CN114292515A - High-wear-resistance and high-strength protective boot and preparation method thereof - Google Patents
High-wear-resistance and high-strength protective boot and preparation method thereof Download PDFInfo
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- 230000001681 protective effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000004814 polyurethane Substances 0.000 claims abstract description 50
- 229920002635 polyurethane Polymers 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 229920001971 elastomer Polymers 0.000 claims abstract description 9
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 238000009958 sewing Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 42
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000377 silicon dioxide Substances 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 30
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 22
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000012286 potassium permanganate Substances 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 12
- 239000004970 Chain extender Substances 0.000 claims description 11
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 241001112258 Moca Species 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- 229940050176 methyl chloride Drugs 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 238000005299 abrasion Methods 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000010025 steaming Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 11
- 238000001816 cooling Methods 0.000 abstract description 4
- 230000002452 interceptive effect Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000004026 adhesive bonding Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 9
- 238000004513 sizing Methods 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000007112 amidation reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
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- 230000003203 everyday effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical group CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a high-wear-resistance and high-strength protective boot and a preparation method thereof, belonging to the technical field of labor protection products, the protective boot is prepared by sewing and gluing a sole and a vamp, and the sole comprises the following raw materials in parts by weight: 45-50 parts of modified polyurethane, 18-23 parts of butyl rubber, 2.7-3.1 parts of lubricant, 0.7-0.9 part of vulcanizing agent and 0.4-0.6 part of accelerator, wherein the sole is prepared by mixing the butyl rubber into a rubber material, adding other raw materials, blending, vulcanizing and cooling to form; the modified polyurethane is prepared in the process of preparing the protective boots, the modified polyurethane takes nano silicon dioxide as a substrate, polyurethane with an interactive network structure is generated on the surface, the nano silicon dioxide is connected with each other and coated, and the strength and the wear resistance of the polyurethane are greatly improved.
Description
Technical Field
The invention belongs to the technical field of labor protection articles, and particularly relates to a high-wear-resistance high-strength protective boot and a preparation method thereof.
Background
The protection boots are used for protecting staff's feet, select different kinds of protection boots for use according to operational environment's harm nature and harm degree, and current protection boots adopt the polyurethane material to make mostly, because of it has good shock attenuation and solvent resistance, and easily machine-shaping.
In the prior art, the wear resistance and the strength of the polyurethane protective boots are not high, particularly in the environment with poor working conditions and in the workplace with more sharp scraps on the ground, the scraps continuously scratch the soles to cause cracks on the soles, and then the cracks are enlarged by bending to cause the bottom breakage of the protective boots, so that the service life of the protective boots is greatly reduced, and the service life of the soles of the protective boots usually determines the whole service life of the protective boots.
Disclosure of Invention
The invention aims to provide a high-wear-resistance high-strength protective boot and a preparation method thereof, so as to solve the technical problems mentioned in the background technology.
The technical problems to be solved by the invention are as follows:
the purpose of the invention can be realized by the following technical scheme:
the utility model provides a high wear-resisting high strength's protection boots, includes sole and vamp, and this sole includes following part by weight raw materials:
45-50 parts of modified polyurethane, 18-23 parts of butyl rubber, 2.7-3.1 parts of lubricant, 0.7-0.9 part of vulcanizing agent and 0.4-0.6 part of accelerator;
the modified polyurethane is prepared by the following steps:
step A1: taking a reactor provided with a conduit, adding dimethyl sulfoxide into the reactor, heating to 40-50 ℃, controlling the stirring speed to be 180-one for 240r/min, adding diphenylmethane diisocyanate into the reactor under the protection of dry nitrogen, stirring until the diphenylmethane diisocyanate is dissolved, then adding anhydrous aluminum trichloride into the reactor, introducing methyl chloride into the mixed solution through the conduit, after the reaction is finished, separating the reaction solution by using water for 2-3 times, removing the dimethyl sulfoxide, reacting the unreacted diphenylmethane diisocyanate with the water, standing, taking the lower layer liquid phase, performing suction filtration on the liquid phase to obtain an intermediate 1, wherein the dimethyl sulfoxide and the anhydrous aluminum trichloride are dried before use, the dosage of the dimethyl sulfoxide, the diphenylmethane diisocyanate and the methyl chloride is 100mL:13-17g:1.1-1.3L, the introduction flow of the methyl chloride is controlled to be 0.9-1.1L/h, under the catalytic action of aluminum trichloride, methyl is connected to a benzene ring of diphenylmethane diisocyanate;
the specific reaction process is as follows:
step A2: adding the intermediate 1 into a stirrer, dropwise adding a potassium permanganate aqueous solution into the intermediate 1 under a stirring state until the potassium permanganate aqueous solution does not fade, standing and layering the reaction solution, taking the lower layer liquid, and removing water by using calcium oxide to obtain an intermediate 2, wherein the mass fraction of the potassium permanganate aqueous solution is 7%, and methyl on a benzene ring of a molecule of the intermediate 1 is oxidized into carboxyl through the strong oxidizing property of potassium permanganate;
the specific reaction process is as follows:
step A3: adding deionized water into nano-silica, performing ultrasonic dispersion for 30-40min at the frequency of 20-25kHz, adding a silane coupling agent KH550 into the dispersion, controlling the stirring speed to be 120-150r/min, reacting for 8-10h at room temperature, then placing the reactant into a vacuum drying box, controlling the drying temperature to be 50-55 ℃, and the solid content of the drying treatment to be 8-10% to prepare the modified nano-silica, wherein the dosage ratio of the nano-silica to the silane coupling agent KH550 is 10 g: 15-18mL, hydrolyzing alkoxy of the silane coupling agent KH550 into silicon hydroxyl, condensing with the silicon hydroxyl on the surface of the nano-silica, grafting a group containing amino on the surface of the nano-silica, and simultaneously enabling the nano-silica treated by the silane coupling agent KH550 to be not easy to agglomerate and improve the compatibility with an organic phase;
the specific reaction process is as follows:
step A4: adding the intermediate 2, toluene and 4-dimethylaminopyridine into a reactor for mixing, heating to 65-70 ℃, stirring at the speed of 200-300r/min, adding modified nano-silica into the reactor, stirring for reacting for 5-8h, then adding polytetrahydrofuran ether glycol and dibutyltin dilaurate into the reactor, heating to 80-90 ℃, keeping the rotating speed, stirring for reacting for 2-3h, then adding a chain extender MOCA into the reactor, stirring for reacting for 1h, and carrying out reduced pressure rotary evaporation on reaction liquid to prepare modified polyurethane, wherein the dosage ratio of the intermediate 2, toluene, 4-dimethylaminopyridine, modified nano-silica, polytetrahydrofuran ether glycol and chain extender MOCA is 100mL: 250mL of: 0.1-0.13 g: 8.5-9.5 g: 360-400 mL: 0.3-0.5g, carrying out amidation reaction on carboxyl on the molecule of the intermediate 2 and amino on the surface of the modified nano-silica under the catalytic action of 4-dimethylamino pyridine, grafting the intermediate 2 to the surface of the modified nano-silica, then generating a prepolymer by the polytetrahydrofuran ether glycol and the intermediate 2, and finally generating a block copolymer by chain extension reaction.
The specific reaction process is as follows:
further, the lubricant is methyl silicone oil.
Further, the vulcanizing agent is vulcanizing agent 3M.
Further, the accelerator is TMTD.
The sole is prepared by the following steps:
step B1: adding butyl rubber into an internal mixer, controlling the temperature at 190-;
step B2: mixing and adding the rubber compound, the modified polyurethane, the vulcanizing agent and the accelerator into a shearing machine, controlling the temperature at 160-.
A preparation method of a high-wear-resistance high-strength protective boot comprises the following steps:
taking the vamp, sewing the bottom end of the vamp and the sole, setting sewing density to be 8-10 mm/needle, then coating adhesive on the joint, naturally drying and curing, and preparing the high-wear-resistance high-strength protective boot.
The vamp is a commercially available polyurethane vamp.
The adhesive is waterborne polyurethane shoe polish adhesive 1654.
The invention has the beneficial effects that:
the sole of the invention is prepared by taking modified polyurethane and butyl rubber as main raw materials through blending, the butyl rubber has good elasticity and water tightness, the modified polyurethane is blended and filled in the sole to improve the comfort and the seepage resistance of the sole, the modified polyurethane is prepared by introducing methyl on a benzene ring of diphenylmethane diisocyanate molecules, then oxidizing the methyl into carboxyl to prepare an intermediate 2, the nano-silica is treated by a silane coupling agent KH550, a large number of groups with amino at the tail end are grafted on the nano-silica, amidation reaction is carried out through the amino and the carboxyl, the intermediate 2 is grafted on the surface of the nano-silica, polytetrahydrofuran ether glycol is added, the nano-silica is taken as a substrate to generate prepolymers with isocyanate of the intermediate 2, then the prepolymers are mutually connected through a chain extender to generate modified polyurethane with an interactive network structure, and the nano-silica is coated by the polyurethane, the dispersivity is good, the strength of the polyurethane is greatly improved, and the wear resistance of the polyurethane is further improved by introducing the nano silicon dioxide.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The modified polyurethane is prepared by the embodiment specifically comprising the following steps:
step A1: taking a reactor provided with a conduit, adding dimethyl sulfoxide into the reactor, heating to 40 ℃, controlling the stirring speed to be 180r/min, adding diphenylmethane diisocyanate into the reactor under the protection of dry nitrogen, stirring until the diphenylmethane diisocyanate is dissolved, then adding anhydrous aluminum trichloride into the reactor, introducing methyl chloride into the mixed solution through the conduit, washing the reaction solution for 2 times by using deionized water after the reaction is finished, removing the dimethyl sulfoxide, reacting unreacted diphenylmethane diisocyanate with water, standing, taking a lower-layer liquid phase, and performing suction filtration on the liquid phase to obtain an intermediate 1;
before using, the dimethyl sulfoxide adopts calcium oxide to remove water, and the anhydrous aluminum trichloride adopts drying to remove water; the dosage of the dimethyl sulfoxide, the diphenylmethane diisocyanate and the monochloromethane is 100mL:13g:1.1L, and the flow rate of introducing the monochloromethane is controlled to be 0.9L/h;
step A2: adding the intermediate 1 into a stirrer, dropwise adding a potassium permanganate aqueous solution into the intermediate 1 under a stirring state until the potassium permanganate aqueous solution does not fade, standing and layering the reaction solution, taking the lower layer liquid, and removing water by using calcium oxide to obtain an intermediate 2, wherein the mass fraction of the potassium permanganate aqueous solution is 7%;
step A3: taking nano silicon dioxide and deionized water according to the dosage ratio of 10 g: 20mL of the mixture is mixed, ultrasonic dispersion is carried out for 30min under the frequency of 20kHz, silane coupling agent KH550 is added into dispersion liquid, the stirring speed is controlled to be 120r/min, the reaction is carried out for 8h at room temperature, then the reactant is placed in a vacuum drying oven, the drying temperature is controlled to be 50 ℃, the solid content of the drying treatment is 10 percent, and the modified nano-silica is prepared, wherein the dosage ratio of the nano-silica to the silane coupling agent KH550 is 10 g: 15 mL;
step A4: adding the intermediate 2, toluene and 4-dimethylaminopyridine into a reactor for mixing, heating to 65 ℃, stirring at a speed of 200r/min, adding modified nano-silica into the reactor, stirring for reacting for 5 hours, then adding polytetrahydrofuran ether glycol and dibutyltin dilaurate into the reactor, heating to 80 ℃, keeping the rotating speed, stirring for reacting for 2 hours, then adding a chain extender MOCA into the reactor, stirring for reacting for 1 hour, decompressing and rotary steaming a reaction solution to prepare the modified polyurethane, wherein the dosage ratio of the intermediate 2, toluene, 4-dimethylaminopyridine, modified nano-silica, polytetrahydrofuran ether glycol and chain extender MOCA is 100mL: 250mL of: 0.1 g: 8.5 g: 360 mL: 0.3 g.
Example 2
The modified polyurethane is prepared by the embodiment specifically comprising the following steps:
step A1: taking a reactor provided with a conduit, adding dimethyl sulfoxide into the reactor, heating to 45 ℃, controlling the stirring speed to be 200r/min, adding diphenylmethane diisocyanate into the reactor under the protection of dry nitrogen, stirring until the diphenylmethane diisocyanate is dissolved, then adding anhydrous aluminum trichloride into the reactor, introducing methyl chloride into the mixed solution through the conduit, washing the reaction solution for 2 times by using deionized water after the reaction is finished, removing the dimethyl sulfoxide, reacting unreacted diphenylmethane diisocyanate with water, standing, taking a lower-layer liquid phase, and performing suction filtration on the liquid phase to obtain an intermediate 1;
before using, the dimethyl sulfoxide adopts calcium oxide to remove water, and the anhydrous aluminum trichloride adopts drying to remove water; the dosage of the dimethyl sulfoxide, the diphenylmethane diisocyanate and the monochloromethane is 100mL:15g:1.2L, and the introduction flow rate of the monochloromethane is controlled to be 1L/h;
step A2: adding the intermediate 1 into a stirrer, dropwise adding a potassium permanganate aqueous solution into the intermediate 1 under a stirring state until the potassium permanganate aqueous solution does not fade, standing and layering the reaction solution, taking the lower layer liquid, and removing water by using calcium oxide to obtain an intermediate 2, wherein the mass fraction of the potassium permanganate aqueous solution is 7%;
step A3: taking nano silicon dioxide and deionized water according to the dosage ratio of 10 g: 20mL of the mixture is mixed, ultrasonic dispersion is carried out for 35min under the frequency of 20kHz, silane coupling agent KH550 is added into dispersion liquid, the stirring speed is controlled to be 120r/min, the reaction is carried out for 9h at room temperature, then the reactant is placed in a vacuum drying oven, the drying temperature is controlled to be 50 ℃, the solid content of the drying treatment is 9 percent, modified nano-silica is prepared, and the dosage ratio of the nano-silica to the silane coupling agent KH550 is 10 g: 17 mL;
step A4: adding the intermediate 2, toluene and 4-dimethylaminopyridine into a reactor for mixing, heating to 65 ℃, stirring at a speed of 250r/min, adding modified nano-silica into the reactor, stirring for reaction for 7 hours, adding polytetrahydrofuran ether glycol and dibutyltin dilaurate into the reactor, heating to 85 ℃, keeping the rotating speed, stirring for reaction for 2 hours, adding a chain extender MOCA into the reactor, stirring for reaction for 1 hour, decompressing and rotary-steaming a reaction solution to prepare the modified polyurethane, wherein the dosage ratio of the intermediate 2, toluene, 4-dimethylaminopyridine, modified nano-silica, polytetrahydrofuran ether glycol and chain extender MOCA is 100mL: 250mL of: 0.11 g: 8 g: 360 mL: 0.4 g.
Example 3
The modified polyurethane is prepared by the embodiment specifically comprising the following steps:
step A1: taking a reactor provided with a conduit, adding dimethyl sulfoxide into the reactor, heating to 50 ℃, controlling the stirring speed to be 240r/min, adding diphenylmethane diisocyanate into the reactor under the protection of dry nitrogen, stirring until the diphenylmethane diisocyanate is dissolved, then adding anhydrous aluminum trichloride into the reactor, introducing methyl chloride into the mixed solution through the conduit, washing the reaction solution for 3 times by using deionized water after the reaction is finished, removing the dimethyl sulfoxide, reacting unreacted diphenylmethane diisocyanate with water, standing, taking a lower-layer liquid phase, and performing suction filtration on the liquid phase to obtain an intermediate 1;
before using, the dimethyl sulfoxide adopts calcium oxide to remove water, and the anhydrous aluminum trichloride adopts drying to remove water; the dosage of the dimethyl sulfoxide, the diphenylmethane diisocyanate and the monochloromethane is 100mL:17g:1.3L, and the introduction flow rate of the monochloromethane is controlled to be 1.1L/h;
step A2: adding the intermediate 1 into a stirrer, dropwise adding a potassium permanganate aqueous solution into the intermediate 1 under a stirring state until the potassium permanganate aqueous solution does not fade, standing and layering the reaction solution, taking the lower layer liquid, and removing water by using calcium oxide to obtain an intermediate 2, wherein the mass fraction of the potassium permanganate aqueous solution is 7%;
step A3: taking nano silicon dioxide and deionized water according to the dosage ratio of 10 g: 20mL of the mixture is mixed, ultrasonic dispersion is carried out for 40min under the frequency of 25kHz, silane coupling agent KH550 is added into dispersion liquid, the stirring speed is controlled to be 150r/min, the reaction is carried out for 10h at room temperature, then the reactant is placed in a vacuum drying oven, the drying temperature is controlled to be 55 ℃, the solid content of the drying treatment is 8 percent, and the modified nano-silica is prepared, wherein the dosage ratio of the nano-silica to the silane coupling agent KH550 is 10 g: 18 mL;
step A4: adding the intermediate 2, toluene and 4-dimethylaminopyridine into a reactor for mixing, heating to 70 ℃, stirring at the speed of 300r/min, adding modified nano-silica into the reactor, stirring for reacting for 8 hours, then adding polytetrahydrofuran ether glycol and dibutyltin dilaurate into the reactor, heating to 90 ℃, keeping the rotating speed, stirring for reacting for 3 hours, then adding a chain extender MOCA into the reactor, stirring for reacting for 1 hour, decompressing and rotary steaming reaction liquid to prepare modified polyurethane, wherein the dosage ratio of the intermediate 2, toluene, 4-dimethylaminopyridine, modified nano-silica, polytetrahydrofuran ether glycol and chain extender MOCA is 100mL: 250mL of: 0.13 g: 9.5 g: 400 mL: 0.5 g.
Example 4
The sole prepared by the embodiment comprises the following raw materials in parts by weight:
45 parts of modified polyurethane prepared in example 1, 18 parts of butyl rubber, 2.7 parts of lubricant, 0.7 part of vulcanizing agent and 0.4 part of accelerator;
the specific preparation process of the sole is as follows:
step B1: adding butyl rubber into an internal mixer, controlling the temperature at 190 ℃ and the stirring speed at 500r/min for internal mixing for 1h, adding a lubricant and continuously stirring for 10min to obtain a rubber material;
step B2: mixing and adding a rubber sizing material, modified polyurethane, a vulcanizing agent and an accelerant into a shearing machine, controlling the temperature at 160 ℃, the rotating speed at 1200r/min, shearing for 8min, carrying out vacuum defoaming treatment on the mixture under 300Pa for 10min, then carrying out vulcanization treatment on the mixture in a hydraulic vulcanizing machine, setting the vulcanization temperature at 150 ℃ and the vulcanization pressure at 18MPa to obtain a mixed sizing material, pouring the mixed sizing material into a mold, and cooling to obtain the sole.
Example 5
The sole prepared by the embodiment comprises the following raw materials in parts by weight:
45 parts of modified polyurethane prepared in example 2, 20 parts of butyl rubber, 2.9 parts of lubricant, 0.8 part of vulcanizing agent and 0.5 part of accelerator;
the specific preparation process of the sole is as follows:
step B1: adding butyl rubber into an internal mixer, controlling the temperature at 200 ℃, stirring at 500r/min for internal mixing for 1.5h, adding a lubricant, and continuously stirring for 15min to obtain a rubber material;
step B2: mixing and adding a rubber compound, modified polyurethane, a vulcanizing agent and an accelerant into a shearing machine, controlling the temperature to be 170 ℃, the rotating speed to be 1300r/min, carrying out shearing treatment for 10min, carrying out vacuum defoaming treatment on the mixture for 10min under 300Pa, then carrying out vulcanization treatment on the mixture in a hydraulic vulcanizing machine, setting the vulcanization temperature to be 150 ℃ and the vulcanization pressure to be 18MPa to prepare a mixed compound, pouring the mixed compound into a mold, and cooling to prepare the sole.
Example 6
The sole prepared by the embodiment comprises the following raw materials in parts by weight:
50 parts of modified polyurethane prepared in example 3, 23 parts of butyl rubber, 3.1 parts of lubricant, 0.9 part of vulcanizing agent and 0.6 part of accelerator;
the specific preparation process of the sole is as follows:
step B1: adding butyl rubber into an internal mixer, controlling the temperature at 220 ℃, stirring at 600r/min for internal mixing for 2h, adding a lubricant, and continuously stirring for 20min to obtain a rubber material;
step B2: mixing and adding a rubber sizing material, modified polyurethane, a vulcanizing agent and an accelerant into a shearing machine, controlling the temperature to be 180 ℃, controlling the rotating speed to be 1500r/min, shearing for 15min, carrying out vacuum defoaming treatment on the mixture under 300Pa for 10min, then carrying out vulcanization treatment on the mixture in a hydraulic vulcanizing machine, setting the vulcanization temperature to be 150 ℃ and the vulcanization pressure to be 18MPa to prepare a mixed sizing material, and pouring the mixed sizing material into a mold for cooling to prepare the sole.
Comparative example 1
The comparative example is the same as the specific preparation process of example 4, and the modified polyurethane is replaced by the common polyurethane resin.
Comparative example 2
This comparative example is the same as the specific preparation process of example 4, and the modified polyurethane was replaced with a mixture of a normal polyurethane resin and the modified nano-silica prepared in step a3 of example 1, with the use ratio of the normal polyurethane resin to the modified nano-silica being 500 mL: 11 g.
Comparative example 3
This comparative example is a commercially available PU protective boot.
The soles obtained in the examples 4-6 and the comparative examples 1-3 are prepared into samples, the wear resistance of the samples is tested according to GB/T1689-:
TABLE 1
As can be seen from Table 1, the Shore A hardness of the soles prepared in examples 4 to 5 reached 82 to 89, and the Akron abrasion volume was 0.543 to 0.641cm3Km, hardness and abrasion resistance are better than those of the conventional PU shoe sole and the shoe soles prepared in examples 4 to 5 have tensile strength of 15.3 to 16.5MPa and elongation at breakThe modified polyurethane with the length of 395-432% has good toughness, because the modified polyurethane added in the raw materials takes the nano-silica as a substrate, and the polyurethane with an interactive network structure is synthesized on the surface, the network structure greatly improves the bonding strength among polyurethane molecules, so that the modified polyurethane has good tensile property, meanwhile, the nano-silica is coated by the polyurethane to form dispersion strengthening, so that the strength of the polyurethane is greatly improved, and the nano-silica has good wear resistance, so that the modified polyurethane is endowed with high hardness and wear resistance.
Example 7
The embodiment prepares a high wear-resistant and high-strength protective boot, and the specific preparation process is as follows:
and (3) taking a polyurethane vamp, sewing the bottom end of the polyurethane vamp with the sole prepared in the example 5, setting the sewing density to be 8 mm/needle, then coating an adhesive on the joint, naturally airing and curing, and preparing the high-wear-resistance high-strength protective boot.
Inviting 10 engineers, respectively issuing 1 pair of the protective boots obtained in example 7 and 1 pair of the comparative example 3, alternately wearing every day, observing the time of crack occurrence of the sole, scoring the wearing comfort of the protective boots, dividing the full score into 10 points, and averaging and dividing the data as shown in table 2:
TABLE 2
| Crack initiation time/d | Comfort/score | |
| Example 7 | 95 | 8 |
| Comparative example 3 | 54 | 6.7 |
As can be seen from Table 2, the boots made according to the present invention have a longer life span and are more favored by engineers.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (6)
1. The utility model provides a high wear-resisting high strength's protection boots, includes sole and vamp, its characterized in that, this sole includes following part by weight raw materials: 45-50 parts of modified polyurethane, 18-23 parts of butyl rubber, 2.7-3.1 parts of lubricant, 0.7-0.9 part of vulcanizing agent and 0.4-0.6 part of accelerator;
the modified polyurethane is prepared by the following steps:
step A1: heating dimethyl sulfoxide to 40-50 ℃, adding diphenylmethane diisocyanate under the protection of dry nitrogen, stirring and dissolving, adding anhydrous aluminum trichloride, introducing monochloromethane into the mixed solution, separating the reaction solution with water, and taking the lower-layer liquid phase to obtain an intermediate 1;
step A2: dropwise adding a potassium permanganate aqueous solution into the intermediate 1 until the reaction solution does not fade, standing the reaction solution for layering, taking a lower-layer liquid phase, and finally removing water by using calcium oxide to prepare an intermediate 2;
step A3: ultrasonically dispersing nano silicon dioxide and deionized water, adding a silane coupling agent KH550 into the dispersion liquid, stirring and reacting for 8-10h, and drying the reactant at 50-55 ℃ until the solid content is 8-10% to prepare modified nano silicon dioxide;
step A4: mixing the intermediate 2 and toluene, adding 4-dimethylaminopyridine, heating to 65-70 ℃, adding modified nano-silicon dioxide while stirring, then adding polytetrahydrofuran ether glycol and dibutyltin dilaurate, heating to 80-90 ℃, stirring for reaction for 2-3h, adding a chain extender MOCA, continuing to react for 1h, and finally decompressing and rotary steaming the reaction solution to obtain the modified polyurethane.
2. The high abrasion-resistant high strength protective boot according to claim 1, wherein in step A1, the amount of dimethyl sulfoxide, diphenylmethane diisocyanate and methyl chloride is 100mL:13-17g: 1.1-1.3L.
3. The high abrasion-resistant high strength protective boot according to claim 1, wherein in step A3, the nano silica and the silane coupling agent KH550 are used in a ratio of 10 g: 15-18 mL.
4. The high-abrasion-resistance high-strength protective boot according to claim 1, wherein in the step A4, the dosage ratio of the intermediate 2, the toluene, the 4-dimethylaminopyridine, the modified nano-silica, the polytetrahydrofuran ether glycol and the chain extender MOCA is 100mL: 250mL of: 0.1-0.13 g: 8.5-9.5 g: 360-400 mL: 0.3-0.5 g.
5. The high abrasion resistant high strength protective boot according to claim 1, wherein said sole is prepared by the steps of:
step B1: taking butyl rubber, banburying for 1-2h at the temperature of 190-;
step B2: mixing and adding the rubber compound, the modified polyurethane, the vulcanizing agent and the accelerator into a shearing machine, controlling the temperature at 160-.
6. A preparation method of a high-wear-resistance high-strength protective boot is characterized in that the bottom end of a vamp and a sole are sewn, sewing density is set to be 8mm-10 mm/needle, then an adhesive is coated on the joint, and the high-wear-resistance high-strength protective boot is prepared by natural airing and curing.
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Application publication date: 20220408 |