | 16.4 |
| Compression temperature rise (. degree.C.) | 24.8 | 24.6 | 25.0 | 25.9 | 26.9 | 32.0 |
| Fatigue life (times) | 19230 | 19478 | 19263 | 17923 | 15769 | 12301 |
As can be seen from the results in Table 4, the rubber composition of the present invention can achieve better dispersibility of the components of the rubber composition in the rubber matrix, so that the further prepared vulcanized rubber can have excellent comprehensive properties such as improved strength, reduced heat generation, improved dynamic fatigue property, etc.
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 (15)
1. A method of preparing a vulcanized rubber for a sidewall of a tire, the method comprising:
(1) carrying out first mixing on a component A containing a rubber matrix, an initiator and a rubber modifier to obtain a section of master batch, wherein the first mixing conditions comprise that: the temperature is 110-;
(2) and carrying out second mixing on the first-stage masterbatch and a component B containing white carbon black, an activating agent, an anti-aging agent and a softening agent to obtain a second-stage masterbatch, wherein the second mixing conditions comprise that: the temperature is 140 ℃ and 160 ℃, and the time is 5-7 min;
(3) and carrying out third mixing on the second-stage masterbatch and a component C containing an accelerator and a vulcanizing agent to obtain a final rubber compound, wherein the third mixing conditions comprise that: the temperature is not more than 130 ℃, and the time is 5-7 min;
(4) subjecting the final batch to vulcanization under conditions comprising: the temperature is 150-;
wherein the rubber modifier is of the general formula (RO)3SiCH2CH2CH2OCH2An organosilane coupling agent represented by X, RO being a hydrolyzable group, X being an epoxy group
R1And R2Each independently is H, C1-5A linear or branched alkyl group of (a);
the rubber matrix comprises, by weight, 100 parts of a rubber matrix, 0.1-0.8 part of an initiator, 3-8 parts of a rubber modifier, 20-50 parts of white carbon black, 30-50 parts of carbon black, 5-10 parts of an activator, 1-3 parts of an anti-aging agent, 5-15 parts of a softener, 1-5 parts of an accelerator and 0.5-4 parts of a vulcanizing agent;
wherein the initiator is at least one selected from dicumyl peroxide, dibenzoyl peroxide, bis (2, 4-dichlorobenzoyl) peroxide, diacetyl peroxide and dilauryl peroxide.
2. The process of claim 1, wherein in the organosilane coupling agent, RO is methoxy, ethoxy, or acetoxy.
3. The method of claim 1, wherein in the organosilane coupling agent, R1And R2Each independently is H, methyl or ethyl.
4. The method according to claim 1, wherein the natural rubber is used in an amount of 40 to 60 parts by weight and the butadiene rubber is used in an amount of 40 to 60 parts by weight, relative to 100 parts by weight of the rubber matrix.
5. The process of claim 4, wherein the natural rubber is SMR-20.
6. A process as claimed in claim 4, wherein the cis content in the butadiene rubber is 90-99% by weight.
7. The method according to any one of claims 1 to 6, wherein the silica has a nitrogen adsorption specific surface area of 10 to 200m2/g。
8. The method according to any one of claims 1 to 6, wherein the carbon black has a CTAB adsorption specific surface area of 10 to 600m2/g。
9. The method of any one of claims 1-6, wherein the activator is a mixture of a metal oxide and a fatty acid.
10. The method according to any one of claims 1 to 6, wherein the antioxidant is at least one of an amine antioxidant, a quinoline antioxidant, and a benzimidazole antioxidant.
11. The method according to any one of claims 1 to 6, wherein the softening agent is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin, and polyethylene glycol.
12. The process of any one of claims 1-6, wherein the accelerator is at least one of a sulfenamide accelerator, a thiazole accelerator, a thiuram accelerator, and a guanidine accelerator.
13. The method according to any one of claims 1-6, wherein the vulcanizing agent is a sulfur donor.
14. A vulcanized rubber produced by the process of any one of claims 1-13.
15. Use of the vulcanizate of claim 14 in a tire sidewall.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711353811.XA CN109929149B (en) | 2017-12-15 | 2017-12-15 | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711353811.XA CN109929149B (en) | 2017-12-15 | 2017-12-15 | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109929149A CN109929149A (en) | 2019-06-25 |
| CN109929149B true CN109929149B (en) | 2021-08-03 |
Family
ID=66980504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711353811.XA Active CN109929149B (en) | 2017-12-15 | 2017-12-15 | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109929149B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551238A (en) * | 2018-06-01 | 2019-12-10 | 中国石油化工股份有限公司 | Modified styrene-butadiene rubber and preparation method thereof, rubber composition, vulcanized rubber and preparation method and application thereof |
| CN112239572B (en) * | 2019-07-19 | 2022-08-19 | 中国石油化工股份有限公司 | Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof |
| CN114149624B (en) * | 2020-09-07 | 2023-08-15 | 中国石油化工股份有限公司 | Rubber composition for light tire sidewall and application thereof, vulcanized rubber and preparation method and application thereof |
| CN116144084B (en) * | 2023-01-12 | 2024-03-22 | 中策橡胶集团股份有限公司 | Low-heat-generation tire sidewall rubber composition, mixing method thereof and low-heat-generation tire |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629126A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Rubber composition, vulcanized rubber and application of vulcanized rubber |
| CN106608990A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Rubber composition and preparation method thereof, and vulcanized rubber |
| CN106700158A (en) * | 2015-11-13 | 2017-05-24 | 中国石油化工股份有限公司 | High-strength rubber composition, vulcanized rubber and preparation method and application of vulcanized rubber |
-
2017
- 2017-12-15 CN CN201711353811.XA patent/CN109929149B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629126A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Rubber composition, vulcanized rubber and application of vulcanized rubber |
| CN106608990A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Rubber composition and preparation method thereof, and vulcanized rubber |
| CN106700158A (en) * | 2015-11-13 | 2017-05-24 | 中国石油化工股份有限公司 | High-strength rubber composition, vulcanized rubber and preparation method and application of vulcanized rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109929149A (en) | 2019-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109384965B (en) | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof | |
| EP3237530B1 (en) | Rubber composition and tire comprising sustainable resources and related methods | |
| EP2740758B1 (en) | Rubber composition for tires, and pneumatic tire | |
| EP3421535B1 (en) | Rubber composition and pneumatic tire | |
| CN109929149B (en) | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof | |
| CN107964138B (en) | Application of mercapto acid monomer, rubber composition, vulcanized rubber and preparation method thereof | |
| CN107641228B (en) | Use of organosilanes and rubber compositions and vulcanizates and process for their preparation | |
| CN107955232B (en) | Application of maleic acid monomer, rubber composition, vulcanized rubber and preparation method thereof | |
| CN109929160B (en) | Application of organosilane coupling agent, rubber composition, vulcanized rubber and preparation method and application thereof | |
| CN109929159B (en) | Rubber composition and vulcanized rubber for tire tread as well as preparation method and application of rubber composition and vulcanized rubber | |
| CN109384966B (en) | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof | |
| CN107641219B (en) | Use of organosilanes and rubber compositions and vulcanizates and process for their preparation | |
| CN112250920B (en) | Sidewall supporting rubber taking synthetic rubber as base rubber and preparation method and application thereof | |
| CN109384964B (en) | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof | |
| CN111117021A (en) | Rubber composition based on solution-polymerized styrene-butadiene, vulcanized rubber, and preparation method and application thereof | |
| CN108003408B (en) | Vulcanized rubber and preparation method and application thereof | |
| CN109929148B (en) | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof | |
| EP3628692B1 (en) | Silica reinforced rubber composition containing a multifunctional group functionalized elastomer and tire with tread | |
| CN109384963B (en) | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof | |
| CN111117026A (en) | Rubber composition based on halogenated butyl rubber, vulcanized rubber, and preparation methods and applications thereof | |
| CN112778591B (en) | Rubber composition, preparation method and application thereof, rubber composition for tire treads and preparation method thereof | |
| JP2019210398A (en) | Rubber composition for tread and pneumatic tire | |
| CN112778590B (en) | Rubber composition, preparation method and application thereof, rubber composition for tire treads and preparation method thereof | |
| CN115716940B (en) | Rubber composition, vulcanized rubber, preparation method and application thereof | |
| CN115716951B (en) | Rubber composition for tread, vulcanized rubber, preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |