CN113845683A - Automatically cleaning plastic rain shoes with super amphiphobic coating - Google Patents
Automatically cleaning plastic rain shoes with super amphiphobic coating Download PDFInfo
- Publication number
- CN113845683A CN113845683A CN202110919583.8A CN202110919583A CN113845683A CN 113845683 A CN113845683 A CN 113845683A CN 202110919583 A CN202110919583 A CN 202110919583A CN 113845683 A CN113845683 A CN 113845683A
- Authority
- CN
- China
- Prior art keywords
- super
- parts
- hydrophobic
- amphiphobic coating
- titanium dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920003023 plastic Polymers 0.000 title claims abstract description 44
- 239000004033 plastic Substances 0.000 title claims abstract description 44
- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 title claims abstract description 32
- 238000004140 cleaning Methods 0.000 title claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 39
- 239000000839 emulsion Substances 0.000 claims abstract description 30
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 30
- 229920002635 polyurethane Polymers 0.000 claims abstract description 30
- 239000004814 polyurethane Substances 0.000 claims abstract description 30
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 24
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000003973 paint Substances 0.000 claims abstract description 17
- 239000007921 spray Substances 0.000 claims abstract description 17
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 239000004014 plasticizer Substances 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 238000005507 spraying Methods 0.000 claims abstract description 6
- 239000012745 toughening agent Substances 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000001746 injection moulding Methods 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- KKBLHVKRIORLHR-UHFFFAOYSA-N 1,3-diisocyanato-1,5,5-trimethyl-2-methylidenecyclohexane Chemical compound N(=C=O)C1(C(C(CC(C1)(C)C)N=C=O)=C)C KKBLHVKRIORLHR-UHFFFAOYSA-N 0.000 claims description 5
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 claims description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 230000000844 anti-bacterial effect Effects 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 239000003899 bactericide agent Substances 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 238000009966 trimming Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000004383 yellowing Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 210000003423 ankle Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/14—Footwear characterised by the material made of plastics
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Public Health (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a self-cleaning plastic rain shoe with a super-amphiphobic coating, wherein the super-amphiphobic coating is sprayed on the surface of the plastic rain shoe, and the preparation method comprises the following steps: s1, preparing rain boot blanks by using PVC resin, carbon black, diethylene glycol, a plasticizer, a toughening agent and an anti-aging agent; s2, preparing hydrophobic aqueous polyurethane emulsion and modified titanium dioxide nanoparticles, and mixing the hydrophobic aqueous polyurethane emulsion, the modified titanium dioxide nanoparticles and auxiliary materials to prepare super-hydrophobic spray paint; and S3, uniformly spraying the super-hydrophobic spray paint prepared in the step S2 on the surface of the plastic rain shoe blank, and curing to obtain the plastic rain shoe. The super-amphiphobic coating is sprayed on the surface of the plastic rain shoe, the modified super-amphiphobic coating is prepared by using hydrophobic aqueous polyurethane emulsion and modified titanium dioxide nano particles as main raw materials, the coating shows super-hydrophobicity and oleophobicity, and the plastic rain shoe adopting the modified super-amphiphobic coating has a self-cleaning function.
Description
Technical Field
The invention relates to the field of rain boot production, in particular to a self-cleaning plastic rain boot with a super-amphiphobic coating.
Background
The rain shoes are waterproof shoes worn in rainy days, the style of the rain shoes is not single, and the tube-shaped rain shoes and the sneakers have similar appearances; the tube height of the tube-shaped rain shoe is about 10 centimeters above the ankle; tube height and knee of high tube-shaped rain shoe. Ordinary people often wear the middle-tube-shaped and short-tube-shaped rain shoes, and some professionals of special trades need the high-tube-shaped rain shoes as labor protection articles for working in rain-proof or water accumulation environments in rainy days. The rain shoes are divided into the following parts by material: rubber rain shoes, PVC rain shoes, EVA rain shoes and the like.
In daily use, the rain shoes can be oxidized, exposed to the sun and heated at high temperature to accelerate aging, so that the rain shoes become hard and soft. Meanwhile, the rain shoes are often used in a water accumulation environment or a workshop environment, are easily infected by the external environment, are stained with oil stains or sludge, and are difficult to clean after being used for a long time. Therefore, a pollution-resistant rain boot with a self-cleaning function is needed to meet the use requirement of a high-pollution environment.
Disclosure of Invention
In order to solve the defects in the background technology, the invention aims to provide the self-cleaning plastic rain shoe with the super-amphiphobic coating.
The purpose of the invention can be realized by the following technical scheme:
a self-cleaning plastic rain shoe with a super-amphiphobic coating is provided, the super-amphiphobic coating is sprayed on the surface of the plastic rain shoe, and the preparation method comprises the following steps:
s1, adding PVC resin, carbon black, diethylene glycol, a plasticizer, a toughening agent and an anti-aging agent into a double-screw extruder, mixing and granulating, adding the obtained composite plastic particles into an injection molding machine, casting and molding, demolding to obtain rain boot blanks, and trimming rough edges of the rain boot blanks by using a cutting tool;
s2, preparing hydrophobic aqueous polyurethane emulsion by taking 3-isocyanato methylene-3, 5, 5-trimethyl cyclohexyl isocyanate and polyoxypropylene glycol as raw materials, preparing modified titanium dioxide nano particles through chemical grafting reaction between octadecyl isocyanate and hydroxyl on the surface of titanium dioxide, and mixing the hydrophobic aqueous polyurethane emulsion, the modified titanium dioxide nano particles and auxiliary materials to prepare super-hydrophobic spray paint;
and S3, uniformly spraying the super-hydrophobic spray paint prepared in the step S2 on the surface of the plastic rain shoe blank, and curing to obtain the plastic rain shoe.
Further preferably, the composite plastic particles in step S1 include the following raw materials in parts by weight: 80-100 parts of PVC resin, 5-10 parts of carbon black, 1-3 parts of diethylene glycol, 30-40 parts of plasticizer, 0.5-1 part of toughening agent and 0.2-0.5 part of anti-aging agent.
Further preferably, the temperature of the twin-screw extruder in the step S1 is 110-125 ℃, and the injection pressure of the injection molding machine in the step S1 is 10-14 MPa.
Further preferably, the super-hydrophobic spray paint of step S3 comprises the following raw materials in parts by weight: 40-60 parts of hydrophobic water-based polyurethane emulsion, 10-15 parts of modified titanium dioxide nanoparticles, 0.1-5 parts of stabilizer, 0.1-5 parts of leveling assistant, 0.1-3 parts of defoaming agent, 0.2-5 parts of bactericide, 0.5-2 parts of flatting agent, 0.1-2 parts of anti-yellowing agent, 0.1-3 parts of other assistant and 30-80 parts of deionized water.
Further preferably, the preparation method of the hydrophobic aqueous polyurethane emulsion in the step S2 includes the following steps:
(1) adding 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate, hydroxyl silicone oil and polyoxypropylene glycol into a reactor, slowly raising the temperature to 70-80 ℃, and reacting for 2-4h at constant temperature;
(2) adding 2, 2-dimethylolpropionic acid and 1, 4-butanediol to continue reacting for 1-3h, and adding monohydroxypolysiloxane for end capping;
(3) cooling to 45-55 ℃, adding triethylamine for neutralization reaction for 20-40min, and adding water containing hydrazine hydrate at a high stirring speed of 25-35 ℃ for emulsification and dispersion to obtain the hydrophobic aqueous polyurethane emulsion.
Further preferably, the preparation method of the modified titanium dioxide nanoparticles in the step S2 includes the steps of:
A. in an ice-water bath environment, adding anhydrous titanium tetrachloride into anhydrous ethanol, then adding the mixed solution into benzyl alcohol, stirring and reacting for 8-10h at 80-85 ℃ to obtain semitransparent TiO2Suspending liquid, washing the precipitate by diethyl ether to obtain TiO2A nanoparticle;
B. purifying the TiO2Dispersing the nano particles in triethylamine, performing ultrasonic dispersion at 55-65 ℃ for 20-30min, adding dibutyltin dilaurate into the well-dispersed suspension, raising the temperature to 70-90 ℃, and stirring for reaction for 12-15h
C. Pumping and filtering the final reaction product by a circulating water vacuum pump, repeatedly washing, filtering and purifying by using toluene, acetone and distilled water, and finally drying for 12-24h at 60-70 ℃ under vacuum to obtain light yellow powder, namely modified TiO2And (3) nanoparticles.
The invention has the beneficial effects that:
the super-amphiphobic coating is sprayed on the surface of the plastic rain shoe, the modified super-amphiphobic coating is prepared by using hydrophobic aqueous polyurethane emulsion and modified titanium dioxide nano particles as main raw materials, the coating shows super-hydrophobicity and oleophobicity, and the plastic rain shoe adopting the modified super-amphiphobic coating has a self-cleaning function.
The invention uses toluene-2, 4-diisocyanate (TDI) with diisocyanato group to TiO2The surface is subjected to hydrophobic modification, a hybrid composite network structure is formed through two-step chemical reaction, the durability of the coating is greatly enhanced, the amphiphobicity of the coating is stable, and almost no change occurs when the coating is placed for 30 days under ultraviolet irradiation or placed in a natural light environment for one year.
The invention takes 3-isocyanate methylene-3, 5, 5-trimethyl cyclohexyl isocyanate, hydroxyl silicone oil, polyoxypropylene glycol, 2-dimethylolpropionic acid and 1, 4-butanediol as main raw materials to synthesize NCO-terminated prepolymer, and then uses monohydroxy polysiloxane for termination to prepare the terminated silicon-containing polyurethane emulsion.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
In the description of the present invention, it is to be understood that the terms "opening," "upper," "lower," "thickness," "top," "middle," "length," "inner," "peripheral," and the like are used in an orientation or positional relationship that is merely for convenience in describing and simplifying the description, and do not indicate or imply that the referenced component or element must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be considered as limiting the present invention.
Example 1
A self-cleaning plastic rain shoe with a super-amphiphobic coating is provided, the super-amphiphobic coating is sprayed on the surface of the plastic rain shoe, and the preparation method comprises the following steps:
s1, adding 80 parts of PVC resin, 5 parts of carbon black, 1 part of diethylene glycol, 30 parts of plasticizer, 0.5 part of flexibilizer and 0.2 part of anti-aging agent into a double-screw extruder, mixing and granulating at 110 ℃, adding the obtained composite plastic particles into an injection molding machine, casting and molding under the pressure of 10Mpa, obtaining rain boot blanks after demolding, and then trimming rough edges of the rain boot blanks by using a cutting tool;
s2, preparing hydrophobic aqueous polyurethane emulsion by taking 3-isocyanato methylene-3, 5, 5-trimethyl cyclohexyl isocyanate and polyoxypropylene glycol as raw materials, preparing modified titanium dioxide nano particles through chemical grafting reaction between octadecyl isocyanate and hydroxyl on the surface of titanium dioxide, and mixing the hydrophobic aqueous polyurethane emulsion, the modified titanium dioxide nano particles and auxiliary materials to prepare super-hydrophobic spray paint;
and S3, uniformly spraying the super-hydrophobic spray paint prepared in the step S2 on the surface of the plastic rain shoe blank, and curing to obtain the plastic rain shoe.
Step S3, the super-hydrophobic spray paint comprises the following raw materials in parts by weight: 40 parts of hydrophobic aqueous polyurethane emulsion, 10 parts of modified titanium dioxide nanoparticles, 0.1 part of stabilizer, 0.1 part of leveling assistant, 0.1 part of defoaming agent, 0.2 part of bactericide, 0.5 part of flatting agent, 0.1 part of anti-yellowing agent, 0.1 part of other assistant and 30 parts of deionized water.
The preparation method of the hydrophobic aqueous polyurethane emulsion in the step S2 comprises the following steps:
(1) adding 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate, hydroxyl silicone oil and polyoxypropylene glycol into a reactor, slowly raising the temperature to 70 ℃, and reacting for 2 hours at constant temperature;
(2) adding 2, 2-dimethylolpropionic acid and 1, 4-butanediol to continue reacting for 1h, and adding monohydroxypolysiloxane to terminate;
(3) cooling to 45 ℃, adding triethylamine for neutralization reaction for 20min, and adding water containing hydrazine hydrate at a high stirring speed of 25 ℃ for emulsification and dispersion to obtain the hydrophobic aqueous polyurethane emulsion.
The preparation method of the modified titanium dioxide nanoparticles in the step S2 includes the steps of:
A. in the environment of ice-water bath, adding anhydrous titanium tetrachloride into anhydrous ethanol, then adding the mixed solution into benzyl alcohol, stirring and reacting for 8h at 80 ℃ to obtain semitransparent TiO2Suspending liquid, washing the precipitate by diethyl ether to obtain TiO2A nanoparticle;
B. purifying the TiO2Dispersing the nano particles in triethylamine, performing ultrasonic dispersion at 55 ℃ for 20min, then adding dibutyltin dilaurate into the well-dispersed suspension, raising the temperature to 70 ℃, and stirring for reaction for 12 h;
C. pumping and filtering the final reaction product by a circulating water vacuum pump, repeatedly washing, filtering and purifying by using toluene, acetone and distilled water, and finally drying for 12-24h at 60-70 ℃ under vacuum to obtain light yellow powder, namely modified TiO2And (3) nanoparticles.
Example 2
A self-cleaning plastic rain shoe with a super-amphiphobic coating is provided, the super-amphiphobic coating is sprayed on the surface of the plastic rain shoe, and the preparation method comprises the following steps:
s1, adding 100 parts of PVC resin, 10 parts of carbon black, 3 parts of diethylene glycol, 40 parts of plasticizer, 1 part of toughening agent and 0.5 part of anti-aging agent into a double-screw extruder, mixing and granulating at 110 ℃, adding the obtained composite plastic particles into an injection molding machine, casting and molding under the pressure of 14Mpa, obtaining rain boot blanks after demolding, and trimming rough edges of the rain boot blanks by using a cutting tool;
s2, preparing hydrophobic aqueous polyurethane emulsion by taking 3-isocyanato methylene-3, 5, 5-trimethyl cyclohexyl isocyanate and polyoxypropylene glycol as raw materials, preparing modified titanium dioxide nano particles through chemical grafting reaction between octadecyl isocyanate and hydroxyl on the surface of titanium dioxide, and mixing the hydrophobic aqueous polyurethane emulsion, the modified titanium dioxide nano particles and auxiliary materials to prepare super-hydrophobic spray paint;
and S3, uniformly spraying the super-hydrophobic spray paint prepared in the step S2 on the surface of the plastic rain shoe blank, and curing to obtain the plastic rain shoe.
Step S3, the super-hydrophobic spray paint comprises the following raw materials in parts by weight: 60 parts of hydrophobic aqueous polyurethane emulsion, 15 parts of modified titanium dioxide nanoparticles, 5 parts of stabilizer, 5 parts of leveling assistant, 3 parts of defoaming agent, 5 parts of bactericide, 2 parts of flatting agent, 2 parts of anti-yellowing agent, 3 parts of other assistant and 80 parts of deionized water.
The preparation method of the hydrophobic aqueous polyurethane emulsion in the step S2 comprises the following steps:
(1) adding 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate, hydroxyl silicone oil and polyoxypropylene glycol into a reactor, slowly raising the temperature to 75 ℃, and reacting for 3 hours at constant temperature;
(2) adding 2, 2-dimethylolpropionic acid and 1, 4-butanediol to continue reacting for 2h, and adding monohydroxypolysiloxane for end capping;
(3) cooling to 50 ℃, adding triethylamine for neutralization reaction for 30min, and adding water containing hydrazine hydrate at a high stirring speed of 30 ℃ for emulsification and dispersion to obtain the hydrophobic aqueous polyurethane emulsion.
The preparation method of the modified titanium dioxide nanoparticles in the step S2 includes the steps of:
A. in the environment of ice-water bath, anhydrous fourAdding titanium chloride into absolute ethyl alcohol, then transferring the mixed solution into benzyl alcohol, stirring and reacting for 9h at the temperature of 80 ℃ to obtain semitransparent TiO2Suspending liquid, washing the precipitate by diethyl ether to obtain TiO2A nanoparticle;
B. purifying the TiO2Dispersing the nano particles in triethylamine, performing ultrasonic dispersion for 25min at 60 ℃, then adding dibutyltin dilaurate into the well-dispersed suspension, raising the temperature to 80 ℃, and stirring for reaction for 14 h;
C. pumping and filtering the final reaction product by a circulating water vacuum pump, repeatedly washing, filtering and purifying by using toluene, acetone and distilled water, and finally drying for 18 hours at 65 ℃ under vacuum to obtain light yellow powder, namely modified TiO2And (3) nanoparticles.
Example 3
A self-cleaning plastic rain shoe with a super-amphiphobic coating is provided, the super-amphiphobic coating is sprayed on the surface of the plastic rain shoe, and the preparation method comprises the following steps:
s1, adding 90 parts of PVC resin, 8 parts of carbon black, 2 parts of diethylene glycol, 35 parts of plasticizer, 0.8 part of flexibilizer and 0.4 part of anti-aging agent into a double-screw extruder, mixing and granulating at 120 ℃, adding the obtained composite plastic particles into an injection molding machine, casting and molding under the pressure of 12MPa, demolding to obtain rain boot blanks, and trimming the rough edges of the rain boot blanks by using a cutting tool;
s2, preparing hydrophobic aqueous polyurethane emulsion by taking 3-isocyanato methylene-3, 5, 5-trimethyl cyclohexyl isocyanate and polyoxypropylene glycol as raw materials, preparing modified titanium dioxide nano particles through chemical grafting reaction between octadecyl isocyanate and hydroxyl on the surface of titanium dioxide, and mixing the hydrophobic aqueous polyurethane emulsion, the modified titanium dioxide nano particles and auxiliary materials to prepare super-hydrophobic spray paint;
and S3, uniformly spraying the super-hydrophobic spray paint prepared in the step S2 on the surface of the plastic rain shoe blank, and curing to obtain the plastic rain shoe.
Step S3, the super-hydrophobic spray paint comprises the following raw materials in parts by weight: 50 parts of hydrophobic aqueous polyurethane emulsion, 12 parts of modified titanium dioxide nanoparticles, 3 parts of stabilizer, 3 parts of leveling assistant, 1 part of defoaming agent, 0.5 part of bactericide, 1 part of flatting agent, 0.5 part of anti-yellowing agent, 1 part of other assistant and 50 parts of deionized water.
The preparation method of the hydrophobic aqueous polyurethane emulsion in the step S2 comprises the following steps:
(1) adding 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate, hydroxyl silicone oil and polyoxypropylene glycol into a reactor, slowly raising the temperature to 75 ℃, and reacting for 3 hours at constant temperature;
(2) adding 2, 2-dimethylolpropionic acid and 1, 4-butanediol to continue reacting for 2h, and adding monohydroxypolysiloxane for end capping;
(3) cooling to 50 ℃, adding triethylamine for neutralization reaction for 30min, and adding water containing hydrazine hydrate at a high stirring speed of 30 ℃ for emulsification and dispersion to obtain the hydrophobic aqueous polyurethane emulsion.
The preparation method of the modified titanium dioxide nanoparticles in the step S2 includes the steps of:
A. in the environment of ice-water bath, adding anhydrous titanium tetrachloride into anhydrous ethanol, then adding the mixed solution into benzyl alcohol, stirring and reacting for 10h at 80 ℃ to obtain semitransparent TiO2Suspending liquid, washing the precipitate by diethyl ether to obtain TiO2A nanoparticle;
B. purifying the TiO2Dispersing the nano particles in triethylamine, performing ultrasonic dispersion for 25min at 60 ℃, then adding dibutyltin dilaurate into the well dispersed suspension, raising the temperature to 80 ℃, and stirring for reaction for 13 h;
C. pumping and filtering the final reaction product by a circulating water vacuum pump, repeatedly washing, filtering and purifying by using toluene, acetone and distilled water, and finally drying for 18 hours at 65 ℃ under vacuum to obtain light yellow powder, namely modified TiO2And (3) nanoparticles.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to 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 invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. 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 shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (6)
1. A self-cleaning plastic rain boot with a super-amphiphobic coating is characterized in that the super-amphiphobic coating is sprayed on the surface of the plastic rain boot, and the preparation method comprises the following steps:
s1, adding PVC resin, carbon black, diethylene glycol, a plasticizer, a toughening agent and an anti-aging agent into a double-screw extruder, mixing and granulating, adding the obtained composite plastic particles into an injection molding machine, casting and molding, demolding to obtain rain boot blanks, and trimming rough edges of the rain boot blanks by using a cutting tool;
s2, preparing hydrophobic aqueous polyurethane emulsion by taking 3-isocyanato methylene-3, 5, 5-trimethyl cyclohexyl isocyanate and polyoxypropylene glycol as raw materials, preparing modified titanium dioxide nano particles through chemical grafting reaction between octadecyl isocyanate and hydroxyl on the surface of titanium dioxide, and mixing the hydrophobic aqueous polyurethane emulsion, the modified titanium dioxide nano particles and auxiliary materials to prepare super-hydrophobic spray paint;
and S3, uniformly spraying the super-hydrophobic spray paint prepared in the step S2 on the surface of the plastic rain shoe blank, and curing to obtain the plastic rain shoe.
2. The self-cleaning plastic rain boot with super-amphiphobic coating of claim 1, wherein the composite plastic particles in the step S1 comprise the following raw materials in parts by weight: 80-100 parts of PVC resin, 5-10 parts of carbon black, 1-3 parts of diethylene glycol, 30-40 parts of plasticizer, 0.5-1 part of toughening agent and 0.2-0.5 part of anti-aging agent.
3. The self-cleaning plastic rain boot with super-amphiphobic coating as claimed in claim 1, wherein the temperature of the twin-screw extruder in the step S1 is 110-125 ℃, and the injection pressure of the injection machine in the step S1 is 10-14 Mpa.
4. The self-cleaning plastic rain boot with super-amphiphobic coating of claim 1, wherein the step S3 super-hydrophobic spray paint comprises the following raw materials in parts by weight: 40-60 parts of hydrophobic water-based polyurethane emulsion, 10-15 parts of modified titanium dioxide nanoparticles, 0.1-5 parts of stabilizer, 0.1-5 parts of leveling assistant, 0.1-3 parts of defoaming agent, 0.2-5 parts of bactericide, 0.5-2 parts of flatting agent, 0.1-2 parts of anti-yellowing agent, 0.1-3 parts of other assistant and 30-80 parts of deionized water.
5. The self-cleaning plastic rain shoe with the super-amphiphobic coating as claimed in claim 1, wherein the preparation method of the hydrophobic aqueous polyurethane emulsion in the step S2 comprises the following steps:
(1) adding 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate, hydroxyl silicone oil and polyoxypropylene glycol into a reactor, slowly raising the temperature to 70-80 ℃, and reacting for 2-4h at constant temperature;
(2) adding 2, 2-dimethylolpropionic acid and 1, 4-butanediol to continue reacting for 1-3h, and adding monohydroxypolysiloxane for end capping;
(3) cooling to 45-55 ℃, adding triethylamine for neutralization reaction for 20-40min, and adding water containing hydrazine hydrate at a high stirring speed of 25-35 ℃ for emulsification and dispersion to obtain the hydrophobic aqueous polyurethane emulsion.
6. The self-cleaning plastic rain shoe with the super-amphiphobic coating as claimed in claim 1, wherein the preparation method of the modified titanium dioxide nano-particles in the step S2 comprises the following steps:
A. in the environment of ice-water bath, anhydrous titanium tetrachloride is added into anhydrous ethanol, and then the mixed solution is added into benzeneStirring and reacting in methanol at 80-85 ℃ for 8-10h to obtain semitransparent TiO2Suspending liquid, washing the precipitate by diethyl ether to obtain TiO2A nanoparticle;
B. purifying the TiO2Dispersing the nano particles in triethylamine, performing ultrasonic dispersion at 55-65 ℃ for 20-30min, adding dibutyltin dilaurate into the well-dispersed suspension, raising the temperature to 70-90 ℃, and stirring for reaction for 12-15h
C. Pumping and filtering the final reaction product by a circulating water vacuum pump, repeatedly washing, filtering and purifying by using toluene, acetone and distilled water, and finally drying for 12-24h at 60-70 ℃ under vacuum to obtain light yellow powder, namely modified TiO2And (3) nanoparticles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110919583.8A CN113845683A (en) | 2021-08-11 | 2021-08-11 | Automatically cleaning plastic rain shoes with super amphiphobic coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110919583.8A CN113845683A (en) | 2021-08-11 | 2021-08-11 | Automatically cleaning plastic rain shoes with super amphiphobic coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113845683A true CN113845683A (en) | 2021-12-28 |
Family
ID=78975764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110919583.8A Pending CN113845683A (en) | 2021-08-11 | 2021-08-11 | Automatically cleaning plastic rain shoes with super amphiphobic coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113845683A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116445069A (en) * | 2023-01-10 | 2023-07-18 | 吉安天晟新材料有限公司 | Heat-insulating rock slice |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150086713A1 (en) * | 2013-09-23 | 2015-03-26 | Tamkang University | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion, and production method and use thereof |
| CN105255348A (en) * | 2015-10-13 | 2016-01-20 | 厦门大学 | One-component transparent waterborne polyurethane emulsion waterproof paint and preparation method thereof |
| CN107880770A (en) * | 2017-11-24 | 2018-04-06 | 武汉理工大学 | A kind of preparation method of environment protection multifunctional super-hydrophobic coat |
| CN111363265A (en) * | 2020-03-10 | 2020-07-03 | 浙江和和塑胶有限公司 | Environment-friendly oil-resistant PVC rain shoes and preparation process thereof |
-
2021
- 2021-08-11 CN CN202110919583.8A patent/CN113845683A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150086713A1 (en) * | 2013-09-23 | 2015-03-26 | Tamkang University | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion, and production method and use thereof |
| CN105255348A (en) * | 2015-10-13 | 2016-01-20 | 厦门大学 | One-component transparent waterborne polyurethane emulsion waterproof paint and preparation method thereof |
| CN107880770A (en) * | 2017-11-24 | 2018-04-06 | 武汉理工大学 | A kind of preparation method of environment protection multifunctional super-hydrophobic coat |
| CN111363265A (en) * | 2020-03-10 | 2020-07-03 | 浙江和和塑胶有限公司 | Environment-friendly oil-resistant PVC rain shoes and preparation process thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116445069A (en) * | 2023-01-10 | 2023-07-18 | 吉安天晟新材料有限公司 | Heat-insulating rock slice |
| CN116445069B (en) * | 2023-01-10 | 2024-01-12 | 吉安天晟新材料有限公司 | Heat-insulating rock slice |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106675370B (en) | A kind of aqueous anti-pollution automatically cleaning polyurethane coating of high abrasion and preparation method thereof | |
| CN105506997A (en) | Delustering waterborne polyurethane leather finishing agent and preparation method thereof | |
| CN113845683A (en) | Automatically cleaning plastic rain shoes with super amphiphobic coating | |
| CN105732938B (en) | A kind of preparation method of polyester polyether type aqueous polyurethane leather finishing agent | |
| CN108977030B (en) | Preparation method of fluorinated halloysite nanotube/waterborne polyurethane composite hydrophobic coating | |
| CN109554935B (en) | Production process of antibacterial and mildewproof synthetic leather | |
| CN104231209A (en) | Preparation method for high-hardness waterborne polyurethane dispersion | |
| CN105131806B (en) | Aqueous fluorescent polyurethane coating and its prepolymer blend method preparation method | |
| CN110791237B (en) | Water-based carpet backing adhesive and preparation method thereof | |
| CN107892895A (en) | A kind of preparation method of modified silane polyethers glue | |
| CN105062347A (en) | Synthetic method for matte waterborne polyurethane resin composite emulsion | |
| CN106519741B (en) | The compound super hydrophilic wear-resistant paint of silicon zirconium | |
| CN110028889A (en) | A kind of environment-protection functional water paint on plastic material | |
| CN114410271B (en) | Double-component polyurethane joint beautifying agent and preparation method and application thereof | |
| CN103232831A (en) | Single-component aqueous polyurethane adhesive and preparation method thereof | |
| CN103467688B (en) | A kind of preparation method of aqueous polyurethane | |
| CN113584898A (en) | Silica gel leather for automobile seat and preparation method thereof | |
| CN115636919B (en) | Preparation method and application of high-performance polyurethane | |
| CN110527475B (en) | Sprayable anti-sagging silane modified polyether sealant and preparation method thereof | |
| CN106349452B (en) | Hold the preparation method of fluoroalkyl super branched polyurethane nano hybridization leather finishing agent | |
| CN106928829A (en) | A kind of Aqueous Polyurethane Leather Finishing Agent preparation method | |
| CN113549187B (en) | Aqueous polyurethane for microfiber leather and preparation method thereof | |
| CN104694064A (en) | Method for preparing polyurethane adhesive by modifying waste polyurethane recovery product by using montmorillonite | |
| CN112538152B (en) | Waterborne polyurethane-polyurea dispersion and preparation method and application thereof | |
| CN109852071A (en) | Fluorosilicone rubber composition, preparation method and the sealant and coating prepared by the composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211228 |
|
| RJ01 | Rejection of invention patent application after publication |