CN117487339A - High-strength wear-resistant shoe material and preparation method thereof - Google Patents
High-strength wear-resistant shoe material and preparation method thereof Download PDFInfo
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- CN117487339A CN117487339A CN202311437574.0A CN202311437574A CN117487339A CN 117487339 A CN117487339 A CN 117487339A CN 202311437574 A CN202311437574 A CN 202311437574A CN 117487339 A CN117487339 A CN 117487339A
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000000945 filler Substances 0.000 claims abstract description 25
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000004611 light stabiliser Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 32
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 238000002390 rotary evaporation Methods 0.000 claims description 17
- 239000000543 intermediate Substances 0.000 claims description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 15
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims description 13
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- QUKGLNCXGVWCJX-UHFFFAOYSA-N 1,3,4-thiadiazol-2-amine Chemical compound NC1=NN=CS1 QUKGLNCXGVWCJX-UHFFFAOYSA-N 0.000 claims description 12
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 claims description 12
- 238000005299 abrasion Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002250 absorbent Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000004200 microcrystalline wax Substances 0.000 claims description 2
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 abstract description 16
- 229920002635 polyurethane Polymers 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000155 melt Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 2
- 238000004073 vulcanization Methods 0.000 abstract description 2
- 230000001133 acceleration Effects 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000010907 mechanical stirring Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical group [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical group O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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 invention relates to a high-strength wear-resistant shoe material and a preparation method thereof, belonging to the technical field of high polymer materials. The adhesive comprises the following components in parts by weight: 100 parts of polyurethane rubber, 14-18 parts of metal-based filler, 2.6-3.4 parts of wear-resistant auxiliary agent, 1.2-1.5 parts of coupling agent, 0.1-0.15 part of light stabilizer, 0.15-0.2 part of antioxidant, 3-4 parts of lubricant and 1-1.5 parts of release agent; the wear-resistant auxiliary agent captures metal-based filler in melt in the melt blending process to form an organic-inorganic combination body, and the quaternary ammonium structure at the molecular end part of the wear-resistant auxiliary agent has an acceleration effect on vulcanization of polyurethane rubber, so that the polyurethane rubber is fully crosslinked in a near layer of the organic-inorganic combination body, the combination strength of the combination body and a polyurethane matrix is enhanced, the wear-resistant effect of the filler is enhanced, the influence on the elastic performance of the polyurethane matrix is small, and the wear-resistant auxiliary agent has better comfort when applied to sole materials.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-strength wear-resistant shoe material and a preparation method thereof.
Background
With the development of social economy and the improvement of living standard, people's consciousness of scientific shoes is continuously improved, and besides pursuing fashion, people pay more attention to the comfort of shoes. Many factors affect the comfort of footwear, in which the sole is in direct contact with the ground, transmitting the impact of a falling foot, the properties of the sole material largely determining the comfort of wearing the footwear.
Polyurethane rubber is a novel elastomer material with rubber and plastic characteristics, has good rebound resilience, tolerance and mechanical property, and is widely applied to sole materials. However, the sole is in direct contact with the ground, and particularly in running, ball playing, etc., the sole and the ground have a large friction, and wear of the sole results in insufficient protection for the foot, resulting in a reduced wear life of the shoe. In the prior art, in order to solve the abrasion problem of the polyurethane sole, the abrasion resistance of polyurethane is generally enhanced by doping abrasion-resistant fillers such as calcium carbonate, glass powder and the like, and meanwhile, the compatibility of the fillers and a matrix is improved by compounding the dispersing agent, so that the uniform enhancement effect is achieved, and the abrasion of sole materials is slowed down to a certain extent. However, the added wear-resistant material is rigid particles, and the polyurethane is reinforced to a certain extent through cohesion combination after polyurethane solidification, so that the mechanical strength is increased, and the wear resistance is improved, but the elasticity of the polyurethane matrix is reduced due to the rigid particle liquid, so that the material is hardened, and the rebound resilience is reduced; in addition, under the condition of repeated stress deformation, the rigid particles and the polyurethane are stripped, and when abrasion occurs, the particles fall off, so that the performance of the composite material is reduced, and the abrasion resistance is also reduced.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a high-strength wear-resistant shoe material and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the high-strength wear-resistant shoe material comprises the following components in parts by weight:
100 parts of polyurethane rubber, 14-18 parts of metal-based filler, 2.6-3.4 parts of wear-resistant auxiliary agent, 1.2-1.5 parts of coupling agent, 0.1-0.15 part of light stabilizer, 0.15-0.2 part of antioxidant, 3-4 parts of lubricant and 1-1.5 parts of release agent;
the wear-resistant additive is prepared by the following method:
step A1: 3-mercaptopropionic acid, dimethylphenylphosphine and toluene are preheated and stirred uniformly under nitrogen atmosphere, then tetramethyl tetravinyl cyclotetrasiloxane is added, the temperature is continuously increased to 60-80 ℃, 240-360rpm mechanical stirring is applied, and 800-1000mw/cm is assisted 2 Ultraviolet irradiation, constant temperature irradiation reaction for 1.4-1.8h, decompression rotary evaporation to remove toluene after the reaction is finished, and obtaining bridging intermediate;
further, the ratio of the amounts of tetramethyl tetravinyl cyclotetrasiloxane, 3-mercaptopropionic acid, dimethylphenylphosphine and toluene was 0.1mol:0.41-0.42mol:0.2-0.3g:160-220mL of mercapto in 3-mercaptopropionic acid reacts with the double bond of tetramethyl tetravinyl cyclotetrasiloxane under ultraviolet initiation, and the 3-mercaptopropionic acid is grafted into the cyclotetrasiloxane structure to form an active bridging soft segment.
Step A2: uniformly mixing a bridging intermediate, thionyl chloride and carbon tetrachloride, heating to 78+/-2 ℃ for refluxing for 2 hours, then removing low-boiling substances by rotary evaporation, adding 2-amino-1, 3, 4-thiadiazole, triethylamine and dimethylacetamide, controlling the temperature to be 30-40 ℃, applying 120-180rpm mechanical stirring, reacting for 2-2.5 hours by constant temperature stirring, adding deionized water after the reaction is finished, removing dimethylacetamide by rotary evaporation under reduced pressure, mixing the precipitate with ice water, and carrying out vacuum drying to obtain a modified substrate;
further, the bridge intermediate, 2-amino-1, 3, 4-thiadiazole, triethylamine, thionyl chloride, carbon tetrachloride and dimethylacetamide were used in an amount ratio of 0.1mol:0.4mol:25-35mL:70-90mL:120-160mL:150-180mL of the carboxyl end group introduced by bridging intermediate is subjected to acyl chlorination by thionyl chloride, then substituted by 2-amino-1, 3, 4-thiadiazole, and a sulfur-nitrogen-containing heterocyclic structure is introduced.
Step A3: uniformly mixing the modified matrix, chlorooctane and dimethyl sulfoxide, adding a solid alkali absorbent, introducing nitrogen for protection, heating to 120-130 ℃, applying 180-240rpm mechanical stirring, stirring at constant temperature for reaction for 4-5h, filtering when the reaction is finished, and decompressing and steaming filtrate to remove low-boiling substances in the dimethyl sulfoxide to obtain the wear-resistant auxiliary agent;
further, the usage ratio of the modified substrate, the chlorooctane and the dimethyl sulfoxide is 0.1mol:100-120mL:150-180mL, the solid alkali absorbent is 0.8-1.2wt% of the mixture, and the chlorooctane is used for quaternizing the nitrogen-containing structure in the modified matrix structure.
The preparation method of the high-strength wear-resistant shoe material comprises the following steps:
step S1: diluting the coupling agent with ethanol, uniformly mixing with the metal-based filler, adding other raw materials, mixing at high speed, and drying by adopting circulating hot air at 90 ℃ until the water content is not higher than 0.05%, so as to form uniform powder, thereby obtaining a batch;
step S2: the batch is melt extruded, and the temperature of an extruder charging barrel is set as follows: the first area is 170-180 ℃, the second area is 190-200 ℃, the third area is 180-190 ℃, the fourth area is 180-190 ℃, the temperature of the machine head is 200-210 ℃, and the high-strength wear-resistant shoe material is obtained by traction cooling and granulating after extrusion.
The invention has the beneficial effects that:
the invention discloses a polyurethane-based shoe material, which takes polyurethane rubber as a base material and metal-based micro powder filler as a reinforcing material, and self-made wear-resistant auxiliary agent is introduced to interact with the filler so as to improve the mechanical property and wear resistance of the composite material. The wear-resistant auxiliary agent takes tetramethyl tetravinyl cyclotetrasiloxane as active neutrality, 3-mercaptopropionic acid is added with the tetramethyl tetravinyl cyclotetrasiloxane in a clicking way to form an active bridging soft segment of a carboxyl end, then the active bridging soft segment is subjected to acyl chlorination treatment on the carboxyl end by thionyl chloride, then the active bridging soft segment is subjected to amidation reaction with 2-amino-1, 3, 4-thiadiazole, a plurality of sulfur-containing nitrogen heterocyclic structures are introduced, and finally the nitrogen-containing structures in the structure are subjected to quaternization treatment by chlorooctane; the sulfur-terminated azacyclic structure in the wear-resistant auxiliary agent molecule has multi-site strong chelation effect on the metal-based filler, the filler in the melt is captured in the melt blending process to form an organic-inorganic combination body, the chelated filler is combined by a flexible organic chain, and the central rigid cyclosiloxane structure provides a supporting effect, so that the organic-inorganic combination body has good toughness, has certain elasticity when being filled in a polyurethane matrix, has small influence on the elasticity performance of the polyurethane matrix compared with the direct doped rigid filler, and has better comfort when being applied to sole materials; in addition, the quaternary ammonium structure at the end of the wear-resistant auxiliary agent molecule has a promoting effect on vulcanization of polyurethane rubber, so that the polyurethane rubber is fully crosslinked in the near layer of the organic-inorganic combination body, the combination strength of the combination body and the polyurethane matrix is enhanced, the introduced long-chain alkyl is inserted into the crosslinked network of the near layer, the insertion toughening effect is achieved on the premise of not influencing the crosslinking strength, the problem of near-layer crosslinking hardening is solved, the combination body and the polyurethane matrix keep good combination toughness, and when the combination body is subjected to forced deformation and friction wear, the filler is not easy to separate from the polyurethane matrix, and the wear resistance of metal-based fillers such as corundum powder is fully exerted.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: preparation of high-strength wear-resistant shoe material
1) Preparation of wear-resistant auxiliary agent
1.1 charging 3-mercaptopropionic acid, dimethylphenylphosphine and toluene, displacing air with nitrogen, preheating, stirring, mixing, adding tetramethyl tetravinyl cyclotetrasiloxane, heating to 80deg.C, mechanically stirring at 360rpm, and adding 1000mw/cm 2 Ultraviolet irradiation, and constant temperature irradiation reaction for 1.4 hours, wherein in the reaction, the dosage ratio of tetramethyl tetravinyl cyclotetrasiloxane, 3-mercaptopropionic acid, dimethyl phenyl phosphine and toluene is 0.1mol:0.42mol:0.3g:220mL, and removing toluene by reduced pressure rotary evaporation after the reaction is finished to obtain a bridging intermediate.
1.2, taking and evenly mixing bridging intermediates, thionyl chloride and carbon tetrachloride, heating to 78+/-2 ℃ and refluxing for 2 hours, removing thionyl chloride and carbon tetrachloride and low-boiling substances generated by the thionyl chloride and the carbon tetrachloride by rotary evaporation, then adding 2-amino-1, 3, 4-thiadiazole, triethylamine and dimethylacetamide, controlling the temperature to be 40 ℃, applying 180rpm mechanical stirring, and stirring at constant temperature for reacting for 2 hours, wherein the dosage ratio of the bridging intermediates, the 2-amino-1, 3, 4-thiadiazole, the triethylamine, the thionyl chloride, the carbon tetrachloride and the dimethylacetamide is 0.1mol:
0.4mol:35mL:90mL:120mL:180mL, adding deionized water after the reaction is finished, removing dimethylacetamide by reduced pressure rotary evaporation, mixing and washing precipitate with ice water, and drying in vacuum to obtain a modified matrix.
1.3, taking a modified matrix, chlorooctane and dimethyl sulfoxide, uniformly mixing, adding a solid alkali absorbent (model is HND-63, the same raw materials are used in the following examples) accounting for 1.2 percent of the weight of the mixture, introducing nitrogen for protection, heating to 130 ℃, applying 240rpm mechanical stirring, and carrying out constant-temperature stirring reaction for 4 hours, wherein the dosage ratio of the modified matrix, chlorooctane and dimethyl sulfoxide is 0.1mol:120mL:180mL, filtering when the reaction is finished and the reaction is hot, and removing low-boiling-point substances including dimethyl sulfoxide from the filtrate by reduced pressure rotary evaporation to obtain the wear-resistant auxiliary agent.
2) Preparation of composite materials
2.1, the following raw materials are taken according to parts by weight:
100 parts of polyurethane rubber, wherein in the embodiment, thermoplastic polyurethane master batch for Bayer KU2-8785A shoes in Germany is selected;
16 parts of metal-based filler, wherein in the embodiment, light calcium carbonate powder, corundum powder and titanium dioxide are adopted according to the weight ratio of 5:2:1, mixing to obtain a fineness of about 5000 meshes;
3.4 parts of wear-resistant auxiliary agent, which is prepared in the embodiment;
1.4 parts of coupling agent, wherein the technical grade silane coupling agent KH-550 is adopted in the examples;
light stabilizer 0.1 parts, examples using products of the type Pasteur Tinuvin PUR 866;
0.18 part of antioxidant, wherein in the embodiment, an antioxidant 1010 and an antioxidant 168 are adopted according to the weight ratio of 1:1, mixing;
3 parts of lubricant, wherein in the embodiment, industrial grade calcium stearate is adopted, and the model is BS-3818;
1.5 parts of release agent, in the examples, 85# microcrystalline wax was used.
2.2, diluting the coupling agent with 10 times of ethanol, mixing with metal-based filler, adding other raw materials, stirring at 1200rpm for 20min, and drying with 90 ℃ circulating hot air until the water content is not higher than 0.05%, thereby forming uniform powder and obtaining the batch.
2.3, throwing the batch into an extruder, and sequentially setting the temperature of a charging barrel to be: the first region is 180 ℃, the second region is 200 ℃, the third region is 190 ℃, the fourth region is 190 ℃, the temperature of the machine head is 210 ℃, the batch is melted and extruded, and the extruded material is cooled and granulated by traction to obtain the high-strength wear-resistant shoe material.
Example 2: preparation of high-strength wear-resistant shoe material
1) Preparation of wear-resistant auxiliary agent
1.1 charging 3-mercaptopropionic acid, dimethylphenylphosphine and toluene, displacing air with nitrogen, preheating, stirring, mixing, adding tetramethyl tetravinyl cyclotetrasiloxane, heating to 60deg.C, mechanically stirring at 240rpm, and adding 800mw/cm 2 Ultraviolet irradiation, and constant temperature irradiation reaction for 1.8 hours, wherein in the reaction, the dosage ratio of tetramethyl tetravinyl cyclotetrasiloxane, 3-mercaptopropionic acid, dimethyl phenyl phosphine and toluene is 0.1mol:0.41mol:0.2g:160mL, and removing toluene by reduced pressure rotary evaporation after the reaction is finished to obtain a bridging intermediate.
1.2, taking and evenly mixing bridging intermediates, thionyl chloride and carbon tetrachloride, heating to 78+/-2 ℃ and refluxing for 2 hours, removing thionyl chloride and carbon tetrachloride and low-boiling substances generated by the thionyl chloride and the carbon tetrachloride by rotary evaporation, then adding 2-amino-1, 3, 4-thiadiazole, triethylamine and dimethylacetamide, controlling the temperature to be 30 ℃, applying 120rpm mechanical stirring, and carrying out constant-temperature stirring reaction for 2.5 hours, wherein the dosage ratio of the bridging intermediates, 2-amino-1, 3, 4-thiadiazole, triethylamine, thionyl chloride, carbon tetrachloride and dimethylacetamide is 0.1mol:0.4mol:25mL:70mL:160mL:150mL, adding deionized water after the reaction, removing dimethylacetamide by reduced pressure rotary evaporation, mixing the precipitate with ice water, and drying in vacuum to obtain the modified matrix.
1.3, taking a modified matrix, chlorooctane and dimethyl sulfoxide, uniformly mixing, adding a solid alkali absorbent with the weight percent of 0.8 percent of the mixture, introducing nitrogen for protection, heating to 120 ℃, applying 180rpm mechanical stirring, and stirring at constant temperature for reaction for 5 hours, wherein the dosage ratio of the modified matrix, chlorooctane and dimethyl sulfoxide is 0.1mol:100mL:150mL, filtering when the reaction is finished and the reaction is hot, and removing low-boiling-point substances including dimethyl sulfoxide from the filtrate by reduced pressure rotary evaporation to obtain the wear-resistant auxiliary agent.
2) Preparation of composite materials
2.1, the following raw materials are taken according to parts by weight:
100 parts of polyurethane rubber, 14-18 parts of metal-based filler, 2.6-3.4 parts of wear-resistant auxiliary agent, 1.2-1.5 parts of coupling agent, 0.1-0.15 part of light stabilizer, 0.15-0.2 part of antioxidant, 3-4 parts of lubricant and 1-1.5 parts of release agent;
2.2, diluting the coupling agent with 10 times of ethanol, mixing with metal-based filler, adding other raw materials, stirring at 1200rpm for 20min, and drying with 90 ℃ circulating hot air until the water content is not higher than 0.05%, thereby forming uniform powder and obtaining the batch.
2.3, throwing the batch into an extruder, and sequentially setting the temperature of a charging barrel to be: the first area is 170 ℃, the second area is 190 ℃, the third area is 180 ℃, the fourth area is 180 ℃, the temperature of the machine head is 200 ℃, the batch is melted and extruded, and the extruded material is cooled and granulated by traction, so that the high-strength wear-resistant shoe material is obtained.
Example 3: preparation of high-strength wear-resistant shoe material
1) Preparation of wear-resistant auxiliary agent
1.1 charging 3-mercaptopropionic acid, dimethylphenylphosphine and toluene, displacing air with nitrogen, preheating, stirring, mixing, adding tetramethyl tetravinyl cyclotetrasiloxane, heating to 70deg.C, mechanically stirring at 300rpm, and adding 900mw/cm 2 Ultraviolet irradiation, constant temperature irradiation reaction for 1.6 hours, wherein in the reaction, the dosage ratio of tetramethyl tetravinyl cyclotetrasiloxane, 3-mercaptopropionic acid, dimethyl phenyl phosphine and toluene is 0.1mol:0.41mol:0.25g:200mL, and removing toluene by reduced pressure rotary evaporation after the reaction is finished to obtain a bridging intermediate.
1.2, taking and evenly mixing bridging intermediates, thionyl chloride and carbon tetrachloride, heating to 78+/-2 ℃ and refluxing for 2 hours, removing thionyl chloride and carbon tetrachloride and low-boiling substances generated by the thionyl chloride and the carbon tetrachloride by rotary evaporation, then adding 2-amino-1, 3, 4-thiadiazole, triethylamine and dimethylacetamide, controlling the temperature to be 35 ℃, applying 180rpm mechanical stirring, and carrying out constant-temperature stirring reaction for 2.2 hours, wherein the dosage ratio of the bridging intermediates, 2-amino-1, 3, 4-thiadiazole, triethylamine, thionyl chloride, carbon tetrachloride and dimethylacetamide is 0.1mol:0.4mol:30mL:80mL:150mL:170mL, adding deionized water after the reaction, decompressing and steaming to remove dimethylacetamide, mixing the precipitate with ice water, and drying in vacuum to obtain the modified matrix.
1.3, taking a modified matrix, chlorooctane and dimethyl sulfoxide, uniformly mixing, adding a solid alkali absorbent accounting for 1wt% of the mixture, introducing nitrogen for protection, heating to 125 ℃, applying 240rpm mechanical stirring, and carrying out constant-temperature stirring reaction for 4.5 hours, wherein the dosage ratio of the modified matrix, chlorooctane and dimethyl sulfoxide is 0.1mol:110mL:160mL, filtering while the reaction is still hot, and removing low-boiling-point substances including dimethyl sulfoxide by rotary evaporation of the filtrate under reduced pressure to obtain the wear-resistant auxiliary agent.
2) Preparation of composite materials
2.1, the following raw materials are taken according to parts by weight:
100 parts of polyurethane rubber, 18 parts of metal-based filler, 3.1 parts of wear-resistant auxiliary agent, 1.5 parts of coupling agent, 0.12 part of light stabilizer, 0.2 part of antioxidant, 3.5 parts of lubricant and 1.2 parts of release agent;
2.2, diluting the coupling agent with 10 times of ethanol, mixing with metal-based filler, adding other raw materials, stirring at 1200rpm for 20min, and drying with 90 ℃ circulating hot air until the water content is not higher than 0.05%, thereby forming uniform powder and obtaining the batch.
2.3, throwing the batch into an extruder, and sequentially setting the temperature of a charging barrel to be: the first region is 180 ℃, the second region is 195 ℃, the third region is 185 ℃, the fourth region is 180 ℃, the temperature of the machine head is 200 ℃, the batch is melted and extruded, and the extruded material is cooled and granulated by traction to obtain the high-strength wear-resistant shoe material.
Comparative example
The comparative example was carried out in the same manner as in example 3, except that no abrasion-resistant auxiliary agent was added to the raw material, the amount of the metal-based filler was increased to 20 parts, the amount of the coupling agent was increased to 1.8 parts, and the remainder was identical.
Taking the shoe materials prepared in the examples and the comparative examples, performing hot press molding by adopting a vulcanizing press, controlling the temperature to be 180 ℃, the pressure to be 1.5MPa, and the holding time to be 3min, and preparing a sheet with the thickness of 2 mm;
the sheets were sampled for mechanical properties, and specific test data are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the tensile and tear properties of the materials prepared in the examples are superior to those of the comparative examples, and the materials exhibit excellent mechanical strength.
Samples were taken from the above sheets for rebound and wear testing, and specific test data are shown in table 2:
TABLE 2
| Test item | Rebound rate/% | DIN abrasion/mm 3 |
| Test standard | GB/T 1681-2009 | GB/T 9867-2008 |
| Example 1 | 33.6 | 26 |
| Examples2 | 35.2 | 31 |
| Example 3 | 31.9 | 25 |
| Comparative example | 24.7 | 42 |
As can be seen from the data in Table 2, the rebound resilience of the materials prepared in the examples is between 31.9 and 35.2%, which is significantly higher than that of the comparative examples, the rebound resilience retention is higher than that of the unreinforced polyurethane materials, the materials have better comfort when applied to shoes, and DIN abrasion is lower than that of the comparative examples, and the materials have higher abrasion resistance.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (9)
1. The high-strength wear-resistant shoe material is characterized by comprising the following components in parts by weight:
100 parts of polyurethane rubber, 14-18 parts of metal-based filler, 2.6-3.4 parts of wear-resistant auxiliary agent, 1.2-1.5 parts of coupling agent, 0.1-0.15 part of light stabilizer, 0.15-0.2 part of antioxidant, 3-4 parts of lubricant and 1-1.5 parts of release agent;
the wear-resistant additive is prepared by the following method:
step A1: 3-mercaptopropionic acid, dimethylphenylphosphine and toluene are preheated and mixed uniformly under the nitrogen atmosphere, tetramethyl tetravinyl cyclotetrasiloxane is added, the temperature is continuously raised to 60-80 ℃, and the mixture is stirred and supplemented with 800-1000mw/cm 2 Ultraviolet irradiation, constant temperature irradiation reaction for 1.4-1.8h, decompression rotary evaporation to remove toluene after the reaction is finished, and obtaining bridging intermediate;
step A2: uniformly mixing a bridging intermediate, thionyl chloride and carbon tetrachloride, heating to 78+/-2 ℃ for refluxing for 2 hours, then removing low-boiling substances by rotary evaporation, adding 2-amino-1, 3, 4-thiadiazole, triethylamine and dimethylacetamide, controlling the temperature to be 30-40 ℃, stirring at constant temperature for reacting for 2-2.5 hours, adding deionized water after the reaction is finished, removing dimethylacetamide by rotary evaporation under reduced pressure, mixing the precipitate with ice water, and drying in vacuum to obtain a modified matrix;
step A3: and uniformly mixing the modified matrix, chlorooctane and dimethyl sulfoxide, adding a solid alkali absorbent, introducing nitrogen for protection, heating to 120-130 ℃, stirring at constant temperature for reaction for 4-5 hours, filtering when the reaction is finished, and decompressing and steaming the filtrate to remove low-boiling-point substances including the dimethyl sulfoxide to obtain the wear-resistant auxiliary agent.
2. The high strength, wear resistant footwear material according to claim 1, wherein the ratio of amounts of tetramethyl tetravinyl cyclotetrasiloxane, 3-mercaptopropionic acid, dimethylphenylphosphine and toluene is 0.1mol:0.41-0.42mol:0.2-0.3g:160-220mL.
3. The high strength, wear resistant footwear material according to claim 2, wherein the bridging intermediate, 2-amino-1, 3, 4-thiadiazole, triethylamine, thionyl chloride, carbon tetrachloride and dimethylacetamide are used in an amount ratio of 0.1mol:0.4mol:25-35mL:70-90mL:120-160mL:150-180mL.
4. The high-strength abrasion-resistant material for shoes according to claim 3, wherein the ratio of the amount of the modified substrate, chlorooctane and dimethyl sulfoxide is 0.1mol:100-120mL:150-180mL, the solid alkali absorbent is 0.8-1.2wt% of the mixture.
5. The high strength, wear resistant footwear material of claim 1 wherein the metal based filler is formed from a blend of light calcium carbonate powder, corundum powder and titanium dioxide.
6. The high-strength abrasion-resistant material for shoes according to claim 1, wherein the coupling agent is a silane coupling agent KH-550.
7. The high strength, wear resistant footwear material of claim 1 wherein the lubricant is calcium stearate.
8. The high strength, wear resistant footwear material according to claim 1, wherein the mold release agent is microcrystalline wax.
9. The method for preparing a high-strength wear-resistant material for shoes according to claim 1, comprising the steps of:
step S1: diluting the coupling agent with ethanol, uniformly mixing with the metal-based filler, adding other raw materials, uniformly mixing, and drying by adopting 90 ℃ circulating hot air until the water content is not higher than 0.05%, so as to form uniform powder, thereby obtaining a batch;
step S2: the batch is melt extruded, and the temperature of an extruder charging barrel is set as follows: the first area is 170-180 ℃, the second area is 190-200 ℃, the third area is 180-190 ℃, the fourth area is 180-190 ℃, the temperature of the machine head is 200-210 ℃, and the high-strength wear-resistant shoe material is obtained by traction cooling and granulating after extrusion.
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