CN117064137A - Efficient breathable waterproof sports shoes and preparation method thereof - Google Patents
Efficient breathable waterproof sports shoes and preparation method thereof Download PDFInfo
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- CN117064137A CN117064137A CN202311040745.6A CN202311040745A CN117064137A CN 117064137 A CN117064137 A CN 117064137A CN 202311040745 A CN202311040745 A CN 202311040745A CN 117064137 A CN117064137 A CN 117064137A
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- waterproof
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000835 fiber Substances 0.000 claims abstract description 23
- 244000025254 Cannabis sativa Species 0.000 claims abstract description 19
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims abstract description 19
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims abstract description 19
- 235000009120 camo Nutrition 0.000 claims abstract description 19
- 235000005607 chanvre indien Nutrition 0.000 claims abstract description 19
- 239000011487 hemp Substances 0.000 claims abstract description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 229920000742 Cotton Polymers 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 106
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 83
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 239000007795 chemical reaction product Substances 0.000 claims description 43
- 239000000377 silicon dioxide Substances 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 39
- 235000012239 silicon dioxide Nutrition 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 30
- 239000000706 filtrate Substances 0.000 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 239000003995 emulsifying agent Substances 0.000 claims description 20
- 238000009941 weaving Methods 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- WTGIOQMHIHCSPZ-UHFFFAOYSA-N sulfanylsilicon Chemical compound S[Si] WTGIOQMHIHCSPZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 claims description 7
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 claims description 7
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- LVKCSZQWLOVUGB-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].C[CH-]C LVKCSZQWLOVUGB-UHFFFAOYSA-M 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
- 239000011241 protective layer Substances 0.000 claims description 6
- 239000012312 sodium hydride Substances 0.000 claims description 6
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 230000000386 athletic effect Effects 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 2
- 210000004243 sweat Anatomy 0.000 abstract description 5
- 239000004744 fabric Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 3
- 229920003043 Cellulose fiber Polymers 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000010992 reflux Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- -1 sulfhydryl silicon dioxide Chemical compound 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 210000002683 foot Anatomy 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 206010060820 Joint injury Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 208000022542 ankle injury Diseases 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B7/00—Footwear with health or hygienic arrangements
- A43B7/12—Special watertight footwear
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/02—Footwear characterised by the material made of fibres or fabrics made therefrom
- A43B1/025—Plant fibres
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/02—Footwear characterised by the material made of fibres or fabrics made therefrom
- A43B1/04—Footwear characterised by the material made of fibres or fabrics made therefrom braided, knotted, knitted or crocheted
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
- A43B23/02—Uppers; Boot legs
- A43B23/0245—Uppers; Boot legs characterised by the constructive form
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B5/00—Footwear for sporting purposes
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B7/00—Footwear with health or hygienic arrangements
- A43B7/06—Footwear with health or hygienic arrangements ventilated
- A43B7/08—Footwear with health or hygienic arrangements ventilated with air-holes, with or without closures
- A43B7/084—Footwear with health or hygienic arrangements ventilated with air-holes, with or without closures characterised by the location of the holes
- A43B7/085—Footwear with health or hygienic arrangements ventilated with air-holes, with or without closures characterised by the location of the holes in the upper
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B9/00—Footwear characterised by the assembling of the individual parts
- A43B9/02—Footwear stitched or nailed through
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Public Health (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Botany (AREA)
- Physical Education & Sports Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
Abstract
The invention relates to the field of sports shoes, in particular to a high-efficiency breathable waterproof sports shoe and a preparation method thereof, which are used for solving the problem that the waterproofness and the breathability of the existing sports shoes cannot be simultaneously considered; according to the preparation method, the hemp fiber and the cotton fiber are used as raw materials to form the fly-knitted vamp, the hemp fiber and the cotton fiber belong to cellulose fiber, the fiber molecules contain a large number of polar hydrophilic groups, the hemp fiber is easy to combine with water molecules to adsorb the water molecules when in contact with water, the hemp fiber has a unique structure, moisture and water vapor in the fabric can be quickly transferred and diffused, sweat or moisture can be timely dredged to the surface of the fabric and is dissipated into the air when the foot sweats due to movement, the air permeability is good, and then super-waterproof emulsion is sprayed on the fly-knitted vamp, so that a super-hydrophobic surface can be formed on the outer surface of the fly-knitted vamp, the waterproof effect is realized, the absorption and the dredging of the sweat or the moisture by the inner surface of the fly-knitted vamp are not influenced, and the wearing comfort of the sports shoes is improved.
Description
Technical Field
The invention relates to the field of sports shoes, in particular to a high-efficiency breathable waterproof sports shoe and a preparation method thereof.
Background
The soles of the sport shoes are different from common leather shoes and rubber shoes, are soft and elastic, can play a certain role in buffering, can strengthen elasticity during sports, and can prevent ankle injury. Therefore, when sports are performed, the sports shoes, especially high intensity physical exercise, are mostly worn, wherein in some sports projects performed in a humid environment, the waterproof requirement on the sports shoes is high, the waterproof performance of the shoes depends on shoe materials and structures, the conventional sports shoe uppers are usually made of leather materials, and have good waterproof performance, but the sports shoes can cause a large amount of perspiration due to the sports, the sealing performance of the leather materials can prevent the evaporation of the perspiration, and the generated heat cannot be diffused through the evaporation of the perspiration due to the fact that the perspiration cannot be rapidly led out, so that the interior of the shoes is relatively humid, the comfort is poor, a large amount of bacteria are bred in the microenvironment inside the shoes, and the feet and the shoes generate great peculiar smell, so that the sports shoes are required to be breathable, but the breathable sports shoes are not waterproof in the humid environment, and the shoes are easy to cause the shoes, and therefore, the two are difficult to combine.
How to improve the waterproof performance and the ventilation performance of the existing sports shoes is not the key of the invention, so that a high-efficiency ventilation waterproof sports shoe and a preparation method thereof are needed to solve the problems.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide the high-efficiency breathable waterproof sports shoes and the preparation method thereof: the hemp fiber and the cotton fiber are blended to form the mixed yarn, the mixed yarn is woven to form the fly-weaving vamp, the outer surface of the fly-weaving vamp is sprayed with the ultra-waterproof emulsion, and then the super-waterproof emulsion is dried to form the waterproof fly-weaving vamp, so that the waterproof fly-weaving vamp is sewn on the sole, and the efficient breathable waterproof sports shoe is obtained, and the problem that the waterproof performance and the breathable performance of the existing sports shoe cannot be simultaneously taken into consideration is solved.
The aim of the invention can be achieved by the following technical scheme:
the high-efficiency breathable waterproof sports shoes comprise soles and waterproof fly-knitted vamps sewn on the soles, wherein the waterproof fly-knitted vamps are prepared by spraying ultra-waterproof emulsion on the fly-knitted vamps.
As a further scheme of the invention: the super waterproof emulsion is prepared by the following steps:
step one: weighing 3-15 parts of super waterproof monomer, 20-25 parts of methyl methacrylate, 10-12 parts of butyl acrylate, 3-5 parts of acrylic acid, 6-14 parts of mercapto silicon dioxide, 1-1.5 parts of emulsifier, 0.15-0.25 part of potassium persulfate and 50-60 parts of deionized water according to parts by weight for standby;
step two: adding a super waterproof monomer, methyl methacrylate, butyl acrylate, acrylic acid, an emulsifier and 4/5 deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 30-40min under the conditions of 25-30 ℃ and stirring speed of 400-500r/min, heating to 80-85 ℃ and continuously stirring and reacting for 15-20min, dissolving potassium persulfate in the rest 1/5 deionized water to form a potassium persulfate solution, dropwise adding the potassium persulfate solution while stirring, controlling the dropwise adding speed to be 1-2 drops/s, continuously stirring and reacting for 1-2h after dropwise adding mercaptosilicon dioxide, continuously stirring and reacting for 3-5h, cooling a reaction product to room temperature after the reaction is finished, and regulating the pH value to 7 by ammonia water to obtain the super waterproof emulsion.
As a further scheme of the invention: the emulsifier is NP-10 emulsifier and DNS-86 emulsifier, and the mass ratio is 1:1.5-2, wherein the mass fraction of the ammonia water is 20-25%.
As a further scheme of the invention: the ultra-waterproof monomer is prepared by the following steps:
step A1: adding diphenylamine, 1, 4-diiodobenzene, copper powder, sodium hydride and anhydrous diethyl ether into a three-neck flask provided with a stirrer, a thermometer, an air duct and a reflux condenser, introducing nitrogen for protection, stirring and reacting for 0.5-1h under the conditions of 25-30 ℃ and stirring speed of 400-500r/min, heating to reflux, continuing stirring and reacting for 8-10h, cooling the reaction product to room temperature after the reaction is finished, then vacuum filtering, washing the filtrate with distilled water for 2-3 times, standing for layering, drying the organic phase with anhydrous sodium sulfate, then vacuum filtering, and rotationally evaporating the filtrate to remove the solvent to obtain an intermediate 1;
the reaction process is as follows:
step A2: adding the intermediate 1, triisopropyl borate and anhydrous diethyl ether into a three-neck flask with a stirrer and a thermometer, stirring at the temperature of-5-0 ℃ and the stirring speed of 400-500r/min for reacting for 40-50min, adding isopropylmagnesium bromide, continuously stirring for reacting for 20-30min, heating to 65-70 ℃ for continuously stirring for reacting for 3-5h, adding the reaction product into a saturated ammonium chloride solution after the reaction is finished, adjusting the pH value to 1-2 with a hydrochloric acid solution, extracting for 2-3 times with ethyl acetate, combining the extracting solutions, and rotationally evaporating the extracting solution to remove the solvent to obtain the intermediate 2;
the reaction process is as follows:
step A3: adding the intermediate 2, concentrated sulfuric acid and concentrated nitric acid into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and reacting for 30-50min under the conditions of the temperature of-10-0 ℃ and the stirring speed of 400-500r/min, heating to reflux and continuously stirring and reacting for 5-6h, adding the reaction product into ice water after the reaction is finished, extracting for 2-3 times by using anhydrous diethyl ether, washing the extract for 2-3 times by using saturated sodium carbonate solution, drying by using anhydrous sodium sulfate, vacuum filtering, and rotationally evaporating the filtrate to remove the solvent to obtain an intermediate 3;
the reaction process is as follows:
step A4: adding an intermediate 3, 4-bromostyrene, tetra (triphenylphosphine) palladium, anhydrous potassium carbonate and anhydrous tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and an air duct, introducing nitrogen for protection, stirring and reacting for 1-2h under the conditions of the temperature of 25-30 ℃ and the stirring speed of 400-500r/min, then continuously stirring and reacting for 10-15h under the conditions of the temperature of 80-85 ℃, cooling the reaction product to room temperature after the reaction is finished, then adding the reaction product into a saturated ammonium chloride solution, standing for layering, extracting an organic phase for 2-3 times by using dichloromethane, washing an extract for 3-5 times by using saturated saline, then drying by using anhydrous sodium sulfate, vacuum filtering, and rotationally evaporating a filtrate to remove the solvent to obtain the intermediate 4;
the reaction process is as follows:
step A5: adding the intermediate 4, 10% palladium carbon and absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and an air duct, introducing hydrogen to maintain the pressure at 0.6-0.8MPa, stirring at 70-75 ℃ for reaction for 5-6h under the condition of stirring speed of 400-500r/min, cooling the reaction product to room temperature after the reaction is finished, vacuum filtering, extracting the filtrate with dichloromethane for 2-3 times, and rotationally evaporating the extract to remove the solvent to obtain an intermediate 5;
the reaction process is as follows:
step A6: adding an intermediate 5, 2-chloro-1, 3-hexafluoropropane, potassium carbonate and N, N-dimethylformamide into a three-neck flask provided with a stirrer, a thermometer and an air duct, introducing nitrogen for protection, stirring and reacting for 30-50min under the condition that the temperature is-10-0 ℃ and the stirring speed is 400-500r/min, then heating to 90-95 ℃ and continuously stirring and reacting for 8-10h, cooling the reaction product to room temperature after the reaction is finished, then carrying out vacuum suction filtration, and rotationally evaporating the filtrate to remove the solvent to obtain the ultra-waterproof monomer.
The reaction process is as follows:
as a further scheme of the invention: the dosage ratio of the diphenylamine, the 1, 4-diiodobenzene, the copper powder, the sodium hydride and the xylene in the step A1 is 10mmol:10mmol:0.5-0.6g:0.11-0.13mmol:50-60mL.
As a further scheme of the invention: the dosage ratio of the intermediate 1, the triisopropyl borate, the anhydrous diethyl ether and the isopropyl magnesium bromide in the step A2 is 10mmol:11-13mmol:50-60mL:11-13mmol, wherein the mass fraction of the hydrochloric acid solution is 20-25%.
As a further scheme of the invention: the dosage ratio of the intermediate 2, the concentrated sulfuric acid and the concentrated nitric acid in the step A3 is 5g:20-30mL:60-70mL, wherein the mass fraction of the concentrated sulfuric acid is 98.3%, and the mass fraction of the concentrated nitric acid is 68%.
As a further scheme of the invention: the dosage ratio of the intermediate 3, 4-bromostyrene, tetrakis (triphenylphosphine) palladium, anhydrous potassium carbonate and anhydrous tetrahydrofuran in the step A4 is 10mmol:10mmol:0.6-0.8g:40-50mmol:80-100mL.
As a further scheme of the invention: the dosage ratio of the intermediate 4 to the 10% palladium carbon to the absolute ethanol in the step A5 is 5g:0.1-0.2g:80-100mL.
As a further scheme of the invention: the dosage ratio of the intermediate 5, 2-chloro-1, 3-hexafluoropropane, potassium carbonate and N, N-dimethylformamide in the step A6 is 10mmol:22-25mmol:80-100mmol:150-180mL.
As a further scheme of the invention: the sulfhydryl silicon dioxide is prepared by the following steps:
step B1: adding nano silicon dioxide and absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, performing ultrasonic dispersion for 30-40min under the condition of ultrasonic power of 300-350W, adding butyl titanate, performing stirring reaction for 20-30min under the condition of temperature of 60-65 ℃ and stirring speed of 400-500r/min, dropwise adding deionized water while stirring, controlling the dropping speed to be 1-2 drops/s, adjusting pH to 2-3 with nitric acid solution after the dropping is finished, continuing stirring reaction for 5-6h, performing vacuum suction filtration on a reaction product while the reaction is still hot, placing a filter cake in a vacuum drying box, drying for 2-2.5h under the condition of temperature of 100-110 ℃, placing in a tube furnace, calcining for 2-3h under the condition of temperature of 350-360 ℃ and naturally cooling along with the furnace to obtain coated silicon dioxide;
step B2: adding coated silicon dioxide and absolute ethyl alcohol into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, performing ultrasonic dispersion for 30-40min under the condition of ultrasonic power of 300-350W, then adding 3-mercaptopropyl trimethoxysilane dropwise while stirring under the condition of 60-65 ℃ and stirring speed of 400-500r/min, controlling the dropping speed to be 1-2 drops/s, heating to reflux after dropping, continuing stirring for reaction for 8-10h, cooling the reaction product to room temperature after the reaction is finished, centrifuging, placing the centrifugal product in a vacuum drying oven, and drying for 3-4h under the condition of 60-65 ℃ to obtain mercaptosilicon dioxide.
As a further scheme of the invention: the dosage ratio of the nano silicon dioxide, the absolute ethyl alcohol, the butyl titanate and the deionized water in the step B1 is 1g:40-50mL:0.5-2.5g:15-20mL, wherein the mass fraction of the nitric acid solution is 30-40%.
As a further scheme of the invention: the dosage ratio of the coated silica, the absolute ethyl alcohol and the 3-mercaptopropyl trimethoxysilane in the step B2 is 5g:55-60mL:1.5-2.5g.
As a further scheme of the invention: a preparation method of high-efficiency breathable waterproof sports shoes comprises the following steps:
step one: weighing 25-45 parts of China hemp fiber and 50-60 parts of cotton fiber according to parts by weight for standby;
step two: blending hemp fibers and cotton fibers to form mixed yarns, weaving the mixed yarns to form a fly-weaving vamp, spraying super waterproof emulsion with the spraying amount of 1.6-1.8g/sf on the outer surface of the fly-weaving vamp, and drying to form a waterproof protective layer to obtain the waterproof fly-weaving vamp;
step three: the waterproof fly-knitted vamp is sewn on the sole, and the high-efficiency breathable waterproof sports shoe is obtained.
The invention has the beneficial effects that:
according to the high-efficiency breathable waterproof sports shoes and the preparation method thereof, the hemp fibers and the cotton fibers are blended to form the mixed spinning threads, the mixed spinning threads are woven to form the fly-woven vamp, the outer surface of the fly-woven vamp is sprayed with the ultra-waterproof emulsion, and then the fly-woven vamp is dried to form the waterproof protective layer, so that the waterproof fly-woven vamp is obtained, and the waterproof fly-woven vamp is sewn on the sole to obtain the high-efficiency breathable waterproof sports shoes; according to the preparation method, the hemp fiber and the cotton fiber are used as raw materials to form the fly-knitted vamp, the hemp fiber and the cotton fiber belong to cellulose fiber, a large number of polar hydrophilic groups are contained in fiber molecules, the hemp fiber is easy to combine with water molecules to adsorb the water molecules when in contact with water, the hemp fiber has a unique structure, a large cavity is formed in the center of the fiber, a plurality of cracks and holes connected with the cavity are formed longitudinally, so that the fiber is provided with a large number of capillary channels, moisture and vapor in the fabric can be quickly transferred and diffused, when the foot sweats due to movement, sweat or moisture can be timely dredged to the surface of the fabric and is dissipated into the air, the air permeability is good, micropores exist between yarns of the woven fly-knitted vamp, ventilation can be further realized, then super-waterproof emulsion is sprayed on the fly-knitted vamp, a super-hydrophobic surface can be formed on the outer surface of the fly-knitted vamp, the super-waterproof emulsion is waterproof, the absorption and the dredged moisture on the inner surface of the hemp fiber are not influenced, and the wearing comfort of the sports shoe is improved;
in the process of preparing the high-efficiency breathable waterproof sports shoes, firstly preparing a super waterproof monomer, firstly utilizing one iodine atom on 1, 4-diiodobenzene to react with secondary amine groups on diphenylamine to obtain an intermediate 1, then utilizing triisopropyl borate to carry out boric acid on the intermediate 1 to obtain an intermediate 2, utilizing nitric acid and sulfuric acid to carry out nitration on the intermediate 2, introducing nitro to obtain an intermediate 3, utilizing the intermediate 3 to react with 4-bromostyrene, introducing alkenyl to obtain an intermediate 4, then utilizing hydrogen to reduce the nitro on the intermediate to amino to obtain an intermediate 5, utilizing the amino on the intermediate 5 to react with chlorine atoms on 2-chloro-1, 3-hexafluoropropane, and introducing a large number of C-F bonds to obtain the super waterproof monomer; in the process of preparing the high-efficiency breathable waterproof sports shoes, sulfhydryl silicon dioxide is also prepared, firstly, titanium dioxide is coated on the outer surface of nano silicon dioxide by utilizing butyl titanate hydrolysis to obtain coated silicon dioxide, then silanol is formed by utilizing siloxane hydrolysis on 3-mercaptopropyl trimethoxy silane to be grafted on the particle surface of the coated silicon dioxide, sulfhydryl is introduced to obtain sulfhydryl silicon dioxide; the super waterproof monomer contains alkenyl groups, so that the super waterproof monomer can be polymerized with methyl methacrylate, butyl acrylate and acrylic acid, a large number of C-F bonds are introduced into the formed polymer to endow the polymer with low surface energy, and the added sulfhydryl silicon dioxide is of an organic-inorganic composite structure, so that the super waterproof monomer has excellent dispersibility, can construct surface roughness, realizes the aim of constructing a super hydrophobic surface on a vamp of a sports shoe, and realizes hydrophobic waterproof and waterproof resistanceThe sulfydryl on the sulfydryl silicon dioxide can carry out sulfydryl-alkenyl click chemical reaction with alkenyl in the sulfydryl-alkenyl click chemical reaction in the process of polymerizing super waterproof monomers, methyl methacrylate, butyl acrylate and acrylic acid, so that the sulfydryl silicon dioxide is connected with a polymer in a chemical bond mode, the sulfydryl silicon dioxide is tightly connected, the sulfydryl silicon dioxide is not easy to fall off, meanwhile, the sulfydryl silicon dioxide can also protect a waterproof protection layer of the polymer, the wear-resistant and scratch-resistant performances of the waterproof protection layer are improved, the long-acting waterproof effect is realized, the silicon dioxide has good adsorptivity, peculiar smell in sports shoes can be adsorbed, meanwhile, the silicon dioxide and titanium dioxide have good ultraviolet absorptivity, the ultraviolet ageing performance of the waterproof protection layer can be improved, holes can be formed after ultraviolet absorption, and the holes are adsorbed on OH on the surface of a photocatalyst - 、H 2 Oxidation of O molecules to OH, HO 2 And (3) the free radicals have strong chemical activity, and when bacteria, viruses and peculiar smell organic matters are contacted with the active oxygen radicals, the free radicals are oxidized, so that the antibacterial deodorizing effect is realized.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, 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:
the embodiment is a preparation method of a super waterproof monomer, comprising the following steps:
step A1: adding 10mmol of diphenylamine, 10mmol of 1, 4-diiodobenzene, 0.5g of copper powder, 0.11mmol of sodium hydride and 50mL of anhydrous diethyl ether into a three-neck flask provided with a stirrer, a thermometer, an air duct and a reflux condenser, introducing nitrogen for protection, stirring at the temperature of 25 ℃ and the stirring speed of 400r/min for reacting for 0.5h, heating to reflux for reacting for 8h, cooling the reaction product to room temperature after the reaction is finished, performing vacuum suction filtration, washing the filtrate with distilled water for 2 times, standing for layering, drying the organic phase with anhydrous sodium sulfate, performing vacuum suction filtration, and performing rotary evaporation on the filtrate to remove the solvent to obtain an intermediate 1;
step A2: adding 10mmol of intermediate 1, 11mmol of triisopropyl borate and 50mL of anhydrous diethyl ether into a three-neck flask with a stirrer and a thermometer, stirring at the temperature of-5 ℃ and the stirring rate of 400r/min for reaction for 40min, adding 11mmol of isopropyl magnesium bromide for continuous stirring for reaction for 20min, heating to 65 ℃ for continuous stirring for reaction for 3h, adding a reaction product into a saturated ammonium chloride solution after the reaction is finished, adjusting the pH value to 1 by using a hydrochloric acid solution with the mass fraction of 20%, extracting for 2 times by using ethyl acetate, combining extract liquid, and rotationally evaporating the extract liquid to remove the solvent to obtain an intermediate 2;
step A3: adding 5g of intermediate 2, 20mL of 98.3% concentrated sulfuric acid and 60mL of 68% concentrated nitric acid into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and reacting for 30min at the temperature of-10 ℃ and the stirring rate of 400r/min, heating to reflux, continuing stirring and reacting for 5h, adding the reaction product into ice water after the reaction is finished, extracting for 2 times by using anhydrous diethyl ether, washing the extract for 2 times by using saturated sodium carbonate solution, drying by using anhydrous sodium sulfate, vacuum filtering, and rotationally evaporating the filtrate to remove the solvent to obtain intermediate 3;
step A4: 10mmol of intermediate 3, 10mmol of 4-bromostyrene, 0.6g of tetra (triphenylphosphine) palladium, 40mmol of anhydrous potassium carbonate and 80mL of anhydrous tetrahydrofuran are added into a three-neck flask provided with a stirrer, a thermometer and an air duct, nitrogen is introduced for protection, stirring is carried out for reaction for 1h under the condition that the temperature is 25 ℃ and the stirring rate is 400r/min, then the temperature is raised to 80 ℃ for continuous stirring reaction for 10h, the reaction product is cooled to room temperature after the reaction is finished, then the reaction product is added into saturated ammonium chloride solution, then the mixture is stood for layering, the organic phase is extracted for 2 times by dichloromethane, the extract is washed for 3 times by saturated saline water, then the mixture is dried by anhydrous sodium sulfate, then vacuum suction filtration is carried out, the solvent is removed by rotary evaporation of filtrate, and the intermediate 4 is obtained;
step A5: adding 5g of an intermediate 4, 0.1g of 10% palladium carbon and 80mL of absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and an air duct, introducing hydrogen to maintain the pressure at 0.6MPa, stirring at 70 ℃ for 5 hours under the condition of stirring rate of 400r/min, cooling a reaction product to room temperature after the reaction is finished, vacuum filtering, extracting filtrate with dichloromethane for 2 times, and rotationally evaporating an extract to remove the solvent to obtain an intermediate 5;
step A6: 10mmol of intermediate 5, 22mmol of 2-chloro-1, 3-hexafluoropropane, 80mmol of potassium carbonate and 150mLN, N-dimethylformamide are added into a three-neck flask provided with a stirrer, a thermometer and an air duct, nitrogen is introduced for protection, stirring is carried out for 30min under the condition that the temperature is minus 10 ℃ and the stirring rate is 400r/min, then the stirring reaction is continued for 8h under the condition that the temperature is raised to 90 ℃, the reaction product is cooled to room temperature after the reaction is finished, then vacuum suction filtration is carried out, and the solvent is removed by rotary evaporation of the filtrate, thus obtaining the ultra-waterproof monomer.
Example 2:
the embodiment is a preparation method of a super waterproof monomer, comprising the following steps:
step A1: adding 10mmol of diphenylamine, 10mmol of 1, 4-diiodobenzene, 0.6g of copper powder, 0.13mmol of sodium hydride and 60mL of anhydrous diethyl ether into a three-neck flask provided with a stirrer, a thermometer, an air duct and a reflux condenser, introducing nitrogen for protection, stirring at a temperature of 30 ℃ and a stirring rate of 500r/min for reaction for 1h, heating to reflux, continuing stirring for reaction for 10h, cooling the reaction product to room temperature after the reaction is finished, performing vacuum suction filtration, washing the filtrate with distilled water for 3 times, standing for layering, drying the organic phase with anhydrous sodium sulfate, performing vacuum suction filtration, and performing rotary evaporation on the filtrate to remove the solvent to obtain an intermediate 1;
step A2: adding 10mmol of intermediate 1, 13mmol of triisopropyl borate and 60mL of anhydrous diethyl ether into a three-neck flask provided with a stirrer and a thermometer, stirring and reacting for 50min at the temperature of 0 ℃ and the stirring rate of 500r/min, adding 13mmol of isopropyl magnesium bromide, continuously stirring and reacting for 30min, heating to 70 ℃ and continuously stirring and reacting for 5h, adding a reaction product into a saturated ammonium chloride solution after the reaction is finished, adjusting the pH value to 2 by using a 25% hydrochloric acid solution by mass fraction, extracting for 3 times by using ethyl acetate, combining extract liquid, and rotationally evaporating the extract liquid to remove a solvent to obtain an intermediate 2;
step A3: adding 5g of intermediate 2, 30mL of 98.3% concentrated sulfuric acid and 70mL of 68% concentrated nitric acid into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and reacting for 50min at the temperature of 0 ℃ and the stirring rate of 500r/min, heating to reflux, continuing stirring and reacting for 6h, adding the reaction product into ice water after the reaction is finished, extracting for 3 times by using anhydrous diethyl ether, washing the extract for 3 times by using saturated sodium carbonate solution, drying by using anhydrous sodium sulfate, vacuum filtering, and rotationally evaporating the filtrate to remove the solvent to obtain intermediate 3;
step A4: 10mmol of intermediate 3, 10mmol of 4-bromostyrene, 0.8g of tetra (triphenylphosphine) palladium, 50mmol of anhydrous potassium carbonate and 100mL of anhydrous tetrahydrofuran are added into a three-neck flask provided with a stirrer, a thermometer and an air duct, nitrogen is introduced for protection, stirring is carried out for 2 hours under the condition that the temperature is 30 ℃ and the stirring speed is 500r/min, then the temperature is raised to 85 ℃ for continuous stirring for 15 hours, the reaction product is cooled to room temperature after the reaction is finished, then the reaction product is added into saturated ammonium chloride solution, then the mixture is stood for layering, the organic phase is extracted for 3 times by methylene dichloride, the extract is washed for 5 times by saturated saline water, then the mixture is dried by anhydrous sodium sulfate, then the mixture is filtered in a vacuum way, the filtrate is subjected to rotary evaporation to remove the solvent, and intermediate 4 is obtained;
step A5: adding 5g of an intermediate 4, 0.2g of 10% palladium carbon and 100mL of absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and an air duct, introducing hydrogen to maintain the pressure at 0.8MPa, stirring at 75 ℃ for reaction for 6 hours under the condition of stirring rate of 500r/min, cooling a reaction product to room temperature after the reaction is finished, vacuum filtering, extracting filtrate with dichloromethane for 3 times, and rotationally evaporating an extract to remove the solvent to obtain an intermediate 5;
step A6: 10mmol of intermediate 5, 25mmol of 2-chloro-1, 3-hexafluoropropane, 100mmol of potassium carbonate and 180mLN, N-dimethylformamide are added into a three-neck flask provided with a stirrer, a thermometer and an air duct, nitrogen is introduced for protection, stirring is carried out for 50min under the condition that the temperature is 0 ℃ and the stirring rate is 500r/min, then the stirring reaction is continued for 10h under the condition that the temperature is raised to 95 ℃, the reaction product is cooled to room temperature after the reaction is finished, then vacuum suction filtration is carried out, and the solvent is removed by rotary evaporation of the filtrate, thus obtaining the ultra-waterproof monomer.
Example 3:
the embodiment is a preparation method of sulfhydryl silicon dioxide, comprising the following steps:
step B1: adding 1g of nano silicon dioxide and 40mL of absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, performing ultrasonic dispersion for 30min under the condition of ultrasonic power of 300W, adding 0.5g of butyl titanate, stirring and reacting for 20min under the condition of 60 ℃ and stirring rate of 400r/min, adding 15mL of deionized water dropwise while stirring, controlling the dropping rate to be 1 drop/s, regulating the pH value to 2 by using a nitric acid solution with mass fraction of 30% after the dropping is finished, continuing stirring and reacting for 5h, performing vacuum suction filtration on a reaction product while the reaction product is still hot, placing a filter cake in a vacuum drying box, drying for 2h under the condition of 100 ℃, placing the filter cake in a tubular furnace, calcining for 2h under the condition of 350 ℃ and naturally cooling along with the furnace to obtain coated silicon dioxide;
step B2: 5g of coated silica and 55mL of absolute ethyl alcohol are added into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, ultrasonic dispersion is carried out for 30min under the condition of ultrasonic power of 300W, then 1.5g of 3-mercaptopropyl trimethoxysilane is added dropwise under the condition of 60 ℃ and 400r/min of stirring speed, the dropping speed is controlled to be 1 drop/s, the temperature is raised to reflux after the dropping is finished, stirring reaction is continued for 8h, the reaction product is cooled to room temperature after the reaction is finished, then centrifugation is carried out, the centrifugation product is placed in a vacuum drying oven, and drying is carried out for 3h under the condition of 60 ℃ to obtain the mercaptosilica.
Example 4:
the embodiment is a preparation method of sulfhydryl silicon dioxide, comprising the following steps:
step B1: adding 1g of nano silicon dioxide and 50mL of absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, performing ultrasonic dispersion for 40min under the condition of ultrasonic power of 350W, adding 2.5g of butyl titanate, performing stirring reaction for 30min under the condition of temperature of 65 ℃ and stirring rate of 500r/min, adding 20mL of deionized water dropwise while stirring, controlling the dropping rate to be 2 drops/s, adjusting the pH value to 3 by using a nitric acid solution with mass fraction of 40% after the dropping is finished, continuing stirring reaction for 6h, performing vacuum suction filtration on a reaction product while the reaction product is still hot, placing a filter cake in a vacuum drying box, drying for 2.5h under the condition of temperature of 110 ℃, placing the filter cake in a tube furnace, calcining for 3h under the condition of temperature of 360 ℃, and naturally cooling along with the furnace to obtain coated silicon dioxide;
step B2: 5g of coated silica and 60mL of absolute ethyl alcohol are added into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, ultrasonic dispersion is carried out for 40min under the condition that ultrasonic power is 350W, then 2.5g of 3-mercaptopropyl trimethoxysilane is added dropwise under the condition that the temperature is 65 ℃ and the stirring rate is 500r/min, the dropping rate is controlled to be 2 drops/s, the stirring reaction is continued under the condition that the temperature is raised to reflux after the dropping is finished for 10h, the reaction product is cooled to room temperature after the reaction is finished, and then the centrifugal product is centrifuged, and is placed in a vacuum drying box and dried for 4h under the condition that the temperature is 65 ℃ to obtain the mercaptosilica.
Example 5:
the embodiment is a preparation method of the high-efficiency breathable waterproof sports shoe, which comprises the following steps:
step one: weighing 3 parts of super waterproof monomer, 20 parts of methyl methacrylate, 10 parts of butyl acrylate, 3 parts of acrylic acid, 6 parts of sulfhydryl silicon dioxide, 1 part of emulsifier, 0.15 part of potassium persulfate and 50 parts of deionized water according to parts by weight for standby; the superwaterproof monomer is the superwaterproof monomer in example 1; the mercapto silica is the mercapto silica of example 3; the emulsifier is NP-10 emulsifier and DNS-86 emulsifier, and the mass ratio is 1: 1.5;
step two: adding a super waterproof monomer, methyl methacrylate, butyl acrylate, acrylic acid, an emulsifier and 4/5 deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 30min under the condition that the temperature is 25 ℃ and the stirring rate is 400r/min, then continuously stirring and reacting for 15min under the condition that the temperature is raised to 80 ℃, dissolving potassium persulfate in the rest 1/5 deionized water to form a potassium persulfate solution, then dropwise adding the potassium persulfate solution while stirring, controlling the dropwise adding rate to be 1 drop/s, continuously stirring and reacting for 1h after the dropwise adding, then continuously stirring and reacting for 3h after the dropwise adding of mercapto silicon dioxide, cooling the reaction product to room temperature after the reaction, and then regulating the pH to 7 by using ammonia water with the mass fraction of 20% to obtain the super waterproof emulsion;
step three: weighing 25 parts of China hemp fibers and 50 parts of cotton fibers according to parts by weight for standby;
step four: blending hemp fibers and cotton fibers to form mixed yarns, weaving the mixed yarns to form a fly-weaving vamp, spraying super waterproof emulsion with the spraying amount of 1.6g/sf on the outer surface of the fly-weaving vamp, and then drying to form a waterproof protective layer to obtain the waterproof fly-weaving vamp;
step five: the waterproof fly-knitted vamp is sewn on the sole, and the high-efficiency breathable waterproof sports shoe is obtained.
Example 6:
the embodiment is a preparation method of the high-efficiency breathable waterproof sports shoe, which comprises the following steps:
step one: weighing 15 parts of super waterproof monomer, 25 parts of methyl methacrylate, 12 parts of butyl acrylate, 5 parts of acrylic acid, 14 parts of sulfhydryl silicon dioxide, 1.5 parts of emulsifier, 0.25 part of potassium persulfate and 60 parts of deionized water according to parts by weight for standby; the superwaterproof monomer is the superwaterproof monomer in example 2; the mercapto silica is the mercapto silica of example 4; the emulsifier is NP-10 emulsifier and DNS-86 emulsifier, and the mass ratio is 1:2, a mixture of two or more of the above-mentioned materials;
step two: adding a super waterproof monomer, methyl methacrylate, butyl acrylate, acrylic acid, an emulsifier and 4/5 deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 40min under the condition of 30 ℃ and 500r/min stirring rate, heating to 85 ℃ and continuously stirring and reacting for 20min, dissolving potassium persulfate in the rest 1/5 deionized water to form a potassium persulfate solution, dropwise adding the potassium persulfate solution while stirring, controlling the dropwise adding rate to be 2 drops/s, continuously stirring and reacting for 2h after the dropwise adding, then adding mercapto silicon dioxide and continuously stirring and reacting for 5h, cooling the reaction product to room temperature after the reaction, and then regulating the pH to 7 by using 25% ammonia water by mass fraction to obtain the super waterproof emulsion;
step three: weighing 45 parts of China hemp fibers and 60 parts of cotton fibers according to parts by weight for standby;
step four: blending hemp fibers and cotton fibers to form mixed yarns, weaving the mixed yarns to form a fly-weaving vamp, spraying super waterproof emulsion with the spraying amount of 1.8g/sf on the outer surface of the fly-weaving vamp, and then drying to form a waterproof protective layer to obtain the waterproof fly-weaving vamp;
step five: the waterproof fly-knitted vamp is sewn on the sole, and the high-efficiency breathable waterproof sports shoe is obtained.
Comparative example 1:
comparative example 1 differs from example 6 in that no superwater-repellent monomer and mercapto silica were added.
Comparative example 2:
comparative example 2 differs from example 6 in that no superwater-repellent monomer was added.
Comparative example 3:
comparative example 3 differs from example 6 in that no mercapto silica was added.
The performance of the waterproof protective layer on the high-efficiency breathable waterproof athletic shoes of examples 5-6 and comparative examples 1-3 was tested and the test results are shown in the following table:
| sample of | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Water drop contact angle, ° | 153 | 161 | 83 | 117 | 135 |
| Coliform bacteria inhibition rate under ultraviolet light, percent | 99.2 | 99.8 | 29.6 | 91.8 | 68.6 |
| Coliform bacteria inhibition rate under natural light, percent | 90.6 | 94.1 | 15.3 | 85.2 | 63.5 |
Under the detection condition of ultraviolet light, a 100WUVA ultraviolet lamp is used as a visible light source to illuminate for 30min, and under the detection condition of natural light, a 40W fluorescent lamp is used as a visible light source to illuminate for 30min.
Referring to the above table data, according to the comparison between examples 5-6 and comparative examples 1-3, it can be known that the addition of the ultra-waterproof monomer and the mercapto silica can greatly improve the hydrophobic and antibacterial properties of the efficient breathable waterproof sports shoe, and can also improve the antibacterial and bacteriostatic properties to a certain extent, wherein the addition of the ultra-waterproof monomer plays a major role in the waterproof properties of the efficient breathable waterproof sports shoe, and the addition of the mercapto silica plays a major role in the antibacterial properties of the efficient breathable waterproof sports shoe.
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-efficiency breathable waterproof sports shoes are characterized by comprising soles and waterproof fly-knitted vamps sewn on the soles, wherein the waterproof fly-knitted vamps are prepared by spraying super waterproof emulsion on the fly-knitted vamps;
wherein, the super waterproof emulsion is prepared by the following steps:
step one: weighing 3-15 parts of super waterproof monomer, 20-25 parts of methyl methacrylate, 10-12 parts of butyl acrylate, 3-5 parts of acrylic acid, 6-14 parts of mercapto silicon dioxide, 1-1.5 parts of emulsifier, 0.15-0.25 part of potassium persulfate and 50-60 parts of deionized water according to parts by weight for standby;
step two: adding a super waterproof monomer, methyl methacrylate, butyl acrylate, acrylic acid, an emulsifier and 4/5 deionized water into a three-neck flask, stirring and reacting, dissolving potassium persulfate in the rest 1/5 deionized water to form a potassium persulfate solution, then dropwise adding the potassium persulfate solution while stirring, continuing stirring and reacting after the dropwise adding is finished, then adding mercapto silicon dioxide, continuing stirring and reacting, cooling the reaction product to room temperature after the reaction is finished, and then adjusting the pH value to obtain the super waterproof emulsion.
2. The efficient breathable waterproof sneaker according to claim 1, wherein the emulsifying agent is an NP-10 emulsifying agent and a DNS-86 emulsifying agent according to a mass ratio of 1: 1.5-2.
3. The efficient breathable waterproof athletic shoe of claim 1, wherein the ultra-waterproof monomer is prepared by:
step A1: adding diphenylamine, 1, 4-diiodobenzene, copper powder, sodium hydride and anhydrous diethyl ether into a three-neck flask, stirring for reaction, cooling a reaction product after the reaction is finished, performing vacuum filtration, washing filtrate, standing for layering, drying an organic phase, performing vacuum filtration, and performing rotary evaporation on the filtrate to obtain an intermediate 1;
step A2: adding the intermediate 1, triisopropyl borate and anhydrous diethyl ether into a three-neck flask, stirring for reaction, adding isopropyl magnesium bromide, continuously stirring for reaction, adding a reaction product into a saturated ammonium chloride solution after the reaction is finished, adjusting the pH, extracting, and rotationally evaporating an extract to obtain an intermediate 2;
step A3: adding the intermediate 2, concentrated sulfuric acid and concentrated nitric acid into a three-neck flask, stirring for reaction, adding a reaction product into ice water after the reaction is finished, extracting, washing and drying an extract, vacuum filtering, and rotationally evaporating filtrate to obtain an intermediate 3;
step A4: adding intermediate 3, 4-bromostyrene, tetra (triphenylphosphine) palladium, anhydrous potassium carbonate and anhydrous tetrahydrofuran into a three-neck flask, stirring for reaction, cooling a reaction product after the reaction is finished, adding the reaction product into a saturated ammonium chloride solution, standing for layering, extracting an organic phase, washing and drying an extract, vacuum filtering, and rotationally evaporating a filtrate to obtain an intermediate 4;
step A5: adding the intermediate 4, 10% palladium carbon and absolute ethyl alcohol into a three-neck flask, introducing hydrogen to stir for reaction, cooling a reaction product to room temperature after the reaction is finished, performing vacuum filtration, extracting filtrate, and rotationally evaporating an extract to obtain an intermediate 5;
step A6: adding the intermediate 5, 2-chloro-1, 3-hexafluoropropane, potassium carbonate and N, N-dimethylformamide into a three-neck flask, stirring for reaction, cooling a reaction product after the reaction is finished, performing vacuum suction filtration, and rotationally evaporating filtrate to obtain the ultra-waterproof monomer.
4. A high-efficiency breathable waterproof athletic shoe according to claim 3, wherein the dosage ratio of diphenylamine, 1, 4-diiodobenzene, copper powder, sodium hydride and xylene in step A1 is 10mmol:10mmol:0.5-0.6g:0.11-0.13mmol:50-60mL; the dosage ratio of the intermediate 1, the triisopropyl borate, the anhydrous diethyl ether and the isopropyl magnesium bromide in the step A2 is 10mmol:11-13mmol:50-60mL:11-13mmol.
5. A high-efficiency breathable waterproof sports shoe according to claim 3, characterized in that the ratio of the amount of intermediate 2, concentrated sulfuric acid and concentrated nitric acid in step A3 is 5g:20-30mL:60-70mL, wherein the mass fraction of the concentrated sulfuric acid is 98.3%, and the mass fraction of the concentrated nitric acid is 68%; the dosage ratio of the intermediate 3, 4-bromostyrene, tetrakis (triphenylphosphine) palladium, anhydrous potassium carbonate and anhydrous tetrahydrofuran in the step A4 is 10mmol:10mmol:0.6-0.8g:40-50mmol:80-100mL.
6. A high-efficiency breathable waterproof sports shoe according to claim 3, characterized in that the intermediate 4 in step A5, 10% palladium on carbon and absolute ethyl alcohol are used in a ratio of 5g:0.1-0.2g:80-100mL; the dosage ratio of the intermediate 5, 2-chloro-1, 3-hexafluoropropane, potassium carbonate and N, N-dimethylformamide in the step A6 is 10mmol:22-25mmol:80-100mmol:150-180mL.
7. A high efficiency vapor permeable waterproof athletic shoe according to claim 3, wherein said mercapto silica is prepared by the steps of:
step B1: adding nano silicon dioxide and absolute ethyl alcohol into a three-neck flask for ultrasonic dispersion, adding butyl titanate for stirring reaction, adding deionized water dropwise while stirring, adjusting pH after the dripping is finished, continuing stirring reaction, carrying out vacuum suction filtration on a reaction product while the reaction product is hot after the reaction is finished, and drying and calcining a filter cake to obtain coated silicon dioxide;
step B2: adding coated silicon dioxide and absolute ethyl alcohol into a four-mouth flask for ultrasonic dispersion, then adding 3-mercaptopropyl trimethoxy silane dropwise while stirring, continuing stirring for reaction after the dripping is finished, cooling a reaction product after the reaction is finished, centrifuging, and drying a centrifugal product to obtain the mercaptosilicon dioxide.
8. The efficient breathable waterproof athletic shoe of claim 7, wherein the nano silica, absolute ethyl alcohol, butyl titanate and deionized water in step B1 are used in a ratio of 1g:40-50mL:0.5-2.5g:15-20mL; the dosage ratio of the coated silica, the absolute ethyl alcohol and the 3-mercaptopropyl trimethoxysilane in the step B2 is 5g:55-60mL:1.5-2.5g.
9. The preparation method of the high-efficiency breathable waterproof sports shoe is characterized by comprising the following steps of:
step one: weighing 25-45 parts of China hemp fiber and 50-60 parts of cotton fiber according to parts by weight for standby;
step two: blending hemp fibers and cotton fibers to form mixed yarns, weaving the mixed yarns to form a fly-weaving vamp, spraying super waterproof emulsion with the spraying amount of 1.6-1.8g/sf on the outer surface of the fly-weaving vamp, and drying to form a waterproof protective layer to obtain the waterproof fly-weaving vamp;
step three: the waterproof fly-knitted vamp is sewn on the sole, and the high-efficiency breathable waterproof sports shoe is obtained.
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