CN108192454A - A kind of water-and acrylate Polymer/nano particle hybrid and the hydrophobic coating and preparation method based on it - Google Patents
A kind of water-and acrylate Polymer/nano particle hybrid and the hydrophobic coating and preparation method based on it Download PDFInfo
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- CN108192454A CN108192454A CN201711487223.5A CN201711487223A CN108192454A CN 108192454 A CN108192454 A CN 108192454A CN 201711487223 A CN201711487223 A CN 201711487223A CN 108192454 A CN108192454 A CN 108192454A
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- 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
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/10—Esters
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
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- C08F220/10—Esters
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Abstract
The invention discloses a kind of water-and acrylate Polymer/nano particle hybrid and the hydrophobic coatings and preparation method based on it, belong to super-hydrophobic coat preparing technical field.The present invention is by using the copolyreaction between the chemical bond and acrylic ester monomer on function nano particle, and the characteristic ionization of the esters polymer containing carboxy acrylic, using water-soluble acrylic polymer as tie, " traction " hydrophobic function nano particle, make it and aqueous medium is good coexists in one, form good aqueous dispersion.This aqueous dispersion reacts again with blocked isocyanate class curing agent, through drying, curing after be built into have both excellent adhesive attraction, excellent abrasive resistance super-hydrophobic coat, the preparation method of the present invention is simple and practicable, raw materials used is conveniently easy to get, process conditions are easy to industry's enlarging production, have broad application prospects.
Description
Technical field
The invention belongs to super-hydrophobic coat preparing technical fields, and in particular to a kind of water-and acrylate Polymer/nano
Particle hybrid and the hydrophobic coating and preparation method based on it.
Background technology
Super-hydrophobic coat with lotus leaf effect can make water droplet present very high static contact angle (>150 °) and it is extremely low
Roll angle (<10 °), it is easily slid from surface, so as to take away the dust on surface and dirt, assigns the self-cleaning function of coating.It is super
Hydrophobic coating is also because its unique wetting removal and self-cleaning performance have extensively in multiple fields such as antifouling, ice-covering-proof and water-oil separatings
Wealthy application prospect.Although reporting numerous methods for preparing super hydrophobic surface in document so far, most of prepare surpasses
The method of hydrophobic surface all there is wear no resistance, base material type is limited, adhesive force is low, it is difficult to permanent that hydrophobicity etc. is kept to ask
Topic, seriously limits its practical application.
By hydrophobic function nano particle with the good high molecular material of film forming is compound is prepared into coating, can be directed to more
Kind base material, large area easily build securely durable super-hydrophobic coat.Epoxy resin, acrylic resin, polyurethane and poly- inclined
Vinyl fluoride etc. is used for and the compound resin-based super-hydrophobic coat of structure of hydrophobic Nano filling.Resin based super hydrophobic is applied
Layer, the macromolecule as film forming matter are often required for being dissolved in certain organic solvent, such as benzene homologues (toluene, diformazan
Benzene), alkane (hexamethylene, normal octane), tetrahydrofuran, dichloromethane, acetone and butyl acetate etc. there is larger toxicity and strong
In the reagent of penetrating odor；Meanwhile in order to ensure the processing performance of cold coating, common dewatering filling particle also must be
Could preferably it disperse in the organic solvent of low pole, for film forming procedure, volatile organic solvent also contributes to lure
It leads and the compound coarse structure of micro-/ nano is formed in coating phase separation.Thus since, most resin base is super thin at this stage
Water coating (>90%) it is all based on made from solvent based coating system.The a large amount of of organic solvent are used inevitably to the mankind
Health and Environmental security cause greatly to threaten.
In view of the unique performance of super-hydrophobic coat and wide application prospect, realize that its environmental-friendly sexual development will have weight
The scientific meaning and social value wanted.Releasing for organic volatile in construction and coating drying process can be greatly decreased in water paint
It puts, is a kind of important channel for obtaining Environmentally friendly coatings.However, super-hydrophobic coat is prepared with water paint, first
The difficulty faced is needed hydrophobic Nano filling dispersion in an aqueous medium, such a system for seeming contradiction of reconciliation.
Just because of there is apparent difficulty, only have several reports using the method that water paint prepares super-hydrophobic coat in document at present,
(Schutzius T M et al.ACS Appl.Mater.Inter.2013,5(24):13419-13425；Swerin A et
al.Colloids Surfaces A.2016,495:79-86；Patent CN106811114A), for excellent adhesive attraction and
The water paint based super hydrophobic coating of wearability is even more related to less.
Obtain having both the report of the super-hydrophobic coat of excellent adhesive attraction, excellent abrasive resistance and durability based on water-based system more
It is fewer and fewer.Document (Zhou et al.Adv.Funct.Mater, 2017,27 (14):1604261) it reports, by using
The fluorocarbon surfactant of commercialization is stablized polytetrafluoroethylparticle particle and fluorine containing silane (FAS) in an aqueous medium, can obtain
The super-hydrophobic coat all good to wearability and durability.However this kind of water paint admittedly containing very low, only 5%, in reality
It will be easy to generate the painting defects such as sagging in coating process.Document (K.Chen et al.Adv.Funct.Mater., 2015,
25,1035-1041) it reports, with a kind of microcapsule coated fluorine containing silane to ultraviolet light response, assists what is modified with silicon fluoride again
Hydrophobic nano-particles and resin aqueous emulsion can obtain firm super-hydrophobic coat, can also be ultraviolet after the coating is frayed
Restore its ultra-hydrophobicity under light irradiation.Unfortunately, this kind prepare super hydrophobic coating method it is very cumbersome, and coating
Ultra-hydrophobicity is strongly depend on the stimulation of ultraviolet light, and applicability is restricted.Document (H.Ye et
Al.J.Mater.Chem.A, 2017,5,9882-9890) by the way that vinyl silanes and acrylic monomers are copolymerized, again in alcohol water
It is hydrolyzed in alkaline medium, products therefrom coating can be obtained into the super-hydrophobic coat with preferable adhesive force and wearability.However,
Hydrolysis pathway, which not only results in, after this more ethyl alcohol in product, and alkaline medium also inevitably influences olefin(e) acid ester
The firmness of Type of Collective object chain, will lead to coating mechanical properties decrease, and medium corrosion resistance is not good enough.Patent CN105349036A
It is reacted with hydrophilic silicon oxides nano-particle and ethyl orthosilicate or silicon tetrachloride, is reacted after adding in silane coupling agent
Concentrated by rotary evaporation is uniformly mixed to solvent type nano paint, then with fluorocarbon resin, by adding in water and surfactant thereto,
Dispersion obtains the water paint of super-amphiphobic coating.However the preparation method need to use specific surfactant, fluorocarbon resin
Introducing inevitably influences the adhesive force of coating, and the durability of the super-amphiphobic coating is still not clear.
Invention content
Dredging the purpose of the present invention is to provide a kind of water-and acrylate Polymer/nano particle hybrid and based on it
Water coating and preparation method, the preparation method is simple and practicable, it is raw materials used be conveniently easy to get, process conditions are easy to industry amplification life
Production；Coating performance obtained is excellent, has superhydrophobic characteristic.
The present invention is to be achieved through the following technical solutions：
The invention discloses a kind of preparation method of water soluble acrylic acid polymer/inorganic nanometer particle hybrid, including with
Lower step：
Step 1：In terms of mass fraction, take 3~7 parts of functional hydrophobic nano-particles, 40~60 parts of water solubilitys organic molten
Agent, 2~5 parts of hard monomers, 1~6 part of soft monomer, 0.5~2 part of water-soluble monomer, 0.5~3 part of reactive monomer, 0.1~0.3 part
Initiator, 1~3 part of alkaloids and 15~25 parts of distilled water；
Step 2：At room temperature, functional hydrophobic nano-particles are scattered in water-miscible organic solvent, are stirred well to and receive
Rice corpuscles is uniformly dispersed, and the finely dispersed nanoparticle system then is warming up to 90~110 DEG C, in nitrogen protective condition
Under, after the mixture that hard monomer, soft monomer, water-soluble monomer, reactive monomer and initiator mix is added dropwise to heating
Nanoparticle system in, unreacted organic solvent, cooling are removed after insulation reaction 6h；
Step 3：Alkaloids are added in into reaction mass after cooling, then under agitation, it is dilute to add in distilled water
It releases, water soluble acrylic acid polymer/inorganic nanometer particle hybrid is made.
Preferably, the functional hydrophobic nano-particles contain double bond isoreactivity group and hydrophobic grouping simultaneously for surface
Nano-particle, specific preparation method is as follows：
At 50 DEG C, in terms of mass fraction, by 1 part of inorganic nano-particle, 0.1~0.7 part of hydrophobic agents, 0.04~
0.28 part of activity modifying agent is placed in the ethyl alcohol and ammonium hydroxide mixed solution that pH value is 11~13, is sufficiently stirred 2~4h of reaction, mistake
Filter, drying, obtain functional hydrophobic nano-particles.
It is further preferred that the grain size of the inorganic nano-particle is 50nm~1 μm, and inorganic nano-particle is titanium dioxide
One or more of silicon, γ types alundum (Al2O3), rutile titanium dioxide and calcium carbonate.
It is further preferred that the hydrophobic agents are tridecafluoro-n-octyltriethoxysilane, 17 fluorine decyl triethoxies
Silane, 17 fluorine decyl trimethoxy silanes, 17 fluorine decyltrichlorosilanes, 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilicanes
One or more of alkane, ten difluoro heptyl propyl trimethoxy silicanes and dodecyltrimethoxysilane；The activity is repaiied
Decorations agent is vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane
One or more of with vinyl trichlorosilane.
Preferably, the hard monomer is the one or both combination in methyl methacrylate and styrene；The soft list
Body is n-butyl acrylate, acrylic acid n-pentyl ester, the just own ester of acrylic acid, n-propyl or acrylic acid-2-ethyl caproite.
Preferably, the water-soluble monomer is acrylic or methacrylic acid；The reactive monomer is acrylic acid -2- hydroxyls
Ethyl ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacry-late, Hydroxypropyl methacrylate or acrylic acid -4- hydroxyl fourths
Ester；The initiator is dibenzoyl peroxide, peroxide -2-ethyl hexanoic acid tert-butyl, peroxidating -2 ethyl hexanoic acid uncle penta
Ester, azodiisobutyronitrile or peroxidating tert-butyl acetate.
Preferably, the water-miscible organic solvent is n-butanol, the tert-butyl alcohol, tetrahydrofuran or isopropanol；The bases object
Matter is ammonium hydroxide, triethylamine or N, N- dimethylethanolamine.
The invention also discloses miscellaneous using water soluble acrylic acid polymer/inorganic nanometer particle made from above-mentioned preparation method
Compound.
The invention also discloses a kind of super-hydrophobic coats based on water-and acrylate Polymer/nano particle hybrid
Preparation method includes the following steps：
1) in terms of mass fraction, 0.05~0.3 part of watersoluble closed type Isocyanates curing agent and 1 part of claim 8 are taken
The water soluble acrylic acid polymer/inorganic nanometer particle hybrid is uniformly mixed；
2) it sprays, is placed at room temperature to surface drying, after being then heat-treated 1h at 80~90 DEG C, then in 120~150 DEG C of curings
2h is handled, the super-hydrophobic coat based on water-and acrylate Polymer/nano particle hybrid is made.
Preferably, the watersoluble closed type Isocyanates curing agent for Trixene BI7986,AQUA
BI 200、AQUA BI 201、AQUA BI 202、BL 2781、
BL 2867、BL 5335 orBL XP 2706。
Compared with prior art, the present invention has technique effect beneficial below：
The present invention by using the copolyreaction between the chemical bond and acrylic ester monomer on function nano particle,
And the characteristic ionization of the esters polymer containing carboxy acrylic, using water-soluble acrylic polymer as tie, " lead
Draw " hydrophobic function nano particle, make it and aqueous medium is good coexists in one, form good aqueous dispersion.It is this
Aqueous dispersion reacts again with blocked isocyanate class curing agent, is built into after drying, curing and has both excellent adhesive attraction, good
The super-hydrophobic coat of wearability.
Specific advantage is as follows：
(1) hydrophobic Nano filling is effectively combined in the film-forming high molecular of water-dispersion type, is replaced with water-based system
Solvent-based system successfully constructs securely durable super-hydrophobic coat, and drastically reducing toxic in coating forming procedure has
The release of evil, irritation volatile matter；
(2) by introducing reactive functional groups on hydrophobic nano-particles surface, make it in the form of covalent bond and acrylate
Adduct molecule of birdsing of the same feather flock together is combined together, and the curing crosslinking of hydroxy acryl acid esters polymer is also ensured by hydrophobic nano-particles
The coarse structure of composition is effectively anchored in coated substrate, it is ensured that the persistence of ultra-hydrophobicity and the wearability of coating；
(3) gained acryllic acid ester polymer/nano particle hybridization object is dispersed in the water containing a small amount of water-miscible organic solvent
Property medium in, compared to single water-based system, the rate of volatilization of blending agent is accelerated, and is conducive to hydrophobic nano-particles to coating
Surface migration forms sufficiently coarse surface, under relatively low hydrophobic particles content, can also obtain super-hydrophobic coating；
(4) this kind of super hydrophobic coating preparation method is simple, can be obtained by conventional synthesis technology, is easy to amplification life
Production, coating application is convenient, is particluarly suitable for constructing super hydrophobic surface in large scale and form parts.
Using water-and acrylate Polymer/nano particle hybrid direct spraying made from the method for the present invention, you can
Super-hydrophobic coat is formed on a variety of base materials such as glass, metal, timber, cotton fabric, sponge and plastics.It is comprehensive after coating is cured
It is more excellent to close performance, after sand paper is polished 300 times, to the contact angle of water still greater than 160 °, roll angle is less than 20 °, this
Excellent wearability and durability ranks among the best in existing aqueous super-hydrophobic coat technology.The adhesive force of coating up to 1 grade,
48h is impregnated in neutral and acid medium and still shows hydrophobicity.It is easily tumbled when water droplet is fallen within thereon, flexibility and impact resistance
Property is splendid.The present invention preparation method it is simple and practicable, it is raw materials used be conveniently easy to get, process conditions be easy to industry amplification life
Production, has broad application prospects.
Description of the drawings
Fig. 1 is different drops in the contact angle photo on different substrate materials；Wherein, (a)~(d) is respectively to use institute of the present invention
It obtains water-and acrylate Polymer/nano particle hybrid and later stage table is handled to glass, cotton, sponge and timber (from top to bottom)
The form of (being followed successively by water, cola, orange juice, tea and soy sauce from left to right) of drop on face.
Fig. 2 investigates result for super-hydrophobic coat wearability produced by the present invention；Wherein, (a)~(f) is respectively different polishings
The configuration of surface of coating and corresponding water droplet basis angle after number.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
At 50 DEG C, 1 part of inorganic nano-particle, 0.1~0.7 part of hydrophobic agents, 0.04~0.28 part of activity are repaiied
Decorations agent is placed in the ethyl alcohol and ammonium hydroxide mixed solution that pH is 11~13, applies ultrasonic wave or mechanical agitation, reacts 2~4h, mistake
Filter, is dried to obtain functional hydrophobic nano-particles.
At room temperature, 3~7 parts of function hydrophobic nano-particles are scattered in 40-60 parts of water-miscible organic solvents, using super
Sound wave or mechanical agitation to nano-particle are uniformly dispersed.The dispersion of this nano-particle is warming up to 90~110 DEG C, is protected in nitrogen
It is added dropwise to thereto under the conditions of shield by 2~5 parts of hard monomer, 1~6 part of soft monomer, 0.5~2 part of water-soluble monomer and 0.5
The mixture that~3 parts of reactive monomer and 0.1~0.3 part of initiator are formed.Vacuum distillation removes more after insulation reaction 6h
Material is cooled to about 50 DEG C or so by remaining organic solvent, is added in 1~3 part of alkaloids thereto and is neutralized, then stirring strongly
The lower distilled water for adding in 15~25 parts of effect is diluted to get the acrylate polymer dissipated to moisture/hydrophobic nano-particles hydridization
Object.
By 1 part synthesize obtain 0.05~0.3 part of water-and acrylate polymer/inorganic nanometer particle hybrid it is aqueous
Blocked curing agent mixes, through spraying, rod coating or drop coating, placed at room temperature to surface drying, again through 80~90 DEG C of heat treatments 1~
1.5h, 120~150 DEG C of 1~2h of curing obtain secured and wear-resisting super-hydrophobic coat.
Embodiment 1
10.0g Nano particles of silicon dioxide is added in the ethyl alcohol of pH=11 and the mixed solution of ammonium hydroxide, then added thereto
Enter 17 fluorine decyl trimethoxy silanes of 1.0g and 0.4g vinyltrimethoxysilanes, apply ultrasonic response 4h at 50 DEG C.
Product is filtered, dry after up to functional dewatering nano silicon dioxide granule.
7.0g functionality dewatering nano silicon dioxide granules and 75mL n-butanols are added in three-necked flask, ultrasonic 30min
Disperse uniform particle, be warming up to 95 DEG C, then under nitrogen protective condition in 3h thereto at the uniform velocity be added dropwise 3.0g methyl-props
E pioic acid methyl ester, 2.0g styrene, 6.0g butyl acrylates, 2.0g acrylic acid, 3.0g acrylic acid -2- hydroxyl ethyl esters and 0.3g peroxidating
Dibenzoyl, subsequent insulation reaction 3h obtain solvent type super hydrophobic coating.Then system is evaporated under reduced pressure, remove it is extra just
Butanol is cooled to 50 DEG C of addition 3mL N, N- dimethylethanolamines and is neutralized, then adds in the emulsification of 25mL deionized waters, obtain water
Property acrylate polymer/inorganic nano particle hybridization material.
Water-and acrylate polymer/inorganic nanometer particle hybrid that 10.0g is synthesized, the watersoluble closed types of 3g are consolidated
Agent Trixene BI 7986 are mixed, through spraying after placed at room temperature to surface drying, again through 90 DEG C heat treatment 1h, 120 DEG C curing
2h obtains secured and wear-resisting super-hydrophobic coat.
Embodiment 2
7.0g titanium dioxide nano-particles are added in the ethyl alcohol of pH=13 and the mixed solution of ammonium hydroxide, then added in thereto
4.9g tridecafluoro-n-octyltriethoxysilanes and 1.96g γ-methacryloxypropyl trimethoxy silane are stirred at 50 DEG C
2h.Product is filtered, dry after up to functional hydrophobic nano-titanium dioxide particle.
5.0g functionality hydrophobic nano-titanium dioxide particles and 50mL tetrahydrofurans are added in three-necked flask, ultrasound
20min disperses uniform particle, is warming up to 90 DEG C, then under nitrogen protective condition in 3h thereto at the uniform velocity be added dropwise 2.5g first
Base methyl acrylate, 1.0g styrene, 4.3g the just own ester of acrylic acid, 1.2g acrylic acid, 1.5g acrylic acid -4- hydroxy butyl esters and 0.2g
Azodiisobutyronitrile, subsequent insulation reaction 3h obtain solvent type super hydrophobic coating.Then system is evaporated under reduced pressure, it is extra to remove
Tetrahydrofuran, be cooled to 50 DEG C add in 2mL N, N- dimethylethanolamines neutralized, then add in 20mL deionization water and milk
Change, obtain water-and acrylate polymer/inorganic nanometer particle hybrid material.
Water-and acrylate polymer/inorganic nanometer particle hybrid, the watersoluble closed types of 0.7g that 6.0g is synthesized
Curing agentBL XP 2706 are mixed, through drop coating after placed at room temperature to surface drying, again through 80 DEG C heat treatment 1.5h,
150 DEG C of curing 2h obtain secured and wear-resisting super-hydrophobic coat.
Embodiment 3
5.0g alundum (Al2O3)s nano-particle is added in the ethyl alcohol of pH=12 and the mixed solution of ammonium hydroxide, then added thereto
Enter ten difluoro heptyl propyl trimethoxy silicanes of 2.0g and 0.8g vinyltriethoxysilane, 3h is stirred at 50 DEG C.By product
Up to functional dewatering nano alundum (Al2O3) particle after filtering, drying.
3.0g functionality dewatering nano alundum (Al2O3) particle and 40mL isopropanols are added in three-necked flask, ultrasound
25min disperses uniform particle, is warming up to 110 DEG C, then under nitrogen protective condition in 1.5g is at the uniform velocity added dropwise in 3h thereto
Methyl methacrylate, 0.5g styrene, 1.0g acrylic acid-2-ethyl caproites, 0.5g methacrylic acids, 0.5g acrylic acid -2-
Hydroxypropyl acrylate and 0.1g peroxidating tert-butyl acetates, subsequent insulation reaction 3h obtain solvent type super hydrophobic coating.Then system is carried out
Vacuum distillation, remove extra isopropanol, be cooled to 50 DEG C add in 1.0mL triethylamines neutralized, then add in 15mL go from
Sub- water emulsification obtains water-and acrylate polymer/inorganic nanometer particle hybrid material.
Water-and acrylate polymer/inorganic nanometer particle hybrid, the watersoluble closed types of 0.25g that 5.0g is synthesized
Curing agentBL XP 2867 are mixed, through drop coating after placed at room temperature to surface drying, again through 90 DEG C heat treatment
1.0h, 130 DEG C of curing 2h obtain secured and wear-resisting super-hydrophobic coat.
Embodiment 4
8.0g calcium carbonate nano particles are added in the ethyl alcohol of pH=11 and the mixed solution of ammonium hydroxide, then added in thereto
4.0g dodecyltrimethoxysilanes and 1.6g vinyl trichlorosilanes apply ultrasonic response 3h at 50 DEG C.By product mistake
Up to functional dewatering nano calcium carbonate particle after filter, drying.
6.0g functionality dewatering nano calcium carbonate particles and 55mL n-butanols are added in three-necked flask, ultrasonic 35min makes
Uniform particle disperse, be warming up to 105 DEG C, then under nitrogen protective condition in 3h thereto at the uniform velocity be added dropwise 2.5g metering systems
Sour methyl esters, 1.0g styrene, 4.0g acrylic acid n-pentyl esters, 1.5g acrylic acid, 1.5g 2-hydroxyethyl methacry-lates and 0.3g mistakes
Oxidation -2 ethyl hexanoic acid tert-pentyl ester, subsequent insulation reaction 3h obtain solvent type super hydrophobic coating.Then decompression steaming is carried out to system
It evaporates, steams extra n-butanol, be cooled to 50 DEG C of addition 3.0mL triethylamines and neutralized, then add in 20mL deionization water and milk
Change, obtain water-and acrylate polymer/inorganic nanometer particle hybrid material.
Water-and acrylate polymer/inorganic nanometer particle hybrid, the watersoluble closed types of 0.9g that 3.0g is synthesized
Curing agentBL XP 2781 are mixed, through rod coating after placed at room temperature to surface drying, again through 80 DEG C heat treatment
2.0h, 140 DEG C of curing 2h obtain secured and wear-resisting super-hydrophobic coat.
Embodiment 5
The mixing of ethyl alcohol and ammonium hydroxide that 9.0g silica and alundum (Al2O3) mix nanoparticles are added in pH=12 is molten
In liquid, then 17 fluorine decyl triethoxysilanes of 5.4g and 2.16g γ-methacryloxypropyl trimethoxy are added in thereto
Base silane applies ultrasonic response 4h at 50 DEG C.Product is filtered, dry after up to functional dewatering nano silica and three
Al 2 O stuff and other stuff.
7.0g functionality dewatering nano silica and alundum (Al2O3) stuff and other stuff and 70mL tetrahydrofurans are added in three
In mouthful flask, ultrasonic 30min disperses uniform particle, is warming up to 90 DEG C, then under nitrogen protective condition in 3h thereto
3.5g methyl methacrylates, 1.0g styrene, 4.0g propyl acrylates, 2.0g acrylic acid, 1.5g metering systems is at the uniform velocity added dropwise
Acid -2- hydroxypropyl acrylates and 0.2g peroxide -2-ethyl hexanoic acid tert-butyls, subsequent insulation reaction 3h obtain solvent type super hydrophobic coating.So
System is evaporated under reduced pressure afterwards, removes extra tetrahydrofuran, 50 DEG C of addition 4.0mL ammonium hydroxide is cooled to and is neutralized, then
The emulsification of 23mL deionized waters is added in, obtains water-and acrylate polymer/inorganic nanometer particle hybrid material.
Water-and acrylate polymer/inorganic nanometer particle hybrid, the watersoluble closed types of 2.5g that 10.0g is synthesized
Curing agentAQUA BI 200 are mixed, through spraying after placed at room temperature to surface drying, again through 90 DEG C heat treatment
2.0h, 135 DEG C of curing 2h obtain secured and wear-resisting super-hydrophobic coat.
Embodiment 6
6.0g silica and titanium dioxide mix nanoparticles are added in into the ethyl alcohol of pH=13 and the mixed solution of ammonium hydroxide
In, then 1.8g 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilanes and 0.72g vinyl trimethoxy silicon are added in thereto
Alkane stirs 2h at 50 DEG C.Product is filtered, dry after up to functional dewatering nano silica and titanium dioxide mangcorn
Son.
4.0g functionality dewatering nano silica and TiO 2 particles and the 45mL tert-butyl alcohols are added in three-necked flask,
Ultrasonic 35min disperses uniform particle, is warming up to 100 DEG C, then under nitrogen protective condition in being at the uniform velocity added dropwise thereto in 3h
1.5g methyl methacrylates, 1.5g styrene, 3.5g acrylic acid-2-ethyl caproites, 1.5g methacrylic acids, 2.0g propylene
Acid -4- hydroxy butyl esters and 0.1g dibenzoyl peroxides, subsequent insulation reaction 3h obtain solvent type super hydrophobic coating.Then to system into
Row vacuum distillation, remove the extra tert-butyl alcohol, be cooled to 50 DEG C add in 3.0mL ammonium hydroxide neutralized, then add in 18mL go from
Sub- water emulsification obtains water-and acrylate polymer/inorganic nanometer particle hybrid material.
Water-and acrylate polymer/inorganic nanometer particle hybrid, the watersoluble closed types of 1.3g that 5.0g is synthesized
Curing agentAQUA BI 201 are mixed, through spraying after placed at room temperature to surface drying, again through 85 DEG C heat treatment
1.0h, 145 DEG C of curing 2h obtain secured and wear-resisting super-hydrophobic coat.
Performance test is tested：
Performance test is carried out to super-hydrophobic coat made from Examples 1 to 6, as a result as shown in the following table 1, Fig. 1 and Fig. 2：
1 embodiment 1 of table is to 6 super-hydrophobic coat performance characterization of embodiment
Water-and acrylate Polymer/nano particle hybrid direct spraying made from the method for the present invention will be used, you can
Super-hydrophobic coat is formed on a variety of base materials such as glass, metal, timber, cotton fabric, sponge and plastics, even for strong absorptive
Sponge and the materials such as cotton, significant hydrophobic effect can be made it have, as shown in Figure 1, wherein, (a)~(d) is respectively
Using water-and acrylate Polymer/nano particle hybrid obtained by the present invention to glass, cotton, sponge and timber (from up to
Under) processing later stage surface on drop (being followed successively by water, cola, orange juice, tea and soy sauce from left to right) form.As can be seen that
Gained super-hydrophobic coat of the invention is for other waterborne liquids in addition to purified water, such as laughable, tea and soy sauce etc. are also with anti-
It refuses to act on, antifouling, automatic cleaning action can be effectively acted as.In Fig. 2, display (a)~(f) is respectively coating after different polishing numbers
Configuration of surface and corresponding water droplet basis angle.
The super-hydrophobic coat obtained by the technology of the present invention has excellent wearability and durability, to base material strong adhesive force,
Coating still has super-hydrophobicity after the coarse structure of coating is polished 300 times under specified load with sand paper.It is this excellent resistance to
Mill property and durability are to be seen in most of water paint based super hydrophobic coatings of report at present to be all difficult to what is reached.
Claims (10)
1. a kind of preparation method of water soluble acrylic acid polymer/inorganic nanometer particle hybrid, which is characterized in that including following step
Suddenly：
Step 1：In terms of mass fraction, take 3~7 parts of functional hydrophobic nano-particles, 40~60 parts of water-miscible organic solvents, 2~
5 parts of hard monomers, 1~6 part of soft monomer, 0.5~2 part of water-soluble monomer, 0.5~3 part of reactive monomer, 0.1~0.3 part of initiation
Agent, 1~3 part of alkaloids and 15~25 parts of distilled water；
Step 2：At room temperature, functional hydrophobic nano-particles are scattered in water-miscible organic solvent, are stirred well to nanoparticle
Son is uniformly dispersed, and the finely dispersed nanoparticle system then is warming up to 90~110 DEG C, will under nitrogen protective condition
The mixture that hard monomer, soft monomer, water-soluble monomer, reactive monomer and initiator mix is added dropwise to the nanometer after heating
In particle system, unreacted organic solvent, cooling are removed after insulation reaction 6h；
Step 3：Alkaloids are added in into reaction mass after cooling, then under agitation, add in distilled water dilution, system
Obtain water soluble acrylic acid polymer/inorganic nanometer particle hybrid.
2. the preparation method of water soluble acrylic acid polymer/inorganic nanometer particle hybrid according to claim 1, feature
It is, the functionality hydrophobic nano-particles are the surface nanoparticle containing double bond isoreactivity group and hydrophobic grouping simultaneously
Son, specific preparation method are as follows：
At 50 DEG C, in terms of mass fraction, by 1 part of inorganic nano-particle, 0.1~0.7 part of hydrophobic agents, 0.04~0.28
The activity modifying agent of part is placed in the ethyl alcohol and ammonium hydroxide mixed solution that pH value is 11~13, is sufficiently stirred 2~4h of reaction, filter,
It is dry, obtain functional hydrophobic nano-particles.
3. the preparation method of water soluble acrylic acid polymer/inorganic nanometer particle hybrid according to claim 2, feature
It is, the grain size of the inorganic nano-particle is 50nm~1 μm, and inorganic nano-particle is silica, the oxidation of γ types three two
One or more of aluminium, rutile titanium dioxide and calcium carbonate.
4. the preparation method of water soluble acrylic acid polymer/inorganic nanometer particle hybrid according to claim 2, feature
It is, the hydrophobic agents are tridecafluoro-n-octyltriethoxysilane, 17 fluorine decyl triethoxysilanes, 17 fluorine decyls three
Methoxy silane, 17 fluorine decyltrichlorosilanes, 1H, 1H, 2H, 2H- perfluoro capryls triethoxysilane, ten difluoro heptyl propyl
One or more of trimethoxy silane and dodecyltrimethoxysilane；The activity modifying agent is vinyl trimethoxy
In base silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane and vinyl trichlorosilane
One or more.
5. the preparation method of water soluble acrylic acid polymer/inorganic nanometer particle hybrid according to claim 1, feature
It is, the hard monomer is the one or both combination in methyl methacrylate and styrene；The soft monomer is acrylic acid
N-butyl, acrylic acid n-pentyl ester, the just own ester of acrylic acid, n-propyl or acrylic acid-2-ethyl caproite.
6. the preparation method of water soluble acrylic acid polymer/inorganic nanometer particle hybrid according to claim 1, feature
It is, the water-soluble monomer is acrylic or methacrylic acid；The reactive monomer is acrylic acid -2- hydroxyl ethyl esters, propylene
Acid -2- hydroxypropyl acrylates, 2-hydroxyethyl methacry-late, Hydroxypropyl methacrylate or acrylic acid -4- hydroxy butyl esters；The initiation
Agent is dibenzoyl peroxide, peroxide -2-ethyl hexanoic acid tert-butyl, peroxidating -2 ethyl hexanoic acid tert-pentyl ester, two isobutyl of azo
Nitrile or peroxidating tert-butyl acetate.
7. the preparation method of water soluble acrylic acid polymer/inorganic nanometer particle hybrid according to claim 1, feature
It is, the water-miscible organic solvent is n-butanol, the tert-butyl alcohol, tetrahydrofuran or isopropanol；The alkaloids are ammonium hydroxide, three
Ethamine or N, N- dimethylethanolamine.
8. using water soluble acrylic acid polymer/inorganic nanometer made from the preparation method described in any one in claim 1~7
Particle hybrid.
9. a kind of preparation method of the super-hydrophobic coat based on water-and acrylate Polymer/nano particle hybrid, feature
It is, includes the following steps：
1) it in terms of mass fraction, takes described in 0.05~0.3 part of watersoluble closed type Isocyanates curing agent and 1 part of claim 8
Water soluble acrylic acid polymer/inorganic nanometer particle hybrid, be uniformly mixed；
2) it sprays, is placed at room temperature to surface drying, after being then heat-treated 1h at 80~90 DEG C, then in 120~150 DEG C of curing process
The super-hydrophobic coat based on water-and acrylate Polymer/nano particle hybrid is made in 2h.
10. the super-hydrophobic coat according to claim 9 based on water-and acrylate Polymer/nano particle hybrid
Preparation method, which is characterized in that the watersoluble closed type Isocyanates curing agent for Trixene BI7986,
AQUA BI 200、AQUA BI 201、AQUA BI 202、BL 2781、BL 2867、BL 5335 orBL XP 2706。
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