CN113462043B - Rubber composition containing matrix modifier, vulcanized rubber, preparation method and application thereof - Google Patents
Rubber composition containing matrix modifier, vulcanized rubber, preparation method and application thereof Download PDFInfo
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- CN113462043B CN113462043B CN202010239306.8A CN202010239306A CN113462043B CN 113462043 B CN113462043 B CN 113462043B CN 202010239306 A CN202010239306 A CN 202010239306A CN 113462043 B CN113462043 B CN 113462043B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- 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
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- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention relates to the field of vulcanized rubber, and discloses a rubber composition containing a matrix modifier, vulcanized rubber, a preparation method and application thereof, wherein the composition contains: the rubber matrix comprises a rubber matrix, a matrix modifier, white carbon black, carbonate, triethanolamine, polyethylene glycol, an organosilane coupling agent, an anti-aging agent and a vulcanizing agent, wherein the rubber matrix is butadiene rubber; the matrix modifier is L-cysteine, and the organosilane coupling agent is at least one of Si69 and Si 75. The vulcanized rubber prepared from the rubber composition has the advantages of good transparency, high strength, good wear resistance, excellent rebound resilience and the like.
Description
Technical Field
The invention relates to the field of vulcanized rubber, in particular to a rubber composition containing a matrix modifier, a method for preparing vulcanized rubber, the vulcanized rubber prepared by the method and application of the vulcanized rubber in sole materials.
Background
The comfort of the sole directly affects the quality of the whole shoe. In the prior art, soles are manufactured by using PVC, TPR, TPU and other materials, and the materials are inferior to soles made of rubber in comfort and skid resistance.
In the prior art, white carbon black is taken as a main reinforcing filler and is widely applied to footwear products, so that the sole has good wear resistance, skid resistance and vamp adhesion performance, and can be processed into colored cowhells, and the white carbon black is widely applied to transparent, light-colored and colored soles (comprising outsoles, midsoles and surrounding strips). Accordingly, the shoe industry has been a large consumer of white carbon black.
The white carbon black has a certain limit in application because of the strong surface polarity, which makes the dispersion of the white carbon black in the rubber matrix become extremely difficult.
That is, the prior art does not fully satisfy the characteristics of good transmittance, abrasion resistance, and strength required for transparent soles containing white carbon black formulations, and it is necessary to provide a rubber composition having improved properties.
Disclosure of Invention
The invention aims to solve the problems of improving the transmittance, strength and wear resistance of vulcanized rubber formed by a sole material formula containing white carbon black.
In order to achieve the above object, a first aspect of the present invention provides a rubber composition containing a matrix modifier, which comprises the following components stored in a mixed or independent manner:
rubber matrix, matrix modifier, white carbon black, carbonate, triethanolamine, polyethylene glycol, organosilane coupling agent, anti-aging agent and vulcanizing agent;
wherein the rubber matrix is butadiene rubber; the matrix modifier is L-cysteine; the organosilane coupling agent is at least one selected from Si69 and Si 75;
the rubber comprises, by weight, relative to 100 parts of a rubber substrate, 5-10 parts of a substrate modifier, 10-30 parts of white carbon black, 2-6 parts of carbonate, 1-4 parts of triethanolamine, 3-6 parts of polyethylene glycol, 1-3 parts of an organosilane coupling agent, 1-5 parts of an anti-aging agent and 5-10 parts of a vulcanizing agent.
In a second aspect the invention provides a process for preparing a vulcanizate, using the components of the composition described in the first aspect of the invention, the process comprising:
(1) First mixing is carried out on the component A containing the rubber matrix and the matrix modifier to obtain a primary rubber, wherein the first mixing conditions comprise: the temperature is 80-120deg.C, and the time is 1-5min;
(2) Performing second mixing on the primary master batch and a component B containing white carbon black, an organosilane coupling agent and polyethylene glycol to obtain a secondary master batch, wherein the second mixing conditions comprise: the temperature is 100-130 ℃ and the time is 1-5min;
(3) And carrying out third mixing on the two-stage master batch and a component C containing carbonate, triethanolamine and an anti-aging agent to obtain a three-stage master batch, wherein the third mixing conditions comprise: the temperature is 110-130 ℃ and the time is 1-5min;
(4) And (3) carrying out fourth mixing on the three-section master batch and the component D containing the vulcanizing agent to obtain final mixing, wherein the fourth mixing conditions comprise: the temperature is not higher than 120 ℃ and the time is 3-6min;
(5) And vulcanizing the final rubber mixture.
In a third aspect the present invention provides a vulcanizate prepared by the foregoing process.
A fourth aspect of the invention provides the use of the aforementioned vulcanizate in sole materials.
The vulcanized rubber prepared by the method has good transmittance, high strength, good wear resistance and excellent rebound resilience through the mutual matching of the components in the composition.
In addition, the specific method for preparing the vulcanized rubber can exert the synergistic effect of the components in the composition provided by the invention, so that the prepared vulcanized rubber has better performance.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As previously described, a first aspect of the present invention provides a rubber composition containing a matrix modifier, the composition comprising the following components, either stored in admixture or separately:
rubber matrix, matrix modifier, white carbon black, carbonate, triethanolamine, polyethylene glycol, organosilane coupling agent, anti-aging agent and vulcanizing agent;
wherein the rubber matrix is butadiene rubber; the matrix modifier is L-cysteine; the organosilane coupling agent is at least one selected from Si69 and Si 75;
the rubber comprises, by weight, relative to 100 parts of a rubber substrate, 5-10 parts of a substrate modifier, 10-30 parts of white carbon black, 2-6 parts of carbonate, 1-4 parts of triethanolamine, 3-6 parts of polyethylene glycol, 1-3 parts of an organosilane coupling agent, 1-5 parts of an anti-aging agent and 5-10 parts of a vulcanizing agent.
Preferably, the cis content in the butadiene rubber is 95 to 99 wt.%.
Preferably, the matrix modifier is L-cysteine represented by formula (1),
preferably, the white carbon black is produced by a gas phase method, and the nitrogen adsorption specific surface area is 350-420m 2 White carbon black per gram, for example, the white carbon black is A380. The inventors found that the nitrogen adsorption specific surface area produced by the gas phase method is 350-420m 2 Per gram of white carbon black, the vulcanized rubber prepared by the composition of the invention has betterThe transparency, higher strength, wear resistance and rebound performance.
Preferably, the polyethylene glycol has a number average molecular weight of 2000-6000, such as PEG4000 and the like.
Preferably, the carbonate is selected from at least one of zinc carbonate and calcium carbonate; preferably, the carbonate is zinc carbonate.
Preferably, the anti-aging agent is at least one of phenolic anti-aging agents; preferably, the antioxidant is at least one selected from the antioxidants 2, 6-di-t-butyl-4-methylphenol (antioxidant 264), 2-methylenebis- (4-methyl-6-t-butylphenol) (antioxidant 2246).
Preferably, the vulcanizing agent is selected from at least one of organic peroxide vulcanizing agents; preferably, the vulcanizing agent is at least one selected from dicumyl peroxide (DCP) and di-tert-butyl peroxide (DTBP).
As previously mentioned, the second aspect of the present invention provides a process for preparing a vulcanizate, using the components of the composition described in the first aspect of the present invention, the process comprising:
(1) First mixing is carried out on the component A containing the rubber matrix and the matrix modifier to obtain a primary rubber, wherein the first mixing conditions comprise: the temperature is 80-120deg.C, and the time is 1-5min;
(2) Performing second mixing on the primary master batch and a component B containing white carbon black, an organosilane coupling agent and polyethylene glycol to obtain a secondary master batch, wherein the second mixing conditions comprise: the temperature is 100-130 ℃ and the time is 1-5min;
(3) And carrying out third mixing on the two-stage master batch and a component C containing carbonate, triethanolamine and an anti-aging agent to obtain a three-stage master batch, wherein the third mixing conditions comprise: the temperature is 110-130 ℃ and the time is 1-5min;
(4) And (3) carrying out fourth mixing on the three-section master batch and the component D containing the vulcanizing agent to obtain final mixing, wherein the fourth mixing conditions comprise: the temperature is not higher than 120 ℃ and the time is 3-6min;
(5) And vulcanizing the final rubber mixture.
The composition of the raw materials for preparing vulcanized rubber in the second aspect of the present invention is the composition described in the foregoing first aspect of the present invention, and therefore, the kinds of the composition of the raw materials in the second aspect of the present invention are all exactly the same as those described in the first aspect of the present invention, and the present invention is not repeated in the second aspect, and the person skilled in the art should not understand the limitation of the present invention.
Preferably, the conditions of the first mixing include: the temperature is 90-100deg.C, and the time is 2-4min.
Preferably, the conditions of the second kneading include: the temperature is 110-120deg.C, and the time is 3-5min.
Preferably, the conditions of the third mixing include: the temperature is 115-125 ℃ and the time is 3-4min.
Preferably, the vulcanization conditions include: the temperature is 150-170 ℃, the pressure is 10-20MPa, and the time is 20-40min.
Preferably, the amount of the matrix modifier is 5 to 10 parts by weight, the amount of the white carbon black is 10 to 30 parts by weight, the amount of the carbonate is 2 to 6 parts by weight, the amount of the triethanolamine is 1 to 4 parts by weight, the amount of the polyethylene glycol is 3 to 6 parts by weight, the amount of the organosilane coupling agent is 1 to 3 parts by weight, the amount of the antioxidant is 1 to 5 parts by weight, and the amount of the vulcanizing agent is 5 to 10 parts by weight, relative to 100 parts by weight of the rubber matrix.
In order to clearly describe the method for producing a vulcanized rubber of the present invention, a preferred embodiment is provided below for explanation:
(1) Preheating an internal mixer to 80-120 ℃, adding a rubber matrix, plasticating for 0.1-3min at the rotating speed of 50-200rpm, adding a matrix modifier into the internal mixer, and carrying out first mixing, wherein the conditions of the first mixing comprise: the temperature is 80-120deg.C, and the time is 1-5min;
(2) Adding white carbon black, an organosilane coupling agent and polyethylene glycol into an internal mixer, and carrying out second mixing at 100-130 ℃, wherein the second mixing conditions comprise: the temperature is 100-130 ℃ and the time is 1-5min;
(3) Adding carbonate, triethanolamine and an anti-aging agent into an internal mixer, and carrying out third mixing at 110-130 ℃ to obtain a mixed rubber, wherein the conditions of the third mixing comprise: the temperature is 110-130 ℃ and the time is 1-5min;
(4) Plasticating the mixed rubber at 20-80 ℃ and 20-150rpm for 0.1-3min, adding a vulcanizing agent into an internal mixer for fourth mixing, and discharging to obtain final rubber, wherein the fourth mixing conditions comprise: the temperature is not higher than 120 ℃ and the time is 3-6min;
(5) And (3) putting the final rubber into a plate vulcanizing machine for vulcanizing.
It should be noted that the plasticating process in step (1) and step (4) of the present invention is not necessarily required, but is merely a preferred embodiment provided for better processability.
As previously mentioned, a third aspect of the present invention provides a vulcanizate prepared by the foregoing process.
As previously mentioned, a fourth aspect of the present invention provides the use of the aforementioned vulcanizate in sole materials.
Unless otherwise indicated, the pressures described herein are all indicated as gauge pressures.
The invention will be described in detail below by way of examples. In the examples below, various raw materials used were available from commercial sources without particular explanation.
Butadiene rubber: BR9000, a Yanshan petrochemical product having a cis content of 97.8% by weight;
white carbon black: a380 Degussa, nitrogen adsorption specific surface area of 380m 2 /g; AEROSIL R974, desoxhlet, nitrogen adsorption specific surface area 180m2/g;
polyethylene glycol: PEG2000, PEG4000, PEG6000, technical grade, dow chemical company, usa;
matrix modifier: l-cysteine (. Beta. -mercaptopropionic acid), analytically pure, company Aba Ding Shiji;
organosilane coupling agent: si69, si75, commercially pure, pinning coupling agent Co., ltd;
zinc carbonate: analytically pure, hongda zinc business company;
calcium carbonate: analytically pure, macro Xin mining Co Ltd;
triethanolamine: analytically pure, chiyuan chemical Co., ltd;
anti-aging agent: anti-aging agent 264, anti-aging agent 2246, panhua chemical (Shanghai) Limited;
vulcanizing agent: DCP, DTBP, company A Ding Shiji.
The rubber processing conditions in the following examples are shown in Table 1, the rubber test equipment conditions are shown in Table 2, and the test conditions are shown in Table 3:
TABLE 1
| Sequence number | Device name | Model number | Manufacturing factories | Use of the same |
| 1 | Banbury mixer | BR1600 | America Rayleigh Corp | Mixing |
| 2 | Flat vulcanizing machine | XLB-D400*400*2 | First rubber machinery plant of Shanghai | Vulcanization |
TABLE 2
TABLE 3 Table 3
The amounts of the components in the examples below are all parts by weight (or parts) and each part by weight represents 1g.
Example 1
The composition formulations are listed in table 4.
The internal mixer was preheated to 90℃and the rubber matrix was added and plasticated at 70rpm for 0.5min (the same conditions were used for the rest of the examples without any particular explanation, and then the first mixing was carried out), and the matrix modifier was added to the internal mixer and the first mixing was carried out for 4min. Then adding white carbon black, an organosilane coupling agent and polyethylene glycol into an internal mixer, and carrying out second mixing for 5min at 110 ℃. Then adding carbonate, triethanolamine and an anti-aging agent into an internal mixer, and carrying out third mixing for 4min at 115 ℃. Subsequently, the above-mentioned rubber mixture was plasticated at 60℃and 60rpm for 0.5min (the same conditions were employed in the other examples without any particular explanation, and then the fourth mixing was carried out), and then the fourth mixing was carried out by continuously adding a vulcanizing agent to the internal mixer at a mixing temperature of 100℃for 5min, and discharging to obtain a final rubber mixture. And (3) putting the final rubber mixture into a plate vulcanizing machine for vulcanization, wherein the vulcanization temperature is 150 ℃, the vulcanization pressure is 20MPa, and the vulcanization time is 40min, so that the vulcanized rubber sample S1 is prepared.
The procedure of example 1 was followed except for example 6, and the specific process conditions are shown in Table 4.
Example 6
The formulation of the composition was the same as in example 1.
The preparation method of the vulcanized rubber comprises the following steps: the process was carried out in a similar manner to example 1, except that the first kneading was not carried out. Specifically:
the internal mixer was preheated to 90℃and the rubber matrix and matrix modifier were added and plasticated at a speed of 70rpm for 0.5min. Then adding white carbon black, an organosilane coupling agent and polyethylene glycol into an internal mixer, and carrying out second mixing for 5min at 110 ℃. Then adding carbonate, triethanolamine and an anti-aging agent into an internal mixer, and carrying out third mixing for 4min at 115 ℃. And then plasticating the mixed rubber at 60 ℃ for 0.5min, continuously adding a vulcanizing agent into an internal mixer for fourth mixing, wherein the mixing temperature is 100 ℃, the mixing time is 5min, and discharging to obtain the final rubber. And (3) putting the final rubber mixture into a plate vulcanizing machine for vulcanization, wherein the vulcanization temperature is 150 ℃, the vulcanization pressure is 20MPa, and the vulcanization time is 40min, so as to prepare a vulcanized rubber sample S6.
The formulation of the compositions of comparative example 1, comparative example 2, comparative example 3 and comparative example 4 are listed in table 4. The preparation process was the same as in example 1, and the specific parameters are listed in table 4.
TABLE 4 Table 4
Table 4 (subsequent table)
Test case
The results of the relevant performance tests performed on the examples and comparative products are shown in Table 5.
TABLE 5
| Test item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Transmittance (%) | 75.3 | 72.2 | 74.1 | 62.0 | 60.6 |
| Hardness (°) | 58 | 57 | 56 | 64 | 63 |
| Breaking strength (MPa) | 9.2 | 9.6 | 9.9 | 8.3 | 8.5 |
| Tear Strength (kN/m) | 30 | 32 | 29 | 25 | 26 |
| DIN abrasion (mm) 3 ) | 54 | 56 | 50 | 69 | 65 |
| Rebound value (%) | 50.3 | 51.4 | 52.7 | 48.2 | 49.7 |
Table 5 (subsequent table)
| Test item | Example 6 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Transmittance (%) | 56.3 | 45.3 | 28.7 | 26.4 | 25.9 |
| Hardness (°) | 67 | 69 | 76 | 75 | 78 |
| Breaking strength (MPa) | 8.0 | 7.2 | 5.0 | 5.7 | 6.0 |
| Tear Strength (kN/m) | 23 | 20 | 17 | 16 | 19 |
| DIN abrasion (mm) 3 ) | 72 | 89 | 135 | 142 | 138 |
| Rebound value (%) | 45.2 | 39.4 | 24.2 | 25.6 | 22.7 |
As can be seen from the results of Table 5, the formulation of the present invention provides a significant improvement in transmittance, strength, abrasion resistance and rebound resilience of the vulcanizate over the prior art.
The rubber composition can enable white carbon black to be better dispersed in a rubber matrix, and further exert the characteristics and advantages of a matrix modifier; so that the vulcanized rubber further prepared has the advantages of good transparency, high strength, good wear resistance, excellent rebound resilience and the like.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (15)
1. A rubber composition containing a matrix modifier, characterized in that the composition contains the following components stored in a mixture or independently:
rubber matrix, matrix modifier, white carbon black, carbonate, triethanolamine, polyethylene glycol, organosilane coupling agent, anti-aging agent and vulcanizing agent;
wherein the rubber matrix is butadiene rubber; the matrix modifier is L-cysteine; the organosilane coupling agent is at least one selected from Si69 and Si 75; the specific surface area of nitrogen adsorption produced by the gas phase method of the white carbon black is 350-420m 2 White carbon black per gram; the anti-aging agent is selected from the group consisting of 2, 6-di-tert-butyl-4-methylphenol and 2, 2-methylenebis- (4-methyl-6-tert-butylphenol)One less;
the rubber comprises, by weight, relative to 100 parts of a rubber substrate, 5-10 parts of a substrate modifier, 10-30 parts of white carbon black, 2-6 parts of carbonate, 1-4 parts of triethanolamine, 3-6 parts of polyethylene glycol, 1-3 parts of an organosilane coupling agent, 1-5 parts of an anti-aging agent and 5-10 parts of a vulcanizing agent.
2. The composition of claim 1, wherein the cis content of the butadiene rubber is 95-99 wt%.
3. The composition according to claim 1 or 2, wherein the polyethylene glycol has a number average molecular weight of 2000-6000.
4. The composition according to claim 1 or 2, wherein the carbonate is selected from at least one of zinc carbonate and calcium carbonate.
5. The composition of claim 4, wherein the carbonate is zinc carbonate.
6. The composition according to claim 1 or 2, wherein the vulcanizing agent is selected from at least one of organic peroxide vulcanizing agents.
7. The composition of claim 6, wherein the vulcanizing agent is selected from at least one of dicumyl peroxide and di-t-butyl peroxide.
8. A process for preparing a vulcanizate, using the components of the composition of any one of claims 1 to 7, the process comprising:
(1) First mixing is carried out on the component A containing the rubber matrix and the matrix modifier to obtain a primary rubber, wherein the first mixing conditions comprise: the temperature is 80-120deg.C, and the time is 1-5min;
(2) Performing second mixing on the primary master batch and a component B containing white carbon black, an organosilane coupling agent and polyethylene glycol to obtain a secondary master batch, wherein the second mixing conditions comprise: the temperature is 100-130 ℃ and the time is 1-5min;
(3) And carrying out third mixing on the two-stage master batch and a component C containing carbonate, triethanolamine and an anti-aging agent to obtain a three-stage master batch, wherein the third mixing conditions comprise: the temperature is 110-130 ℃ and the time is 1-5min;
(4) And (3) carrying out fourth mixing on the three-section master batch and the component D containing the vulcanizing agent to obtain final mixing, wherein the fourth mixing conditions comprise: the temperature is not higher than 120 ℃ and the time is 3-6min;
(5) And vulcanizing the final rubber mixture.
9. The method of claim 8, wherein the conditions of the first mixing comprise: the temperature is 90-100deg.C, and the time is 2-4min.
10. The method of claim 8 or 9, wherein the conditions of the second mixing comprise: the temperature is 110-120deg.C, and the time is 3-5min.
11. The method of claim 8 or 9, wherein the conditions of the third mixing comprise: the temperature is 115-125 ℃ and the time is 3-4min.
12. The method of claim 8 or 9, wherein the vulcanization conditions include: the temperature is 150-170 ℃, the pressure is 10-20MPa, and the time is 20-40min.
13. The method according to claim 8 or 9, wherein the amount of the matrix modifier is 5 to 10 parts by weight, the amount of the white carbon black is 10 to 30 parts by weight, the amount of the carbonate is 2 to 6 parts by weight, the amount of the triethanolamine is 1 to 4 parts by weight, the amount of the polyethylene glycol is 3 to 6 parts by weight, the amount of the organosilane coupling agent is 1 to 3 parts by weight, the amount of the age resistor is 1 to 5 parts by weight, and the amount of the vulcanizing agent is 5 to 10 parts by weight, relative to 100 parts by weight of the rubber matrix.
14. A vulcanized rubber prepared by the process of any one of claims 8-13.
15. Use of the vulcanized rubber of claim 14 in sole materials.
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