CN112029222B - Wear-resistant rubber material for soles and preparation method and application thereof - Google Patents
Wear-resistant rubber material for soles and preparation method and application thereof Download PDFInfo
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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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
- A43B13/026—Composites, e.g. carbon fibre or aramid fibre; the sole, one or more sole layers or sole part being made of a composite
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K2003/265—Calcium, strontium or barium carbonate
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
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Abstract
The application relates to a wear-resistant rubber material for soles and a preparation method and application thereof, belonging to the technical field of sole processing, wherein the wear-resistant rubber material comprises, by weight, 38-55 parts of SBS, 20-27 parts of PS, 13-20.5 parts of maleic anhydride graft modified EVA, 4-6.5 parts of modified nano calcium carbonate, 0.5-1.5 parts of polypropylene fiber, 4-6 parts of petroleum resin and 1-3 parts of an additive. The wear-resistant rubber material for the shoe sole has good tensile strength and wear resistance and shows good comprehensive performance.
Description
Technical Field
The application relates to the technical field of sole processing, in particular to a wear-resistant rubber material for soles and a preparation method and application thereof.
Background
Styrene-butadiene-styrene triblock copolymer (SBS) is an important thermoplastic elastomer, which has advantages of light weight, wet skid resistance, no odor, recyclability, and is widely used for soles of sneakers and sports shoes. Pure SBS is used as the sole material, and although the sole material has high flexibility, the sole material has poor wear resistance.
Disclosure of Invention
The application aims to provide a wear-resistant rubber material for soles, which has good tensile strength and wear resistance and shows good comprehensive performance.
The second purpose of the present application is to provide a preparation method of a wear-resistant rubber material for shoe soles, which has the advantages of simple preparation and convenient control.
The third purpose of the application is to provide application of the wear-resistant rubber material for the shoe sole.
The above object of the present application is achieved by the following technical solutions:
the wear-resistant rubber material for the soles comprises, by weight, 38-55 parts of SBS, 13-20.5 parts of PS20-27 parts of maleic anhydride graft modified EVA, 4-6.5 parts of modified nano calcium carbonate, 0.5-1.5 parts of polypropylene fiber, 4-6 parts of petroleum resin and 1-3 parts of an additive.
By adopting the technical scheme, the maleic anhydride graft modified EVA and the modified nano calcium carbonate are added into the raw materials of the wear-resistant rubber material, so that the tensile strength and the wear resistance of the wear-resistant rubber material are improved through the synergistic effect of the raw materials, and the wear-resistant rubber material has good comprehensive performance.
More preferably, the raw materials of the maleic anhydride graft modified EVA comprise, by weight, 90-100 parts of EVA, 5-10 parts of absolute ethyl alcohol, 1-3 parts of an initiator and 1-4 parts of maleic anhydride.
More preferably, the initiator is dicumyl peroxide.
By adopting the technical scheme, maleic anhydride is grafted to EVA, and maleic anhydride graft modification EVA plays a good medium role in SBS and PS, so that the compatibility and the bonding strength of the raw materials of the wear-resistant rubber material are increased, and the tensile strength of the wear-resistant rubber material is improved.
More preferably, the maleic anhydride graft modified EVA is prepared by the following method:
adding an initiator and maleic anhydride into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material A;
heating EVA to 40-50 ℃ under the condition of continuous stirring, then adding the mixed material A into the EVA in a spraying mode, completing spraying of the mixed material A within 20-30min, standing for 1-2h after completing spraying of the mixed material A, continuing stirring, heating to 170-180 ℃, performing heat preservation for 10-20min, cooling, and crushing to obtain the maleic anhydride graft modified EVA.
By adopting the technical scheme, maleic anhydride is dissolved in absolute ethyl alcohol to obtain the mixed material A, then the mixed material A is added into EVA in a spraying mode, the mixed material A is coated on the surface of the EVA and enters the interior of the EVA, the contact area of the maleic anhydride and the EVA is increased, the grafting rate of the maleic anhydride grafted to the EVA is increased, and the using effect of the maleic anhydride grafted modified EVA is improved.
Preferably, the raw materials of the modified nano calcium carbonate comprise, by weight, 90-100 parts of water, 20-30 parts of absolute ethyl alcohol, 10-20 parts of nano calcium carbonate, 1-2 parts of a coupling agent and 3-5 parts of stearic acid.
More preferably, the coupling agent is isopropyl triisostearoyl titanate.
By adopting the technical scheme, the nano calcium carbonate is modified, so that stearic acid is coated on the surface of the nano calcium carbonate, an organic film is formed on the surface of the nano calcium carbonate, the compatibility of the modified nano calcium carbonate and the wear-resistant rubber material is improved, the dispersity of the modified nano calcium carbonate is also improved, and the tensile strength and the wear resistance of the wear-resistant rubber material are improved.
More preferably, the modified nano calcium carbonate is prepared by the following method:
heating absolute ethanol to 30-40 ℃, adding stearic acid into the absolute ethanol, uniformly mixing, and carrying out heat preservation treatment for 10-20min to obtain a mixed material B;
heating water to 60-70 ℃, adding a coupling agent into the water, uniformly mixing, then adding nano calcium carbonate, uniformly mixing, carrying out heat preservation treatment for 50-60min, and carrying out ultrasonic treatment for 10-20min to obtain a mixed material C;
heating the mixed material C to 60-70 ℃ under the condition of continuous stirring, then adding the mixed material B into the mixed material C in a dropwise adding mode for multiple times, finishing dropwise adding the mixed material B within 50-60min, wherein the intermediate interval between two adjacent dropwise adding processes of the mixed material B is 10-20min, carrying out ultrasonic treatment within the intermediate interval between two adjacent dropwise adding processes of the mixed material B, carrying out heat preservation treatment for 70-90min after the dropwise adding processes of the mixed material B are finished, filtering and drying to obtain the modified nano calcium carbonate.
By adopting the technical scheme, the stearic acid is dissolved in the absolute ethyl alcohol to obtain the mixed material B, and the uniformity of the mixed material B is improved. Adding a coupling agent into water to disperse the coupling agent in the water, then adding nano calcium carbonate, wherein the coupling agent is in contact with the nano calcium carbonate, part of the coupling agent enters pores inside the nano calcium carbonate, and part of the coupling agent is coated on the surface of the nano calcium carbonate and coats the nano calcium carbonate, so that the agglomeration of the nano calcium carbonate in the water is reduced, and meanwhile, ultrasonic treatment is adopted to disperse the agglomerated nano calcium carbonate, so that the dispersibility of the nano calcium carbonate is improved, and the mixed material C is obtained. And adding the mixed material B into the mixed material C, wherein the mixed material B is dropwise added, the coupling agent and stearic acid are given reaction time, ultrasonic treatment is also adopted, the agglomeration of the nano calcium carbonate is reduced, the dispersibility of the modified nano calcium carbonate is improved, and the using effect of the nano calcium carbonate is improved.
More preferably, the additive is one or two of a light stabilizer and an antioxidant.
Through adopting above-mentioned technical scheme, improve wear-resisting rubber material and store and use stability.
The second application object of the present application is achieved by the following technical scheme:
a preparation method of a wear-resistant rubber material for soles specifically adopts the following steps:
under the conditions of continuous stirring and the temperature of 125-135 ℃, SBS, PS, maleic anhydride graft modified EVA and modified nano calcium carbonate are uniformly mixed, heat preservation treatment is carried out for 10-20min, then polypropylene fiber, petroleum resin and additive are added, uniform mixing is carried out, the temperature is raised to 170-180 ℃, heat preservation treatment is carried out for 3-10min, and the temperature is reduced, so as to obtain the wear-resistant rubber material.
By adopting the technical scheme, the preparation method has the advantages of simple preparation and convenience in control.
The second application object of the present application is achieved by the following technical scheme:
the application of the wear-resistant rubber material for the soles is to use the wear-resistant rubber material for the soles of women shoes.
In summary, the present application has the following beneficial effects:
according to the wear-resistant rubber material for the soles, the maleic anhydride graft modification EVA and the modified nano calcium carbonate are added into the raw materials of the wear-resistant rubber material, so that the wear-resistant rubber material has good tensile strength and wear resistance and shows good comprehensive performance through the synergistic effect of the raw materials.
Secondly, raw material proportion and a preparation method of the maleic anhydride grafted modified EVA are optimized, and maleic anhydride is grafted to the EVA, so that compatibility and bonding strength of the raw materials of the wear-resistant rubber material are improved, and tensile strength of the wear-resistant rubber material is improved. The mixed material A is added into the EVA in a spraying mode, so that the grafting rate of maleic anhydride grafted to the EVA is increased, and the using effect of maleic anhydride grafted modified EVA is improved.
And thirdly, optimizing the raw material proportion and the preparation method of the modified nano calcium carbonate, coating stearic acid on the surface of the nano calcium carbonate, forming an organic film, increasing the compatibility and the dispersibility of the modified nano calcium carbonate and the wear-resistant rubber material, and improving the tensile strength and the wear resistance of the wear-resistant rubber material. And the mixed material B is added into the mixed material C in a dropwise adding mode, so that the agglomeration of the nano calcium carbonate is reduced, the dispersibility of the modified nano calcium carbonate is improved, and the using effect of the nano calcium carbonate is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Raw materials
SBS is styrene-butadiene-styrene triblock thermoplastic elastomer F475B selected from Dongguan Yuetai plastics materials Co., Ltd; PS is polypropylene ethylene PG-33, and polypropylene ethylene PG-33 is selected from Beijing Yanshan Xin Tianze chemical Co., Ltd; the polypropylene fiber is selected from Shanghai polypropylene fiber company; the petroleum resin is selected from Shanghai Australian industry Co., Ltd; the light stabilizer is light stabilizer 119, and the light stabilizer 119 is selected from Hangzhou landscape optimization engineering Co., Ltd; the antioxidant is antioxidant 1726 selected from TITAN-FREE COMBINATION CHEMICAL CORPORATION; the EVA is EVA3340, and the EVA3340 is selected from Dow; the initiator is dicumyl peroxide; the average particle size of the nano calcium carbonate is 50nm, and the nano calcium carbonate is selected from Shanghai Huizi sub-nano new materials Co; the coupling agent is isopropyl triisostearyl titanate.
TABLE 1 examples of the contents (unit: Kg) of respective raw materials of abrasion resistant rubber materials
| Raw materials | Example 1 | Example 2 | Example 3 |
| SBS | 38 | 46 | 55 |
| PS | 27 | 23 | 20 |
| Maleic anhydride graft modified EVA | 20.5 | 17.4 | 13 |
| Modified nano calcium carbonate | 4 | 5.6 | 6.5 |
| Polypropylene fiber | 1.5 | 1 | 0.5 |
| Petroleum resins | 6 | 5 | 4 |
| Additive agent | 3 | 2 | 1 |
Table 2 examples content (unit: Kg) of each raw material of maleic anhydride graft-modified EVA
| Raw materials | Example 1 | Example 4 | Example 5 |
| EVA | 90 | 95 | 100 |
| Anhydrous ethanol | 5 | 8 | 10 |
| Initiator | 1 | 1.9 | 3 |
| Maleic anhydride | 1 | 3.1 | 4 |
TABLE 3 examples the contents (unit: Kg) of the modified nano calcium carbonate in each raw material
| Raw materials | Example 1 | Example 6 | Example 7 |
| Water (W) | 90 | 95 | 100 |
| Anhydrous ethanol | 20 | 25 | 30 |
| Nano calcium carbonate | 10 | 16 | 20 |
| Coupling agent | 1 | 1.6 | 2 |
| Stearic acid | 3 | 4 | 5 |
Preparation example 1 of maleic anhydride graft-modified EVA
The maleic anhydride grafted modified EVA is prepared by the following method:
adding an initiator and maleic anhydride into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material A.
Heating EVA to 40 ℃ under the condition of continuous stirring, then adding the mixed material A into the EVA in a spraying mode, spraying the mixed material A within 30min, standing for 2h after the mixed material A is sprayed, continuously stirring, heating to 170 ℃, carrying out heat preservation treatment for 20min, cooling, and crushing to obtain the maleic anhydride graft modified EVA.
Preparation example 2 of maleic anhydride graft-modified EVA
The maleic anhydride grafted modified EVA is prepared by the following method:
adding an initiator and maleic anhydride into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material A.
Heating EVA to 45 ℃ under the condition of continuous stirring, then adding the mixed material A into the EVA in a spraying mode, spraying the mixed material A within 25min, standing for 1.5h after the mixed material A is sprayed, continuously stirring, heating to 175 ℃, carrying out heat preservation treatment for 15min, cooling, and crushing to obtain the maleic anhydride graft modified EVA.
Preparation example 3 of maleic anhydride graft-modified EVA
The maleic anhydride grafted modified EVA is prepared by the following method:
adding an initiator and maleic anhydride into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material A.
Heating EVA to 50 ℃ under the condition of continuous stirring, then adding the mixed material A into the EVA in a spraying mode, spraying the mixed material A within 20min, standing for 1h after the mixed material A is sprayed, continuously stirring, heating to 180 ℃, carrying out heat preservation treatment for 10min, cooling, and crushing to obtain the maleic anhydride graft modified EVA.
Preparation example 1 of modified Nano calcium carbonate
The modified nano calcium carbonate is prepared by the following method:
heating absolute ethyl alcohol to 30 ℃, adding stearic acid into the absolute ethyl alcohol, uniformly mixing, and carrying out heat preservation treatment for 20min to obtain a mixed material B.
Heating water to 60 ℃, adding a coupling agent into the water, uniformly mixing, then adding nano calcium carbonate, uniformly mixing, carrying out heat preservation treatment for 60min, and carrying out ultrasonic treatment for 20min to obtain a mixed material C.
Heating the mixed material C to 60 ℃ under the condition of continuous stirring, then adding the mixed material B into the mixed material C in a dropwise adding mode for multiple times, finishing dropwise adding the mixed material B within 50min, wherein the intermediate interval between two adjacent dropwise adding processes of the mixed material B is 10min, carrying out ultrasonic treatment in the intermediate interval between two adjacent dropwise adding processes of the mixed material B, after finishing dropwise adding of the mixed material B, carrying out heat preservation treatment for 70min, filtering and drying to obtain the modified nano calcium carbonate.
Preparation example 2 of modified Nano calcium carbonate
The modified nano calcium carbonate is prepared by the following method:
heating absolute ethyl alcohol to 35 ℃, adding stearic acid into the absolute ethyl alcohol, uniformly mixing, and carrying out heat preservation treatment for 15min to obtain a mixed material B.
Heating water to 65 ℃, adding a coupling agent into the water, uniformly mixing, then adding nano calcium carbonate, uniformly mixing, carrying out heat preservation treatment for 55min, and carrying out ultrasonic treatment for 15min to obtain a mixed material C.
Heating the mixed material C to 65 ℃ under the condition of continuous stirring, then adding the mixed material B into the mixed material C in a dropwise adding mode for multiple times, finishing dropwise adding the mixed material B within 60min, wherein the intermediate interval between two adjacent dropwise adding processes of the mixed material B is 10min, carrying out ultrasonic treatment within the intermediate interval between two adjacent dropwise adding processes of the mixed material B, after finishing dropwise adding of the mixed material B, carrying out heat preservation treatment for 80min, filtering and drying to obtain the modified nano calcium carbonate.
Preparation example 3 of modified Nano calcium carbonate
The modified nano calcium carbonate is prepared by the following method:
heating absolute ethyl alcohol to 40 ℃, adding stearic acid into the absolute ethyl alcohol, uniformly mixing, and carrying out heat preservation treatment for 10min to obtain a mixed material B.
Heating water to 70 ℃, adding a coupling agent into the water, uniformly mixing, then adding nano calcium carbonate, uniformly mixing, carrying out heat preservation treatment for 50min, and carrying out ultrasonic treatment for 10min to obtain a mixed material C.
Heating the mixed material C to 70 ℃ under the condition of continuous stirring, then adding the mixed material B into the mixed material C in a dropwise adding mode for multiple times, finishing dropwise adding the mixed material B within 60min, wherein the intermediate interval between two adjacent dropwise adding processes of the mixed material B is 20min, carrying out ultrasonic treatment within the intermediate interval between two adjacent dropwise adding processes of the mixed material B, after finishing dropwise adding of the mixed material B, carrying out heat preservation treatment for 90min, filtering and drying to obtain the modified nano calcium carbonate.
Example 1
The wear-resistant rubber material for the soles comprises the following raw materials in proportion as shown in table 1;
wherein, the maleic anhydride graft modification EVA adopts preparation example 1 of maleic anhydride graft modification EVA, and the raw material ratio of the maleic anhydride graft modification EVA is shown in Table 2;
the modified nano calcium carbonate is prepared by the method of preparation example 1 of modified nano calcium carbonate, and the raw material ratio of the modified nano calcium carbonate is shown in table 3; the additive adopts light stabilizer.
A preparation method of a wear-resistant rubber material for soles specifically adopts the following steps:
under the conditions of continuously stirring and 125 ℃, SBS, PS, maleic anhydride graft modified EVA and modified nano calcium carbonate are uniformly mixed, heat preservation treatment is carried out for 20min, then polypropylene fiber, petroleum resin and additives are added, uniform mixing is carried out, the temperature is raised to 170 ℃, heat preservation treatment is carried out for 10min, and the temperature is reduced, so that the wear-resistant rubber material is obtained.
Example 2
The raw material proportion of the wear-resistant rubber material for the sole is shown in table 1;
wherein, the maleic anhydride graft modification EVA adopts preparation example 2 of maleic anhydride graft modification EVA, and the raw material proportion of the maleic anhydride graft modification EVA is the same as that of the example 1;
the modified nano calcium carbonate is prepared by the preparation example 2 of the modified nano calcium carbonate, and the raw material proportion of the modified nano calcium carbonate is the same as that of the modified nano calcium carbonate in the example 1;
the additive adopts antioxidant.
A preparation method of a wear-resistant rubber material for soles specifically adopts the following steps:
under the conditions of continuously stirring and 130 ℃, SBS, PS, maleic anhydride graft modified EVA and modified nano calcium carbonate are uniformly mixed, heat preservation treatment is carried out for 15min, then polypropylene fiber, petroleum resin and additives are added, uniform mixing is carried out, the temperature is raised to 175 ℃, heat preservation treatment is carried out for 6min, and the temperature is reduced, so that the wear-resistant rubber material is obtained.
Example 3
The wear-resistant rubber material for the soles comprises the following raw materials in proportion as shown in table 1;
wherein, the maleic anhydride graft modification EVA adopts preparation example 3 of maleic anhydride graft modification EVA, and the raw material ratio of the maleic anhydride graft modification EVA is the same as that of the example 1;
the modified nano calcium carbonate is prepared in preparation example 3, and the raw material ratio of the modified nano calcium carbonate is the same as that in example 1;
the additive adopts antioxidant.
A preparation method of a wear-resistant rubber material for soles specifically adopts the following steps:
under the conditions of continuous stirring and 135 ℃ temperature, SBS, PS, maleic anhydride graft modified EVA and modified nano calcium carbonate are uniformly mixed, heat preservation treatment is carried out for 10min, then polypropylene fiber, petroleum resin and additives are added, uniform mixing is carried out, the temperature is raised to 180 ℃, heat preservation treatment is carried out for 3min, and the temperature is reduced, so that the wear-resistant rubber material is obtained.
Example 4
The difference between the embodiment and the embodiment 2 is that the raw material proportion of the maleic anhydride grafted modified EVA is shown in Table 2.
Example 5
The difference between the embodiment and the embodiment 2 is that the raw material proportion of the maleic anhydride grafted modified EVA is shown in Table 2.
Example 6
The embodiment of the wear-resistant rubber material for the shoe sole is different from the embodiment 4 in that the raw material proportion of the modified nano calcium carbonate is shown in Table 3.
Example 7
The embodiment of the wear-resistant rubber material for the shoe sole is different from the embodiment 4 in that the raw material proportion of the modified nano calcium carbonate is shown in Table 3.
Example 8
An application of a wear-resistant rubber material for soles, wherein the wear-resistant rubber material is used for soles of women's shoes.
Comparative example 1
The comparative example and the example 6 are different in that maleic anhydride graft modified EVA is not added in the raw material of the wear-resistant rubber material.
Comparative example 2
A wear-resistant rubber material for shoe soles, which is different from that of example 6 in that the maleic anhydride graft-modified EVA was replaced with an equivalent amount of EVA in the raw material of the wear-resistant rubber material.
Comparative example 3
The comparative example and the example 6 are characterized in that the modified nano calcium carbonate is not added in the raw materials of the wear-resistant rubber material.
Comparative example 4
The difference between the comparative example and the example 6 is that the raw materials of the wear-resistant rubber material are modified with the same amount of nano calcium carbonate instead of the nano calcium carbonate.
Comparative example 5
The difference between the comparative example and the example 6 is that maleic anhydride graft modified EVA and modified nano calcium carbonate are not added in the raw materials of the wear-resistant rubber material.
Samples were prepared for the abrasion resistant rubber materials for shoe soles of examples 1 to 7 and comparative examples 1 to 5, and the following property tests were carried out, and the test results are shown in table 4.
Wherein, the tensile strength is detected according to GB/T528-2009 determination of vulcanized rubber or thermoplastic rubber-tensile stress strain performance;
GB/T531-2008 'vulcanized rubber or thermoplastic rubber-press-in hardness test method' for Shore hardness detection; GB/T689 2014 (for determination of abrasion resistance of vulcanized rubber) performs abrasion volume detection.
TABLE 4 test results
| Detecting items | Tensile Strength/(MPa) | Shore hardness/(mN) | Abrasion volume/(cm)3/1.61km) |
| Example 1 | 19.1 | 91.6 | 0.277 |
| Example 2 | 19.8 | 92.3 | 0.268 |
| Example 3 | 18.3 | 90.5 | 0.273 |
| Example 4 | 20.8 | 92.4 | 0.265 |
| Example 5 | 20.5 | 92.3 | 0.263 |
| Example 6 | 21.5 | 94.6 | 0.246 |
| Example 7 | 21.1 | 94.2 | 0.253 |
| Comparative example 1 | 18.9 | 85.9 | 0.248 |
| Comparative example 2 | 18.7 | 85.8 | 0.249 |
| Comparative example 3 | 20.3 | 91.9 | 0.553 |
| Comparative example 4 | 18.1 | 85.8 | 0.347 |
| Comparative example 5 | 18.5 | 86.1 | 0.544 |
As can be seen from Table 4, the wear-resistant rubber material of the present application has good tensile strength and Shore hardness, the tensile strength is up to 21.5MPa, the Shore hardness is up to 94.6mN, and the wear-resistant rubber material also has a low wear volume, the wear volume is 0.246cm at least3/1.61km。
Comparing the example 6 with the comparative examples 1-2, it can be seen that the tensile strength and shore hardness of the wear-resistant rubber material can be significantly improved by adding the maleic anhydride graft modified EVA to the raw material of the wear-resistant rubber material, probably because the molecular weight of PS is much larger than that of the PS block in SBS, so that PS is difficult to enter SBS, and forms three phases, and the structure of SBS is damaged, and the maleic anhydride graft modified EVA is added to SBS and PS, and plays a good role as a medium in SBS and PS, so that the compatibility and bonding strength of SBS and PS are increased, and the tensile strength and shore hardness of the wear-resistant rubber material are improved.
Comparing example 6 with comparative examples 3 to 4, it can be seen that the addition of the modified nano calcium carbonate to the raw material of the wear-resistant rubber material can significantly reduce the wear-resistant volume of the wear-resistant rubber material and improve the tensile strength and shore hardness of the wear-resistant rubber material, mainly because the nano calcium carbonate can increase the wear resistance of the wear-resistant rubber material, but the nano calcium carbonate is easy to agglomerate in the wear-resistant rubber material and affect the dispersibility of the nano calcium carbonate and the compatibility of the nano calcium carbonate and the wear-resistant rubber material.
Comparing example 6 with comparative example 1 and comparative example 5, it can be seen that the addition of maleic anhydride graft modified EVA and modified nano calcium carbonate to the raw materials of the wear-resistant rubber material can significantly improve the tensile strength and shore hardness of the wear-resistant rubber material and significantly reduce the wear-resistant volume of the wear-resistant rubber material, which is mainly due to the synergistic effect between the maleic anhydride graft modified EVA and the modified nano calcium carbonate.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.
Claims (5)
1. The wear-resistant rubber material for the soles is characterized in that: the raw materials of the wear-resistant rubber material comprise, by weight, 38-55 parts of SBS, 20-27 parts of PS, 13-20.5 parts of maleic anhydride graft modified EVA, 4-6.5 parts of modified nano calcium carbonate, 0.5-1.5 parts of polypropylene fiber, 4-6 parts of petroleum resin and 1-3 parts of additive;
the raw materials of the maleic anhydride graft modification EVA comprise 90-100 parts of EVA, 5-10 parts of absolute ethyl alcohol, 1-3 parts of initiator and 1-4 parts of maleic anhydride;
the maleic anhydride grafted and modified EVA is prepared by the following method:
adding an initiator and maleic anhydride into absolute ethyl alcohol, and uniformly mixing to obtain a mixed material A; heating EVA to 40-50 ℃ under the condition of continuous stirring, then adding the mixed material A into the EVA in a spraying mode, completing spraying of the mixed material A within 20-30min, standing for 1-2h after completing spraying of the mixed material A, continuing stirring, heating to 170-180 ℃, performing heat preservation for 10-20min, cooling, and crushing to obtain maleic anhydride graft modified EVA;
the modified nano calcium carbonate comprises, by weight, 90-100 parts of water, 20-30 parts of absolute ethyl alcohol, 10-20 parts of nano calcium carbonate, 1-2 parts of a coupling agent and 3-5 parts of stearic acid; the coupling agent is isopropyl triisostearoyl titanate;
the modified nano calcium carbonate is prepared by the following method:
heating absolute ethanol to 30-40 deg.C, adding stearic acid into the absolute ethanol, mixing, and maintaining the temperature for 10-20min to obtain mixture B; heating water to 60-70 ℃, adding a coupling agent into the water, uniformly mixing, then adding nano calcium carbonate, uniformly mixing, carrying out heat preservation treatment for 50-60min, and carrying out ultrasonic treatment for 10-20min to obtain a mixed material C; heating the mixed material C to 60-70 ℃ under the condition of continuous stirring, then adding the mixed material B into the mixed material C in a dropwise adding mode for multiple times, finishing dropwise adding the mixed material B within 50-60min, wherein the intermediate interval between two adjacent dropwise adding processes of the mixed material B is 10-20min, carrying out ultrasonic treatment within the intermediate interval between two adjacent dropwise adding processes of the mixed material B, carrying out heat preservation treatment for 70-90min after the dropwise adding processes of the mixed material B are finished, filtering and drying to obtain the modified nano calcium carbonate.
2. The wear-resistant rubber material for soles according to claim 1, wherein: the initiator is dicumyl peroxide.
3. The wear-resistant rubber material for soles according to claim 1, wherein: the additive is one or two of a light stabilizer and an antioxidant.
4. A method for preparing the wear-resistant rubber material for shoe soles according to any one of claims 1 to 3, characterized in that: the method specifically comprises the following steps:
under the conditions of continuous stirring and the temperature of 125-.
5. Use of a wear-resistant rubber material for soles according to any one of claims 1 to 3, characterized in that: the wear-resistant rubber material is used for soles of women's shoes.
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| CN113105713A (en) * | 2021-02-23 | 2021-07-13 | 温州程泓鞋业有限公司 | Sandal with wear-resistant sole and preparation method thereof |
| CN115246978B (en) * | 2021-04-25 | 2023-10-03 | 江苏汉德纳米材料科技有限公司 | Uniform and stable wear-resistant TPE material and preparation method thereof |
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| CN1454928A (en) * | 2003-05-14 | 2003-11-12 | 阳范文 | Ultrahigh wear-resistant thermoplastic rubber sole material |
| CN104448671A (en) * | 2014-12-19 | 2015-03-25 | 东莞市国立科技有限公司 | Low-cost and high-wear-resistance TPR modified material and preparation method thereof |
| CN107033520A (en) * | 2016-10-21 | 2017-08-11 | 广西师范学院 | The preparation method of wear-resisting SBS material for sole of shoe |
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| CA2635236A1 (en) * | 2006-07-26 | 2008-01-30 | Ube Industries, Ltd. | Rubber composition for shoe sole and rubber foam composition |
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| CN104448671A (en) * | 2014-12-19 | 2015-03-25 | 东莞市国立科技有限公司 | Low-cost and high-wear-resistance TPR modified material and preparation method thereof |
| CN107033520A (en) * | 2016-10-21 | 2017-08-11 | 广西师范学院 | The preparation method of wear-resisting SBS material for sole of shoe |
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