CN112239571B - Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof - Google Patents

Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof Download PDF

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CN112239571B
CN112239571B CN201910655850.8A CN201910655850A CN112239571B CN 112239571 B CN112239571 B CN 112239571B CN 201910655850 A CN201910655850 A CN 201910655850A CN 112239571 B CN112239571 B CN 112239571B
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rubber
composition
white carbon
parts
mixing
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CN112239571A (en
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王丽丽
解希铭
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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Abstract

The invention relates to the field of rubber, and discloses a rubber composition for soles, vulcanized rubber, a preparation method and an application thereof. The vulcanized rubber prepared from the rubber composition for soles has excellent hardness and rebound resilience.

Description

Rubber composition for shoe sole, 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 soles, a method for preparing vulcanized rubber, the vulcanized rubber prepared by the method and application of the vulcanized rubber in preparing soles.
Background
The comfort of the sole directly influences the quality of the whole shoe, and the soles produced by a plurality of international large brands give people a comfortable, high-end and fashionable feeling.
In the prior art, the sole is produced by using PVC, TPR, TPU and other materials, and the materials are inferior to the sole made of rubber in the aspects of comfort and skid resistance.
In the prior art, white carbon black is used as a main reinforcing filler and is widely applied to shoe products, so that soles have good wear resistance, skid resistance and vamp adhesion, colored cowhells soles can be processed, and the white carbon black is widely applied to light-colored and colored soles (including undersoles, midsoles and foxings). Therefore, the shoe industry is always a large consumer of white carbon black.
The dispersion of white carbon black in a rubber matrix becomes extremely difficult due to the strong surface polarity of the white carbon black, so that the application is limited to a certain extent.
CN105440341A discloses an antiskid sole material, and the invention discloses the application of white carbon black in a sole material, wherein the white carbon black is added with a silane coupling agent to improve the dispersibility, and the silane coupling agent is a sulfur-containing compound, so that the requirement on process control is high in the high-temperature mixing process, scorching is possibly caused by improper control, and the overall performance of the composite material is influenced.
The above prior art cannot completely satisfy the requirements of proper hardness and good rebound resilience required for soles containing white carbon black formulations. Therefore, there is a need to provide a rubber composition with improved properties.
Disclosure of Invention
The invention aims to solve the problem of how to improve the resilience of the shoe sole material containing the white carbon black formula on the premise of ensuring the hardness of the shoe sole material.
In order to achieve the purpose, the invention provides a rubber composition for soles, which comprises a rubber matrix, a rubber modifier, white carbon black, polyethylene glycol, a surface modifier, an activator, an anti-aging agent, a softener, an accelerator and a vulcanizing agent, wherein the rubber modifier is dimercaptosuccinic acid shown in a formula (1), and the rubber matrix is cis-butadiene rubber and solution-polymerized styrene-butadiene rubber; and, relative to 100 parts by weight of the rubber matrix, the content of the rubber modifier is 2-6 parts by weight, the content of the white carbon black is 40-60 parts by weight, the content of the polyethylene glycol is 5-10 parts by weight, the content of the surface modifier is 4-6 parts by weight, the content of the activator is 4-6 parts by weight, the content of the anti-aging agent is 1-5 parts by weight, the content of the softener is 6-12 parts by weight, the content of the accelerator is 3-6 parts by weight, and the content of the vulcanizing agent is 2-5 parts by weight; and, in the rubber matrix, the content of the butadiene rubber is 55 to 90 wt%, and the content of the solution polymerized styrene-butadiene rubber is 10 to 45 wt%;
Figure GDA0003703578100000021
the present invention also provides a process for preparing a vulcanized rubber, the process comprising:
(1) carrying out first mixing on a component A containing a rubber matrix and a rubber modifier to obtain a section of master batch;
(2) performing second mixing on the first-section masterbatch and a component B containing first white carbon black, polyethylene glycol and a surface modifier to obtain a second-section masterbatch;
(3) performing third mixing on the second-stage masterbatch and a component C containing second white carbon black, an activator, an anti-aging agent and a softening agent to obtain a third-stage masterbatch;
(4) performing fourth mixing on the three-section master batch and a component D containing an accelerant and a vulcanizing agent to obtain a final rubber;
(5) vulcanizing the final rubber;
wherein the weight ratio of the first white carbon black to the second white carbon black is 1: (1-3), and,
the rubber matrix, the rubber modifier, the white carbon black, the polyethylene glycol, the surface modifier, the activator, the antioxidant, the softener, the accelerator and the vulcanizing agent are correspondingly the same as the components in the rubber composition for the sole, and the first white carbon black in the step (2) and the second white carbon black in the step (3) together constitute the white carbon black in the rubber composition for the sole.
The invention also provides vulcanized rubber prepared by the method.
The invention also provides application of the vulcanized rubber in preparation of shoe soles.
The vulcanized rubber prepared from the rubber composition for soles has excellent hardness and rebound resilience.
The process for preparing the vulcanized rubber provided by the invention can exert the synergistic effect of the components in the composition provided by the invention, so that the vulcanized rubber prepared from the components in the composition provided by the invention by adopting the method provided by the invention has more excellent hardness and rebound resilience.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these 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 shoe soles, which contains a rubber matrix, a rubber modifier, white carbon black, polyethylene glycol, a surface modifier, an activator, an anti-aging agent, a softener, an accelerator and a vulcanizing agent, wherein the rubber modifier is dimercaptosuccinic acid represented by formula (1), and the rubber matrix is cis-butadiene rubber and solution-polymerized styrene-butadiene rubber; and, relative to 100 parts by weight of the rubber matrix, the content of the rubber modifier is 2-6 parts by weight, the content of the white carbon black is 40-60 parts by weight, the content of the polyethylene glycol is 5-10 parts by weight, the content of the surface modifier is 4-6 parts by weight, the content of the activator is 4-6 parts by weight, the content of the anti-aging agent is 1-5 parts by weight, the content of the softener is 6-12 parts by weight, the content of the accelerator is 3-6 parts by weight, and the content of the vulcanizing agent is 2-5 parts by weight; and, in the rubber matrix, the content of the butadiene rubber is 55-90 wt%, and the content of the solution-polymerized styrene-butadiene rubber is 10-45 wt%;
Figure GDA0003703578100000041
the inventor of the invention finds that when the rubber composition which contains white carbon black and takes the butadiene rubber and the solution polymerized butadiene styrene rubber as rubber carriers and is formed by adopting the dimercaptosuccinic acid shown in the formula (1) as a rubber modifier is used for preparing vulcanized rubber, the vulcanized rubber has the advantages of soft quality, good wearing comfort, favorable rebound resilience and favorable buffer protection on feet when jumping up and landing, and the vulcanized rubber also has proper hardness.
Preferably, the content of the butadiene rubber in the rubber matrix is 60 to 80 wt%, and the content of the solution-polymerized styrene-butadiene rubber in the rubber matrix is 20 to 40 wt%. The inventors have found that this preferred embodiment enables the rubber matrix and the rubber modifier in the composition of the invention to act synergistically, thereby giving better resilience to the vulcanizate thus obtained.
Preferably, the cis content in the butadiene rubber is 90 to 99% by weight.
Preferably, the vinyl content of the solution-polymerized styrene-butadiene rubber is 50 to 70 wt%.
Preferably, the white carbon black is fumed silica, and more preferably, the nitrogen adsorption specific surface area of the white carbon black is 350-420m 2 The silica may be, for example, A380 (Degussa corporation) having a nitrogen adsorption specific surface area of 380m 2 /g。
Preferably, the polyethylene glycol has an average molecular weight of 2000-.
Preferably, the surface modifier is at least one of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide (Si69) and bis- [3- (triethoxysilyl) propyl ] -disulfide.
Preferably, the antioxidant is a phenolic antioxidant. For example, the antioxidant is antioxidant 264.
Preferably, the softening agent is a naphthenic oil, which may be, for example, ASTM103# oil.
Preferably, the activator is a fatty acid and/or a fatty acid metal soap salt. For example, the fatty acid may be stearic acid; the fatty acid metal soap salt may be, for example, zinc stearate.
Preferably, the accelerator is at least one of a thiazole accelerator, a thiuram accelerator and a guanidine accelerator. Preferably, the accelerator is at least one of 2,2' -Dithiodibenzothiazole (DM), tetramethylthiuram disulfide (TMTD), and diphenylguanidine (accelerator D).
Preferably, the vulcanizing agent is sulfur and/or 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.
The composition provided by the invention can be used for preparing vulcanized rubber by adopting various methods in the prior art, and the prepared vulcanized rubber has better properties, such as better hardness and elasticity, and the like compared with the vulcanized rubber obtained by the composition provided by the prior art.
However, the inventor of the present invention found through a great deal of experimental studies that, by using the composition provided by the present invention, vulcanized rubber is prepared by adopting a staged mixing and stepwise feeding manner, particularly, a rubber matrix and a rubber modifier in the composition of the present invention are firstly mixed, then a masterbatch obtained by the mixing and other components in the composition of the present invention are mixed (particularly, staged mixing), and white carbon black in the composition is added in two parts, the white carbon black added for the first time is mixed with the primary masterbatch, the surface modifier and the polyethylene glycol, the white carbon black added for the second time is mixed with the secondary masterbatch, the activator, the anti-aging agent and the softener, and the ratio of the mass of the white carbon black added for the first time to the mass of the white carbon black added for the second time is controlled to be 1: (1-3), the vulcanizates thus obtained have a clear advantage in terms of resilience compared to the vulcanizates obtained by the processes of the prior art. Thus, the inventors of the present invention provide a preferred method for producing a vulcanized rubber as described in the second aspect below.
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 and a rubber modifier to obtain a section of master batch;
(2) performing second mixing on the first-section masterbatch and a component B containing first white carbon black, polyethylene glycol and a surface modifier to obtain a second-section masterbatch;
(3) carrying out third mixing on the second-section masterbatch and a component C containing second white carbon black, an activating agent, an anti-aging agent and a softening agent to obtain a third-section masterbatch;
(4) performing fourth mixing on the three-section master batch and a component D containing an accelerant and a vulcanizing agent to obtain a final rubber;
(5) vulcanizing the final rubber;
wherein the weight ratio of the first white carbon black to the second white carbon black is 1: (1-3), and,
the rubber matrix, the rubber modifier, the white carbon black, the polyethylene glycol, the surface modifier, the activator, the antioxidant, the softener, the accelerator and the vulcanizing agent are correspondingly the same as the components of the rubber composition for soles in the invention, and the first white carbon black in the step (2) and the second white carbon black in the step (3) together form the white carbon black in the rubber composition for soles in the invention.
The species, characteristics and relative amounts (or contents) of the components involved in the second aspect of the present invention are the same as those described in the first aspect of the present invention, and in order to avoid repetition, some characteristics (such as optional species of the substance, etc.) of the substance in the second aspect of the present invention are not described repeatedly, and those skilled in the art should not be construed as limiting the second aspect of the present invention.
The first white carbon and the second white carbon in this aspect of the invention together form the white carbon described in the foregoing composition. That is, the white carbon black in the composition is preferably added at least 2 times, and the weight ratio of the first white carbon black to the second white carbon black is controlled to be 1: (1-3) to form a vulcanized rubber. The inventor finds that the method can better play a role of a rubber modifier in a rubber matrix and white carbon black, is beneficial to dispersion of the white carbon black in the rubber matrix, and can better improve the strength of vulcanized rubber prepared by further vulcanization, improve the hardness of the vulcanized rubber and improve the elasticity of a vulcanized rubber material.
Particularly preferably, the weight ratio of the first white carbon black to the second white carbon black is 1: (1.5-2.5).
The addition amount of the second white carbon black is controlled to be larger than that of the first white carbon black, so that the vulcanized rubber obtained by the method has better resilience, and the feet can be protected by buffering when jumping up and landing.
Preferably, the conditions of the first mixing include: the temperature is 60-100 deg.C, and the time is 0.5-4 min; more preferably, the conditions for the first mixing include: the temperature is 75-85 deg.C, and the time is 1-2 min.
Preferably, the conditions of the second mixing include: the temperature is 90-130 deg.C, and the time is 3-7 min; more preferably, the conditions for the second mixing include: the temperature is 100-120 ℃, and the time is 4-6 min.
Preferably, the conditions of the third mixing include: the temperature is 120-; more preferably, the third mixing conditions include: the temperature is 140 ℃ and 160 ℃, and the time is 4-6 min.
Preferably, the fourth mixing conditions include: the temperature is not more than 120 deg.C, and the time is 4-6 min.
According to a preferred embodiment of the method according to the invention,
the conditions of the first mixing include: the temperature is 60-100 deg.C, and the time is 0.5-4 min;
the conditions of the second mixing include: the temperature is 90-130 deg.C, and the time is 3-7 min;
the conditions of the third mixing include: the temperature is 120-;
the fourth mixing conditions include: the temperature is not more than 120 deg.C, and the time is 4-6 min.
According to a more preferred embodiment of the present invention,
the conditions of the first mixing include: the temperature is 75-85 deg.C, and the time is 1-2 min;
the conditions of the second mixing include: the temperature is 100-120 ℃, and the time is 4-6 min;
the conditions of the third mixing include: the temperature is 140-160 ℃, and the time is 4-6 min;
the fourth mixing conditions include: the temperature is not more than 120 deg.C, and the time is 4-6 min.
Preferably, the conditions of the vulcanization include: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 30-50 min.
To specifically illustrate the process for preparing the vulcanizates of this invention, 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 the rubber modifier into the internal mixer for first mixing to obtain a section of master batch;
(2) adding the first-section masterbatch and a component B containing first white carbon black, polyethylene glycol and a surface modifier into an internal mixer for second mixing to obtain a second-section masterbatch;
(3) adding the second-section masterbatch and a component C containing second white carbon black, an activating agent, an anti-aging agent and a softening agent into an internal mixer for third mixing to obtain third-section masterbatch;
(4) setting the rotation speed of an internal mixer to be 50-100 rpm, setting the initial mixing temperature to be 25-50 ℃, plasticating the three-section master batch for 0.5-1.5 min, and adding a component D containing an accelerator and a vulcanizing agent to carry out fourth mixing to obtain final mixed batch;
(5) and putting the final rubber compound into a vulcanizing press for vulcanization.
In the case where no explanation is given to the contrary, the pressures used in the present invention are gauge pressures.
As previously mentioned, a third aspect of the present invention provides a vulcanizate prepared by the foregoing method.
As previously mentioned, a fourth aspect of the invention provides the use of the aforementioned vulcanized rubber in the preparation of shoe soles.
The present invention will be described in detail below by way of examples.
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 chemical reagents used in the examples and comparative examples are commercially available, unless otherwise specified, and are specifically as follows:
butadiene rubber: BR9000, yanshan petrochemical (wherein, cis content is 97.8% by weight);
solution polymerized styrene-butadiene rubber: SSBR2506, a yanshan petrochemical (wherein the vinyl content is 60 wt%);
white carbon black: a380, Degussa, nitrogen adsorption specific surface area 380m 2 /g；
Polyethylene glycol: PEG2000, PEG4000, PEG6000, technical grade, dow chemical company, usa;
rubber modifier: dimercaptodibutyrate represented by formula (1), analytically pure, Lignin chemical Co., Ltd;
softening agent: ASTM103# naphthenic oil, Shandong Taichang petrochemical Co., Ltd;
activating agent: stearic acid, Weifang Hengfeng chemical Limited;
an anti-aging agent: 4, 6-di-tert-butyl-p-cresol (anti-aging agent 264), Panhua chemistry (Shanghai) Co., Ltd;
accelerator (b): 2,2' -Dithiodibenzothiazyl (DM), tetramethylthiuram disulfide (TMTD), Shanghai Yongzhen chemical technology, Inc.
Vulcanizing agent: sulfur, Weifang Zhongheng chemical Limited company.
The amounts of the components in the following examples and comparative examples are in parts by weight, each representing 10 g.
TABLE 1
Serial number Device name Type 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
Serial number Test item Model of the test apparatus Manufacturer of the product
1 Hardness of TH210 Yingkou material testing machine factory
2 Rebound resilience GT-7012-D Taiwan high speed railway, China
TABLE 3
Figure GDA0003703578100000091
Figure GDA0003703578100000101
Example 1
The rubber composition formula comprises the following components: 60 parts of butadiene rubber, 40 parts of solution-polymerized styrene-butadiene rubber, 6 parts of dimercaptodibutyrate, 4 parts of Si69 (surface modifier), 40 parts of white carbon black, 5 parts of PEG4000, 12 parts of ASTM103# (softener), 4 parts of stearic acid (activator), 5 parts of sulfur (vulcanizing agent), 1.5 parts of DM (accelerator), 1.5 parts of TMTD (accelerator) and 1 part of anti-aging agent 264 (anti-aging agent).
The preparation process of the vulcanized rubber comprises the following steps:
(1) adding the rubber matrix into an internal mixer, setting the rotating speed to be 70rpm, setting the initial mixing temperature to be 75 ℃, and setting the raw rubber plastication time to be 0.5 min; adding a rubber modifier into the internal mixer for mixing at 75 ℃ for 2min to obtain a section of master batch;
(2) adding the primary masterbatch, a surface modifier, polyethylene glycol and 1/3 white carbon black into an internal mixer, and carrying out secondary mixing with the primary masterbatch for 6min at a rubber discharge temperature of 100 ℃ to obtain secondary masterbatch;
(3) adding the second-section masterbatch, an activating agent, an anti-aging agent, a softening agent and the rest white carbon black into an internal mixer, and carrying out third mixing with the second-section masterbatch, wherein the mixing time is 6min, and the rubber discharge temperature is 140 ℃, so as to obtain third-section masterbatch;
(4) setting the rotation speed of an internal mixer to be 75rpm, setting the initial mixing temperature to be 50 ℃, plasticating the three-section master batch for 0.5min, adding a vulcanizing agent and an accelerator to perform fourth mixing, setting the mixing temperature to be 105 ℃, mixing the mixture for 6min, and discharging to obtain final mixed rubber;
(5) 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 the following components: 70 parts of butadiene rubber, 30 parts of solution-polymerized styrene-butadiene rubber, 4 parts of dimercaptodibutyrylicacid, 5 parts of Si69 (surface modifier), 50 parts of white carbon black, 8 parts of PEG2000, 9 parts of ASTM103# (softener), 5 parts of stearic acid (activator), 3 parts of sulfur (vulcanizing agent), 3 parts of DM (accelerator), 1.5 parts of TMTD (accelerator) and 3 parts of anti-aging agent 264 (anti-aging agent).
The preparation process of the vulcanized rubber comprises the following steps:
(1) adding the rubber matrix into an internal mixer, setting the rotating speed to be 70rpm, setting the initial mixing temperature to be 80 ℃, and setting the raw rubber plastication time to be 0.5 min; adding a rubber modifier into the internal mixer for mixing at the mixing temperature of 80 ℃ for 1.5min to obtain a section of master batch;
(2) adding the first-section masterbatch, a surface modifier, polyethylene glycol and 2/5 white carbon black into an internal mixer, and carrying out second mixing with the first-section masterbatch, wherein the mixing time is 5min, and the rubber discharge temperature is 110 ℃, so as to obtain second-section masterbatch;
(3) adding the second-section masterbatch, an activating agent, an anti-aging agent, a softening agent and the rest white carbon black into an internal mixer, and carrying out third mixing with the second-section masterbatch, wherein the mixing time is 5min, and the rubber discharge temperature is 150 ℃, so as to obtain third-section masterbatch;
(4) setting the rotation speed of an internal mixer to be 75rpm, setting the initial mixing temperature to be 50 ℃, plasticating the three sections of master batch for 0.5min, adding a vulcanizing agent and an accelerant to carry out fourth mixing, setting the mixing temperature to be 110 ℃, mixing for 5min, and discharging to obtain final mixed rubber;
(5) 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 vulcanized rubber sample S2 was subjected to the performance test, and the results are shown in Table 4.
Example 3
The rubber composition formula comprises: 80 parts of butadiene rubber, 20 parts of solution-polymerized styrene-butadiene rubber, 2 parts of dimercaptodibutyrric acid, 6 parts of Si69 (surface modifier), 60 parts of white carbon black, 10 parts of PEG4000, 6 parts of ASTM103# (softener), 6 parts of stearic acid (activator), 2 parts of sulfur (vulcanizing agent), 4 parts of DM (accelerator), 2 parts of TMTD (accelerator) and 5 parts of anti-aging agent 264 (anti-aging agent).
The preparation process of the vulcanized rubber comprises the following steps:
(1) adding the rubber matrix into an internal mixer, setting the rotating speed to be 70rpm, the initial mixing temperature to be 85 ℃, and the raw rubber plasticating time to be 0.5 min; adding a rubber modifier into the internal mixer for mixing at 85 ℃ for 1min to obtain a section of master batch;
(2) adding the first-stage masterbatch, a surface modifier, polyethylene glycol and 1/3 white carbon black into an internal mixer, and carrying out second mixing with the first-stage masterbatch, wherein the mixing time is 4min, and the rubber discharge temperature is 120 ℃, so as to obtain second-stage masterbatch;
(3) adding the second-section masterbatch, an activating agent, an anti-aging agent, a softening agent and the rest white carbon black into an internal mixer, and carrying out third mixing with the second-section masterbatch, wherein the mixing time is 4min, and the rubber discharge temperature is 160 ℃, so as to obtain third-section masterbatch;
(4) setting the rotation speed of an internal mixer to be 75rpm, setting the initial mixing temperature to be 50 ℃, plasticating the three-section master batch for 0.5min, adding a vulcanizing agent and an accelerator to perform fourth mixing, setting the mixing temperature to be 120 ℃, setting the mixing time to be 4min, and discharging to obtain final mixed rubber;
(5) 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
The rubber composition formulation of this example was similar to the rubber composition formulation of example 1, except that the solution-polymerized styrene-butadiene rubber was present in an amount of 10 parts by weight and the butadiene rubber was present in an amount of 90 parts by weight.
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 formula comprises: the same formulation as the rubber composition of example 1.
The preparation process of the vulcanized rubber comprises the following steps:
(1) adding the rubber matrix into an internal mixer, setting the rotating speed to be 70rpm, setting the initial mixing temperature to be 75 ℃, and setting the raw rubber plastication time to be 0.5 min; adding a rubber modifier into the internal mixer for mixing at 75 ℃ for 2min to obtain a section of master batch;
(2) adding the first-stage masterbatch, a surface modifier, polyethylene glycol, white carbon black, an activator, an anti-aging agent and a softener into an internal mixer, and carrying out second mixing with the first-stage masterbatch for 6min at a rubber discharge temperature of 100 ℃ to obtain second-stage masterbatch;
(3) setting the rotation speed of an internal mixer to be 75rpm, setting the initial mixing temperature to be 50 ℃, plasticating the two-section master batch for 0.5min, adding a vulcanizing agent and an accelerant to carry out fourth mixing, setting the mixing temperature to be 105 ℃, 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 150 ℃, the vulcanization pressure is 20MPa, and the vulcanization time is 50min, so that a vulcanized rubber sample S5 is obtained.
The cured rubber sample S5 was subjected to the performance test, and the results are shown in Table 4.
Example 6
The rubber composition formulation of this example was the same as that of example 1.
The process for preparing the vulcanized rubber is similar to that of the vulcanized rubber in example 1, except that the ratio of the first silica in the step (2) to the second silica in the step (3) is 1: 1.
a vulcanized rubber sample S6 was obtained.
The vulcanized rubber sample S6 was subjected to the performance test, and the results are shown in Table 4.
Example 7
The rubber composition formulation of this example was the same as that of example 1.
The process for producing the vulcanized rubber was similar to that of example 1, except that step (1) of this example was:
(1) adding the rubber matrix into an internal mixer, setting the rotating speed to be 70rpm, setting the initial mixing temperature to be 90 ℃, and plasticating the raw rubber for 0.5 min; and adding the rubber modifier into the internal mixer for mixing at 90 ℃ for 2min to obtain a section of master batch.
A vulcanized rubber sample S7 was obtained.
The cured rubber sample S7 was subjected to the performance test, and the results are shown in Table 4.
Comparative example 1
The rubber composition formulation of this comparative example was similar to that of example 1 except that the same parts by weight of natural rubber (No. 20 standard rubber available from Shanghai Donkang Kogyo Co., Ltd.) was used in place of the solution-polymerized styrene-butadiene rubber of example 1.
The procedure for the preparation of the vulcanizates was exactly the same as that in example 1.
Comparative example 2
The formulation of the rubber composition of this comparative example was similar to that of the rubber composition of example 1, except that the same parts by weight of gamma- (2, 3-glycidoxy) propyltriethoxysilane (Chishiei chemical industry development Co., Ltd.) was used in place of dimercaptodibutyric acid in example 1.
The preparation process of the vulcanized rubber comprises the following steps: the procedure was the same as for the preparation of the vulcanized rubber in example 1.
A vulcanizate sample DS2 was prepared.
The cured rubber sample DS2 was subjected to performance testing and the results are shown in Table 4.
Comparative example 3
The rubber composition formula comprises the following components: similar to the rubber composition formulation of example 1, except that the contents of the butadiene rubber and the solution-polymerized styrene-butadiene rubber in the comparative example are each 50 parts by weight.
The preparation process of the vulcanized rubber comprises the following steps: the procedure was the same as for the preparation of the vulcanized rubber in example 1.
A vulcanizate sample DS3 was prepared.
The cured rubber sample DS3 was subjected to performance testing and the results are shown in Table 4.
TABLE 4
Sample numbering S1 S2 S3 S4 S5 S6 S7 DS1 DS2 DS3
Hardness (°) 60 59 61 60 63 61 62 57 65 63
Rebound value (%) 50.2 51.4 52.0 47.2 43.9 45.7 49.3 37.6 34.2 42.1
As can be seen from the results in Table 4, the vulcanizates of this invention are capable of exhibiting excellent hardness and rebound resilience.
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 various technical features being combined 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 (18)

1. A vulcanized rubber composition for soles comprises a rubber matrix, a rubber modifier, white carbon black, polyethylene glycol, a surface modifier, an activator, an anti-aging agent, a softener, an accelerator and a vulcanizing agent, wherein the rubber modifier is dimercaptosuccinic acid shown in a formula (1), and the rubber matrix is butadiene rubber and solution polymerized butadiene styrene rubber; the rubber matrix comprises, by weight, 100 parts of a rubber matrix, 2-6 parts of a rubber modifier, 40-60 parts of white carbon black, 5-10 parts of polyethylene glycol, 4-6 parts of a surface modifier, 4-6 parts of an activator, 1-5 parts of an anti-aging agent, 6-12 parts of a softener, 3-6 parts of an accelerator and 2-5 parts of a vulcanizing agent; and, in the rubber matrix, the content of the butadiene rubber is 55-90 wt%, and the content of the solution-polymerized styrene-butadiene rubber is 10-45 wt%;
the preparation method of the vulcanized rubber composition comprises the following steps:
(1) performing first mixing on a component A containing a rubber matrix and a rubber modifier to obtain a section of masterbatch;
(2) performing second mixing on the first-section masterbatch and a component B containing first white carbon black, polyethylene glycol and a surface modifier to obtain a second-section masterbatch;
(3) carrying out third mixing on the second-section masterbatch and a component C containing second white carbon black, an activating agent, an anti-aging agent and a softening agent to obtain a third-section masterbatch;
(4) performing fourth mixing on the three-section master batch and a component D containing an accelerant and a vulcanizing agent to obtain a final rubber;
(5) vulcanizing the final rubber;
wherein the weight ratio of the first white carbon black to the second white carbon black is 1: (1-3) the first white carbon in the step (2) and the second white carbon in the step (3) together constitute white carbon in the rubber composition for shoe soles;
wherein the first mixing conditions include: the temperature is 75-90 deg.C, and the time is 1-2 min;
the conditions of the second mixing include: the temperature is 100 ℃ and 120 ℃, and the time is 4-6 min;
the conditions of the third mixing include: the temperature is 140-160 ℃, and the time is 4-6 min;
Figure FDA0003703578090000021
2. the composition as claimed in claim 1, wherein the cis-butadiene rubber is contained in an amount of 60 to 80 wt% and the solution-polymerized styrene-butadiene rubber is contained in an amount of 20 to 40 wt% in the rubber matrix.
3. The composition according to claim 1 or 2, wherein the cis content in the butadiene rubber is 90-99 wt%.
4. The composition according to claim 1 or 2, wherein the vinyl content of the solution-polymerized styrene-butadiene rubber is from 50 to 70% by weight.
5. The composition of claim 1 or 2, wherein the silica is fumed silica.
6. The composition as claimed in claim 5, wherein the silica white has a nitrogen adsorption specific surface area of 350-420m 2 /g。
7. The composition as claimed in claim 1 or 2, wherein the polyethylene glycol has an average molecular weight of 2000-6000.
8. The composition of claim 1 or 2, wherein the surface modifier is at least one of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, bis- [3- (triethoxysilyl) propyl ] -disulfide.
9. The composition according to claim 1 or 2, wherein the antioxidant is a phenolic antioxidant.
10. The composition of claim 1 or 2, wherein the softening agent is a naphthenic oil.
11. A composition according to claim 1 or 2, wherein the activator is a fatty acid and/or a fatty acid metal soap salt.
12. A composition according to claim 1 or 2, wherein the accelerator is at least one of a thiazole accelerator, a thiuram accelerator and a guanidine accelerator.
13. The composition of claim 12, wherein the accelerator is selected from at least one of 2,2' -dithiodibenzothiazole, tetramethylthiuram disulfide, diphenylguanidine.
14. The composition according to claim 1 or 2, wherein the vulcanizing agent is sulphur and/or a sulphur donor.
15. The composition according to claim 1 or 2, wherein the first white carbon black and the second white carbon black are used in an amount by weight ratio of 1: (1.5-2.5).
16. The composition of claim 1 or 2, wherein the conditions of the fourth mixing comprise: the temperature is not more than 120 deg.C, and the time is 4-6 min.
17. The composition of claim 1 or 2, wherein the vulcanization conditions include: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 30-50 min.
18. Use of the vulcanized rubber composition for shoe soles according to any one of claims 1 to 17 for the preparation of shoe soles.
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Publication number Priority date Publication date Assignee Title
CN107964138A (en) * 2016-10-18 2018-04-27 中国石油化工股份有限公司 The application of mercaptan acid system monomer and rubber composition and vulcanization rubber and preparation method thereof
CN109384964A (en) * 2017-08-03 2019-02-26 中国石油化工股份有限公司 For the rubber composition on tire sidewall and vulcanized rubber and its preparation method and application
CN109929160A (en) * 2017-12-15 2019-06-25 中国石油化工股份有限公司 The application of organo silane coupling agent and rubber composition and vulcanized rubber and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107964138A (en) * 2016-10-18 2018-04-27 中国石油化工股份有限公司 The application of mercaptan acid system monomer and rubber composition and vulcanization rubber and preparation method thereof
CN109384964A (en) * 2017-08-03 2019-02-26 中国石油化工股份有限公司 For the rubber composition on tire sidewall and vulcanized rubber and its preparation method and application
CN109929160A (en) * 2017-12-15 2019-06-25 中国石油化工股份有限公司 The application of organo silane coupling agent and rubber composition and vulcanized rubber and its preparation method and application

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