CN114773829A - Wear-resistant sole and preparation method thereof - Google Patents
Wear-resistant sole and preparation method thereof Download PDFInfo
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- CN114773829A CN114773829A CN202210549402.1A CN202210549402A CN114773829A CN 114773829 A CN114773829 A CN 114773829A CN 202210549402 A CN202210549402 A CN 202210549402A CN 114773829 A CN114773829 A CN 114773829A
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- 238000002360 preparation method Methods 0.000 title claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000463 material Substances 0.000 claims abstract description 61
- 239000010439 graphite Substances 0.000 claims abstract description 58
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 13
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 12
- 229920001194 natural rubber Polymers 0.000 claims abstract description 12
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 6
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- 239000004014 plasticizer Substances 0.000 claims abstract description 5
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 36
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 229920001971 elastomer Polymers 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- YVOFTMXWTWHRBH-UHFFFAOYSA-N pentanedioyl dichloride Chemical compound ClC(=O)CCCC(Cl)=O YVOFTMXWTWHRBH-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 17
- 230000032683 aging Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 125000003368 amide group Chemical group 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000001069 triethyl citrate Substances 0.000 description 3
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 3
- 235000013769 triethyl citrate Nutrition 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
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)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The application relates to the technical field of shoes, and discloses a wear-resistant sole, which is prepared from the following components in parts by weight: 50-100 parts of TPU particles; 20-30 parts of natural rubber; 10-30 parts of PVC particles; 10-20 parts of a plasticizer; 3-6 parts of a stabilizer; 1-2 parts of a crosslinking agent; 20-40 parts of a filler; 0-1 part of lubricant; 1-2 parts of a vulcanizing agent; 1-2 parts of an anti-aging agent; 5-30 parts of modified graphite. The method can improve the dispersion performance of the graphite in the TPU material.
Description
Technical Field
The application relates to the technical field of shoes, in particular to a wear-resistant sole and a preparation method thereof.
Background
The TPU micro-foaming material has extremely excellent elasticity and lower permanent deformation, so that the TPU micro-foaming material has been widely used for replacing EVA foaming materials in the fields of running shoes and sports protection.
The graphite resource in nature is rich, and is an important nonmetallic mineral resource. The graphite has unique performance and low price and is widely applied in production and life. Graphite can be used as a filler for TPU materials to improve their properties. The graphite is used as a lubricant, so that the friction factor of the TPU material can be reduced, the wear resistance of the TPU material is improved, and the service life of a TPU product is effectively prolonged.
However, the graphite has high surface energy and self-aggregation, the graphite is easy to agglomerate when being added into a TPU product, a great amount of cracks can be generated in a TPU material due to the addition of the graphite, and the TPU material can be peeled off in the using process, so that the use of the graphite in the TPU material is limited, and the improvement is needed.
Disclosure of Invention
In order to improve the dispersion performance of graphite in a TPU material, the application provides a wear-resistant sole and a preparation method thereof.
In a first aspect, the application provides a wear-resistant sole which adopts the following technical scheme:
a wear-resistant sole is prepared from the following components in parts by weight: 50-100 parts of TPU particles; 20-30 parts of natural rubber; 10-30 parts of PVC particles; 10-20 parts of a plasticizer; 3-6 parts of a stabilizer; 1-2 parts of a crosslinking agent; 20-40 parts of a filler; 0-1 part of lubricant; 1-2 parts of a vulcanizing agent; 1-2 parts of an anti-aging agent; 5-30 parts of modified graphite;
the preparation process of the modified graphite comprises the following steps:
s1 oxidation: adding graphite with the particle size of 0.05-0.15mm into 3-6wt% nitric acid solution, stirring at 60-80 deg.C for 1.5-2.5h, filtering to obtain precipitate, and washing with water to neutrality to obtain graphite oxide;
s2 grafting: dissolving glutaryl chloride in ethanol solution to form 15-20wt% of mixed solution, adding graphite oxide prepared by expansion of S1 into the mixed solution, stirring at 50-70 ℃ to keep the reaction for 2-3h, standing for layering after the reaction is finished, filtering to obtain precipitate, and drying to obtain the modified graphite.
By adopting the technical scheme, the TPU material has good elasticity, toughness and adhesive force, and the sole made of the TPU material has good anti-skid property and wear resistance. Graphite is added into the TPU sole material, the graphite can form a lubricating film on the surface of the sole material, the lubricating film can reduce the direct contact between the sole material and a friction surface, the friction is generated between the lubricating film and a contact surface, and therefore, the sole is not easy to be worn, and the wear resistance of the sole material is improved. However, graphite has a strong self-aggregation capability, and the graphite is easy to agglomerate when being added into a TPU product.
The graphite is oxidized by nitric acid to obtain graphite oxide, and the surface of the graphite oxide has active groups such as hydroxyl groups. Meanwhile, in the process of oxidizing graphite by nitric acid, the nitric acid is inserted between adjacent graphite molecular layers, so that the graphite molecular layers are dispersed, and the agglomeration phenomenon among the graphite molecular layers is reduced. Then, the dispersed graphite oxide reacts with glutaryl chloride, so that the glutaryl chloride is grafted on the surface of the graphite oxide, the glutaryl chloride can be chemically bonded with terminal amino or amide groups in the TPU material, the binding capacity of the graphite oxide and the TPU material is improved, and the interface compatibility of the graphite oxide and the TPU material is improved.
After the graphite is modified, the dispersibility of the graphite can be improved, and the compatibility of the graphite and the TPU material can be improved, so that the wear-resisting effect of the graphite on the TPU material is improved.
In addition, glutaryl chloride molecules can be chemically bonded with terminal amino groups of different TPU molecules at the same time, so that a three-dimensional network cross-linking structure is formed among the TPU molecules, the cross-linking degree among the TPU molecules is improved, and active groups in the TPU molecules are reduced, so that the tensile strength and the aging resistance of the TPU molecules are improved.
Optionally, the vulcanizing agent is an accelerator TMTD.
By adopting the technical scheme, the vulcanization effect of the accelerator TMTD is good.
Optionally, the wear-resistant sole raw material system further comprises 3-5 parts by weight of ethylenediamine.
By adopting the technical scheme, active amido groups in the ethylene diamine molecules can be chemically bonded with glutaryl chloride and can also be subjected to addition reaction with terminal amido groups of TPU molecules, so that a certain cross-linked net structure is formed between the glutaryl chloride molecules and the TPU molecules, the sole material is not easily abraded, and the wear resistance and tensile strength of the sole material are improved.
Optionally, the wear-resistant sole raw material system further comprises 6-8 parts by weight of magnesium alloy particles, and the particle size of the magnesium alloy particles is 20-500 meshes.
By adopting the technical scheme, the magnesium alloy has the advantages of small density, specific strength, specific stiffness, abundant resources and the like, and can form micro-protrusions on the surface of the sole material, so that the anti-skid performance of the sole material is improved. In addition, the ethylene diamine molecules and the magnesium atoms are easy to generate complex reaction, so that the interface bonding capability of the magnesium atoms and the TPU material is improved, the sole material is not easy to abrade and peel off, and the wear resistance of the sole material is improved.
Optionally, the particle size of the magnesium alloy particles is 200-300 meshes.
By adopting the technical scheme, when the magnesium alloy particles are large, the surface of the sole material is rough, the bonding capability of the magnesium alloy and the sole material is not enough, and when the magnesium alloy particles are small, the wear resistance of the magnesium alloy in the sole material is not obvious and agglomeration is easy to occur. Through tests, when the granularity of the magnesium alloy particles is 200-300 meshes, the prepared sole material has better anti-skid performance.
Optionally, the surface of the magnesium alloy is modified as follows: dissolving thiourea in ethanol, adding the magnesium alloy into a thiourea/ethanol mixed solution, adding a dispersing agent, stirring uniformly, standing to react for 30-50min, and filtering to obtain the thiourea-coated magnesium alloy.
By adopting the technical scheme, the thiourea can form chemical bonding with the TPU material, and the thiourea is coated on the surface of the magnesium alloy, so that the magnesium alloy and the sole material have better compatibility, the agglomeration of the magnesium alloy can be reduced, and the surface energy of the magnesium alloy can be reduced. In addition, the amide group in the thiourea molecule can be chemically bonded with the amine group in the TPU molecule and the terminal hydroxyl group in the natural rubber molecule, so that a cross-linked net structure is formed among the sole materials, the cross-linking degree of the sole materials is improved, and the anti-aging performance and the tensile strength of the sole materials are obviously improved.
In a second aspect, the application provides a preparation method of a wear-resistant sole, which adopts the following technical scheme:
the preparation method of the wear-resistant sole comprises the following steps:
s1, mixing: putting TPU particles, natural rubber and PVC particles into an open mill according to the weight parts required by the formula, and mixing for 20-25min at the temperature of 60-70 ℃ to obtain a rubber compound;
coupling of S2: mixing the rubber compound, the filler, the cross-linking agent, the lubricant, the plasticizer, the stabilizer and the anti-aging agent, heating to 70-80 ℃, and continuously mixing for 10-15min to obtain semi-rubber;
s3 vulcanization: mixing the semi-gel, a vulcanizing agent and the modified graphite, and vulcanizing at 150-180 ℃ for 18-20min to obtain a wear-resistant sole material;
s4 cutting: and cutting and molding the wear-resistant sole material to obtain the wear-resistant sole.
In summary, the present application includes at least one of the following beneficial technical effects:
1. after the graphite is modified, the dispersibility of the graphite can be improved, and the compatibility of the graphite and a TPU material can be improved, so that the wear-resistant effect of the graphite on the TPU material is improved;
2. the amino group can be chemically bonded with glutaryl chloride and can also perform addition reaction with the terminal amide group of the TPU molecule, so that a certain cross-linked network structure is formed between the glutaryl chloride molecule and the TPU molecule;
3. the ethylene diamine molecules and the magnesium atoms are easy to generate a complex reaction, so that the interface bonding capability of the magnesium atoms and the TPU material is improved, the sole material is not easy to abrade and peel off, and the wear resistance of the sole material is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
The embodiment of the application adopts the following raw materials:
preparation example
Preparation example 1
The preparation process of the modified graphite comprises the following steps:
s1 oxidation: adding graphite with the particle size of 0.05mm into a 3 wt% nitric acid solution, stirring for 1.5h at 60 ℃, then filtering to obtain a precipitate, and washing to neutrality to obtain graphite oxide;
s2 grafting: dissolving glutaryl chloride in an ethanol solution to form a 15 wt% mixed solution, completely soaking the graphite oxide prepared by S1 in the mixed solution, stirring and reacting for 2 hours at 50 ℃, standing and layering after the reaction is finished, finally filtering to obtain a precipitate, and drying to obtain the modified graphite.
Preparation example 2:
the preparation process of the modified graphite comprises the following steps:
s1 oxidation: adding graphite with the particle size of 0.1mm into a 4.5 wt% nitric acid solution, stirring for 2.0h at 70 ℃, then filtering to obtain a precipitate, and washing to neutrality to obtain graphite oxide;
s2 grafting: dissolving glutaryl chloride in an ethanol solution to form a 17.5 wt% mixed solution, then completely immersing the graphite oxide prepared by S1 in the mixed solution, stirring and reacting for 2.5h at 60 ℃, standing and layering after the reaction is finished, finally filtering to obtain a precipitate, and drying to obtain the modified graphite.
Preparation example 3:
the preparation process of the modified graphite comprises the following steps:
s1 oxidation: adding graphite with the particle size of 0.15mm into a 6wt% nitric acid solution, stirring for 2.5h at the temperature of 80 ℃, filtering to obtain a precipitate, and washing to be neutral to obtain graphite oxide;
s2 grafting: dissolving glutaryl chloride in an ethanol solution to form a 20wt% mixed solution, then completely immersing the graphite oxide prepared by S1 in the mixed solution, stirring and reacting for 3 hours at 70 ℃, standing and layering after the reaction is finished, finally filtering to obtain a precipitate, and drying to obtain the modified graphite.
Preparation example 4:
the preparation process of the thiourea-coated magnesium alloy comprises the following steps:
dissolving thiourea in ethanol to form a saturated solution, then immersing the magnesium alloy into a thiourea/ethanol mixed solution, adding a dispersing agent, stirring uniformly, standing to react for 40min, and filtering to obtain the thiourea-coated magnesium alloy.
Preparation example 5:
the preparation process of the graphite oxide comprises the following steps: adding graphite with the particle size of 0.15mm into a 6wt% nitric acid solution, stirring for 2.5h at the temperature of 80 ℃, then filtering to obtain a precipitate, and washing to be neutral to obtain the graphite oxide.
Examples
Example 1:
the wear-resistant sole comprises the raw material components shown in the table 1.
A preparation method of a wear-resistant sole comprises the following steps:
s1, mixing: putting TPU particles, natural rubber and PVC particles into an open mill according to the weight parts required by the formula, and mixing for 20min at the temperature of 60 ℃ to obtain mixed rubber;
coupling of S2: mixing the mixed rubber, white carbon black, dicumyl peroxide, paraffin, triethyl citrate, stearic acid and p-phenylenediamine, heating to 70 ℃, and continuously mixing for 10min to obtain semi-rubber;
s3 vulcanization: mixing the semi-gel, the accelerant TMTD and the modified graphite prepared in the preparation example 1, and vulcanizing at 150 ℃ for 18min to obtain a wear-resistant sole material;
s4 cutting: and cutting and molding the wear-resistant sole material to obtain the wear-resistant sole.
Wherein: the grade of TPU particles is 8798, the grade of PVC particles is MG701-7AB990, the type of natural rubber is 3L, and the physical and chemical properties of graphite are as follows: the density was 2.25g/cm3The ash content is 0.5 percent, the scale size is 0.18mm, and the specification is 80 meshes.
Example 2:
a preparation method of a wear-resistant sole comprises the following steps:
s1, mixing: putting TPU particles, natural rubber and PVC particles into an open mill according to the weight parts required by the formula, and mixing for 22min at the temperature of 65 ℃ to obtain mixed rubber;
coupling of S2: mixing the mixed rubber, white carbon black, dicumyl peroxide, paraffin, triethyl citrate, stearic acid and p-phenylenediamine, heating to 75 ℃, and continuously mixing for 12min to obtain semi-finished rubber;
s3 vulcanization: mixing the semi-gel, the accelerant TMTD and the modified graphite prepared in the preparation example 2, and vulcanizing at 165 ℃ for 19min to obtain a wear-resistant sole material;
s4 cutting: and cutting and molding the wear-resistant sole material to obtain the wear-resistant sole.
Wherein: the grade of TPU particles is 8798, the grade of PVC particles is MG701-7AB990, the type of natural rubber is 3L, and the physical and chemical properties of graphite are as follows: the density is 2.25g/cm3The ash content is 0.5 percent, the scale size is 0.18mm, and the specification is 80 meshes.
Example 3:
a preparation method of a wear-resistant sole comprises the following steps:
s1 mixing: putting TPU particles, natural rubber and PVC particles into an open mill according to the weight parts required by the formula, and mixing for 25min at the temperature of 70 ℃ to obtain mixed rubber;
coupling of S2: mixing the mixed rubber, white carbon black, dicumyl peroxide, paraffin, triethyl citrate, stearic acid and p-phenylenediamine, heating to 80 ℃, and continuously mixing for 15min to obtain semi-rubber;
s3 vulcanization: mixing the semi-gel, the accelerant TMTD and the modified graphite prepared in the preparation example 3, and vulcanizing at 180 ℃ for 20min to obtain a wear-resistant sole material;
s4 cutting: and cutting and molding the wear-resistant sole material to obtain the wear-resistant sole.
Wherein: the grade of TPU particles is 8798, the grade of PVC particles is MG701-7AB990, the type of natural rubber is 3L, and the physical and chemical properties of graphite are as follows: the density was 2.25g/cm3The ash content is 0.5 percent, the scale size is 0.18mm, and the specification is 80 meshes.
Example 4:
the difference from example 2 is that ethylenediamine was added during the kneading of S1.
Example 5:
the difference from the example 4 is that magnesium alloy particles are added in the mixing process of S1, and the particle size of the magnesium alloy particles is 100 meshes.
Example 6:
the difference from example 5 is that the particle size of the magnesium alloy particles was 250 mesh.
Example 7:
the difference from example 6 is that ethylenediamine was not added to the raw material system.
Example 8:
the difference from example 6 is that the magnesium alloy and the like were mass-replaced with the thiourea-coated magnesium alloy prepared in preparation example 4.
Comparative example
Comparative example 1:
the difference from example 2 is that: the modified graphite obtained in preparation example 2 was replaced with graphite in equal mass.
Comparative example 2:
the difference from example 2 is that: the modified graphite obtained in preparation example 2 and the like were replaced by the graphite oxide obtained in preparation example 5.
The raw material formulation in examples 1 to 8 and comparative examples 1 to 2 is shown in Table 1.
Table 1 raw material table
TABLE 1 continuation
And (3) testing the performance of the wear-resistant sole:
the soles of examples 1-8 and comparative examples 1-2 were tested according to the method described in GB/T3903.6-2017 "method for testing the grip performance of shoes in the entire shoes" for shoes ", the test interface was the ceramic tile interface, the test medium used three-stage water in the wet interface test, the test mode was horizontal, and the results are shown in Table 2.
The abrasion resistance (Akron abrasion) of the sole was tested according to the method described in GB/T1689 2014 abrasion resistance test for vulcanized rubber (Acron abrasion tester).
The anti-aging properties of the sole materials were characterized by testing the rate of change in tensile strength before and after aging treatment in examples 1 to 8 and comparative examples 1 to 2 according to the method described in GB/T3903.22-2008 "test methods for outsole of footwear tensile Strength and elongation", the aging treatment procedure being as follows: each sole sample was heated at 100 ℃ for 12h, respectively, and the results are reported in Table 2.
As can be seen from table 2:
1. the test data of examples 1-3 and comparative example 1 can be obtained, and the wear resistance and the ageing resistance of the sole material prepared by modifying the graphite are both obviously improved.
2. The test data of examples 1-3 and comparative example 2 can show that the wear resistance of the sole material prepared by grafting the graphite oxide with glutaryl chloride is improved to a certain extent, and the ageing resistance is obviously improved.
3. The test data of the embodiment 4 and the embodiment 2 can be obtained, and the wear resistance and the aging resistance of the sole are obviously improved by adding the ethylenediamine into the raw material system of the sole.
4. The test data of the embodiment 5 and the embodiment 4 can obtain that after the magnesium alloy is added into the raw material system of the sole, the dry friction coefficient and the wet friction coefficient of the prepared sole are obviously improved, so that the anti-skid performance of the sole is improved.
5. The test data of the embodiment 6 and the embodiment 5 can show that when the granularity of the magnesium alloy particles is 250 meshes, the prepared sole material has better wear resistance, skid resistance and ageing resistance.
6. Comparing the test data of examples 1-3 with that of example 7, the anti-skid property of the sole material obtained by adding the magnesium alloy particles to the sole material is obviously improved, but the anti-aging property is slightly reduced.
7. The test data of the embodiment 7 and the embodiment 6 can obtain that the wear resistance and the ageing resistance of the sole material prepared by adding the ethylenediamine into the raw material system of the magnesium alloy are obviously improved.
8. The test data of the embodiment 8 and the embodiment 6 can obtain that the wear resistance and the ageing resistance of the sole material prepared by the magnesium alloy after thiourea coating treatment are obviously improved.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: equivalent changes in structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (8)
1. A wear-resisting sole which is characterized in that: the composition is prepared from the following components in parts by weight: 50-100 parts of TPU particles; 20-30 parts of natural rubber; 10-30 parts of PVC particles; 10-20 parts of a plasticizer; 3-6 parts of a stabilizer; 1-2 parts of a crosslinking agent; 20-40 parts of a filler; 0-1 part of a lubricant; 1-2 parts of a vulcanizing agent; 1-2 parts of an anti-aging agent; 5-30 parts of modified graphite;
the preparation process of the modified graphite comprises the following steps:
s1 oxidation: adding graphite with the particle size of 0.05-0.15mm into 3-6wt% nitric acid solution, stirring at 60-80 deg.C for 1.5-2.5h, filtering to obtain precipitate, and washing with water to neutrality to obtain graphite oxide;
s2 grafting: dissolving glutaryl chloride in ethanol solution to form 15-20wt% of mixed solution, then adding the graphite oxide prepared by S1 into the mixed solution, stirring at 50-70 ℃ to keep the reaction for 2-3h, standing for layering after the reaction is finished, finally filtering to obtain precipitate, and drying to obtain the modified graphite.
2. A wear-resistant sole as claimed in claim 1, wherein: the vulcanizing agent is an accelerator TMTD.
3. A wear-resistant sole as claimed in claim 1, wherein: the wear-resistant sole comprises 3-5 parts by weight of ethylenediamine.
4. A wear-resistant sole as claimed in claim 3, wherein: the wear-resistant sole comprises a raw material system and is characterized in that the raw material system of the wear-resistant sole also comprises 6-8 parts of magnesium alloy particles by weight, and the particle size of the magnesium alloy particles is 20-500 meshes.
5. A wear-resistant sole as claimed in claim 4, wherein: the particle size of the magnesium alloy particles is 200-300 meshes.
6. A wear-resistant sole as claimed in claim 4, wherein: the surface of the magnesium alloy is modified as follows: dissolving thiourea in ethanol, adding the magnesium alloy into a thiourea/ethanol mixed solution, adding a dispersing agent, uniformly stirring, standing to react for 30-50min, and filtering to obtain the thiourea-coated magnesium alloy.
7. A method for preparing a wear-resistant sole according to any one of claims 1-2, wherein: the method comprises the following steps:
s1 mixing: putting TPU particles, natural rubber and PVC particles into an open mill according to the weight parts required by the formula, and mixing for 20-25min at the temperature of 60-70 ℃ to obtain a rubber compound;
coupling of S2: mixing the rubber compound, the filler, the cross-linking agent, the lubricant, the plasticizer, the stabilizer and the anti-aging agent, heating to 70-80 ℃, and continuing to mix for 10-15min to obtain semi-gel;
s3 vulcanization: mixing the semi-gel, a vulcanizing agent and the modified graphite, and vulcanizing at 150-180 ℃ for 18-20min to obtain a wear-resistant sole material;
s4 cutting: and cutting and molding the wear-resistant sole material to obtain the wear-resistant sole.
8. The method for preparing a wear-resistant sole according to claim 7, wherein: in the S1 mixing process, 3-5 parts of ethylenediamine and 6-8 parts of magnesium alloy particles are added into the raw material system together according to the parts by weight.
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Denomination of invention: A wear-resistant sole and its preparation method Effective date of registration: 20231212 Granted publication date: 20231208 Pledgee: Zhejiang Tailong Commercial Bank Co.,Ltd. Wenzhou Ouhai Louqiao small and micro franchise sub branch Pledgor: Wenzhou Tianma New Material Technology Co.,Ltd. Registration number: Y2023980070720 |