CN106433437A - Spray method for preparing super-hydrophobic and super-oleophilic copper net - Google Patents
Spray method for preparing super-hydrophobic and super-oleophilic copper net Download PDFInfo
- Publication number
- CN106433437A CN106433437A CN201610821663.9A CN201610821663A CN106433437A CN 106433437 A CN106433437 A CN 106433437A CN 201610821663 A CN201610821663 A CN 201610821663A CN 106433437 A CN106433437 A CN 106433437A
- Authority
- CN
- China
- Prior art keywords
- super
- hydrophobic
- copper mesh
- glycol
- oil
- 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.)
- Granted
Links
Classifications
-
- 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
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C09D175/08—Polyurethanes from polyethers
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
-
- 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
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
-
- 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
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- 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
Abstract
The invention relates to a spray method for preparing a super-hydrophobic and super-oleophilic copper net. An existing oil-water separation method is long in separation time, adopts complicated procedures and is low in separation efficiency, and oil and water in an oil-water mixture cannot be completely separated. Polymer polyatomic alcohols and polyisocyanate are taken and mixed for a reaction, a hydrophilic chain extender and dibutyltin dilaurate are added, a neutralizer is added for neutralization after the reaction, amino silicon oil is added, a prepolymer containing hydrophobic side chains is obtained and dispersed in deionized water, a waterborne polyurethane emulsion containing hydrophilic side groups is obtained, hydrophobic fumed nano silica is dispersed in acetone, the waterborne polyurethane emulsion containing the hydrophilic side groups is added, a coating agent is obtained, applied to the surface of the copper net and dried, and the super-hydrophobic/super-oleophilic copper net is obtained. The copper net is good in repairability, wear-resistant and acid-alkaline-resistant, and an oil-water separator made by the copper net has great advantages in separation efficiency and separation rate and has broad market prospect.
Description
The method that spraying process prepares super-hydrophobic super-oleophylic copper mesh.
Technical field
The invention belongs to technical field of function materials is and in particular to a kind of spraying process prepares the side of super-hydrophobic super-oleophylic copper mesh
Method.
Background technology
With the high speed development of offshore oil exploitation and modernization industry, offshore oil and chemical reagent leakage accident are increasingly
Frequently, the water pollution thus causing constitutes grave danger to environmental and human health impacts.Traditional oil-water separation method mainly has
Gravitational separation process, Filtration, centrifuging, floatation and electrochemical process etc..These separation method low separation efficiencies, separate not thorough
Bottom, and separation equipment is costly.Therefore, compared with traditional separation method, super-hydrophobic/super-oleophilic material is because having separation efficiency
High high with selectivity the features such as, be a kind of booming new function material.
At present, in document, the oil-water separation base material of report mainly has foamed materialss, fiber-based material, mesh materials and many
Hole material with carbon element etc..Foamed materialss are with low cost, are industrially used widely, but relatively low porosity leads to its separation efficiency
Low.Though porous carbon materials have higher porosity, mechanical property is weaker, at present still in research among.Fiber base separation material
Material has with low cost, the advantage such as separation efficiency height, but in the sea water of high salinity, fiber itself is ageing-resistant, ph stability
Difference, limits its application.And copper mesh is as inert oil-water separation base material, corrosion resistance preferably, in the weakly alkaline sea of high salinity
There is in water the using value of reality.Additionally, being also with the catalysis characteristicses of copper, the other organic pollution thing of degraded.Therefore, exist
In numerous water-oil separating materials, copper mesh application potential is huge.
Preparing the common method of super-hydrophobic/super-oleophilic copper mesh has dip-coating method, etching method, liquid-phase growth method, and air sprays
Coating etc..Wherein, air spray finishing process is simple, can large-area construction, and do not limited by any base material, be therefore most readily available
Extensively apply, but the copper mesh wearable stripping-off resistant performance of existing method is not high.
Content of the invention
It is an object of the invention to provide a kind of method that spraying process prepares super-hydrophobic super-oleophylic copper mesh, improve copper mesh wear-resisting resistance to
Stripping performance.
The technical solution adopted in the present invention is：
Spraying process prepare super-hydrophobic super-oleophylic copper mesh method it is characterised in that：
Realized by following steps：
Step one：The preparation of hydrophobic type aqueous polyurethane：
Mol ratio is taken to be 1：（2-3）Polymer polyatomic alcohol and polyisocyanates 70-85 DEG C of stirring reaction 1- under nitrogen protection
1.5h；
Addition is counted with polymer polyatomic alcohol and polyisocyanates gross mass, the hydrophilic chain extender as 3%-3.5% for the mass fraction, and drips
Plus 3-5 drips dibutyl tin laurate, at a temperature of 85-90 DEG C, react 1.5-2h；
It is cooled to 40-60 DEG C, add nertralizer reaction, nNertralizer：nHydrophilic chain extender=0.8-1:1；
Addition is counted with polymer polyatomic alcohol and polyisocyanates gross mass, the amido silicon oil as 4%-8% for the mass fraction, 10-30 DEG C
Lower reaction 0.5-1h, obtains the performed polymer containing hydrophobic side chain；
Then the performed polymer containing hydrophobic side chain is scattered in deionized water under high velocity agitation, obtains the aqueouss containing hydrophobic side base
Polyaminoester emulsion；
Step 2：The preparation of coating agent：
Take 0.2-0.4g hydrophobic type gas phase nano silicon dioxide ultrasonic disperse in 50ml acetone, after being uniformly dispersed, add
0.04-0.08g contains the aqueous polyurethane emulsion of hydrophobic side base, and high-speed stirred 5-10min obtains coating agent；
Step 3：The preparation of super-hydrophobic/super-oleophilic copper mesh：
Dried up standby after copper mesh is cleaned with acetone and deionized water successively with nitrogen；Followed by air gun, by step 2
In coating agent be sprayed on copper mesh surface, obtain super-hydrophobic/super-oleophilic copper mesh after being dried.
In step：
Polymer polyatomic alcohol is selected from 10PE27 glycol, polyneopentyl glycol adipate glycol, polyadipate second two
Alcohol propylene glycol ester glycol, polybutylene glyool adipate, polyhexamethylene adipate glycol, polyadipate ethylene glycol one contracting two
Glycol ester glycol, polytetrahydrofuran diol, PCDL；
Polyisocyanates is selected from 4,4- dicyclohexyl methyl hydride diisocyanate, isophorone diisocyanate, 1,6- hexylidene two
Isocyanates, XDI；
Hydrophilic chain extender is selected from dihydromethyl propionic acid, dihydroxy half ester, diethylenetriamine, methyl diethanolamine；
Nertralizer is selected from triethylamine, sodium hydroxide, triethanolamine；
Amido silicon oil is aminoethylaminopropyl polydimethylsiloxane.
In step one, the acetone being not more than 2 times of polymer polyatomic alcohol quality was added to reduce viscosity before adding nertralizer,
After the performed polymer containing hydrophobic side chain is scattered in deionized water, vacuum distillation removes acetone.
In step 2：Hydrophobic type gas phase nano silicon dioxide specific surface area is 120m2/ g, particle diameter is 1 ~ 40nm.
In step 3：
The copper mesh being used is brass screen, and the aperture of copper mesh is 100-200 mesh；
The operating pressure of aerial spraying is 4-6kPa, and spray distance is 10-20cm；
The translational speed of copper mesh is 3-5cm/s；
Described baking temperature is 70-90 DEG C, and drying time is 1h-2h.
The present invention has advantages below：
1 compares with traditional oil-water separation method, and the water-oil separating material of present invention preparation has high separation efficiency and divides
From speed, effectively overcome traditional oil-water separation low separation efficiency, separate not thoroughly the problems such as.
2nd, the present invention adopts copper mesh as base material, and corrosion resistance preferably, has answering of reality in the sea water of high salt weak base
Use performance.Additionally, coating adopts polyurethane material as binding agent, there is excellent wear-resisting, weather-proof and acid and alkali-resistance stability.
3rd, the present invention adopts spraying process preparation water-oil separating material simple, and the prices of raw materials used are cheap, come
Source extensively, has great application prospect.
Brief description
Fig. 1：The scanning electron microscope (SEM) photograph one of the super-hydrophobic/super-oleophilic copper mesh of present invention preparation；
Fig. 2：The scanning electron microscope (SEM) photograph two of the super-hydrophobic/super-oleophilic copper mesh of present invention preparation；
Fig. 3：The separation efficiency figure to different solvents for the super-hydrophobic/super-oleophilic copper mesh of present invention preparation；
Fig. 4：The recycling efficiency chart of the super-hydrophobic/super-oleophilic copper mesh of present invention preparation.
Specific embodiment
With reference to specific embodiment, the present invention will be described in detail.
The method that spraying process according to the present invention prepares super-hydrophobic super-oleophylic copper mesh, different with water surface tension using oil,
Select the super-hydrophobic/super-oleophilic copper mesh different with water affinity to oil it to be carried out separate, first aqueous polyurethane is dredged
Aquation is modified.Subsequently, add it in the acetone dispersion liquor of hydrophobic nano silicon dioxide.After mix homogeneously, using spraying
Method prepares super-hydrophobic/super-oleophilic copper mesh, and is applied in oil water separator, is specifically realized by following steps：
Step one：The preparation of hydrophobic type aqueous polyurethane：
Mol ratio is taken to be 1：（2-3）Polymer polyatomic alcohol and polyisocyanates 70-85 DEG C of stirring reaction 1- under nitrogen protection
1.5h；
Addition is counted with polymer polyatomic alcohol and polyisocyanates gross mass, the hydrophilic chain extender as 3%-3.5% for the mass fraction, and drips
Plus 3-5 drips dibutyl tin laurate, at a temperature of 85-90 DEG C, react 1.5-2h；
It is cooled to 40-60 DEG C, add nertralizer reaction, nNertralizer：nHydrophilic chain extender=0.8-1:1；
Addition is counted with polymer polyatomic alcohol and polyisocyanates gross mass, the amido silicon oil as 4%-8% for the mass fraction, 10-30 DEG C
Lower reaction 0.5-1h, obtains the performed polymer containing hydrophobic side chain；
Then the performed polymer containing hydrophobic side chain is scattered in deionized water under high velocity agitation, obtains the aqueouss containing hydrophobic side base
Polyaminoester emulsion；
Step 2：The preparation of coating agent：
Take 0.2-0.4g hydrophobic type gas phase nano silicon dioxide ultrasonic disperse in 50ml acetone, after being uniformly dispersed, add
0.04-0.08g contains the aqueous polyurethane emulsion of hydrophobic side base, and high-speed stirred 5-10min obtains coating agent；
Step 3：The preparation of super-hydrophobic/super-oleophilic copper mesh：
Dried up standby after copper mesh is cleaned with acetone and deionized water successively with nitrogen；Followed by air gun, by step 2
In coating agent be sprayed on copper mesh surface, obtain super-hydrophobic/super-oleophilic copper mesh after being dried.
In step：
Polymer polyatomic alcohol is selected from 10PE27 glycol, polyneopentyl glycol adipate glycol, polyadipate second two
Alcohol propylene glycol ester glycol, polybutylene glyool adipate, polyhexamethylene adipate glycol, polyadipate ethylene glycol one contracting two
Glycol ester glycol, polytetrahydrofuran diol, PCDL；
Polyisocyanates is selected from 4,4- dicyclohexyl methyl hydride diisocyanate, isophorone diisocyanate, 1,6- hexylidene two
Isocyanates, XDI；
Hydrophilic chain extender is selected from dihydromethyl propionic acid, dihydroxy half ester, diethylenetriamine, methyl diethanolamine；
Nertralizer is selected from triethylamine, sodium hydroxide, triethanolamine；
Amido silicon oil is aminoethylaminopropyl polydimethylsiloxane.
In step one, the acetone being not more than 2 times of polymer polyatomic alcohol quality was added to reduce viscosity before adding nertralizer,
After the performed polymer containing hydrophobic side chain is scattered in deionized water, vacuum distillation removes acetone.
In step 2：Hydrophobic type gas phase nano silicon dioxide specific surface area is 120m2/ g, particle diameter is 1 ~ 40nm.
In step 3：
The copper mesh being used is brass screen, and the aperture of copper mesh is 100-200 mesh；
The operating pressure of aerial spraying is 4-6kPa, and spray distance is 10-20cm；
The translational speed of copper mesh is 3-5cm/s；
Described baking temperature is 70-90 DEG C, and drying time is 1h-2h.
Embodiment 1：
Step one：The preparation of hydrophobic type aqueous polyurethane
Mol ratio is taken to be 1：2 polymer polyatomic alcohol and polyisocyanates 70 DEG C of stirring reactions 1.5h under nitrogen protection；Add
Mass fraction is 3%（In terms of Waterborne Polyurethane Prepolymer gross mass）Hydrophilic chain extender, and 3 di lauric dibutyls of Deca
Stannum, reacts 2h at a temperature of 85 DEG C；It is cooled to 50 DEG C, add the acetone of 1 times of polymer polyatomic alcohol quality to reduce viscosity, add
Nertralizer（nNertralizer：nHydrophilic chain extender=0.8:1）；Add 4% amido silicon oil, at 10 DEG C, react 1h, then will be pre- containing hydrophobic side chain
Aggressiveness is scattered in deionized water under high velocity agitation；Vacuum distillation removes the acetone in emulsion, obtains the water containing hydrophobic side base
Property polyaminoester emulsion.
Polymer polyatomic alcohol is 10PE27 glycol；Polyisocyanates is 4,4- dicyclohexyl methyl hydride two isocyanide
Acid esters；Hydrophilic chain extender is dihydroxy half ester；Nertralizer is triethanolamine；Amido silicon oil is aminoethylaminopropyl poly dimethyl silicon
Oxygen alkane.
Step 2：The preparation of coating agent
Take 0.2g hydrophobic type gas phase nano silicon dioxide ultrasonic disperse in 50ml acetone, after being uniformly dispersed, add 0.04g
Aqueous polyurethane emulsion containing hydrophobic side base, high-speed stirred 5min obtains coating agent.
Hydrophobic type gas phase nano silicon dioxide specific surface area is 120m2/ g, particle diameter is 1 ~ 40nm, is carried by Aladdin reagent net
For.
Step 3：The preparation of super-hydrophobic/super-oleophilic copper mesh
Dried up standby after copper mesh is cleaned with acetone and deionized water successively with nitrogen；Followed by air gun, by step 2
In coating agent be sprayed on copper mesh surface under certain operating pressure, obtain super-hydrophobic/super-oleophilic copper mesh after being dried.
The copper mesh being used is brass screen, and the aperture of copper mesh is 100 mesh；Aerial spraying operating pressure be 4kPa, spraying away from
From for 10cm；The translational speed of copper mesh is 3cm/s；Described baking temperature is 70 DEG C, and drying time is 1h.
Embodiment 2：
Step one：The preparation of hydrophobic type aqueous polyurethane
Mol ratio is taken to be 1：2.5 polymer polyatomic alcohol and polyisocyanates 80 DEG C of stirring reactions 1.25h under nitrogen protection；Plus
Entering mass fraction is 3.25%（In terms of Waterborne Polyurethane Prepolymer gross mass）Hydrophilic chain extender, and 4 tin dilaurate two of Deca
Butyl tin, reacts 1.7h at a temperature of 87 DEG C；It is cooled to 50 DEG C, add the acetone of 1 times of polymer polyatomic alcohol quality to reduce viscosity,
Add nertralizer（nNertralizer：nHydrophilic chain extender=0.9:1）；Add 6% amido silicon oil, react 0.75h at 20 DEG C, then will contain hydrophobic
The performed polymer of side chain is scattered in deionized water under high velocity agitation；Vacuum distillation removes the acetone in emulsion, obtains containing hydrophobic
The aqueous polyurethane emulsion of side base.
Polymer polyatomic alcohol is PCDL；Polyisocyanates is 1,6- hexylidene diisocyanate；Hydrophilic chain extension
Agent is dihydroxy half ester；Nertralizer is sodium hydroxide；Amido silicon oil is aminoethylaminopropyl polydimethylsiloxane.
Step 2：The preparation of coating agent
Take 0.3g hydrophobic type gas phase nano silicon dioxide ultrasonic disperse in 50ml acetone, after being uniformly dispersed, add 0.06g
Aqueous polyurethane emulsion containing hydrophobic side base, high-speed stirred 7min obtains coating agent.
Hydrophobic type gas phase nano silicon dioxide specific surface area is 120m2/ g, particle diameter is 1 ~ 40nm, is carried by Aladdin reagent net
For.
Step 3：The preparation of super-hydrophobic/super-oleophilic copper mesh
Dried up standby after copper mesh is cleaned with acetone and deionized water successively with nitrogen；Followed by air gun, by step 2
In coating agent be sprayed on copper mesh surface under certain operating pressure, obtain super-hydrophobic/super-oleophilic copper mesh after being dried.
The copper mesh being used is brass screen, and the aperture of copper mesh is 150 mesh；Aerial spraying operating pressure be 5kPa, spraying away from
From for 15cm；The translational speed of copper mesh is 4cm/s；Described baking temperature is 80 DEG C, and drying time is 1.5h.
Embodiment 3：
Step one：The preparation of hydrophobic type aqueous polyurethane
Mol ratio is taken to be 1：3 polymer polyatomic alcohol and polyisocyanates 85 DEG C of stirring reactions 1h under nitrogen protection；Add matter
Amount fraction is 3.5%（In terms of Waterborne Polyurethane Prepolymer gross mass）Hydrophilic chain extender, and 5 di lauric dibutyls of Deca
Stannum, reacts 1.5h at a temperature of 90 DEG C；It is cooled to 40 DEG C, add the acetone of 2 times of polymer polyatomic alcohol quality to reduce viscosity, then
Add nertralizer（nNertralizer：nHydrophilic chain extender=1:1）；Add 8% amido silicon oil, react 0.5h at 30 DEG C, then will contain hydrophobic side chain
Performed polymer be scattered under high velocity agitation in deionized water；Vacuum distillation removes the acetone in emulsion, obtains containing hydrophobic side base
Aqueous polyurethane emulsion.
Polymer polyatomic alcohol is polytetrahydrofuran diol；Polyisocyanates is isophorone diisocyanate；Hydrophilic chain extension
Agent is dihydromethyl propionic acid；Nertralizer is triethylamine；Amido silicon oil is aminoethylaminopropyl polydimethylsiloxane.
Step 2：The preparation of coating agent
Take 0.4g hydrophobic type gas phase nano silicon dioxide ultrasonic disperse in 50ml acetone, after being uniformly dispersed, add 0.08g
Aqueous polyurethane emulsion containing hydrophobic side base, high-speed stirred 10min obtains coating agent.
Hydrophobic type gas phase nano silicon dioxide specific surface area is 120m2/ g, particle diameter is 1 ~ 40nm, is carried by Aladdin reagent net
For.
Step 3：The preparation of super-hydrophobic/super-oleophilic copper mesh
Dried up standby after copper mesh is cleaned with acetone and deionized water successively with nitrogen；Followed by air gun, by step 2
In coating agent be sprayed on copper mesh surface under certain operating pressure, obtain super-hydrophobic/super-oleophilic copper mesh after being dried.
The copper mesh being used is brass screen, and the aperture of copper mesh is 200 mesh；Aerial spraying operating pressure be 6kPa, spraying away from
From for 20cm；The translational speed of copper mesh is 5cm/s；Described baking temperature is 90 DEG C, and drying time is 2h.
The present invention is prepared for a kind of super-hydrophobic/super-oleophilic coating using spraying process on copper mesh surface.This coating is received with hydrophobic
Rice silicon dioxide granule constructs coarse structure, serves as between nanoparticle with hydrophobic polyurethane resin and nano coating and copper mesh
Between binding agent, improve copper mesh wearable stripping-off resistant performance.This oil-water separation copper mesh preparation method is simple, low cost of manufacture
Honest and clean, recoverability is good, and wear-resisting, acid and alkali-resistance good stability, and oil-water separation efficiency and the rate of departure are all higher and with low cost,
Range of application and the field of water-oil separating material will significantly be expanded.
Present disclosure is not limited to cited by embodiment, and those of ordinary skill in the art pass through to read description of the invention
And any equivalent conversion that technical solution of the present invention is taken, the claim being the present invention covered.
Claims (5)
1. spraying process prepare super-hydrophobic super-oleophylic copper mesh method it is characterised in that：
Realized by following steps：
Step one：The preparation of hydrophobic type aqueous polyurethane：
Mol ratio is taken to be 1：（2-3）Polymer polyatomic alcohol and polyisocyanates 70-85 DEG C of stirring reaction 1- under nitrogen protection
1.5h；
Addition is counted with polymer polyatomic alcohol and polyisocyanates gross mass, the hydrophilic chain extender as 3%-3.5% for the mass fraction, and drips
Plus 3-5 drips dibutyl tin laurate, at a temperature of 85-90 DEG C, react 1.5-2h；
It is cooled to 40-60 DEG C, add nertralizer reaction, nNertralizer：nHydrophilic chain extender=0.8-1:1；
Addition is counted with polymer polyatomic alcohol and polyisocyanates gross mass, the amido silicon oil as 4%-8% for the mass fraction, 10-30 DEG C
Lower reaction 0.5-1h, obtains the performed polymer containing hydrophobic side chain；
Then the performed polymer containing hydrophobic side chain is scattered in deionized water under high velocity agitation, obtains the aqueouss containing hydrophobic side base
Polyaminoester emulsion；
Step 2：The preparation of coating agent：
Take 0.2-0.4g hydrophobic type gas phase nano silicon dioxide ultrasonic disperse in 50ml acetone, after being uniformly dispersed, add
0.04-0.08g contains the aqueous polyurethane emulsion of hydrophobic side base, and high-speed stirred 5-10min obtains coating agent；
Step 3：The preparation of super-hydrophobic/super-oleophilic copper mesh：
Dried up standby after copper mesh is cleaned with acetone and deionized water successively with nitrogen；Followed by air gun, by step 2
In coating agent be sprayed on copper mesh surface, obtain super-hydrophobic/super-oleophilic copper mesh after being dried.
2. spraying process according to claim 1 prepare super-hydrophobic super-oleophylic copper mesh method it is characterised in that：
In step：
Polymer polyatomic alcohol is selected from 10PE27 glycol, polyneopentyl glycol adipate glycol, polyadipate second two
Alcohol propylene glycol ester glycol, polybutylene glyool adipate, polyhexamethylene adipate glycol, polyadipate ethylene glycol one contracting two
Glycol ester glycol, polytetrahydrofuran diol, PCDL；
Polyisocyanates is selected from 4,4- dicyclohexyl methyl hydride diisocyanate, isophorone diisocyanate, 1,6- hexylidene two
Isocyanates, XDI；
Hydrophilic chain extender is selected from dihydromethyl propionic acid, dihydroxy half ester, diethylenetriamine, methyl diethanolamine；
Nertralizer is selected from triethylamine, sodium hydroxide, triethanolamine；
Amido silicon oil is aminoethylaminopropyl polydimethylsiloxane.
3. spraying process according to claim 1 prepare super-hydrophobic super-oleophylic copper mesh method it is characterised in that：
In step one, add nertralizer before add be not more than 2 times of polymer polyatomic alcohol quality acetone reduce viscosity, will
After performed polymer containing hydrophobic side chain is scattered in deionized water, vacuum distillation removes acetone.
4. spraying process according to claim 1 prepare super-hydrophobic super-oleophylic copper mesh method it is characterised in that：
In step 2：Hydrophobic type gas phase nano silicon dioxide specific surface area is 120m2/ g, particle diameter is 1 ~ 40nm.
5. spraying process according to claim 1 prepare super-hydrophobic super-oleophylic copper mesh method it is characterised in that：
In step 3：
The copper mesh being used is brass screen, and the aperture of copper mesh is 100-200 mesh；
The operating pressure of aerial spraying is 4-6kPa, and spray distance is 10-20cm；
The translational speed of copper mesh is 3-5cm/s；
Described baking temperature is 70-90 DEG C, and drying time is 1h-2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610821663.9A CN106433437B (en) | 2016-09-14 | 2016-09-14 | The method of spray coating method preparation super-hydrophobic super-oleophylic copper mesh |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610821663.9A CN106433437B (en) | 2016-09-14 | 2016-09-14 | The method of spray coating method preparation super-hydrophobic super-oleophylic copper mesh |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106433437A true CN106433437A (en) | 2017-02-22 |
| CN106433437B CN106433437B (en) | 2019-01-25 |
Family
ID=58167972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610821663.9A Active CN106433437B (en) | 2016-09-14 | 2016-09-14 | The method of spray coating method preparation super-hydrophobic super-oleophylic copper mesh |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106433437B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106995521A (en) * | 2017-05-11 | 2017-08-01 | 佛山市尚峰高分子科技有限公司 | A kind of waterborne polyurethane resin |
| CN107118638A (en) * | 2017-06-09 | 2017-09-01 | 天津昌海新材料科技发展有限公司 | Impervious high adhesiveness material of a kind of two-component for ceramic tile and preparation method thereof |
| CN109943213A (en) * | 2019-03-19 | 2019-06-28 | 山东科技大学 | A kind of preparation method of the environmentally friendly super-hydrophobic coat of high mechanical endurance |
| CN110755887A (en) * | 2019-11-20 | 2020-02-07 | 赣南师范大学 | Preparation method and application of super-infiltrated Janus material |
| CN111494987A (en) * | 2020-04-27 | 2020-08-07 | 广州大学 | Fluorine-free super-hydrophobic fabric and preparation method thereof |
| CN114292379A (en) * | 2022-01-14 | 2022-04-08 | 陕西科技大学 | Preparation method of antifouling bio-based polyurethane film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838496A (en) * | 2010-04-09 | 2010-09-22 | 南京工业大学 | Super-hydrophobic polyurethane/ oxide nano particle hybrid coating material and preparation method thereof |
| CN102167795A (en) * | 2010-12-31 | 2011-08-31 | 王奇 | Amino silicone modified waterborne polyurethane and preparation method thereof |
| CN103642378A (en) * | 2013-11-14 | 2014-03-19 | 重庆大学 | Antiseptic super-hydrophobic paint for electric power system fittings and preparation method |
-
2016
- 2016-09-14 CN CN201610821663.9A patent/CN106433437B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838496A (en) * | 2010-04-09 | 2010-09-22 | 南京工业大学 | Super-hydrophobic polyurethane/ oxide nano particle hybrid coating material and preparation method thereof |
| CN102167795A (en) * | 2010-12-31 | 2011-08-31 | 王奇 | Amino silicone modified waterborne polyurethane and preparation method thereof |
| CN103642378A (en) * | 2013-11-14 | 2014-03-19 | 重庆大学 | Antiseptic super-hydrophobic paint for electric power system fittings and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 宋海香等: "氨基硅油微乳液改性水性聚氨酯的合成和性能", 《化工进展》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106995521A (en) * | 2017-05-11 | 2017-08-01 | 佛山市尚峰高分子科技有限公司 | A kind of waterborne polyurethane resin |
| CN107118638A (en) * | 2017-06-09 | 2017-09-01 | 天津昌海新材料科技发展有限公司 | Impervious high adhesiveness material of a kind of two-component for ceramic tile and preparation method thereof |
| CN107118638B (en) * | 2017-06-09 | 2019-04-23 | 天津昌海新材料科技发展有限公司 | Impervious high adhesiveness material of a kind of two-component for ceramic tile and preparation method thereof |
| CN109943213A (en) * | 2019-03-19 | 2019-06-28 | 山东科技大学 | A kind of preparation method of the environmentally friendly super-hydrophobic coat of high mechanical endurance |
| CN109943213B (en) * | 2019-03-19 | 2020-09-04 | 山东科技大学 | Preparation method of environment-friendly super-hydrophobic coating with high mechanical durability |
| WO2020186579A1 (en) * | 2019-03-19 | 2020-09-24 | 山东科技大学 | Preparation method for environmentally friendly super-hydrophobic coating with high mechanical durability |
| CN110755887A (en) * | 2019-11-20 | 2020-02-07 | 赣南师范大学 | Preparation method and application of super-infiltrated Janus material |
| CN111494987A (en) * | 2020-04-27 | 2020-08-07 | 广州大学 | Fluorine-free super-hydrophobic fabric and preparation method thereof |
| CN111494987B (en) * | 2020-04-27 | 2022-01-11 | 广州大学 | Fluorine-free super-hydrophobic fabric and preparation method thereof |
| CN114292379A (en) * | 2022-01-14 | 2022-04-08 | 陕西科技大学 | Preparation method of antifouling bio-based polyurethane film |
| CN114292379B (en) * | 2022-01-14 | 2023-10-13 | 陕西科技大学 | Preparation method of antifouling bio-based polyurethane film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106433437B (en) | 2019-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106433437A (en) | Spray method for preparing super-hydrophobic and super-oleophilic copper net | |
| CN100567357C (en) | A kind of preparation method of fluorinated water based polyurethane | |
| CN106883588B (en) | One kind is for super-hydrophobic luffa of water-oil separating and preparation method thereof | |
| CN102786655B (en) | Branched waterborne polyurethane with hydrophobic group and preparation method thereof | |
| CN101121869A (en) | Method for preparing water polyurethane binder for shoe | |
| CN1639278A (en) | Anti-corrosion paint for steel with polyaniline | |
| CN106589281B (en) | Carbon dioxide-based waterborne polyurethane-polyurea, preparation method and coating/adhesive | |
| CN103524696A (en) | Silicane modified sulfonic waterborne polyurethane emulsion and preparation method thereof | |
| CN103980461B (en) | A kind of hydrolysis-resistant waterborne polyurethane dispersion and preparation method thereof | |
| CN105778029B (en) | A kind of preparation method of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane | |
| CN103357394B (en) | For being manufactured the catalyst of carbonic acid glyceride, its manufacture method by glycerine and utilizing this method being manufactured carbonic acid glyceride by glycerine | |
| CN109721698B (en) | Hydrophilic chain extender suitable for synthesis of waterborne polyurethane and preparation method and application thereof | |
| CN106833340B (en) | The method that spray coating method prepares corrosion-resistant super-hydrophobic copper mesh | |
| CN105369388A (en) | Preparation method for high-alkali-resistance spandex | |
| CN107151520B (en) | A kind of tung oil base water polyurethane coating and preparation method thereof | |
| CN101058637A (en) | Method of preparing fatty acid polyether polyhydric alcohol by using recovery grease | |
| CN115745792A (en) | Bio-based polyol, preparation method thereof and application thereof in waterborne polyurethane coating | |
| CN110511347A (en) | A kind of side chain degradable polyurethane and its preparation method and application | |
| CN102702467A (en) | Waterborne polyurethane resin, waterborne polyaniline anticorrosive paint and preparation methods thereof | |
| CN101824272A (en) | Environmentally friendly waterbone polyurethane coating for wall paper and preparation method thereof | |
| US20090130485A1 (en) | Oligomer/halloysite composite material and method for preparing the same, and hydrocarbon adsorbent using the same | |
| CN111621000B (en) | Polyisocyanate composition, coating composition and coating film | |
| CN106947385B (en) | The super coating of resistance to steel wool of one kind and its application method | |
| CN105199072A (en) | Water-based polyurethane dispersoid and preparation method thereof | |
| CN108546262A (en) | Aqueous syrups cyclic carbonate ester lotion and preparation method thereof and the application in water-based non-isocyanate polyurethane coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |