CN109384972A - For the rubber composition of sole and vulcanized rubber and its preparation method and application - Google Patents
For the rubber composition of sole and vulcanized rubber and its preparation method and application Download PDFInfo
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- CN109384972A CN109384972A CN201710655287.5A CN201710655287A CN109384972A CN 109384972 A CN109384972 A CN 109384972A CN 201710655287 A CN201710655287 A CN 201710655287A CN 109384972 A CN109384972 A CN 109384972A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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Abstract
The present invention relates to rubber materials, disclose a kind of rubber composition for sole, contain rubber matrix, rubber modifier, initiator, white carbon black, carbonate, activator, anti-aging agent, softening agent, promotor and vulcanizing agent in the composition, wherein, the general formula of the rubber modifier is (R1O)3Si-X, the R1O is hydrolyzable groups；X is-CH=CH-R2, wherein R2For H atom or C1‑C4Alkyl.Rubber composition for sole of the invention can be improved the intensity of the rubber for the sole containing white carbon black formula, wearability, dynamic flexing.
Description
Technical field
The present invention relates to rubber materials, and in particular, to a kind of to vulcanize rubber for the rubber composition of sole, a kind of prepare
The method of glue and the vulcanized rubber being prepared by this method and vulcanized rubber are preparing the application in sole.
Background technique
Sole directly affects the aesthetics of whole shoes, the sole of many world famous brand productions, all high-end, fashion to people's one kind
Feeling.
In the prior art, sole is mostly used the materials such as PVC, TPR, TPU and manufactures, and such material is in comfort, anti-skidding
Property aspect not as good as rubber production sole.
The commonly used white carbon black of the prior art is widely used in footwear product, no as main reinforcing filler
It can only make sole that there is good wear-resisting property, non-skid property and vamp adhesive performance, while colour can also be processed
Cowhells sole, it is very widely used in light color, colored half and sole (including outsole, indsole and foxing).
But due to the stronger surface polarity of white carbon black, its dispersion in rubber matrix is made to become abnormal difficult, thus
Using receiving certain limitation.
CN105440341A discloses a kind of anti-slip sole material, and the prior art discloses white carbon blacks in sole material
Application, wherein white carbon black improves dispersibility by addition silane coupling agent, and silane coupling agent used is sulfur-containing compound,
It is higher to process control needs during high-temperature mixing, it controls improper its and is possible to cause incipient scorch, and then influence whether compound
The overall performance of material.
CN104311918A also discloses a kind of composite-material abrasive sole, and the prior art applies different by toluene two
The white carbon black of cyanate graft modification, to improve dispersibility of the white carbon black in rubber matrix.Although modified white carbon black technique can
Change white carbon black polarity, increases the contact force with rubber, but the technics comparing is complicated, energy and material consumption is higher.
Therefore, it is high, resistance to can not to fully meet intensity required for the sole containing white carbon black formula for the above-mentioned prior art
The feature that mill property is good, dynamic flexing is good, it is necessary to which a kind of rubber composition of performance improvement is provided.
Summary of the invention
Present invention aim to address the intensity, wear-resisting for how improving the rubber for the sole containing white carbon black formula
The problem of property, dynamic flexing, provide a kind of rubber composition for sole and thus obtained vulcanized rubber.
To achieve the goals above, in a first aspect, the present invention provides a kind of rubber composition for sole, the composition
In containing rubber matrix, rubber modifier, initiator, white carbon black, carbonate, activator, anti-aging agent, softening agent, promotor and
Vulcanizing agent, wherein the general formula of the rubber modifier is (R1O)3Si-X, the R1O is hydrolyzable groups；X is-CH=CH-
R2, wherein R2For H atom or C1-C4Alkyl.
Second aspect, the present invention provides a kind of method for preparing vulcanized rubber, this method comprises: (1) will contain rubber-based
The component A of body, initiator and rubber modifier carries out first and is kneaded, and obtains one section of rubber master batch；
(2) one section of rubber master batch and the component B containing white carbon black, carbonate, activator, anti-aging agent and softening agent are carried out
Second is kneaded, and obtains two sections of rubber master batch；
(3) two sections of rubber master batch are subjected to third mixing with containing the component C of promotor and vulcanizing agent, obtain finished composition；
(4) finished composition is vulcanized；
The general formula of the rubber modifier is (R1O)3Si-X, the R1O is hydrolyzable groups；X is-CH=CH-R2,
Middle R2For H atom or C1-C4Alkyl.
Vulcanized rubber of the invention is obtained by a kind of new mixing method, in this method first by rubber matrix, initiator,
Rubber modifier is mixed to be prepared into matrix rubber master batch；Then using white carbon black, activator, anti-aging agent, soft is added in matrix rubber master batch
Agent etc. is mixed with two sections of rubber master batch；Then addition vulcanizing agent, promotor are prepared into finished composition in two sections of rubber master batch, finally will be whole
Refining glue carries out vulcanizing obtained vulcanized rubber.
In processing technology of the invention, bridge of the rubber modifier in rubber matrix and white carbon black can be preferably played
Effect, is conducive to dispersion of the white carbon black in rubber matrix, can preferably improve the vulcanization rubber as made from further vulcanizing
The intensity of glue improves vulcanized rubber wearability, improves the anti-flexibility of vulcanizate compound.
The third aspect, the present invention provide a kind of vulcanized rubber that the method as described in second aspect is prepared.
Fourth aspect, the present invention provide vulcanized rubber described in a kind of third aspect and are preparing the application in sole.
Rubber composition for sole of the invention can be improved the rubber for the sole containing white carbon black formula
Intensity, wearability, dynamic flexing.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, the first aspect of the present invention provides a kind of rubber composition for sole, contain in the composition
There are rubber matrix, rubber modifier, initiator, white carbon black, carbonate, activator, anti-aging agent, softening agent, promotor and vulcanization
Agent, wherein the general formula of the rubber modifier is (R1O)3Si-X, the R1O is hydrolyzable groups；X is-CH=CH-R2,
Middle R2For H atom or C1-C4Alkyl.
The C1-C4Alkyl include C1-C4Straight chained alkyl and C1-C4Branched alkyl.
Rubber modifier in rubber composition of the invention enables to rubber matrix modified, to be conducive to rubber-based
Interaction between body and white carbon black is conducive to dispersion of the white carbon black in rubber matrix, can preferably improve by into
One step vulcanizes the intensity of vulcanized rubber obtained, improves vulcanized rubber wearability, improves the anti-flexibility of vulcanizate compound.
Preferably, in the rubber modifier, the R1O is methoxyl group, ethyoxyl or acetoxyl group, the R2For H original
Son or C1-C4Straight chained alkyl.
The C1-C4Straight chained alkyl include at least one of methyl, ethyl, n-propyl and normal-butyl.
It is particularly preferred that in the rubber modifier, the R2For H atom.It was found by the inventors of the present invention that working as R2For H
Atomic time, the rubber modifier being consequently formed is when preparing vulcanized rubber, intensity, wearability, the dynamic of the vulcanized rubber of acquisition
Flexibility can further be improved.
Preferably, the rubber matrix is butadiene rubber.
It is highly preferred that the cis-content in the butadiene rubber is 90-99 weight %.
Under preferable case, relative to the rubber matrix of 100 parts by weight, the content of the rubber modifier is 0.5-
4.5 parts by weight, the content of the initiator are 0.05-0.5 parts by weight, and the content of the white carbon black is 40-70 parts by weight, described
The content of carbonate is 2-8 parts by weight, and the content of the activator is 1-5 parts by weight, and the content of the anti-aging agent is 0.5-3 weight
Part is measured, the content of the softening agent is 10-25 parts by weight, and the content of the vulcanizing agent is 1-4 parts by weight, and the promotor contains
Amount is 2-6 parts by weight.
The initiator can be organic peroxide evocating agent.Preferably, the initiator is selected from peroxidating diisopropyl
Benzene, benzoyl peroxide, peroxidating two (2,4 dichloro benzene formyl), diacetyl peroxide, dioctanoyl peroxide and peroxidating two
At least one of lauroyl.
In the case of, according to the invention it is preferred to, the white carbon black is silica；It is highly preferred that the nitrogen of the white carbon black is inhaled
Attached specific surface area is 10-200m2/g.For example, the white carbon black is 115GR (French Rhodia) and/or 165GR (France
Rhodia).
Preferably, the carbonate is at least one of magnesium carbonate, zinc carbonate and calcium carbonate；The present inventor's hair
Existing, when using zinc carbonate, the rubber composition for sole of the invention being consequently formed has more excellent performance.
Preferably, the activator is fatty acid or fatty acid metal soap salt.The fatty acid is preferably stearic acid；It is described
Fatty acid metal soap salt is zinc stearate and/or zinc borate.
Preferably, the anti-aging agent is phenol antiager.For example, the anti-aging agent is antioxidant 264.
Preferably, the softening agent is White Mineral Oil.The White Mineral Oil for example can be 10# White Mineral Oil.
Preferably, the promotor is at least one in thiazole accelerator, thuriam acceserator and guanidines
Kind.Preferably, the promotor is 2,2'- dithio-bis-benzothiazole (DM), tetramethylthiuram disulfide (TMTD), hexichol
Guanidine (diphenylguanidine).
Preferably, the vulcanizing agent is sulfur donor.The sulfur donor refers to the substance for being capable of providing sulphur.Institute
Stating sulphur includes at least one of insoluble sulfur, soluble sulfur and oil-filled sulphur.For example, the vulcanizing agent is common sulphur
Sulphur S, oil-filled insoluble sulfur IS etc..
As previously mentioned, the second aspect of the present invention provides a kind of method for preparing vulcanized rubber, this method comprises:
(1) the component A containing rubber matrix, initiator and rubber modifier is carried out first to be kneaded, obtains one section of rubber master batch；
(2) one section of rubber master batch and the component B containing white carbon black, carbonate, activator, anti-aging agent and softening agent are carried out
Second is kneaded, and obtains two sections of rubber master batch；
(3) two sections of rubber master batch are subjected to third mixing with containing the component C of promotor and vulcanizing agent, obtain finished composition；
(4) finished composition is vulcanized；
The general formula of the rubber modifier is (R1O)3Si-X, the R1O is hydrolyzable groups；X is-CH=CH-R2,
Middle R2For H atom or C1-C4Alkyl.
Component A, component B involved in second aspect of the present invention and component C are formed together in first aspect present invention
The rubber composition for sole, therefore, various substances involved in second aspect of the present invention with the present invention the
Same substance in one side has corresponding identical property, and in order to avoid repeating, the present invention is in second aspect to substance
Certain features (such as optional type of substance etc.) are not repeated to describe, and those skilled in the art should not be construed as to of the invention
The limitation of second aspect.
The present invention is obtained using the component A containing rubber matrix, initiator and rubber modifier is first carried out the first mixing
Then one section of rubber master batch carries out the subsequent processing step of the present invention, the property such as intensity and wearability of thus obtained vulcanized rubber again
It can be more excellent.
Under preferable case, in second aspect, in the rubber modifier, the R1O is methoxyl group, ethyoxyl or second
Acyloxy, the R2For H atom or C1-C4Straight chained alkyl.
Under preferable case, in second aspect, the rubber matrix is butadiene rubber.
It is highly preferred that the cis-content in the butadiene rubber is 90-99 weight % in second aspect.
Under preferable case, in second aspect, relative to the rubber matrix of 100 parts by weight, the rubber modifier
Dosage be 0.5-4.5 parts by weight, the dosage of the initiator is 0.05-0.5 parts by weight, and the dosage of the white carbon black is 40-
70 parts by weight, the dosage of the carbonate are 2-8 parts by weight, and the dosage of the activator is 1-5 parts by weight, the anti-aging agent
Dosage is 0.5-3 parts by weight, and the dosage of the softening agent is 10-25 parts by weight, and the dosage of the vulcanizing agent is 1-4 parts by weight,
The dosage of the promotor is 2-6 parts by weight.
Under preferable case, in second aspect, it is 120-170 DEG C that the described first condition being kneaded, which includes: temperature, and the time is
2-10min；Preferably, it is 130-150 DEG C that the described first condition being kneaded, which includes: temperature, time 2-5min.
Under preferable case, in second aspect, it is 90-140 DEG C that the described second condition being kneaded, which includes: temperature, and the time is
3-10min；It is highly preferred that it is 100-120 DEG C that the described second condition being kneaded, which includes: temperature, time 5-7min.
Under preferable case, in second aspect, the condition that the third is kneaded includes: that temperature is the time no more than 120 DEG C
For 5-7min.
Under preferable case, in second aspect, the condition of the vulcanization includes: that temperature is 150-170 DEG C, pressure 10-
20MPa, time 30-50min.
In the second aspect of the present invention, according to a kind of preferred embodiment, the described first condition packet being kneaded
Include: temperature is 130-150 DEG C, time 2-5min；It is 100-120 DEG C that described second condition being kneaded, which includes: temperature, and the time is
5-7min；The condition that the third is kneaded includes: that temperature is the time 5-7min no more than 120 DEG C；The condition packet of the vulcanization
Include: temperature is 150-170 DEG C, pressure 10-20MPa, time 30-50min.It is prepared using the preferred embodiment
The mechanical property of vulcanized rubber is more excellent (intensity raising), and abrasion resistance properties are well and the fatigue life of vulcanized rubber improves.
Method in order to specifically describe preparation vulcanized rubber of the invention, a kind of preferred specific embodiment party presented below
Formula is illustrated:
(1) rubber matrix is placed in mixer, revolving speed is 50~120rpm, and initial melting temperature is 70~90 DEG C, raw
Glue plasticates the time to plasticate under the conditions of 0.1~1min；It then will be in the component A introducing containing initiator and rubber modifier
It states and carries out the first mixing in mixer, obtain one section of rubber master batch；
(2) one section of rubber master batch is added with the component B containing white carbon black, carbon black, activator, anti-aging agent and softening agent close
Second is carried out in mill to be kneaded, and is discharged and is parked 3-5 hours, obtains two sections of rubber master batch；
(3) revolving speed that mixer is arranged is 50~100rpm, and initial melting temperature is 25~50 DEG C, by two sections of rubber master batch
It plasticates after 0.5~1.5min, is added and carries out third mixing containing the component C of promotor and vulcanizing agent, obtain finished composition；
(4) finished composition is put into vulcanizing press and is vulcanized；
The general formula of the rubber modifier is (R1O)3Si-X, the R1O is hydrolyzable groups；X is-CH=CH-R2,
Middle R2For H atom or C1-C4Alkyl.
Pressure used is gauge in the present invention.
As previously mentioned, the third aspect of the present invention provides the vulcanization that the method as described in aforementioned second aspect is prepared
Rubber.
As previously mentioned, the fourth aspect of the present invention provides vulcanized rubber described in the aforementioned third aspect in preparing sole
Application.
It below will the present invention will be described in detail by example.
In case of no particular description, extensive stock used below is all from commercially available.
The equipment situation of following embodiment and comparative example preparation vulcanized rubber is shown in Table 1.
The test equipment of vulcanized rubber made from embodiment and comparative example is shown in Table 2, and test condition is shown in Table 3.
The chemical reagent that embodiment and comparative example uses is commercially available product, specific as follows:
Butadiene rubber: BR9000, Yanshan Petrochemical product (wherein, cis-content is 97.8 weight %)；
White carbon black: 165GR, French Rhodia, N2 adsorption specific surface area are 170m2/g；
Carbonate: zinc carbonate, technical grade, Shenzhen Stock Exchange Xin Yuanheng Chemical Co., Ltd.；Calcium carbonate, technical grade, Shanghai calcium carbonate
Factory；Magnesium carbonate, technical grade, Hebei Mei Shen Science and Technology Ltd.；
Initiator: cumyl peroxide (DCP) Hai Jing Chemical Co., Ltd. analyzes pure；
Rubber modifier: vinyltriethoxysilane (wherein, R1O is CH3CH2O-, R2For H), (the uncommon love (Shanghai) of ladder is changed
At industrial development Co., Ltd), vinyltrimethoxysilane (wherein, R1O is CH3O-, R2For H) (uncommon love (Shanghai) chemical conversion of ladder
Industrial development Co., Ltd), vinyltriacetoxy silane (wherein, R1O is CH3COO-, R2For H) (section, Huainan City Dihua work
Science and Technology Ltd.), ethyl triethoxy silicane ethylene (wherein, R1O is CH3CH2O-, R2For CH3CH2), double-[γ-(three ethoxies
Base silicon) propyl] tetrasulfide (Si69) (Hangzhou Jesse blocks Chemical Co., Ltd.)；
Softening agent: White Mineral Oil 10# (abbreviation 10# white oil), Shandong Tai Chang petrochemical industry Science and Technology Ltd.；
Activator: stearic acid, Weifang Hengfeng Chemical Co., Ltd.；
Anti-aging agent: 4,6- di-tert-butyl p-cresol (antioxidant 264) climb and spend chemical (Shanghai) Co., Ltd.；
Vulcanizing agent: sulphur, Weifang Zhong Heng Chemical Co., Ltd.；
Promotor: 2,2'- dithio-bis-benzothiazoles (DM), diphenylguanidine (diphenylguanidine), tetramethylthiuram disulfide
(TMTD), Shanghai Yong Yan Chemical Industry Science Co., Ltd.
Amounts of components in following embodiment and comparative example is parts by weight, and every parts by weight represent 1g.
Embodiment is for illustrating rubber composition of the invention, vulcanized rubber and preparation method thereof.
Table 1
| Serial number | Device name | Model | Manufacturer |
| 1 | Mixer | BR1600 | Farrel Corp. (US) 25 Main Street, Ansonia, CT 06401, U.S.A., the U.S. |
| 2 | Vulcanizing press | XLB-D400*400*2 | The first rubber machinery plant of Shanghai |
Table 2
Table 3
Embodiment 1
Building rubber compound composition formula: 100 parts by weight of butadiene rubber, 0.5 weight of vinyltriethoxysilane (rubber modifier)
Measure part, 0.05 parts by weight of DCP (initiator), 40 parts by weight of white carbon black, 8 parts by weight of zinc carbonate, 10 weight of 10# white oil (softening agent)
Part, 5 parts by weight of stearic acid (activator), 1 parts by weight of sulphur (vulcanizing agent), 6 parts by weight of DM (promotor), antioxidant 264 are (anti-old
Agent) 0.5 parts by weight.
The preparation process of vulcanized rubber:
(1) rubber matrix, initiator, rubber modifier are carried out first to be kneaded, obtains one section of rubber master batch；It specifically, will be suitable
Buna is added in mixer, and setting revolving speed is 80rpm, and initial melting temperature is 80 DEG C, and raw rubber plasticates the time as 0.5min；It will
Initiator, rubber modifier are added in above-mentioned mixer and are kneaded, and melting temperature is 130 DEG C, and mixing time 5min obtains one section
Rubber master batch；
(2) one section of rubber master batch and white carbon black, activator, anti-aging agent, softening agent etc. are carried out second to be kneaded, obtains two sections
Rubber master batch；Specifically, white carbon black, 10# white oil, stearic acid, antioxidant 264 are added in mixer, are carried out with one section of rubber master batch
Second is kneaded, mixing time 5min, and dump temperature is 100 DEG C, discharges and parks 4 hours, obtains two sections of rubber master batch；
(3) two sections of rubber master batch and promotor and vulcanizing agent are subjected to third mixing, obtain finished composition；Specifically, it is arranged
The revolving speed of mixer is 80rpm, and initial melting temperature is 40 DEG C, and two sections of rubber master batch are plasticated after 1min, and addition vulcanizing agent promotees
Third mixing is carried out into agent, melting temperature is 105 DEG C, mixing time 5min, and discharging obtains finished composition；
(4) finished composition is put into vulcanizing press and is vulcanized, curing temperature is 150 DEG C, sulfide stress is
Cured rubber samples S1 is made in 20MPa, vulcanization time 50min.
Cured rubber samples S1 is tested for the property, the results are shown in Table 4.
Embodiment 2
Building rubber compound composition formula: 100 parts by weight of butadiene rubber, 3 weight of vinyltrimethoxysilane (rubber modifier)
Part, 0.3 parts by weight of DCP (initiator), 50 parts by weight of white carbon black, 5 parts by weight of zinc carbonate, 18 parts by weight of 10# white oil (softening agent),
3 parts by weight of stearic acid (activator), 4 parts by weight of sulphur (vulcanizing agent), 2 parts by weight of DM (promotor), 2 weight of TMTD (promotor)
Part, 2 parts by weight of antioxidant 264 (anti-aging agent).
The preparation process of vulcanized rubber:
(1) rubber matrix, initiator, rubber modifier are carried out first to be kneaded, obtains one section of rubber master batch；It specifically, will be suitable
Buna is added in mixer, and setting revolving speed is 80rpm, and initial melting temperature is 80 DEG C, and raw rubber plasticates the time as 0.5min；It will
Initiator, rubber modifier are added in above-mentioned mixer and are kneaded, and melting temperature is 140 DEG C, and mixing time 3.5min obtains one
Section rubber master batch；
(2) one section of rubber master batch and white carbon black, activator, anti-aging agent, softening agent etc. are carried out second to be kneaded, obtains two sections
Rubber master batch；Specifically, white carbon black, 10# white oil, stearic acid, antioxidant 264 are added in mixer, are carried out with one section of rubber master batch
Second is kneaded, mixing time 6min, and dump temperature is 110 DEG C, discharges and parks 4 hours, obtains two sections of rubber master batch；
(3) two sections of rubber master batch and promotor and vulcanizing agent are subjected to third mixing, obtain finished composition；Specifically, it is arranged
The revolving speed of mixer is 80rpm, and initial melting temperature is 40 DEG C, and two sections of rubber master batch are plasticated after 1min, and addition vulcanizing agent promotees
Third mixing is carried out into agent, melting temperature is 110 DEG C, mixing time 7min, and discharging obtains finished composition；
(4) finished composition is put into vulcanizing press and is vulcanized, curing temperature is 170 DEG C, sulfide stress is
Cured rubber samples S2 is made in 10MPa, vulcanization time 30min.
Cured rubber samples S2 is tested for the property, the results are shown in Table 4.
Embodiment 3
Building rubber compound composition formula: 100 parts by weight of butadiene rubber, vinyltriacetoxy silane (rubber modifier) 4.5
Parts by weight, 0.5 parts by weight of DCP (initiator), 70 parts by weight of white carbon black, 2 parts by weight of zinc carbonate, 25 weight of 10# white oil (softening agent)
Measure part, 1 parts by weight of stearic acid (activator), 2 parts by weight of sulphur (vulcanizing agent), 1 parts by weight of DM (promotor), TMTD (promotor)
0.5 parts by weight, 0.5 parts by weight of D (promotor), 3 parts by weight of antioxidant 264 (anti-aging agent).
The preparation process of vulcanized rubber:
(1) rubber matrix, initiator, rubber modifier are carried out first to be kneaded, obtains one section of rubber master batch；It specifically, will be suitable
Buna is added in mixer, and setting revolving speed is 80rpm, and initial melting temperature is 80 DEG C, and raw rubber plasticates the time as 0.5min；It will
Initiator, rubber modifier are added in above-mentioned mixer and are kneaded, and melting temperature is 150 DEG C, and mixing time 2min obtains one section
Rubber master batch；
(2) one section of rubber master batch and white carbon black, activator, anti-aging agent, softening agent etc. are carried out second to be kneaded, obtains two sections
Rubber master batch；Specifically, white carbon black, 10# white oil, stearic acid, antioxidant 264 are added in mixer, are carried out with one section of rubber master batch
Second is kneaded, mixing time 7min, and dump temperature is 120 DEG C, discharges and parks 4 hours, obtains two sections of rubber master batch；
(3) two sections of rubber master batch and promotor and vulcanizing agent are subjected to third mixing, obtain finished composition；Specifically, it is arranged
The revolving speed of mixer is 80rpm, and initial melting temperature is 40 DEG C, and two sections of rubber master batch are plasticated after 1min, and addition vulcanizing agent promotees
Third mixing is carried out into agent, melting temperature is 120 DEG C, mixing time 6min, and discharging obtains finished composition；
(4) finished composition is put into vulcanizing press and is vulcanized, curing temperature is 160 DEG C, sulfide stress is
Cured rubber samples S3 is made in 15MPa, vulcanization time 40min.
Cured rubber samples S3 is tested for the property, the results are shown in Table 4.
Embodiment 4
Building rubber compound composition formula: 100 parts by weight of butadiene rubber, 4.5 weight of ethyl triethoxy silicane ethylene (rubber modifier)
Measure part, 0.5 parts by weight of DCP (initiator), 50 parts by weight of white carbon black, 5 parts by weight of zinc carbonate, 18 weight of 10# white oil (softening agent)
Part, 3 parts by weight of stearic acid (activator), 4 parts by weight of sulphur (vulcanizing agent), 2 parts by weight of DM (promotor), TMTD (promotor) 1
Parts by weight, 1 parts by weight of D (promotor), 2 parts by weight of antioxidant 264 (anti-aging agent).
The preparation process of vulcanized rubber is in the same manner as in Example 3.Cured rubber samples S4 is made.
Cured rubber samples S4 is tested for the property, the results are shown in Table 4.
Embodiment 5
The building rubber compound composition formula of the present embodiment is in the same manner as in Example 3, and uses method system similar to Example 3
Standby vulcanized rubber, except that:
During preparing one section of rubber master batch, the first temperature being kneaded is 120 DEG C, time 8min；
During preparing two sections of rubber master batch, the second temperature being kneaded is 140 DEG C, time 8min；
During preparing finished composition, the time that third is kneaded is 6min, and dump temperature is 120 DEG C.
Cured rubber samples S5 is made.
Cured rubber samples S5 is tested for the property, the results are shown in Table 4.
Embodiment 6
The formula of the rubber composition of the present embodiment is similar to embodiment 1, and uses method same as Example 1
Prepare vulcanized rubber, in formula except that:
Carbonate used in the present embodiment is magnesium carbonate, and dosage is 8 parts by weight.
Cured rubber samples S6 is made.
Cured rubber samples S6 is tested for the property, the results are shown in Table 4.
Embodiment 7
The formula of the rubber composition of the present embodiment is similar to embodiment 2, and uses method same as Example 2
Prepare vulcanized rubber, in formula except that:
Carbonate used in the present embodiment is calcium carbonate, and dosage is 5 parts by weight.Cured rubber samples S7 is made.
Cured rubber samples S7 is tested for the property, the results are shown in Table 4.
Comparative example 1
Building rubber compound composition formula: 100 parts by weight of butadiene rubber, 4.5 parts by weight of Si69,70 parts by weight of white carbon black, zinc carbonate
2 parts by weight, 25 parts by weight of 10# white oil (softening agent), 1 parts by weight of stearic acid (activator), 2 parts by weight of sulphur (vulcanizing agent), DM
(promotor) 1 parts by weight, 0.5 parts by weight of TMTD (promotor), 0.5 parts by weight of D (promotor), 3 weight of antioxidant 264 (anti-aging agent)
Measure part.
The preparation process of vulcanized rubber is in the same manner as in Example 3.Cured rubber samples DS1 is made.
Cured rubber samples DS1 is tested for the property, the results are shown in Table 4.
Table 4
| Sample number into spectrum | S1 | S2 | S3 | S4 | S5 | S6 | S7 | DS1 |
| Breaking strength/MPa | 8.9 | 9.2 | 9.6 | 8.5 | 8.6 | 8.6 | 9.0 | 7.3 |
| Akron abrasion/cm3 | 0.31 | 0.32 | 0.33 | 0.45 | 0.44 | 0.33 | 0.32 | 0.68 |
| Fatigue life/ten thousand time | 3.56 | 3.43 | 3.41 | 3.08 | 3.09 | 3.41 | 3.30 | 2.13 |
As can be seen from Table 4, rubber composition of the invention can achieve each component of rubber composition in rubber
It is preferably dispersed in matrix, it improves intensity so that further manufactured vulcanized rubber be enable to have, improve wearability, raising
The excellent comprehensive performance such as dynamic fatigue.Also, from above-mentioned performance can be seen that vulcanized rubber of the invention have be applied to
Prepare the potentiality of sole.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (12)
1. a kind of rubber composition for sole, rubber matrix, rubber modifier, initiator, hard charcoal are contained in the composition
Black, carbonate, activator, anti-aging agent, softening agent, promotor and vulcanizing agent, wherein the general formula of the rubber modifier is
(R1O)3Si-X, the R1O is hydrolyzable groups；X is-CH=CH-R2, wherein R2For H atom or C1-C4Alkyl.
2. composition according to claim 1, wherein in the rubber modifier, the R1O is methoxyl group, ethyoxyl
Or acetoxyl group, the R2For H atom or C1-C4Straight chained alkyl.
3. composition according to claim 1 or 2, wherein the rubber matrix is butadiene rubber；Preferably,
Cis-content in the butadiene rubber is 90-99 weight %.
4. composition described in any one of -3 according to claim 1, wherein the rubber-based relative to 100 parts by weight
Body, the content of the rubber modifier are 0.5-4.5 parts by weight, and the content of the initiator is 0.05-0.5 parts by weight, described
The content of white carbon black is 40-70 parts by weight, and the content of the carbonate is 2-8 parts by weight, and the content of the activator is 1-5 weight
Part is measured, the content of the anti-aging agent is 0.5-3 parts by weight, and the content of the softening agent is 10-25 parts by weight, the vulcanizing agent
Content is 1-4 parts by weight, and the content of the promotor is 2-6 parts by weight.
5. composition according to claim 1, wherein the initiator is selected from cumyl peroxide, benzoyl peroxide first
In acyl, peroxidating two (2,4 dichloro benzene formyl), diacetyl peroxide, dioctanoyl peroxide and dilauroyl peroxide at least
It is a kind of；Preferably,
The N2 adsorption specific surface area of the white carbon black is 10-200m2/g；Preferably,
The carbonate is at least one of magnesium carbonate, zinc carbonate and calcium carbonate；Preferably,
The activator is fatty acid or fatty acid metal soap salt.
6. composition according to claim 1, wherein the anti-aging agent is phenol antiager；Preferably,
The softening agent is White Mineral Oil；Preferably,
The promotor is at least one of thiazole accelerator, thuriam acceserator and guanidines；Preferably,
The vulcanizing agent is sulfur donor.
7. a kind of method for preparing vulcanized rubber, this method comprises:
(1) the component A containing rubber matrix, initiator and rubber modifier is carried out first to be kneaded, obtains one section of rubber master batch；
(2) one section of rubber master batch and the component B containing white carbon black, carbonate, activator, anti-aging agent and softening agent are carried out second
It is kneaded, obtains two sections of rubber master batch；
(3) two sections of rubber master batch are subjected to third mixing with containing the component C of promotor and vulcanizing agent, obtain finished composition；
(4) finished composition is vulcanized；
The general formula of the rubber modifier is (R1O)3Si-X, the R1O is hydrolyzable groups；X is-CH=CH-R2, wherein R2For
H atom or C1-C4Alkyl；Preferably,
In the rubber modifier, the R1O is methoxyl group, ethyoxyl or acetoxyl group, the R2For H atom or C1-C4's
Straight chained alkyl.
8. according to the method described in claim 7, wherein, the rubber matrix is butadiene rubber；Preferably,
Cis-content in the butadiene rubber is 90-99 weight %.
9. method according to claim 7 or 8, wherein relative to the rubber matrix of 100 parts by weight, the rubber
The dosage of modifying agent is 0.5-4.5 parts by weight, and the dosage of the initiator is 0.05-0.5 parts by weight, the dosage of the white carbon black
For 40-70 parts by weight, the dosage of the carbonate is 2-8 parts by weight, and the dosage of the activator is 1-5 parts by weight, described anti-
The dosage of old agent is 0.5-3 parts by weight, and the dosage of the softening agent is 10-25 parts by weight, and the dosage of the vulcanizing agent is 1-4 weight
Part is measured, the dosage of the promotor is 2-6 parts by weight.
10. method according to claim 7 or 8, wherein it is 120-170 that the described first condition being kneaded, which includes: temperature,
DEG C, time 2-10min；Preferably,
It is 90-140 DEG C that described second condition being kneaded, which includes: temperature, time 3-10min；Preferably,
The condition that the third is kneaded includes: that temperature is the time 5-7min no more than 120 DEG C；Preferably,
The condition of the vulcanization includes: that temperature is 150-170 DEG C, pressure 10-20MPa, time 30-50min.
11. the vulcanized rubber that the method as described in any one of claim 8-12 is prepared.
12. vulcanized rubber described in claim 11 is preparing the application in sole.
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| CN114437422A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Rubber composition for shoe sole and application thereof, vulcanized rubber and preparation method and application thereof |
| CN115109399A (en) * | 2021-03-17 | 2022-09-27 | 北京化工大学 | Rubber material capable of degrading sole and shoe edge strip as well as preparation method and application thereof |
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| CN114437422A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Rubber composition for shoe sole and application thereof, vulcanized rubber and preparation method and application thereof |
| CN114437422B (en) * | 2020-11-02 | 2023-05-09 | 中国石油化工股份有限公司 | Rubber composition for shoe soles and application thereof, vulcanized rubber and preparation method and application thereof |
| CN115109399A (en) * | 2021-03-17 | 2022-09-27 | 北京化工大学 | Rubber material capable of degrading sole and shoe edge strip as well as preparation method and application thereof |
| CN115109399B (en) * | 2021-03-17 | 2024-04-26 | 北京化工大学 | Degradable sole and welt rubber material, and preparation method and application thereof |
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