CN113968998A - Rubber composition containing dimercaptosuccinic acid and used for shoe sole, application of rubber composition, vulcanized rubber, preparation method and application of vulcanized rubber, and shoe sole - Google Patents
Rubber composition containing dimercaptosuccinic acid and used for shoe sole, application of rubber composition, vulcanized rubber, preparation method and application of vulcanized rubber, and shoe sole Download PDFInfo
- Publication number
- CN113968998A CN113968998A CN202010723598.2A CN202010723598A CN113968998A CN 113968998 A CN113968998 A CN 113968998A CN 202010723598 A CN202010723598 A CN 202010723598A CN 113968998 A CN113968998 A CN 113968998A
- Authority
- CN
- China
- Prior art keywords
- rubber
- weight
- parts
- content
- component
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of vulcanized rubber, and discloses a rubber composition containing dimercaptosuccinic acid and used for soles and application thereof, vulcanized rubber and a preparation method and application thereof, and soles, wherein the composition contains the following components which are stored in a mixing way or are respectively and independently stored: the rubber composition comprises a rubber matrix, a rubber modifier, white carbon black, titanium dioxide, polyethylene glycol, active zinc oxide, an organosilane coupling agent, an activating agent, an anti-aging agent, a softening agent, a vulcanizing agent, a vulcanization accelerator and microcrystalline wax. The rubber composition provided by the invention improves the dispersibility of each component in a rubber matrix, particularly the dispersibility of white carbon black in the rubber matrix, and the prepared vulcanized rubber has excellent comprehensive properties such as hard texture, high strength, good wear resistance, good resilience and the like.
Description
Technical Field
The invention relates to the technical field of vulcanized rubber, in particular to a rubber composition for soles, application of the rubber composition in preparation of vulcanized rubber, a method for preparing the vulcanized rubber, the vulcanized rubber prepared by the method, application of the vulcanized rubber in preparation of soles and soles containing the vulcanized rubber.
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 materials such as PVC, TPR, TPU and the like, but the materials are inferior to the sole made of rubber in the aspects of comfort and skid resistance.
At present, 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, and colored cowhells soles can be processed and are widely applied to light-colored and colored soles (including undersoles, midsoles and foxes), and therefore, the shoe industry is always a large user of white carbon black.
However, the dispersion of white carbon black in a rubber matrix is extremely difficult due to its strong surface polarity, and thus the application is limited to a certain extent.
CN105440341A discloses an antiskid sole material, and the invention discloses 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, but the dispersibility of the white carbon black cannot reach ideal dispersion, so that the performance of the performance is influenced.
CN104311918A discloses a composite wear-resistant sole, in which white carbon black modified by toluene diisocyanate grafting is applied to improve the dispersibility of the white carbon black in a rubber matrix. Although the modified white carbon black process can change the polarity of white carbon black and increase the contact force with rubber, the process is more complex and has higher energy consumption and material consumption.
The above prior art cannot fully satisfy the requirements of high hardness, high strength and good wear resistance of the shoe sole containing the white carbon black formula, and therefore, there is a need to provide a rubber composition with improved properties.
Disclosure of Invention
The invention aims to provide a novel rubber composition which can prepare vulcanized rubber with high hardness, high strength, good wear resistance, good rebound performance and excellent comprehensive performance.
In order to achieve the above object, a first aspect of the present invention provides a dimercaptosuccinic acid-containing rubber composition for shoe soles, which contains the following components stored in admixture with or independently of two or more of:
the rubber composition comprises a rubber matrix, a rubber modifier, white carbon black, titanium dioxide, polyethylene glycol, active zinc oxide, an organosilane coupling agent, an activating agent, an anti-aging agent, a softening agent, a vulcanizing agent, a vulcanization accelerator and microcrystalline wax;
relative to 100 parts by weight of the rubber matrix, the content of the rubber modifier is 3-7 parts by weight, the content of the white carbon black is 40-60 parts by weight, the content of the titanium dioxide is 10-20 parts by weight, the content of the polyethylene glycol is 2-8 parts by weight, the content of the active zinc oxide is 5-10 parts by weight, the content of the organosilane coupling agent 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 4-10 parts by weight, the content of the vulcanizing agent is 2-5 parts by weight, the content of the vulcanization accelerator is 2-7 parts by weight, and the content of the microcrystalline wax is 1-4 parts by weight;
wherein the rubber matrix is butadiene rubber and/or solution polymerized styrene-butadiene rubber; the rubber modifier is dimercaptosuccinic acid with a structure shown in a formula (1);
a second aspect of the present invention provides the use of a rubber composition as described in the first aspect above for the preparation of a vulcanized rubber.
In a third aspect, the present invention provides a process for preparing a vulcanized rubber, the process comprising: subjecting each component of the rubber composition described in the foregoing first aspect to a treatment comprising:
(1) carrying out first mixing on each component in the component A to obtain a section of master batch, wherein the component A contains a rubber matrix and a rubber modifier;
(2) performing second mixing on the first-stage masterbatch and each component in the component B to obtain a second-stage masterbatch, wherein the component B contains an organosilane coupling agent, polyethylene glycol and a part of white carbon black;
(3) performing third mixing on the second-stage masterbatch and each component in the component C to obtain third-stage masterbatch, wherein the component C contains titanium dioxide, active zinc oxide, an activator, an anti-aging agent, a softener, microcrystalline wax and residual white carbon black;
(4) performing fourth mixing on the three-section master batch and each component in the component D to obtain a final rubber compound, wherein the component D contains a vulcanization accelerator and a vulcanizing agent;
(5) vulcanizing the final rubber;
the rubber modifier is used in an amount of 3-7 parts by weight, the white carbon black is used in an amount of 40-60 parts by weight, the titanium dioxide is used in an amount of 10-20 parts by weight, the polyethylene glycol is used in an amount of 2-8 parts by weight, the active zinc oxide is used in an amount of 5-10 parts by weight, the organosilane coupling agent is used in an amount of 4-6 parts by weight, the activator is used in an amount of 4-6 parts by weight, the anti-aging agent is used in an amount of 1-5 parts by weight, the softener is used in an amount of 4-10 parts by weight, the vulcanizing agent is used in an amount of 2-5 parts by weight, the vulcanization accelerator is used in an amount of 2-7 parts by weight, and the microcrystalline wax is used in an amount of 1-4 parts by weight, relative to 100 parts by weight of the rubber substrate.
A fourth aspect of the present invention provides a vulcanizate prepared by the method of the third aspect described above.
A fifth aspect of the present invention provides the use of a vulcanizate according to the fourth aspect described above for the preparation of a shoe sole.
In a sixth aspect, the present invention provides a shoe sole comprising the vulcanized rubber described in the fourth aspect.
According to the rubber composition provided by the invention, the components with specific contents and types are matched with each other, the dispersibility of each component in the composition is improved, particularly the dispersion of white carbon black in a rubber matrix is improved, and the prepared vulcanized rubber has excellent comprehensive properties such as hard texture, high strength, good wear resistance and good resilience.
Additional features and advantages of the invention will be described in detail in the detailed description which follows.
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 dimercaptosuccinic acid-containing rubber composition for shoe soles, which contains the following components stored in a mixed manner or independently from each other:
the rubber composition comprises a rubber matrix, a rubber modifier, white carbon black, titanium dioxide, polyethylene glycol, active zinc oxide, an organosilane coupling agent, an activating agent, an anti-aging agent, a softening agent, a vulcanizing agent, a vulcanization accelerator and microcrystalline wax;
relative to 100 parts by weight of the rubber matrix, the content of the rubber modifier is 3-7 parts by weight, the content of the white carbon black is 40-60 parts by weight, the content of the titanium dioxide is 10-20 parts by weight, the content of the polyethylene glycol is 2-8 parts by weight, the content of the active zinc oxide is 5-10 parts by weight, the content of the organosilane coupling agent 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 4-10 parts by weight, the content of the vulcanizing agent is 2-5 parts by weight, the content of the vulcanization accelerator is 2-7 parts by weight, and the content of the microcrystalline wax is 1-4 parts by weight;
wherein the rubber matrix is butadiene rubber and/or solution polymerized styrene-butadiene rubber; the rubber modifier is dimercaptosuccinic acid with a structure shown in a formula (1);
preferably, the cis content in the butadiene rubber is 90 to 99 wt%.
Preferably, the vinyl content of the solution-polymerized styrene-butadiene rubber is 50 to 70 wt%.
According to a preferred embodiment of the present invention, the rubber matrix is a mixture of the butadiene rubber and the solution-polymerized styrene-butadiene rubber, and the content of the butadiene rubber is 80 to 95 wt% based on the total weight of the rubber matrix; the content of the solution-polymerized styrene-butadiene rubber is 5 to 20% by weight, whereby the inventors found that the compounding of the rubber matrix with other components in the rubber composition enables obtaining a vulcanized rubber having higher hardness and strength.
Preferably, the nitrogen adsorption specific surface area of the white carbon black is 350-420m2(ii) in terms of/g. More preferably, the white carbon black is silica prepared by a gas phase method, for example, the white carbon black is A380 (Degussa).
In the present invention, the source of the titanium dioxide is not particularly limited, but is preferably titanium dioxide, and more preferably, TiO in the titanium dioxide2The purity of the product is more than or equal to 93.5 percent by weight. The invention has no special limit on other performance parameters of the titanium dioxide, and can be the existing titanium dioxide in the field, such as TiO produced by Weifang Hezee chemical company Limited2Titanium dioxide with a content of 96 wt.%.
Preferably, the number average molecular weight of the polyethylene glycol is 2000-6000, such as PEG4000, PEG2000 and PEG 6000.
Preferably, the active zinc oxide has an average particle size of 20nm to 50nm, for example 20nm, 40nm, 50 nm.
Preferably, the organosilane coupling agent is selected from at least one of bis- [ gamma- (triethoxysilyl) propyl ] -tetrasulfide (Si69), bis- [3- (triethoxysilyl) propyl ] -disulfide (Si75), more preferably Si 69.
In the present invention, the activator may be an activator for vulcanized rubber existing in the art, but in order to obtain vulcanized rubber with better performance, preferably, the activator is selected from at least one of fatty acid and fatty acid metal soap salt, and the fatty acid is more preferably stearic acid; the fatty acid metal soap salt is more preferably zinc stearate.
Preferably, the antioxidant is a phenolic antioxidant; more preferably, the phenolic antioxidant is at least one selected from the group consisting of 2, 6-di-tert-butyl-p-cresol (antioxidant 264), pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), and 2, 4-di (n-octylthiomethylene) -6-methylphenol (antioxidant 1520); still more preferably, the antioxidant is 2, 6-di-tert-butyl-p-cresol (antioxidant 264).
Preferably, the softener is a naphthenic oil, such as ASTM103# oil.
Preferably, the vulcanizing agent is sulfur and/or a sulfur donor, which means a substance capable of providing sulfur. Preferably, the sulphur is selected from at least one of insoluble sulphur, soluble sulphur and oil-extended sulphur. For example, the vulcanizing agent IS ordinary sulfur S, oil-extended insoluble sulfur IS, or the like.
Preferably, the vulcanization accelerator is selected from at least one of thiazole accelerators, thiuram accelerators and guanidine accelerators; more preferably, the vulcanization accelerator is selected from at least one of 2,2' -Dithiodibenzothiazole (DM), tetramethylthiuram disulfide (TMTD), diphenylguanidine (D); still further preferably, the vulcanization accelerator is a combination of 2,2' -Dithiodibenzothiazole (DM) and tetramethylthiuram disulfide (TMTD), and the content of the tetramethylthiuram disulfide (TMTD) in the combination is 30 to 80% by weight.
In the present invention, preferably, the microcrystalline wax is a mixture of C30-C50-containing cycloalkane, normal alkane, and isoparaffin.
According to the rubber composition provided by the invention, the components with specific contents and types are matched with each other, especially, dimercaptosuccinic acid is used as a rubber modifier, so that a rubber matrix can be modified, the dispersity of each component in the composition is improved, especially, the interaction between the rubber matrix and white carbon black is facilitated, and the dispersion of the white carbon black in the rubber matrix is effectively improved, so that the prepared vulcanized rubber has excellent comprehensive properties such as hard texture, high strength, good wear resistance, good resilience and the like.
As previously mentioned, a second aspect of the present invention provides the use of a rubber composition as described in the first aspect above for the preparation of a vulcanizate.
The method for producing a vulcanized rubber from the rubber composition of the present invention is not particularly limited, and a method for producing a vulcanized rubber known in the art can be used, but the present invention provides the following production method as described above in order to obtain a vulcanized rubber having higher hardness and strength and better abrasion resistance.
The method comprises the following steps: subjecting each component of the rubber composition described in the foregoing first aspect to a treatment comprising:
(1) carrying out first mixing on each component in the component A to obtain a section of master batch, wherein the component A contains a rubber matrix and a rubber modifier;
(2) performing second mixing on the first-stage masterbatch and each component in the component B to obtain a second-stage masterbatch, wherein the component B contains an organosilane coupling agent, polyethylene glycol and a part of white carbon black;
(3) performing third mixing on the second-stage masterbatch and each component in the component C to obtain third-stage masterbatch, wherein the component C contains titanium dioxide, active zinc oxide, an activator, an anti-aging agent, a softener, microcrystalline wax and residual white carbon black;
(4) performing fourth mixing on the three-section master batch and each component in the component D to obtain a final rubber compound, wherein the component D contains a vulcanization accelerator and a vulcanizing agent;
(5) vulcanizing the final rubber;
the rubber modifier is used in an amount of 3-7 parts by weight, the white carbon black is used in an amount of 40-60 parts by weight, the titanium dioxide is used in an amount of 10-20 parts by weight, the polyethylene glycol is used in an amount of 2-8 parts by weight, the active zinc oxide is used in an amount of 5-10 parts by weight, the organosilane coupling agent is used in an amount of 4-6 parts by weight, the activator is used in an amount of 4-6 parts by weight, the anti-aging agent is used in an amount of 1-5 parts by weight, the softener is used in an amount of 4-10 parts by weight, the vulcanizing agent is used in an amount of 2-5 parts by weight, the vulcanization accelerator is used in an amount of 2-7 parts by weight, and the microcrystalline wax is used in an amount of 1-4 parts by weight, relative to 100 parts by weight of the rubber substrate.
In the method according to the third aspect of the present invention, the types, properties, and the like of the components in the rubber composition are the same as those of the components in the composition according to the first aspect, and for avoiding redundant description, the detailed description of the components is omitted here, and those skilled in the art should not be construed as limiting the present invention.
According to a preferred embodiment of the present invention, the part of the white carbon black in step (2) accounts for 20-40 wt% of the total white carbon black used in the method, and more preferably accounts for one third of the total white carbon black used in the method, so that the inventors have found that each component, especially white carbon black, in the composition can be better dispersed, thereby improving the properties of hardness, strength and the like of the vulcanized rubber prepared.
Preferably, in step (1), the conditions of the first mixing are at least satisfied: the rotation speed is 60-120rpm, the temperature is 70-130 ℃, and the time is 1-6 min; more preferably, the first mixing conditions at least satisfy: the rotation speed is 70-90rpm, the temperature is 80-100 ℃, and the time is 2-3 min.
According to a particularly preferred embodiment, step (1) further comprises, before the first mixing, first mixing the rubber matrix and then the rubber modifier, wherein the mixing conditions comprise: the temperature is 80-100 deg.C, the time is 0.5-2min, and the rotation speed is 70-90 rpm.
Preferably, in step (2), the conditions of the second mixing are at least satisfied: the temperature is 90-150 deg.C, and the time is 2-6 min. More preferably, the second mixing conditions at least satisfy: the temperature is 100 ℃ and 130 ℃, and the time is 3-5 min.
Preferably, in step (3), the conditions of the third mixing are at least satisfied: the temperature is 140 ℃ and 170 ℃, and the time is 2-8 min. More preferably, the third mixing conditions at least satisfy: the temperature is 150 ℃ and 160 ℃, and the time is 4-7 min.
Preferably, in step (4), the fourth mixing condition at least satisfies: the rotation speed is 30-80rpm, preferably 30-50rpm, the temperature is less than or equal to 120 ℃, and the time is 4-6 min.
According to a particularly preferred embodiment, step (4) further comprises, before the fourth mixing, plasticating the three-segment masterbatch, and then performing the fourth mixing with the component D, wherein the plasticating conditions comprise: the temperature is 30-50 deg.C, the time is 0.5-2min, and the rotation speed is 30-80rpm, preferably 30-50 rpm.
Preferably, in step (5), the vulcanization condition at least satisfies: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 30-50 min.
Preferably, the vulcanization is carried out in a press vulcanizer.
The method can better play a role of a rubber modifier in a rubber matrix and white carbon black, and improve the dispersion of each component in the composition, particularly white carbon black in the rubber matrix, so that the hardness and strength of vulcanized rubber prepared by further vulcanization can be better improved, the wear resistance of the vulcanized rubber is improved, and the vulcanized rubber with excellent comprehensive properties such as high hardness, high strength, good wear resistance, good rebound resilience and the like is prepared.
As previously mentioned, a fourth aspect of the present invention provides a vulcanizate prepared by the method of the third aspect described above.
The vulcanized rubber prepared by the method has high hardness, high strength and excellent wear resistance.
As previously mentioned, a fifth aspect of the present invention provides the use of a vulcanizate according to the fourth aspect as described above for the preparation of a shoe sole.
The specific operation of the application is not particularly limited by the invention, and the operation of preparing the sole by using vulcanized rubber known in the art can be adopted, so that the invention is not described in detail herein, and the person skilled in the art should not be understood as limiting the invention.
As described above, a sixth aspect of the present invention provides a shoe sole comprising the vulcanized rubber described in the fourth aspect.
The sole made of the vulcanized rubber provided by the invention has excellent comprehensive properties such as high hardness, high strength, good wear resistance, good rebound resilience and the like.
In the present invention, unless otherwise specified, the pressure refers to gauge pressure.
The present invention will be described in detail below by way of examples.
In the following examples, all the raw materials used are commercially available ones unless otherwise specified.
A rubber matrix: butadiene rubber: BR9000, a yanshan petrochemical (wherein, the cis content is 97.8 wt%); solution polymerized styrene-butadiene rubber: SSBR2506, a yanshan petrochemical (wherein the vinyl content is 60 wt%);
rubber modifier: dimercaptosuccinic acid, alatin chemical company;
white carbon black: a380, Degussa, nitrogen adsorption specific surface area 380m2/g；
Titanium dioxide:TiO2the content is 96 percent by weight, and the Weifang Weizee chemical company is adopted;
polyethylene glycol: PEG2000, PEG4000, PEG6000, PEG8000, technical grade, dow chemical company, usa;
active zinc oxide: the average particle diameters are respectively 20nm, 40nm, 50nm and 80nm, Hebei Hengshan chemical company;
organosilane coupling agent: si69, available from Nanjing Pinny coupling agent;
activating agent: stearic acid, Weifang Hengfeng chemical Limited;
an anti-aging agent: 2, 6-di-tert-butyl-p-cresol (anti-aging agent 264), Panhua chemistry (Shanghai) Co., Ltd;
softening agent: ASTM103# naphthenic oil, Shandong Taichang petrochemical Co., Ltd; epoxidized soybean oil, alatin Biotechnology Ltd;
vulcanizing agent: sulfur, Heicheng Hechenghuai chemical Limited; dicumyl peroxide (DCP), Aladdin reagent, Inc.;
vulcanization accelerator (b): 2,2' -Dithiodibenzothiazole (DM), tetramethylthiuram disulfide (TMTD), N-cyclohexyl-2-benzothiazolesulfenamide (CZ), Shanghai Yongzhen chemical technology Ltd.
Microcrystalline wax: shanghai Qipo chemical Co., Ltd, model number 80 #.
The amounts of the components in the following examples and comparative examples are in parts by weight, each part by weight (per part) representing 1 g.
The following examples show the equipment conditions for the preparation of vulcanizates in Table 1.
The apparatus for testing the vulcanizates prepared in the examples below is shown in Table 2 and the specific test conditions are shown in Table 3.
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 specific formulation of the rubber composition is shown in Table 4;
the preparation process of the vulcanized rubber comprises the following steps:
(1) carrying out first mixing on each component in a component A, wherein the component A contains a rubber matrix and a rubber modifier; specifically, adding a rubber matrix (butadiene rubber and solution polymerized styrene-butadiene rubber) into an internal mixer, setting the rotating speed to be 70rpm, the initial mixing temperature to be 80 ℃, and 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 3min to obtain a section of master batch;
(2) performing second mixing on the first-stage masterbatch and each component in the component B, wherein the component B contains an organosilane coupling agent, polyethylene glycol and one third of white carbon black (accounting for one third of the total used white carbon black), the mixing time is 5min, and the rubber discharge temperature is 100 ℃, so as to obtain a second-stage masterbatch;
(3) performing third mixing on the second-stage masterbatch and each component in the component C, wherein the component C contains titanium dioxide, active zinc oxide, an activator, an anti-aging agent, a softener, microcrystalline wax and the remaining two thirds of white carbon black, the mixing time is 7min, and the rubber discharge temperature is 150 ℃, so as to obtain third-stage masterbatch;
(4) carrying out fourth mixing on the three-section master batch and each component in the component D, wherein the component D contains a vulcanization accelerator and a vulcanizing agent; specifically, 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 a vulcanization accelerator to perform fourth mixing, wherein the mixing temperature is 105 ℃, the mixing time is 6min, and discharging to obtain final mixed rubber;
(5) and putting the final rubber compound into a vulcanizing press for vulcanization, wherein the vulcanization conditions comprise that: the vulcanization temperature was 150 ℃, the vulcanization pressure was 20MPa, and the vulcanization time was 50min, to obtain a vulcanized rubber sample S1.
The remaining examples were conducted in a similar manner to example 1 except that the rubber composition used was different in formulation and/or process parameters from example 1, and the specific conditions are shown in Table 4.
TABLE 4
Table 4 (continuation 1)
Table 4 (continuation 2)
Example 12
In a similar manner to example 1, except that, in the step (2), the amount of the part of white carbon black was 80% by weight based on the total amount of white carbon black used in the process, vulcanized rubber S12 was obtained.
A comparative example was conducted in a similar procedure to that of example 1 except that the rubber composition used was different in formulation and/or process parameters from that of example 1, and the specific conditions were as shown in Table 4 (continuation 3).
Table 4 (continuation 3)
The properties of the vulcanizates prepared in the above examples were tested separately and the results are shown in Table 5.
TABLE 5
| Examples of the invention | Hardness/° degree | Tensile strength at break/MPa | Tear Strength/kN/m | DIN abrasion/mm3 | Rebound value/%) |
| Example 1 | 81 | 13.0 | 40 | 75 | 33.6 |
| Example 2 | 80 | 12.8 | 39 | 73 | 34.2 |
| Example 3 | 80 | 12.9 | 38 | 71 | 33.8 |
| Example 4 | 77 | 11.0 | 35 | 94 | 31.2 |
| Example 5 | 78 | 12.2 | 38 | 80 | 33.1 |
| Example 6 | 77 | 12.7 | 36 | 85 | 32.0 |
| Example 7 | 75 | 11.8 | 35 | 75 | 33.5 |
| Example 8 | 79 | 12.5 | 34 | 87 | 32.0 |
| Example 9 | 77 | 12.0 | 34 | 86 | 31.5 |
| Example 10 | 74 | 11.9 | 33 | 89 | 30.7 |
| Example 11 | 72 | 11.2 | 32 | 94 | 29.7 |
| Example 12 | 76 | 12.1 | 34 | 82 | 31.4 |
| Comparative example 1 | 70 | 7.9 | 29 | 110 | 24.6 |
| Comparative example 2 | 88 | 5.7 | 20 | 195 | 20.1 |
| Comparative example 3 | 78 | 8.9 | 24 | 106 | 22.2 |
| Comparative example 4 | 89 | 5.2 | 19 | 187 | 21.3 |
| Comparative example 5 | 87 | 7.5 | 21 | 175 | 21.7 |
From the above results, it can be seen that the rubber composition provided by the present invention improves the dispersibility of each component in the rubber matrix, particularly the dispersibility of white carbon black in the rubber matrix, through the mutual matching of each component with a specific content and type in the composition, improves the hardness, strength and wear resistance of the prepared vulcanized rubber, and simultaneously has excellent rebound resilience, thereby obtaining the vulcanized rubber with excellent comprehensive properties of hardness, strength, wear resistance and rebound resilience.
It should be noted that although the vulcanized rubbers prepared in comparative examples 1 to 5, particularly comparative example 2 and comparative examples 4 to 5, have high hardness, the vulcanized rubbers obtained therefrom have poor strength, abrasion resistance and rebound resilience, and the overall properties are far inferior to those of the vulcanized rubbers provided by the present invention.
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 (14)
1. A rubber composition containing dimercaptosuccinic acid and used for soles is characterized by comprising the following components which are mixed and stored or respectively and independently stored:
the rubber composition comprises a rubber matrix, a rubber modifier, white carbon black, titanium dioxide, polyethylene glycol, active zinc oxide, an organosilane coupling agent, an activating agent, an anti-aging agent, a softening agent, a vulcanizing agent, a vulcanization accelerator and microcrystalline wax;
relative to 100 parts by weight of the rubber matrix, the content of the rubber modifier is 3-7 parts by weight, the content of the white carbon black is 40-60 parts by weight, the content of the titanium dioxide is 10-20 parts by weight, the content of the polyethylene glycol is 2-8 parts by weight, the content of the active zinc oxide is 5-10 parts by weight, the content of the organosilane coupling agent 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 4-10 parts by weight, the content of the vulcanizing agent is 2-5 parts by weight, the content of the vulcanization accelerator is 2-7 parts by weight, and the content of the microcrystalline wax is 1-4 parts by weight;
wherein the rubber matrix is butadiene rubber and/or solution polymerized styrene-butadiene rubber; the rubber modifier is dimercaptosuccinic acid with a structure shown in a formula (1);
2. the rubber composition of claim 1, wherein the cis content in the butadiene rubber is 90-99 wt%;
preferably, the vinyl content of the solution-polymerized styrene-butadiene rubber is 50 to 70 wt%.
3. The rubber composition according to claim 1 or 2, wherein the rubber matrix is a mixture of the butadiene rubber and the solution-polymerized styrene-butadiene rubber, and the content of the butadiene rubber is 80 to 95% by weight based on the total weight of the rubber matrix; the content of the solution polymerized styrene-butadiene rubber is 5-20 wt%.
4. The rubber composition according to any one of claims 1 to 3, wherein the silica has a nitrogen adsorption specific surface area of 350-420m2/g；
Preferably, the number average molecular weight of the polyethylene glycol is 2000-;
preferably, the active zinc oxide has an average particle size of 20nm to 50 nm;
preferably, the organosilane coupling agent is selected from at least one of bis- [ gamma- (triethoxysilyl) propyl ] -tetrasulfide, bis- [3- (triethoxysilyl) propyl ] -disulfide, more preferably bis- [ gamma- (triethoxysilyl) propyl ] -tetrasulfide.
5. The rubber composition of any of claims 1-4, wherein the activator is selected from at least one of a fatty acid and a fatty acid metal soap salt;
preferably, the fatty acid is stearic acid;
preferably, the fatty acid metal soap salt is zinc stearate.
6. The rubber composition according to any one of claims 1 to 5, wherein the antioxidant is a phenolic antioxidant;
preferably, the softening agent is naphthenic oil;
preferably, the vulcanizing agent is sulfur and/or a sulfur donor;
preferably, the sulphur is selected from at least one of insoluble sulphur, soluble sulphur and oil-extended sulphur;
preferably, the vulcanization accelerator is selected from at least one of thiazole accelerators, thiuram accelerators and guanidine accelerators;
preferably, the vulcanization accelerator is selected from at least one of 2,2' -dithiodibenzothiazole, tetramethylthiuram disulfide, and diphenylguanidine.
7. Use of the rubber composition according to any one of claims 1 to 6 for the preparation of vulcanizates.
8. A method of preparing a vulcanizate, the method comprising: treating the components of the rubber composition of any of claims 1-6, the treating comprising:
(1) carrying out first mixing on each component in the component A to obtain a section of master batch, wherein the component A contains a rubber matrix and a rubber modifier;
(2) performing second mixing on the first-stage masterbatch and each component in the component B to obtain a second-stage masterbatch, wherein the component B contains an organosilane coupling agent, polyethylene glycol and a part of white carbon black;
(3) performing third mixing on the second-stage masterbatch and each component in the component C to obtain third-stage masterbatch, wherein the component C contains titanium dioxide, active zinc oxide, an activator, an anti-aging agent, a softener, microcrystalline wax and residual white carbon black;
(4) performing fourth mixing on the three-section master batch and each component in the component D to obtain a final rubber compound, wherein the component D contains a vulcanization accelerator and a vulcanizing agent;
(5) vulcanizing the final rubber;
the rubber modifier is used in an amount of 3-7 parts by weight, the white carbon black is used in an amount of 40-60 parts by weight, the titanium dioxide is used in an amount of 10-20 parts by weight, the polyethylene glycol is used in an amount of 2-8 parts by weight, the active zinc oxide is used in an amount of 5-10 parts by weight, the organosilane coupling agent is used in an amount of 4-6 parts by weight, the activator is used in an amount of 4-6 parts by weight, the anti-aging agent is used in an amount of 1-5 parts by weight, the softener is used in an amount of 4-10 parts by weight, the vulcanizing agent is used in an amount of 2-5 parts by weight, the vulcanization accelerator is used in an amount of 2-7 parts by weight, and the microcrystalline wax is used in an amount of 1-4 parts by weight, relative to 100 parts by weight of the rubber substrate.
9. The method according to claim 8, wherein the portion of white carbon in step (2) comprises 20-40 wt% of the total white carbon used in the method.
10. The method according to claim 8 or 9, wherein in step (1), the conditions of the first mixing are at least satisfied: the rotation speed is 60-120rpm, the temperature is 70-130 ℃, and the time is 1-6 min;
preferably, the first mixing conditions at least satisfy: the rotation speed is 70-90rpm, the temperature is 80-100 ℃, and the time is 2-3 min;
preferably, in step (2), the conditions of the second mixing are at least satisfied: the temperature is 90-150 deg.C, and the time is 2-6 min;
preferably, the second mixing conditions at least satisfy: the temperature is 100-;
preferably, in step (3), the conditions of the third mixing are at least satisfied: the temperature is 140 ℃ and 170 ℃, and the time is 2-8 min;
preferably, the third mixing conditions at least satisfy: the temperature is 150 ℃ and 160 ℃, and the time is 4-7 min;
preferably, in step (4), the fourth mixing condition at least satisfies: the rotation speed is 30-50rpm, the temperature is less than or equal to 120 ℃, and the time is 4-6 min.
11. The method according to any one of claims 8-10, wherein in step (5), the vulcanization conditions at least satisfy: the temperature is 150-;
preferably, the vulcanization is carried out in a press vulcanizer.
12. A vulcanized rubber produced by the method of any one of claims 8 to 11.
13. Use of the vulcanizate of claim 12 for the preparation of shoe soles.
14. A shoe sole comprising the vulcanized rubber of claim 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010723598.2A CN113968998B (en) | 2020-07-24 | 2020-07-24 | Rubber composition containing dimercaptosuccinic acid for soles and application thereof, vulcanized rubber, preparation method and application thereof and soles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010723598.2A CN113968998B (en) | 2020-07-24 | 2020-07-24 | Rubber composition containing dimercaptosuccinic acid for soles and application thereof, vulcanized rubber, preparation method and application thereof and soles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113968998A true CN113968998A (en) | 2022-01-25 |
| CN113968998B CN113968998B (en) | 2023-05-12 |
Family
ID=79585837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010723598.2A Active CN113968998B (en) | 2020-07-24 | 2020-07-24 | Rubber composition containing dimercaptosuccinic acid for soles and application thereof, vulcanized rubber, preparation method and application thereof and soles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113968998B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746422A (en) * | 2022-10-28 | 2023-03-07 | 北京彤程创展科技有限公司 | Rubber composition, equal-wall-thickness screw drill stator and drill |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101970562A (en) * | 2008-02-25 | 2011-02-09 | 倍耐力轮胎股份公司 | Tire and crosslinkable elastomeric composition |
| CN104231119A (en) * | 2013-06-24 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of long-chain branched cis-rich polybutadiene |
| CN104231120A (en) * | 2013-06-24 | 2014-12-24 | 北京化工大学 | Long-chain branched high-cis-polyisoprene and preparation method thereof |
| JP2015044918A (en) * | 2013-08-27 | 2015-03-12 | 横浜ゴム株式会社 | Rubber composition, production method thereof and pneumatic tire |
| CN104428359A (en) * | 2012-05-09 | 2015-03-18 | 株式会社普利司通 | Natural rubber, rubber composition comprising natural rubber and method for producing same, and tire |
| US20180016409A1 (en) * | 2016-07-12 | 2018-01-18 | Twolink Sdn Bhd | Accelerator free and high filler load nitrile glove |
| 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 |
| CN108017727A (en) * | 2016-11-02 | 2018-05-11 | 中国石油化工股份有限公司 | Modified diene polymer and preparation method thereof and rubber composition and vulcanization rubber |
| CN109384965A (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 |
| JP2019077751A (en) * | 2017-10-20 | 2019-05-23 | 株式会社ブリヂストン | Rubber composition |
-
2020
- 2020-07-24 CN CN202010723598.2A patent/CN113968998B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101970562A (en) * | 2008-02-25 | 2011-02-09 | 倍耐力轮胎股份公司 | Tire and crosslinkable elastomeric composition |
| CN104428359A (en) * | 2012-05-09 | 2015-03-18 | 株式会社普利司通 | Natural rubber, rubber composition comprising natural rubber and method for producing same, and tire |
| CN104231119A (en) * | 2013-06-24 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of long-chain branched cis-rich polybutadiene |
| CN104231120A (en) * | 2013-06-24 | 2014-12-24 | 北京化工大学 | Long-chain branched high-cis-polyisoprene and preparation method thereof |
| JP2015044918A (en) * | 2013-08-27 | 2015-03-12 | 横浜ゴム株式会社 | Rubber composition, production method thereof and pneumatic tire |
| US20180016409A1 (en) * | 2016-07-12 | 2018-01-18 | Twolink Sdn Bhd | Accelerator free and high filler load nitrile glove |
| 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 |
| CN108017727A (en) * | 2016-11-02 | 2018-05-11 | 中国石油化工股份有限公司 | Modified diene polymer and preparation method thereof and rubber composition and vulcanization rubber |
| CN109384965A (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 |
| JP2019077751A (en) * | 2017-10-20 | 2019-05-23 | 株式会社ブリヂストン | Rubber composition |
Non-Patent Citations (1)
| Title |
|---|
| YANLONG LUO等: "Temperature dependence of the interfical bonding characterizatics of silica/styrene butadiene rubber composites: a molecular dynamics simulation study", 《POLYMER SOCIETY OF CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746422A (en) * | 2022-10-28 | 2023-03-07 | 北京彤程创展科技有限公司 | Rubber composition, equal-wall-thickness screw drill stator and drill |
| CN115746422B (en) * | 2022-10-28 | 2024-05-03 | 北京彤程创展科技有限公司 | Rubber composition, equal-wall-thickness screw drilling tool stator and drilling tool |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113968998B (en) | 2023-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112239573B (en) | Rubber composition for wear-resistant sole, vulcanized rubber, and preparation method and application thereof | |
| CN107955232B (en) | Application of maleic 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 | |
| WO2004067625A1 (en) | Diene rubber composition and process for producing the same | |
| 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 | |
| EP1081162B1 (en) | Conjugated diene rubber, process for producing the same, and rubber composition | |
| CN107641219B (en) | Use of organosilanes and rubber compositions and vulcanizates and process for their preparation | |
| CN113968998A (en) | Rubber composition containing dimercaptosuccinic acid and used for shoe sole, application of rubber composition, vulcanized rubber, preparation method and application of vulcanized rubber, and shoe sole | |
| CN109929155B (en) | Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof | |
| CN109384972B (en) | Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof | |
| CN109384974B (en) | Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof | |
| CN109384973B (en) | Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof | |
| CN113968997B (en) | Rubber composition containing L-cysteine for sole, application of rubber composition, vulcanized rubber, preparation method and application of vulcanized rubber and sole | |
| CN113968999B (en) | Rubber composition for shoe sole and application thereof, vulcanized rubber and preparation method and application thereof, and shoe sole containing vulcanized rubber | |
| CN110551239A (en) | modified styrene-butadiene rubber and preparation method thereof, rubber composition, vulcanized rubber and preparation method and application thereof | |
| CN109384975B (en) | Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof | |
| CN113462043A (en) | Rubber composition containing matrix modifier, vulcanized rubber, and preparation method and application thereof | |
| CN109929207B (en) | Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof | |
| CN112239571B (en) | Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof | |
| CN112239572B (en) | Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof | |
| CN113444300B (en) | Rubber composition for sole material, vulcanized rubber, and preparation method and application thereof | |
| CN114437422A (en) | Rubber composition for shoe sole and application thereof, vulcanized rubber and preparation method and application thereof | |
| CN113462034B (en) | Thiol organic acid-containing rubber composition, vulcanized rubber and preparation method and application thereof | |
| CN114149623B (en) | Rubber composition for shoe soles and application thereof, vulcanized rubber and 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 |