CN110484085A - A kind of cationic water-base hydrophobic coating and preparation method thereof - Google Patents
A kind of cationic water-base hydrophobic coating and preparation method thereof Download PDFInfo
- Publication number
- CN110484085A CN110484085A CN201910716171.7A CN201910716171A CN110484085A CN 110484085 A CN110484085 A CN 110484085A CN 201910716171 A CN201910716171 A CN 201910716171A CN 110484085 A CN110484085 A CN 110484085A
- Authority
- CN
- China
- Prior art keywords
- acrylate
- hydrophobic coating
- monomer
- nano
- cationic water
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09D123/0853—Vinylacetate
-
- 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
- C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of 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
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
-
- 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
- C09D7/20—Diluents or solvents
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K2201/003—Additives being defined by their diameter
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a kind of cationic water-base hydrophobic coating, including following components by weight percent: fluorinated acrylate and ester block copolymer containing aminoacrylic acid 5~80%, Nano/micron particle 5~50%, polymer emulsion 0~90%；The wherein structural formula of fluorinated acrylate and the ester block copolymer containing aminoacrylic acid are as follows:
Description
Technical field
The present invention relates to hydrophobic coating field, in particular to a kind of cationic water-base hydrophobic coating and preparation method thereof.
Background technique
Hydrophobic coating has many unique performances, therefore in automatically cleaning, waterproof fabric, ice-covering-proof, anticorrosion and drag reduction
Equal fields have very big application value.However, existing hydrophobic coating is based on solvent type, as various countries are to VOC content
Limit it is increasingly strict, using organic solvent as the hydrophobic coating of filming medium application receive certain limitation.Therefore, develop
Water-based hydrophobic coating has a very important significance.Current water-base hydrophobic coating, mostly be using nano particle and it is fluorine-containing or
Siliceous small molecule coupling agent is compound to be prepared, and which has limited its performance and its applications.Patent CN201711095275.8 gives
Go out for a kind of greenhouse film water-based hydrophobic coating and its preparation method and application, but has not provided the preparation side of fluororesin
Method, and using the method for being additional emulsifier.Patent CN108517154A gives a kind of aqueous, floride-free super hydrophobic coating
And preparation method.But the patent uses hydrophobic coupling agent and nano-particles reinforcement and prepares hydrophobic coating.
Summary of the invention
The technical problem to be solved by the present invention is based on the above issues, the present invention provides a kind of cationic water-base hydrophobic
Coating and preparation method thereof.
The technical solution adopted by the present invention to solve the technical problems is: a kind of cationic water-base hydrophobic coating, special
Sign is: including following components by weight percent: fluorinated acrylate and ester block copolymer containing aminoacrylic acid 5~80%, nanometer/micro-
Rice grain 5~50%, polymer emulsion 0~90%；Wherein fluorinated acrylate and the ester block copolymer containing aminoacrylic acid
Structural formula are as follows:
In formula, M1 is fluorinated acrylate structural unit, and X is the integer between 2~100；M2 is containing amino acrylates
Structural unit, Y are the integer between 2~100；M3 is the structural unit of vinyl monomer, and Z is the integer between 0~100.
Further, the Nano/micron particle is micron TiO2, micron CaCO3, micron SiO2, micron ZnO, nanometer
TiO2, Nano-meter CaCO33, Nano-meter SiO_22, any one or a few in nano-ZnO, the partial size of Nano/micron particle be 10nm~
10μm；
And/or the polymer emulsion be polyethylene-vinyl acetate lotion, polyacrylate dispersion, styrene-acrylic emulsion,
Any one in polyaminoester emulsion.
The preparation method of cationic water-base hydrophobic coating as described above, includes the following steps:
Step 1, functionality is contained into amido acrylate monomer, vinyl monomer, solvent, initiator, the addition of RAFT reagent
Into three-necked flask.After mixing, system vacuumizes logical argon gas, after recycling 3 times, reacts under initiation temperature, interval sampling
Conversion ratio is measured, when conversion ratio is up to 80% or more, stops reaction, obtains Macro RAFT agent containing amino acrylates；
Step 2, by fluorinated acrylate monomer, solvent, initiator, which is added to, contains amino acrylates obtained by step 1
In Macro RAFT agent, after mixing, system vacuumizes logical argon gas, after recycling 3 times, reacts under initiation temperature, is spaced
Conversion ratio is measured by sampling, reaction terminates after conversion ratio is greater than 80%, and the fluorinated acrylate is made and contains aminoacrylic acid
Ester block copolymer；
Step 3, by the fluorinated acrylate made from step 2 and ester block copolymer containing aminoacrylic acid it is acidified after
It is dispersed in water, aqueous dispersions is made, add the Nano/micron particle, after ultrasonic disperse, add the polymer cream
The cationic water-base hydrophobic coating is made after mixing in liquid.
Further, acrylate-functional monomer described in step 1 is Dimethylaminoethyl Methacrylate, propylene
One or more of sour dimethylaminoethyl, N hydroxymethyl acrylamide, the vinyl monomer are methyl methacrylate
Ester, butyl acrylate, butyl methacrylate, ethyl acrylate, Isooctyl acrylate monomer, ethyl methacrylate, metering system
One or more of sour isobutyl ester, styrene.
Further, fluorinated acrylate monomer described in step 2 is trifluoroethyl methacrylate, acrylic acid trifluoro
Ethyl ester, Hexafluorobutyl mathacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate, perfluoroalkyl acrylate,
One or more of perfluoroalkyl methacrylate.
Further, solvent described in step 1 and step 2 is ethyl alcohol, propylene glycol, propylene glycol monomethyl ether, propylene glycol first
Ether, glycol monoethyl ether, ethylene glycol monomethyl ether, propylene glycol monobutyl ether, propandiol butyl ether, ethylene glycol monobutyl ether, butyl glycol ether, four
One or more of hydrogen furans, the initiator are one of azodiisobutyronitrile, azobisisoheptonitrile or both
Mixture.
Further, be acidified described in step 3 acid used be one of acetic acid, hydrochloric acid, phosphoric acid, p-methyl benzenesulfonic acid or
Several, dosage is 0.5~20 times of amino molal quantity in block copolymer.
Further, acrylate-functional monomer described in step 1 and the molar ratio of vinyl monomer be 20:1~
1:10, initiator amount are the 10%~0.1% of acrylate-functional monomer and vinyl monomer total weight；RAFT reagent is used
Amount is 10%~0.01% containing amido acrylate monomer and vinyl monomer integral molar quantity；；Solvent usage is containing functionality
0.1~10 times of acrylate monomer and vinyl monomer total weight.
Further, fluorinated acrylate monomer and ester large molecule containing aminoacrylic acid obtained in step 1 in step 2
The molar ratio of RAFT reagent is 10:1~1000:1；Solvent usage is that fluorinated acrylate monomer divides greatly with containing amino acrylates
Sub- RAFT reagent total weight 10%~80%；Initiator amount is the 10%~0.1% of fluorinated acrylate monomer weight.
Further, the quality solid content of aqueous dispersions described in step 3 is 0.1%~40%, described fluorine-containing third
The weight ratio of olefin(e) acid ester and block copolymer and Nano/micron particle containing amino acrylates is 1:10~10:1；Polymer
The dosage of lotion is the fluorinated acrylate and block copolymer and Nano/micron particle total weight containing amino acrylates
0%~500%；And/or the initiation temperature in step 1 and step 2 is room temperature to 100 degree.
Compared with the prior art, beneficial technical effect obtained by the present invention are as follows: cationic of the invention is water base to dredge
Water paint has excellent hydrophobicity, and preparation method is simple, and fluorochemical monomer dosage is few, and using water as decentralized medium, is environment
Excellent good type coating.
Specific embodiment
Presently in connection with specific embodiment, the invention will be further described, following embodiment be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment 1
Step 1, dimethylamino ethyl acrylate (DMAEA) monomer 12.5g (0.0875mol) is weighed, styrene (St) is single
Body 49.9g (0.48mol), solvent propylene glycol methyl ether 41.9g, initiator (AIBN) 1.14 × 10-3Mol, RAFT reagent (S- positive ten
Dialkyl group-S '-(2- isobutyl acidic group) trithiocarbonate) mixed solution of 1.82g (0.005mol) is added to tri- mouthfuls of 250mL burnings
In bottle.After mixing, system vacuumizes logical argon gas, after recycling 3 times, 560min is reacted under 70 DEG C of oil baths, interval sampling is adopted
With gas chromatograph for determination conversion ratio.Conversion ratio stops reaction up to 80% or more, obtains the RAFT of ester large molecule containing aminoacrylic acid examination
It is 7800 that agent P (DMAEA-co-St), GPC, which measure molecular weight,.
Step 2, hexafluorobutyl acrylate (HFBA) monomer 23.6g (0.1mol), propylene containing amino made from step 1 are weighed
Acid esters Macro RAFT agent P (DMAEA-co-St) 35.4g (4.72 × 10-3Mol), propylene glycol monomethyl ether 15.75g, initiator
(AIBN)1.14×10-3The mixed solution of mol is added in 250mL three-necked flask.After mixing, system vacuumizes logical argon
Gas after recycling 3 times, reacts 365min, interval sampling, using gas chromatograph for determination conversion ratio under 70 DEG C of oil baths.Conversion ratio
Reaction terminates after up to 80%, obtains fluorine-containing block copolymer P (DMAEA-co-St)-b-PHFBA.
Step 3, fluorine-containing block copolymer P (DMAEA-co-St)-b-PHFBA made from step 2 is weighed into 0.2g, through acid
It is dispersed in water after change, aqueous dispersions, pH value 4, solid content 10% is made.The nanometer for being again 200nm by 0.2g partial size
SiO2It is added in aqueous dispersions, after ultrasonic disperse 10min, cationic water-base hydrophobic coating is made, and (corresponding should be right
It is required that the cationic water-base hydrophobic coating when polymer emulsion dosage in 1 is 0).Cationic water-base hydrophobic coating is equal
It is even to be spun on clean glass sheet surface, it is put into baking 2h in vacuum drying oven and obtains compound hydrophobic coating, measure it and water is connect
Feeler is 153 degree.
Embodiment 2
Step 1, dimethylamino ethyl acrylate (DMAEA) monomer 12.5g (0.0875mol) is weighed, styrene (St) is single
Body 49.9g (0.48mol), solvent propylene glycol methyl ether 41.9g, initiator (AIBN) 1.14 × 10-3Mol, RAFT reagent (S- positive ten
Dialkyl group-S '-(2- isobutyl acidic group) trithiocarbonate) mixed solution of 1.82g (0.005mol) is added to tri- mouthfuls of 250mL burnings
In bottle.After mixing, system vacuumizes logical argon gas, after recycling 3 times, 560min is reacted under 70 DEG C of oil baths, interval sampling is adopted
With gas chromatograph for determination conversion ratio.Conversion ratio stops reaction, obtains Macro RAFT agent P (DMAEA-co- up to 80% or more
St), it is 7800 that GPC, which measures molecular weight,.
Step 2, dodecafluorhe-ptylacrylate (DDFHA) monomer 38.6g (0.1mol) is weighed, step 1 is obtained to contain amino
Acrylate Macro RAFT agent P (DMAEA-co-St) 35.4g (4.72 × 10-3Mol), propylene glycol monobutyl ether 15.75g draws
Send out agent (AIBN) 1.14 × 10-3The mixed solution of mol is added in 250mL three-necked flask.After mixing, system vacuumizes logical
Argon gas after recycling 3 times, reacts 365min, interval sampling, using gas chromatograph for determination conversion ratio under 70 DEG C of oil baths.Conversion
Rate terminates up to reacting after 80%, obtains fluorinated acrylate and the P of ester block copolymer containing aminoacrylic acid (DMAEA-co-St)-b-
PDDFHA。
Step 3, by 0.2g fluorine-containing block copolymer P (DMAEA-co-St)-b-PDDFHA it is acidified after rear water dispersion is made
Liquid, pH value 4, solid content 10%.The Nano-meter SiO_2 for being again 200nm by 0.2g partial size2It is added in aqueous dispersions, ultrasound point
After dissipating 10min, the compound of fluorinated acrylate Yu ester block copolymer containing aminoacrylic acid and Nano/micron particle is obtained.In
In 10g (solid content 10%) above-mentioned compound, 2g ethylene-vinyl acetate copolymer emulsion (VAE lotion, solid content is added
50%), after mixing, cationic water-base hydrophobic coating.Measuring it is 142 to water contact angleo。
Embodiment 3
Step 1, Dimethylaminoethyl Methacrylate (DMAEMA) monomer 13.7g (0.0875mol), metering system are weighed
Sour methyl esters (MMA) monomer 48.1g (0.48mol), solvent propylene glycol methyl ether 30g, initiator (AIBN) 5.07 × 10-4Mol, RAFT
The mixed solution of reagent (S- dodecyl-S '-(2- isobutyl acidic group) trithiocarbonate) 1.82g (0.005mol) is added to
In 250mL three-necked flask.After mixing, system vacuumizes logical argon gas, after recycling 3 times, reacts 560min under 70 DEG C of oil baths,
Interval sampling, using gas chromatograph for determination conversion ratio.Conversion ratio stops reaction, obtains Macro RAFT agent P up to 80% or more
(DMAEMA-co-MMA), it is 8800 that GPC, which measures molecular weight,.
Step 2, hexafluorobutyl acrylate (HFBA) monomer 23.6g (0.1mol), propylene containing amino made from step 1 are weighed
Acid esters Macro RAFT agent P (DMAEA-co-MMA) 41.5g (4.72 × 10-3Mol), propylene glycol monomethyl ether 15.75g, initiator
(AIBN)1.14×10-3The mixed solution of mol is added in 250mL three-necked flask.After mixing, system vacuumizes logical argon
Gas after recycling 3 times, reacts 365min, interval sampling, using gas chromatograph for determination conversion ratio under 70 DEG C of oil baths.Conversion ratio
Reaction terminates after up to 80%, obtains fluorine-containing block copolymer P (DMAEA-co-MMA)-b-PHFBA.
Step 3, by 0.2g fluorine-containing block copolymer P (DMAEA-co-MMA)-b-PHFBA it is acidified after rear water dispersion is made
Liquid, pH value 4, solid content 10%.The nano-TiO for being again 500nm by 0.2g partial size2It is added in aqueous dispersions, ultrasound point
After dissipating 10min, the compound of fluorinated acrylate Yu ester block copolymer containing aminoacrylic acid and Nano/micron particle is obtained.In
In 10g (solid content 10%) above-mentioned compound, be added 2g polyacrylate dispersion (solid content 40%), after mixing, sun from
Subtype water-base hydrophobic coating.Measuring it is 138o to water contact angle.
Embodiment 4
Step 1, with embodiment 1.
Step 2, with embodiment 1.
Step 3, by 0.2g fluorine-containing block copolymer P (DMAEA-co-St)-b-PHFBA it is acidified after rear water dispersion is made
Liquid, pH value 4, solid content 10%.The Nano-meter SiO_2 for being again 200nm by 0.2g partial size2It is added in aqueous dispersions, ultrasound point
After dissipating 10min, the compound of fluorinated acrylate Yu ester block copolymer containing aminoacrylic acid and Nano/micron particle is obtained.In
In 10g (solid content 10%) above-mentioned compound, be added different proportion ethylene-vinyl acetate copolymer emulsion (VAE lotion, Gu
Content 50%), after mixing, cationic water-base hydrophobic coating.Its performance can be seen attached list.
Embodiment 5
Step 1, with embodiment 1.
Step 2, with embodiment 1.
Step 3, by 0.2g fluorine-containing block copolymer P (DMAEA-co-St)-b-PHFBAA it is acidified after rear water dispersion is made
Liquid, pH value 4, solid content 10%.The Nano-meter CaCO3 for being again 800nm by 0.2g partial size3It is added in aqueous dispersions, ultrasound point
After dissipating 10min, the compound of fluorinated acrylate Yu ester block copolymer containing aminoacrylic acid and Nano/micron particle is obtained.In
In 10g (solid content 10%) above-mentioned compound, it is added 3g polyaminoester emulsion (solid content 30%), after mixing, cationic
Water-base hydrophobic coating.Measuring it is 145o to water contact angle.
The performance of the cation-type water-thinned hydrophobic coating of table 1
A: drop volume is 4 μ L；B: drop volume is 8 μ L；Coating layer thickness: 8 μm
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications done without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of cationic water-base hydrophobic coating, it is characterised in that: including following components by weight percent: fluorinated acrylate with contain ammonia
Base acrylate block copolymer 5~80%, Nano/micron particle 5~50%, polymer emulsion 0~90%；Wherein fluorine-containing third
The structural formula of olefin(e) acid ester and the ester block copolymer containing aminoacrylic acid are as follows:
In formula, M1 is fluorinated acrylate structural unit, and X is the integer between 2~100；M2 is knot containing acrylate-functional
Structure unit, Y are the integer between 2~100；M3 is the structural unit of vinyl monomer, and Z is the integer between 0~100.
2. cationic water-base hydrophobic coating according to claim 1, it is characterised in that: the Nano/micron particle is
Micron TiO2, micron CaCO3, micron SiO2, micron ZnO, nano-TiO2, Nano-meter CaCO33, Nano-meter SiO_22, it is any in nano-ZnO
One or more, the partial size of Nano/micron particle are 10nm~10 μm；
And/or the polymer emulsion is polyethylene-vinyl acetate lotion, polyacrylate dispersion, styrene-acrylic emulsion, poly- ammonia
Any one in ester lotion.
3. the preparation method of cationic water-base hydrophobic coating as claimed in claim 1 or 2, it is characterised in that: including as follows
Step:
Step 1, by acrylate-functional monomer, vinyl monomer, solvent, initiator, RAFT reagent is added to three-necked flask
In.After mixing, system vacuumizes logical argon gas, after recycling 3 times, reacts under initiation temperature, and conversion ratio is measured by sampling in interval,
When conversion ratio is up to 80% or more, stop reaction, Macro RAFT agent containing amino acrylates is made；
Step 2, by fluorinated acrylate monomer, solvent, initiator is added to obtained by step 1 to be divided greatly containing amino acrylates
In sub- RAFT reagent, after mixing, system vacuumizes logical argon gas, after recycling 3 times, reacts under initiation temperature, interval sampling
Measure conversion ratio, when conversion ratio be greater than 80% after reaction terminate, be made the fluorinated acrylate with contain amino acrylates it is embedding
Section copolymer；
Step 3, by the acidified rear dispersion of the fluorinated acrylate made from step 2 and ester block copolymer containing aminoacrylic acid
Aqueous dispersions are made in Yu Shuizhong, add the Nano/micron particle, after ultrasonic disperse, add the polymer emulsion,
After mixing, the cationic water-base hydrophobic coating is made.
4. the preparation method of cationic water-base hydrophobic coating according to claim 3, it is characterised in that: institute in step 1
The acrylate-functional monomer stated is Dimethylaminoethyl Methacrylate, dimethylaminoethyl acrylate, N- methylol third
One or more of acrylamide, the vinyl monomer are methyl methacrylate, butyl acrylate, methacrylic acid fourth
Ester, ethyl acrylate, Isooctyl acrylate monomer, one of ethyl methacrylate, Isobutyl methacrylate, styrene or several
Kind.
5. the preparation method of cationic water-base hydrophobic coating according to claim 3, it is characterised in that: institute in step 2
The fluorinated acrylate monomer stated is trifluoroethyl methacrylate, acrylic acid trifluoro ethyl ester, Hexafluorobutyl mathacrylate, third
Olefin(e) acid hexafluoro butyl ester, dodecafluoroheptyl methacrylate, perfluoroalkyl acrylate, one in perfluoroalkyl methacrylate
Kind is several.
6. the preparation method of cationic water-base hydrophobic coating according to claim 3, it is characterised in that: step 1 and step
Solvent described in rapid 2 be ethyl alcohol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether, glycol monoethyl ether, ethylene glycol monomethyl ether,
One or more of propylene glycol monobutyl ether, propandiol butyl ether, ethylene glycol monobutyl ether, butyl glycol ether, tetrahydrofuran, it is described
Initiator is the mixture of one of azodiisobutyronitrile, azobisisoheptonitrile or both.
7. the preparation method of cationic water-base hydrophobic coating according to claim 3, it is characterised in that: institute in step 3
Stating acidification acid used is one or more of acetic acid, hydrochloric acid, phosphoric acid, p-methyl benzenesulfonic acid, and dosage is ammonia in block copolymer
0.5~20 times of base molal quantity.
8. the preparation method of cationic water-base hydrophobic coating according to claim 3, it is characterised in that: institute in step 1
The molar ratio of the acrylate-functional monomer and vinyl monomer stated is 20:1~1:10, and initiator amount is functional propylene
The 10%~0.1% of acid ester monomer and vinyl monomer total weight；RAFT reagent dosage is acrylate-functional monomer and second
The 10%~0.01% of alkenyl monomer total weight integral molar quantity；；Solvent usage is acrylate-functional monomer and vinyl list
0.1~10 times of body total weight.
9. the preparation method of cationic water-base hydrophobic coating according to claim 3, it is characterised in that: contain in step 2
In fluoroacrylate monomers and step 1 molar ratio of the Macro RAFT agent obtained containing amino acrylates be 10:1~
1000:1；Solvent usage be fluorinated acrylate and the total monomer weight of Macro RAFT agent containing amino acrylates 10%~
80%；Initiator amount is the 10%~0.1% of fluorinated acrylate monomer weight.
10. the preparation method of cationic water-base hydrophobic coating according to claim 3, it is characterised in that: institute in step 3
The quality solid content for the aqueous dispersions stated is 0.1%~40%, the fluorinated acrylate and the block containing amino acrylates
The weight ratio of copolymer and Nano/micron particle is 1:10~10:1；The dosage of polymer emulsion is the fluorinated acrylate
With 0%~500% of block copolymer and Nano/micron particle total weight containing amino acrylates；And/or step 1 and step
The initiation temperature in rapid 2 is room temperature to 100 degree.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910716171.7A CN110484085A (en) | 2019-08-05 | 2019-08-05 | A kind of cationic water-base hydrophobic coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910716171.7A CN110484085A (en) | 2019-08-05 | 2019-08-05 | A kind of cationic water-base hydrophobic coating and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110484085A true CN110484085A (en) | 2019-11-22 |
Family
ID=68549412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910716171.7A Pending CN110484085A (en) | 2019-08-05 | 2019-08-05 | A kind of cationic water-base hydrophobic coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110484085A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112048225A (en) * | 2020-09-10 | 2020-12-08 | 赵玮 | Super-hydrophobic coating with micro-nano hierarchical structure and preparation method thereof |
| CN112708320A (en) * | 2021-01-08 | 2021-04-27 | 杭州廖仕科技有限公司 | Anti-aging nano TiO2Modified acrylic resin composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189609A (en) * | 2017-05-24 | 2017-09-22 | 广州大学 | A kind of emulsion comprising micro-nano hydrophobic material and preparation method and application |
-
2019
- 2019-08-05 CN CN201910716171.7A patent/CN110484085A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189609A (en) * | 2017-05-24 | 2017-09-22 | 广州大学 | A kind of emulsion comprising micro-nano hydrophobic material and preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 潘才元: "《高分子化学》", 31 July 2012, 中国科学技术大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112048225A (en) * | 2020-09-10 | 2020-12-08 | 赵玮 | Super-hydrophobic coating with micro-nano hierarchical structure and preparation method thereof |
| CN112048225B (en) * | 2020-09-10 | 2021-09-14 | 赵玮 | Super-hydrophobic coating with micro-nano hierarchical structure and preparation method thereof |
| CN112708320A (en) * | 2021-01-08 | 2021-04-27 | 杭州廖仕科技有限公司 | Anti-aging nano TiO2Modified acrylic resin composite material and preparation method thereof |
| CN112708320B (en) * | 2021-01-08 | 2022-06-21 | 合肥市丽红塑胶材料有限公司 | Anti-aging nano TiO2Modified acrylic resin composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104558447B (en) | Inorganic nano composite anti-doodling resin and preparation method thereof | |
| CN102898932B (en) | Composite ultraviolet-curing coating containing vinyl-terminated fluorinated alkyl ester polymer, its preparation and application | |
| CN102532436B (en) | Method for preparing single-component room-temperature crosslinked waterborne fluorine-containing coating | |
| CN100389156C (en) | Aqueous coating containing three layer nuclear shell structure rubber particle latex and its preparation method | |
| CN103602193B (en) | A kind of aqueous heavy anti-corrosion paint priming paint and preparation method thereof | |
| CN103435742B (en) | Hydrophobicity POSS base hydridization fluorinated acrylate resin and preparation method thereof and application | |
| CN106433364A (en) | Superhydrophobicity coating based on waterborne emulsion and preparing method and application thereof | |
| CN101580653A (en) | Organic-inorganic hybrid nanometer film coating aluminum powder pigment and preparation method and application thereof | |
| CN106280832B (en) | Fluorinated silicone modified hydrophobic soil resistant acrylic resin and varnish and preparation method containing the resin | |
| CN110484085A (en) | A kind of cationic water-base hydrophobic coating and preparation method thereof | |
| CN106967191A (en) | A kind of environment-friendly preparation method thereof of super-amphiphobic fluoropolymer nano material | |
| CN104513579A (en) | Super-hydrophobic coating and preparation method thereof | |
| CN104877089A (en) | Preparation method of modified fluorine-containing acrylic superhydrophobic resin emulsion | |
| CN101982512A (en) | Silicone acrylate coating resin and preparation method thereof | |
| CN101845114B (en) | Preparation method of fluorinated acrylate microemulsion | |
| CN101560278B (en) | Methyl methacrylate-styrene copolymer containing fluoro-acrylate and preparation method thereof | |
| CN103435741A (en) | POSS (Polyhedral Oligomeric Silsesquioxane) based hybridized fluorinated acrylate resin, and preparation method and application thereof | |
| CN109666111A (en) | A kind of Nano-meter SiO_22/ organosilicon-modified acrylate emulsion | |
| CN1281643C (en) | Silicofluoride containing acrylic copolyresin emulsion and paint | |
| CN106833251A (en) | A kind of floride-free super-hydrophobic coating and preparation method thereof | |
| CN107828251A (en) | A kind of preparation method of fluoropolymer and silica double-layer coated water aluminum paste | |
| TW200528511A (en) | Acrylic compositions | |
| CN110294825A (en) | A kind of hud typed tertiary carbon redispersable latex powder and preparation method thereof | |
| CN106366238A (en) | Fluorine and nano-particle modified ethylene-propylene antibacterial emulsion | |
| JPH028285A (en) | Composition capable of forming water repellent coating film |
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 |