CN106632875A - Inorganic nanoparticle-modified fluorinated acrylate hydrophobic emulsion and preparation method thereof - Google Patents
Inorganic nanoparticle-modified fluorinated acrylate hydrophobic emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN106632875A CN106632875A CN201610876620.0A CN201610876620A CN106632875A CN 106632875 A CN106632875 A CN 106632875A CN 201610876620 A CN201610876620 A CN 201610876620A CN 106632875 A CN106632875 A CN 106632875A
- Authority
- CN
- China
- Prior art keywords
- preparation
- parts
- emulsion
- modified
- monomer
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses inorganic nanoparticle-modified fluorinated acrylate hydrophobic emulsion and a preparation method thereof; the method modifies fluorinated acrylate hydrophobic emulsion with inorganic nanoparticles through emulsion polymerization and comprises the specific steps of reacting butyl acrylate, methyl methacrylate and a functional soft monomer to obtain seed, compositing a surfactant with reactive anionic emulsifier and nonionic emulsifier, and adding a fluorinated monomer, butyl acrylate, methyl methacrylate and functional soft monomer under the protection of N2 to prepare the hydrophobic polymerized emulsion with core-shell structure. The defects of existing polyacrylate emulsion, such as poor stability, poor adhesive strength, poor ultraviolet resistance, low water resistance and low heat resistance, are overcome.
Description
Technical field
The present invention relates to high molecular polymerization emulsion field, and in particular to a kind of inorganic nano particle modified fluorinated acrylate
Hydrophobic lotions and preparation method thereof；The emulsion is prepared using emulsion polymerisation process.
Background technology
Nano-meter SiO_22As a kind of important inorganic particulate, due to its excellent properties, such as special photoelectric property, high temperature
Under the conditions of high-strength, high-ductility, high stability, have been widely used for various material modifications.For emulsion modified, Nano-meter SiO_22It is conventional
Preparation method be sol-gel process.The Nano-meter SiO_2 that sol-gel process is not only prepared2Purity is high, particle good dispersion, and
And reaction condition is gentle, process is simple is not high to equipment requirement, and particle is easy to surface and is modified.However, prepared by sol-gel process
Nano-meter SiO_22In alcohols solvent, when directly it is applied into emulsion polymerization systems, the alcohols solvent of high concentration can change polydispersion
Become the property of water in emulsion system, increase the solubility of emulsifying agent, critical micelle concentration (CMC) value for making emulsifying agent significantly goes up
Rise, and then make emulsion polymerization systems loss of stability.Therefore, the Nano-meter SiO_2 that prepared by sol-gel process2Before polymerization, generally
Pre-processed using means such as dialysis, vacuum distillation, centrifugations, be then scattered in monomer again, and this process easily causes
Nano-meter SiO_22" secondary agglomeration " of particle forms bigger particle, makes Nano-meter SiO_22Particle diameter distribution broadens, or even affects nanometer
SiO2The final good dispersion in latex film, can not play due modified effect.
Hydrophobic coating possesses very wide application prospect, but it has certain lacking in the application of current each side
Fall into, no matter from preparation method or integrated application aspect of performance, also there are many problem demanding prompt solutions.At present, great majority are existing
Hydrophobic, the super-hydrophobic coat preparation method having all has difficulties in every respect, for example：Experiment condition is harsh, and process is numerous and diverse, equipment
The problems such as costliness, high cost.For researcher, simple economy, eco-friendly Hydrophobic coating preparation method are also to be developed.
On the other hand, during in design micro/nano level structure improving coating roughness, and then improve hydrophobicity, other property of hydrophobic coating
Can well take into account, for example, coating surface fine structure low intensity, easily aging, easy to wear, easy pollution, service life occur
The shortcoming of short grade, the mechanical strength of coating is not satisfactory, and stability of material is poor, and environmental suitability is not strong etc..Therefore hydrophobic coating
Preparation, application study need the following aspects strengthen：(1) simplify；How simple, cheap, effective method is utilized
Coarse structure is constructed, the hydrophobic finish material for obtaining excellent performance is the important goal that it is pursued.(2) durableization；Hydrophobic painting
The coarse structure of layer surface easily causes because yardstick is smaller and relatively more fragile in the mechanism such as external impacts or friction
Hydrophobic surface is damaged, and loses hydrophobic performance.Thus, improve one that hydrophobic persistence is that hydrophobic coating application faces
Major issue.(3) multifunction.In specific application, its hydrophobicity is not the function uniquely to be met to hydrophobic coating, is applied
Layer also needs to meet many other functional requirements, and to meet special use occasion, such as papery, stone cultural artifact protection is outdoor
Building glass, solar panel, windshield and rearview mirror, garden glass wall etc., except requiring that it is good that coating has
Hydrophobicity, also require that coating has high transparent, hardness, rub resistance, the heat-resisting performance characteristics such as weather-proof.
In recent years, due to outstanding features such as excellent machinery, optics, electronics, hydrophobic, the thermally-stabilised, anti-flammabilitys of oleophobic,
Composite organic-inorganic material have been a great concern and be applied to film, the quick coating of function intelligence, fuel and solar cell,
Many fields such as catalyst.In numerous organic components, fluoropolymer is because of its remarkable lipophobic hydrophobic, pollution resistance, Zi Run
Slip, heat-resisting, chemicals-resistant stability and good biocompatibility, special dielectric properties etc. become a class especially extremely
The selecting object of material supply section scholar favor.At present, fluoropolymer is in sapecial coating, biomaterial coating and bio-sensing
The fields such as device, anti-flaming dope, novel microelectronic device, history relic protection are applied.Additionally, SiO2、TiO2、Al2O3、
ZrO2、CaCO3Nano composite material, wherein SiO are used to prepare etc. many nano-particles2The power of organic polymer can be improved
Learn performance, heat endurance, abrasion resistance and durability and most widely applied.If inorganic particulate can be well dispersed in
In organic polymer matrix, the hardness of final composite, scratch-resistant, impact resistance, optical property will be significantly improved.Cause
This, is expected to by introducing SiO in fluoropolymer2Particle, prepares excellent combination property, with the new of potential using value
Type composite.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to " secondary agglomeration " that overcome inorganic nano-particle is formed more
Big particle and polyacrylate dispersion easily forms gel, glues glutinous intensity deficiency, the also not enough problem of its water-fast heat resistance,
High to glue glutinous intensity there is provided a kind of stable, hardness is high, and ultraviolet light, resistance to water are heat-resist, the easy polygalacto of preparation condition
Liquid, the modified inorganic nano particle modified fluorinated acrylate polymerized emulsion of application and preparation method thereof.
To realize above-mentioned technical purpose, the present invention is employed the following technical solutions.
A kind of preparation method of inorganic nano particle modified fluorinated acrylate hydrophobic lotions, comprises the steps of：
(1) preparation of modified monomer dispersion liquid：According to mass fraction meter, under conditions of 30-50 DEG C, 20-100 parts are gone
The stirring of ionized water, 1.0-6.0 parts reactive emulsifier and 0.1-1.0 parts nonionic emulsifier obtains breast until fully dissolving
The agent aqueous solution；Add 5-10 part tetraethyl orthosilicates, 0.6-1.8 part silane couplers, 5-50 part methyl methacrylates, 5-
50 parts of butyl acrylates and 0.5-5.0 part feature soft monomers, then at room temperature magnetic agitation 12-24h forms modified monomer
Dispersion liquid；
(2) synthesis of seed emulsion：According to mass fraction meter, by 40-160 part deionized waters, 0.5-3 part polymerization inhibitors, 5-
Modified monomer dispersion liquid prepared by 40 parts of initiators and 1/4-1/2 steps (1), 70-75 DEG C of heating water bath, and it is passed through N2As guarantor
Shield gas, using mechanical stirring at low speed accelerate react, after emulsion it is pink then become again it is light blue after in 2.5-4h successively plus
Enter remaining modified monomer dispersion liquid and 5-15 part initiators, continue to be incubated 1-2h afterwards, synthesize seed emulsion；
(3) preparation of inorganic nano particle modified fluorinated acrylate hydrophobic lotions：According to mass fraction meter, in reactor
Middle addition 10-60 parts deionized water and 0.5-3.0 parts reactive emulsifier and 0.05-0.4 parts nonionic emulsifier emulsification 15-
40 minutes, afterwards add 5-30 part methyl methacrylates, 5-30 part butyl acrylates, 0.5-2.0 part feature soft monomers,
1.0-10 part fluorochemical monomers, magnetic agitation 0.5-2h carries out monomer emulsification；Afterwards in 70-75 DEG C of heating water bath, and it is passed through N2Make
For shielding gas, accelerate to be added under reaction in the seed emulsion of step (2) synthesis using mechanical stirring at low speed, while 0.1- is added dropwise
2.0 parts of initiator, the completion of dropping in 2-4h；Finally it is brought rapidly up to 80-85 DEG C of insulation 1-3 hour, 25- is cooled to afterwards
45 DEG C, discharging by adjusting pH obtains inorganic nano particle modified fluorinated acrylate hydrophobic lotions.
Preferably, described reactive emulsifier is allyloxy Nonyl pheno (10) ether ammonium sulfate (DNS-86)
With the one kind in allyloxy nonyl sweet smell polyoxyethylene ether ammonium sulfate salt (SE-10N).
It is further preferred that described reactive emulsifier is in DNS-86, NP-10 and SE-10N type emulsifying agent
Kind.
Preferably, described nonionic emulsifier is in APES and AEO
Kind.
It is further preferred that described nonionic emulsifier is APES (TX, NP, OP), fatty alcohol
One kind in APEO (AEO, MOA, TO).
Preferably, described silane coupler is γ-aminopropyl triethoxysilane KH-550, γ-glycidyl ether oxygen
Propyl trimethoxy silicane KH-560, γ-methacryloxypropyl trimethoxy silane KH-570 and γ-methacryl
One kind in epoxide propyl-triethoxysilicane KH-572.
Preferably, described feature soft monomer is hydroxy-ethyl acrylate；Described polymerization inhibitor be hydroquinones, benzoquinones and
NaHCO3In one kind.
Preferably, described initiator is benzoyl peroxide (BPO), dilauroyl peroxide (LPO), azodiisobutyronitrile
(AIBN), one kind in ammonium persulfate and potassium persulfate solution.
It is further preferred that described initiator is potassium persulfate solution, mass fraction is 2%-4%.
Preferably, described fluorochemical monomer is tetrafluoroacetate vinyl acetate, fluorinated ethylene carbonate, the difluoro of methacrylic acid ten
At least one in heptyl ester and dodecafluorhe-ptylacrylate.
Preferably, the rotating speed of the stirring at low speed is 280-350r/min；The scope of the regulation pH is 6～8；It is described fast
It is to be warming up to 80-85 DEG C with 3-10 DEG C/min that speed heats up.
A kind of inorganic nano particle modified fluorinated acrylate hydrophobic lotions by obtained in above-described preparation method.
Silane coupler be a class in the molecule simultaneously containing the organo-silicon compound of two kinds of different chemical property groups, it is right
Formula YSiX can be used for the present invention3Represent.In formula, Y is the group with C=C double bonds of non-hydrolytic, and X is alkoxyl；This
Invention is dehydrated bonding using the hydroxyl that is hydrolyzed into of its alkoxyl with Si-OH, at the same time C=C double bonds and alkene in silane coupler
Hydrocarbon monomer is polymerized, so as to reach the effective integration of inorganic nano-particle and organic substance.Coupling agent can connect inorganic
Modified Nano particle, makes inorganic particulate be better dispersed in the middle of organic solution.When the consumption of modified nano-particle is 1-5
During part/100 parts of fluorinated acrylates, the contact angle of prepared nanometer particle-modified fluorinated acrylate is 73.03～
121.310.Silane coupler can process filler as surface modifier, contribute to its dispersion in organic polymer.
Inorganic nano-particle is easy to reunite and forms bulky grain together；The present invention passes through hydrolysis of the presoma in monomer
Prepared inorganic nano-particle, adding appropriate silane coupler can be obtained the dispersion liquid of modified nano-particle and monomer, so as to
The extensive serious agglomeration of the presence of inorganic nano-particle can effectively be avoided.
The hardness of acrylate, scratch-resistant, impact resistance, heat-resisting can significantly be improved by the introducing of inorganic nano-particle
And UV Aging Resistance, then wherein add fluorochemical monomer then to improve the hydrophobic performance of acrylate, add this
The hardness of the polyacrylate of preparation, scratch-resistant, impact resistance, heat-resisting, ultraviolet light and hydrophobicity under two kinds of material conditions
It is significantly improved.
In polymerization process, compounded using various emulsifying agents, doping type can be formed in emulsion particle or micellar surface
Emulsifying agent monomolecular film, is so conducive to reducing the electrostatic repulsion in monomolecular film, can greatly enhance self-strength, emulsion particle table
Surface charge is reduced also less, and final system combination property is improved.So the present invention is using anionic and nonionic emulsifier
Compounding use, based on anionic reactive emulsifier.
The emulsion nano particle of polymerization is easy to reunite, so the appropriate polymerization inhibitor of present invention addition, the addition of polymerization inhibitor
And adopt composite emulsifier system make polymerized emulsion at normal temperatures can long-time stable preserve.
Nano-meter SiO_22With special optical performance, it has extremely strong UV absorption, the characteristic of infrared external reflection.It is added to
The composite latex film to be formed can be dried in hydrophobic lotions to emulsion and forms ultraviolet shielded effect, reach anti-ultraviolet ageing and heat ageing
Purpose, by nano particle filling method, by mixed nanometer to ultraviolet-curing paint, can also significantly enhance ultraviolet light
The hardness and adhesive force of solidification, also reduces the degree that ultraviolet-curing paint absorbs UV radiation, so as to reduce UV-curing
Change the curing rate of coating.
The present invention compared with the existing technology, has the advantage that：
(1) the invention provides using modified inorganic nano particle modified fluorinated acrylate polymerized emulsion and its preparation
Method.Coupling agent can link inorganic modified nano-particle, inorganic particulate is better dispersed in the middle of organic solution.When modified
Nano-particle consumption be 1-20 part/100 part fluorinated acrylate when, prepared nanometer particle-modified fluorine-containing
The contact angle of ester is 73.03～121.31 °.
(2) silane coupler is a class in the molecule simultaneously containing the organosilicon compound of two kinds of different chemical property groups
Thing, can use for the present invention formula YSiX3Represent.In formula, Y is the group with C=C double bonds of non-hydrolytic, and X is alcoxyl
Base；The present invention is dehydrated bonding using the hydroxyl that is hydrolyzed into of its alkoxyl with Si-OH, at the same time C=C double bonds in silane coupler
It is polymerized with olefinic monomer, so as to reach the effective integration of inorganic nano-particle and organic substance.
(3) hardness, adhesive force and the heat resistance of acrylate can significantly be improved by the introducing of inorganic nano-particle
Can, while it has extremely strong ultraviolet absorption characteristic.It is added in emulsion can dry the composite latex film shape to be formed to emulsion
Into ultraviolet shielded effect, the purpose of anti-ultraviolet ageing and heat ageing is reached, then wherein add fluorochemical monomer then to improve third
The resistance to water of olefin(e) acid ester, the heat-resisting resistance to water of the acrylate prepared under the material conditions of both for adding has been obtained substantially
Raising.
(4) in polymerization process, compounded using various emulsifying agents, doping type can be formed in emulsion particle or micellar surface
Emulsifying agent monomolecular film, be so conducive to reduce monomolecular film in electrostatic repulsion, self-strength, emulsion particle can be greatly enhanced
Surface charge is reduced also less, and final system combination property is improved.So the present invention is emulsified using anionic and nonionic
Agent compounding use, based on anionic reactive emulsifier.
(5) the emulsion nano particle of polymerization is easy to reunite, so the present invention appropriate polymerization inhibitor of addition, polymerization inhibitor plus
The composite emulsifier system for entering and adopting make polymerized emulsion at normal temperatures can long-time stable preserve.
(6) inorganic nano particle modified fluorinated acrylate hydrophobic lotions of the invention are because of its excellent hydrophobicity, remarkable
Corrosion resistance, soil resistance, chemical stability and weatherability, in textile finishing, leather process, paper industry, historical relic's protection, oil gas
The field such as exploitation and purification, antifouling paint has wide application prospect.
Description of the drawings
Fig. 1 is the TEM figures of emulsion particle in inorganic nano particle modified fluorinated acrylate hydrophobic lotions.
Fig. 2 is the latex film (SiO of inorganic nano particle modified fluorinated acrylate hydrophobic lotions2Content a：1.0%, b：
2.5%, c：5.0%) TG figures.
Fig. 3 is the Nano-meter SiO_2 in inorganic nano particle modified fluorinated acrylate hydrophobic lotions2(SiO2Content a：2.0%,
b：6.0%, c：10%) to the absorption curve figure of ultraviolet.
Specific implementation method
To more fully understand the present invention, with reference to example, the present invention is further illustrated, but embodiment is not constituted
Limiting the scope of the present invention.
Following part is mass parts, per part of expression 1g
Embodiment 1
(1) preparation of modified monomer dispersion liquid：Under conditions of 30 DEG C, by 20 parts of deionized waters and 1 part of DNS-86 reaction
Type emulsifying agent and 0.3 part of OP-10 are added in beaker with glass bar stirring fully dissolving；So as to obtain emulsifier aqueous solution, so
Add 10 parts of methyl methacrylates, 10 parts of butyl acrylates, 0.6 part of γ-methacryloxypropyl three in beaker afterwards
Ethoxysilane, 0.5 part of hydroxy-ethyl acrylate and 5 parts of tetraethyl orthosilicates, then at room temperature magnetic agitation formation in 24 hours changes
The nano-SiO of property2Monomer dispersion liquid.
(2) synthesis of seed emulsion：70 DEG C of water-bath constant temperature is opened, mechanical agitation rotating speed is opened and is adjusted to as 300r/min,
Use N2Shielding gas is done, 40 parts of deionized waters, 0.5 part of NaHCO are added in four-hole boiling flask3, 5 parts of KPS (potassium peroxydisulfate) initiators it is molten
Modified nano-SiO prepared by liquid (mass fraction is 2%) and 1/4 step (1)2Monomer dispersion liquid is little 3 after reaction 30min
When the interior remaining dispersion liquid of addition successively and 10 parts of KPS initiator solutions (mass fraction is 2%), continue to be incubated 1 afterwards little
When, you can synthesis seed emulsion.
(3) preparation of nanometer particle-modified fluorinated acrylate hydrophobic lotions：Add in conical flask 7 parts of deionized waters and
0.6 part of DNS-86 reactive emulsifiers and 0.1 part of OP-10 are emulsified 20 minutes, then add 5 parts of methyl methacrylates, 3
Part butyl acrylate, 0.2 part of hydroxy-ethyl acrylate and 4 parts of dodecafluoroheptyl methacrylates, then magnetic agitation carry out within 1 hour
Monomer is emulsified, and afterwards in 70 DEG C of heating water baths, and is passed through N2As shielding gas, accelerated using mechanical 300r/min stirring at low speed anti-
During the seed emulsion of step (2) synthesis should be down added to, while 5 parts of KPS solution (mass fraction is 2%) is added dropwise, it is little three
When interior completion of dropping, be finally brought rapidly up being warming up to 80 DEG C of insulations with 3 DEG C/min and be cooled within 1 hour 25 DEG C afterwards, adjusting pH is
6, you can discharging obtains inorganic nano particle modified fluorinated acrylate hydrophobic lotions.
Embodiment 2
(1) preparation of modified monomer dispersion liquid：Under conditions of 40 DEG C, by 40 parts of deionized waters, 1.6 parts of DNS-86 reactions
Type emulsifying agent and 0.5 part of OP-10 are added in beaker with glass bar stirring fully dissolving；So as to obtain emulsifier aqueous solution, so
Add 7.5 parts of tetraethyl orthosilicates, 0.9 part of γ-methacryloxypropyl, 25 parts of methyl in beaker afterwards
Methyl acrylate, 15 parts of butyl acrylates and 1.5 parts of hydroxy-ethyl acrylates, then at room temperature magnetic agitation formation in 24 hours changes
The nano-SiO of property2Monomer dispersion liquid.
(2) synthesis of seed emulsion：70 DEG C of water-bath constant temperature is opened, it is 300r/min to open mechanical agitation and be adjusted to rotating speed,
Use N2Shielding gas is done, 70 parts of deionized waters, 0.3 part of NaHCO are added in four-hole boiling flask3, 10 parts of KPS initiator solutions (quality point
Number is the modified nano-SiO for 2%) preparing with 1/3 step (1)2Monomer dispersion liquid, after reaction 30min in 3 hours successively
The remaining dispersion liquid of addition and 15 parts of KPS initiator solutions (mass fraction is 2%), afterwards continue be incubated 1.5 hours
Synthesis seed emulsion.
(3) preparation of nanometer particle-modified fluorinated acrylate hydrophobic lotions：15 parts of water and 0.6 part are added in conical flask
DNS-86 reactive emulsifiers and 0.2 part of OP-10 are emulsified 20 minutes, then add 9 parts of methyl methacrylates, 5 parts of propylene
Acid butyl ester, 0.7 part of hydroxy-ethyl acrylate, 6 parts of dodecafluoroheptyl methacrylates, then magnetic agitation carry out within 1 hour monomer breast
Change, afterwards in 70 DEG C of heating water baths, and be passed through N2As shielding gas, accelerate to add under reaction using mechanical 300r/min stirring at low speed
Enter in the seed emulsion of step (2) synthesis, while 5 parts of KPS solution (mass fraction is 2%) is added dropwise, dripped in three hours
Plus finish, finally it is brought rapidly up being cooled within 2 hours 30 DEG C afterwards with 5 DEG C/min to 82.5 DEG C of insulation, it is discharging by 7 to adjust pH
Obtain inorganic nano particle modified fluorinated acrylate hydrophobic lotions.
Embodiment 3
(1) preparation of modified monomer dispersion liquid：Under conditions of 45 DEG C, by 60 parts of deionized waters, 3 parts of DNS-86 response types
Emulsifying agent and 0.75 part of OP-10 are added in beaker with glass bar stirring fully dissolving；So as to obtain emulsifier aqueous solution, then
8.5 parts of tetraethyl orthosilicates, 1.2 parts of γ-methacryloxypropyls, 40 parts of methyl-props are added in beaker
E pioic acid methyl ester, 20 parts of butyl acrylates and 2.25 parts of hydroxy-ethyl acrylates, then form modified for 24 hours in room temperature magnetic agitation
Nano-SiO2Monomer dispersion liquid.
(2) synthesis of seed emulsion：70 DEG C of water-bath constant temperature is opened, mechanical agitation rotating speed is opened and is adjusted to 300r/min, used
N2Shielding gas is done, 100 parts of deionized waters, 0.3 part of NaHCO are added in four-hole boiling flask3, 20 parts of KPS initiator solutions (quality point
Number is the modified nano-SiO for 2%) preparing with 1/3 step (1)2Monomer dispersion liquid, after reaction 30min in 3 hours successively
The remaining dispersion liquid of addition and 30 parts of KPS initiator solutions (mass fraction is 2%), afterwards continue be incubated 1.5 hours
Synthesis seed emulsion.
(3) preparation of nanometer particle-modified fluorinated acrylate hydrophobic lotions：20 parts of deionized waters are added in conical flask
Emulsify 20 minutes with 1 part of DNS-86 reactive emulsifier and 0.25 part of OP-10, then add 12 parts of methyl methacrylates, 5
Part butyl acrylate, 0.7 part of hydroxy-ethyl acrylate, 8 parts of dodecafluoroheptyl methacrylates, then magnetic agitation carry out within 1 hour
Monomer is emulsified, and afterwards in 70 DEG C of heating water baths, and is passed through N2As shielding gas, accelerated using mechanical 300r/min stirring at low speed anti-
During the seed emulsion of step (2) synthesis should be down added to, while 10 parts of KPS solution (mass fraction is 2%) is added dropwise, it is little three
When interior completion of dropping, be finally brought rapidly up being warming up to 85 DEG C of insulations with 6.5 DEG C/min and be cooled within 2 hours 40 DEG C afterwards, adjust pH
Can discharge for 8 and obtain inorganic nano particle modified fluorinated acrylate hydrophobic lotions.
Embodiment 4
(1) preparation of modified monomer dispersion liquid：Under conditions of 50 DEG C, by 100 parts of deionized waters, 6 parts of DNS-86 reactions
Type emulsifying agent and 1 part of OP-10 are added in beaker with glass bar stirring fully dissolving；So as to obtain emulsifier aqueous solution, then
10 parts of tetraethyl orthosilicates, 1.8 parts of γ-methacryloxypropyls, 50 parts of methyl-props are added in beaker
E pioic acid methyl ester, 50 parts of butyl acrylates and 5 parts of hydroxy-ethyl acrylates, then form what is be modified in 24 hours in room temperature magnetic agitation
nano-SiO2Monomer dispersion liquid.
(2) synthesis of seed emulsion：70 DEG C of water-bath constant temperature is opened, mechanical agitation rotating speed is opened and is adjusted to as 300r/min,
Use N2Shielding gas is done, 160 parts of deionized waters, 3 parts of NaHCO are added in four-hole boiling flask3, 30 parts of KPS initiator solutions (quality point
Number is the modified nano-SiO for 2%) preparing with 1/2 step (1)2Monomer dispersion liquid, after reaction 30min in 3 hours successively
The remaining dispersion liquid of addition and 15 parts of KPS initiator solutions (mass fraction is 2%), afterwards continue be incubated 2 hours can close
Into seed emulsion.
(3) preparation of nanometer particle-modified fluorinated acrylate hydrophobic lotions：According to mass fraction meter, add in conical flask
Enter 35 parts of deionized waters and 2 parts of DNS-86 reactive emulsifiers and 0.35 part of OP-10 is emulsified 20 minutes, then add 15 parts of first
Base methyl acrylate, 15 parts of butyl acrylates, 2 parts of hydroxy-ethyl acrylates, 25 parts of dodecafluoroheptyl methacrylates, then magnetic force
Stirring carries out monomer emulsification in 1 hour, afterwards in 70 DEG C of heating water baths, and is passed through N2As shielding gas, using mechanical 300r/min
Stirring at low speed accelerates to be added under reaction in the seed emulsion of step (2) synthesis, while 5 parts of KPS solution are added dropwise, (mass fraction is
2%), the completion of dropping in three hours, is finally brought rapidly up being warming up to 85 DEG C of insulations with 10 DEG C/min and is cooled to 45 afterwards in 2 hours
DEG C, regulation pH can discharge for 8 and obtain inorganic nano particle modified fluorinated acrylate hydrophobic lotions.
Comparative example 1
(1) toluene of 150mL is poured into the there-necked flask with agitator, and receives 10 parts under conditions of stirring
Rice SiO2Powder is added in the middle of toluene, and under the reflux temperature of 8000r/min high-speed stirreds and toluene 1 hour is incubated；Add 5
Part γ-methacryloxypropyl trimethoxy silane, 8000r/min high-speed stirreds are simultaneously incubated 2 hours.Solution Jing ethanol is washed
Wash, suction filtration, be dried at 75 DEG C, dry obtain monomer until permanent.
(2) 30 parts of deionized waters and 1.8 parts of response type DNS-86 type emulsifying agents are added in beaker and are stirred with glass bar
Fully dissolving, so as to obtain emulsifier aqueous solution, then adds 15 parts of methyl methacrylates, 15 parts of acrylic acid fourths in beaker
Ester, 2 parts of acrylic acid are mixed into oil phase, open 75 DEG C of water-bath constant temperature, open mechanical agitation under the condition of 350r/min,
80 parts of deionized waters, 0.13 part of KPS solution (mass fraction is 2%) and 10 parts of monomers are added in beaker, is become after basket to emulsion
The remaining monomer of addition and 10 parts of KPS solution (mass fraction is 2%) in 2 hours successively, continues to be incubated 1 hour i.e. afterwards
Into seed emulsion.
(3) preparation of nanometer particle-modified fluorinated acrylate hydrophobic lotions：10 parts of water and 0.6 is added in conical flask
Part DNS-86 reactive emulsifiers emulsify 20 minutes, then add 5 parts of methyl methacrylates, 5 parts of butyl acrylates, 2
Part dodecafluoroheptyl methacrylate, then magnetic agitation carry out monomer emulsification, be added under identical reaction conditions afterwards
Seed emulsion prepared by step (2), while 0.05 part of KPS solution (mass fraction is 2%) is added dropwise, was added dropwise in 2.5 hours
Finish, when being finally warmed up to 95 DEG C of insulations 1 after be cooled to 40 DEG C, adjust pH be 7 can discharging obtain required product.
The present invention prepares the TEM figures of the emulsion particle in inorganic nano particle modified fluorinated acrylate hydrophobic lotions as schemed
Shown in 1.As shown in Figure 1, the emulsion particle that the polymerisation is formed has nucleocapsid structure, and the average grain diameter of emulsion particle is
100nm or so.
Latex film (SiO in the inorganic nano particle modified fluorinated acrylate hydrophobic lotions of the present invention2Content a：1.0%,
b：2..5%, c：5.0%) TG figures are as shown in Figure 2.Shown by Fig. 2, Nano-meter SiO_22Being incorporated into polymerized emulsion can be notable
Increase the heat resistance of latex film.
Nano-meter SiO_2 in the inorganic nano particle modified fluorinated acrylate hydrophobic lotions of the present invention2(SiO2Content a：
2.0%, b：6.0%, c：10%) it is as shown in Figure 3 to the absorption curve figure of ultraviolet.From the figure 3, it may be seen that with Nano-meter SiO_22Content
Increase, the UV absorption of latex film significantly increases.
By embodiment 1-4, the inorganic nano particle modified fluorinated acrylate polymerized emulsion prepared by comparative example 1 is in normal temperature
It is lower to measure the hydrophobic of it, water suction, stability and heat resistance.It is inorganic nano particle modified prepared by embodiment and comparative example
Each performance parameter of fluorinated acrylate is shown in Table 1.
Table 1
The embodiment of contrast table 1 understands with comparative example and accompanying drawing, with polymerization process, the addition of polymerization inhibitor,
The introducing of composite emulsifier system, inorganic nano-particle and F atom, using inorganic nano particle modified the containing of present invention offer
Fluorinated monomer method, prepared complex emulsions have good stability, glue glutinous intensity by force, and hardness is high, ultraviolet shielded strong, water-fast
The characteristics of property is heat-resist, preparation condition is simple.Acrylate can significantly be improved by the introducing of inorganic nano-particle
Hardness, adhesive force and heat resistance, while its extremely strong ultraviolet absorption characteristic.To the later stage, it is protected in papery, stone cultural artifact, family
The application of External building glass, solar panel etc. provides wide prospect.
Claims (10)
1. a kind of preparation method of inorganic nano particle modified fluorinated acrylate hydrophobic lotions, it is characterised in that comprising following
Step：
（1）The preparation of modified monomer dispersion liquid：According to mass fraction meter, under conditions of 30-50 DEG C, by 20-100 parts go from
The stirring of sub- water, 1.0-6.0 parts reactive emulsifier and 0.1-1.0 parts nonionic emulsifier is emulsified until fully dissolving
The agent aqueous solution；Add 5-10 part tetraethyl orthosilicates, 0.6-1.8 part silane couplers, 5-50 part methyl methacrylates, 5-50
Part butyl acrylate and 0.5-5.0 part feature soft monomers, then at room temperature magnetic agitation 12-24 H-shaped divides into modified monomer
Dispersion liquid；
（2）The synthesis of seed emulsion：According to mass fraction meter, by 40-160 part deionized waters, 0.5-3 part polymerization inhibitors, 5-40 parts
Initiator and 1/4-1/2 steps（1）The modified monomer dispersion liquid of preparation, 70-75 DEG C of heating water bath, and it is passed through N2As protection
Gas, using mechanical stirring at low speed accelerate react, after emulsion it is pink then become again it is light blue after add successively in 2.5-4 h
Remaining modified monomer dispersion liquid and 5-15 part initiators, continue to be incubated 1-2 h afterwards, synthesize seed emulsion；
（3）The preparation of inorganic nano particle modified fluorinated acrylate hydrophobic lotions：According to mass fraction meter, add in a kettle.
Enter 10-60 parts deionized water and 0.5-3.0 parts reactive emulsifier and 0.05-0.4 parts nonionic emulsifier emulsification 15-40
Minute, afterwards add 5-30 part methyl methacrylates, 5-30 part butyl acrylates, 0.5-2.0 part feature soft monomers,
1.0-10 part fluorochemical monomers, magnetic agitation 0.5-2 h carries out monomer emulsification；Afterwards in 70-75 DEG C of heating water bath, and it is passed through N2
As shielding gas, accelerate to be added to step under reaction using mechanical stirring at low speed（2）In the seed emulsion of synthesis, while being added dropwise
The initiator of 0.1-2.0 parts, the completion of dropping in 2-4 h；Finally it is brought rapidly up to 80-85 DEG C of insulation 1-3 hour, drops afterwards
To 25-45 DEG C, discharging by adjusting pH obtains inorganic nano particle modified fluorinated acrylate hydrophobic lotions to temperature.
2. preparation method according to claim 1, it is characterised in that described reactive emulsifier is DNS-86, NP-10
With the one kind in SE-10N type emulsifying agents.
3. preparation method according to claim 1, it is characterised in that described nonionic emulsifier is alkyl phenol polyoxy
One kind in vinethene and AEO.
4. preparation method according to claim 1, it is characterised in that described silane coupler is γ-aminopropyl three
Ethoxysilane KH-550, γ-glycidyl ether oxygen propyl trimethoxy silicane KH-560, γ-methacryloxypropyl
One kind in trimethoxy silane KH-570 and γ-methacryloxypropyl KH-572.
5. preparation method according to claim 1, it is characterised in that described feature soft monomer is acrylic acid hydroxyl second
Ester；Described polymerization inhibitor is hydroquinones, benzoquinones and NaHCO3In one kind.
6. preparation method according to claim 1, it is characterised in that described initiator is benzoyl peroxide, peroxide
Change the one kind in lauroyl, azodiisobutyronitrile, ammonium persulfate and potassium persulfate solution.
7. preparation method according to claim 1, it is characterised in that described initiator is potassium persulfate solution, quality
Fraction is 2%-4%.
8. preparation method according to claim 1, it is characterised in that described fluorochemical monomer be tetrafluoroacetate vinyl acetate,
At least one in fluorinated ethylene carbonate, dodecafluoroheptyl methacrylate and dodecafluorhe-ptylacrylate.
9. preparation method according to claim 1, it is characterised in that the rotating speed of the stirring at low speed is 280-350 r/
min；The scope of the regulation pH is 6 ~ 8；It is described to be brought rapidly up being to be warming up to 80-85 DEG C with 3-10 DEG C/min.
10. a kind of inorganic nano particle modified fluorine-containing obtained in the preparation method by described in any one of claim 1-9
Ester hydrophobic lotions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610876620.0A CN106632875A (en) | 2016-09-30 | 2016-09-30 | Inorganic nanoparticle-modified fluorinated acrylate hydrophobic emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610876620.0A CN106632875A (en) | 2016-09-30 | 2016-09-30 | Inorganic nanoparticle-modified fluorinated acrylate hydrophobic emulsion and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106632875A true CN106632875A (en) | 2017-05-10 |
Family
ID=58855057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610876620.0A Pending CN106632875A (en) | 2016-09-30 | 2016-09-30 | Inorganic nanoparticle-modified fluorinated acrylate hydrophobic emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106632875A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108893985A (en) * | 2018-06-12 | 2018-11-27 | 苏州联胜化学有限公司 | A kind of no fluorine-type waterproofing agent and preparation method thereof |
| CN111172748A (en) * | 2020-01-20 | 2020-05-19 | 宁波萌恒线业有限公司 | Fluorine-free waterproof agent for textiles and preparation method thereof |
| CN112341891A (en) * | 2020-11-26 | 2021-02-09 | 简珍霞 | Water-based antifouling paint and preparation method thereof |
| CN115521679A (en) * | 2022-08-29 | 2022-12-27 | 广东美涂士建材股份有限公司 | Non-top-coat silicone-acrylic self-cleaning stone-like paint and preparation process thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010033932A1 (en) * | 2000-01-18 | 2001-10-25 | Jsr Corporation | Composite particles, composite particle dispersion composition, and method of preparing composite particle dispersion composition |
| CN102030873A (en) * | 2010-10-27 | 2011-04-27 | 华南理工大学 | Method for preparing nano silicon/polyacrylate composite emulsion |
| CN102604003A (en) * | 2012-03-14 | 2012-07-25 | 大连工业大学 | Self-layering organic-inorganic nano composite emulsion and method for preparing same |
| CN103059188A (en) * | 2012-12-18 | 2013-04-24 | 华中科技大学 | Preparing method of composite styrene-acrylic emulsion containing silicon dioxide |
| CN103396518A (en) * | 2013-08-26 | 2013-11-20 | 张家港康得新光电材料有限公司 | Organic silicon modified water-based acrylate resin and preparation method thereof |
| CN103788312A (en) * | 2014-01-21 | 2014-05-14 | 江苏大学 | Preparation method of fluorine-silicon polymer and seal guard thereof applied to stone historical relic |
| CN104830192A (en) * | 2015-04-29 | 2015-08-12 | 广德嘉宝莉化工有限公司 | High-weatherability and high-toughness aqueous paint |
| CN104877089A (en) * | 2015-05-08 | 2015-09-02 | 中山职业技术学院 | Preparation method of modified fluorine-containing acrylic superhydrophobic resin emulsion |
-
2016
- 2016-09-30 CN CN201610876620.0A patent/CN106632875A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010033932A1 (en) * | 2000-01-18 | 2001-10-25 | Jsr Corporation | Composite particles, composite particle dispersion composition, and method of preparing composite particle dispersion composition |
| CN102030873A (en) * | 2010-10-27 | 2011-04-27 | 华南理工大学 | Method for preparing nano silicon/polyacrylate composite emulsion |
| CN102604003A (en) * | 2012-03-14 | 2012-07-25 | 大连工业大学 | Self-layering organic-inorganic nano composite emulsion and method for preparing same |
| CN103059188A (en) * | 2012-12-18 | 2013-04-24 | 华中科技大学 | Preparing method of composite styrene-acrylic emulsion containing silicon dioxide |
| CN103396518A (en) * | 2013-08-26 | 2013-11-20 | 张家港康得新光电材料有限公司 | Organic silicon modified water-based acrylate resin and preparation method thereof |
| CN103788312A (en) * | 2014-01-21 | 2014-05-14 | 江苏大学 | Preparation method of fluorine-silicon polymer and seal guard thereof applied to stone historical relic |
| CN104830192A (en) * | 2015-04-29 | 2015-08-12 | 广德嘉宝莉化工有限公司 | High-weatherability and high-toughness aqueous paint |
| CN104877089A (en) * | 2015-05-08 | 2015-09-02 | 中山职业技术学院 | Preparation method of modified fluorine-containing acrylic superhydrophobic resin emulsion |
Non-Patent Citations (4)
| Title |
|---|
| FUCHUN ZHAO，等: "Preparation and characterization of nano-SiO2/fluorinated polyacrylate composite latex via nano-SiO2/acrylate dispersion", 《COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS》 * |
| FUCHUN ZHAO，等: "Preparation of fluorinated polyacrylate composite latex with in situ generated nano-silica dispersion and film durability", 《IRAN POLYMER JOURNAL》 * |
| 屈撑囤: "《精细有机合成反应与工艺》", 30 September 2000, 西北大学出版社 * |
| 陈兴娟: "《环保型涂料生产工艺及应用》", 30 September 2004, 化学工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108893985A (en) * | 2018-06-12 | 2018-11-27 | 苏州联胜化学有限公司 | A kind of no fluorine-type waterproofing agent and preparation method thereof |
| CN111172748A (en) * | 2020-01-20 | 2020-05-19 | 宁波萌恒线业有限公司 | Fluorine-free waterproof agent for textiles and preparation method thereof |
| CN111172748B (en) * | 2020-01-20 | 2022-08-30 | 宁波萌恒线业有限公司 | Fluoride-free waterproof agent for textiles and preparation method thereof |
| CN112341891A (en) * | 2020-11-26 | 2021-02-09 | 简珍霞 | Water-based antifouling paint and preparation method thereof |
| CN115521679A (en) * | 2022-08-29 | 2022-12-27 | 广东美涂士建材股份有限公司 | Non-top-coat silicone-acrylic self-cleaning stone-like paint and preparation process thereof |
| CN115521679B (en) * | 2022-08-29 | 2024-04-12 | 广东美涂士建材股份有限公司 | Finishing-free silicone-acrylic self-cleaning real stone paint and preparation process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105061700B (en) | Nano silicon/polyacrylate organic inorganic hybridization water-dispersed resin and preparation method thereof | |
| CN100545184C (en) | The organosilicon resin composition and the formed body thereof that contain silicon-dioxide | |
| CN106632875A (en) | Inorganic nanoparticle-modified fluorinated acrylate hydrophobic emulsion and preparation method thereof | |
| CN105176371B (en) | Ultraviolet-curing paint and preparation method and ultra-hydrophilic transparent antifogging coating and preparation method | |
| CN103030752B (en) | Polymer microballoon and its preparation method and application and composition and light diffusing sheet or optical diffusion film and light fixture and backlight module | |
| CN103193924B (en) | Phased film forming styrene-acrylic coating emulsion and preparation method | |
| EP3000785B1 (en) | Porous metal oxide particles, production method thereof and application thereof | |
| CN1300191C (en) | Process for preparing nano silicon dioxide-acrylate composite emulsion | |
| CN102719158B (en) | Antireflective coating composition and method for preparing same | |
| CN103289021A (en) | Waterborne organic and inorganic fluorosiloxane modified acrylate polymer emulsion and preparation method and application thereof | |
| CN104262552A (en) | Silica sol/silicone acrylate core-shell nanocomposite emulsion and preparation method thereof | |
| CN105384864A (en) | Room temperature multiple self-crosslinking nano acrylate copolymer emulsion and preparation method and water-based woodenware paint using emulsion as base material | |
| CN100348627C (en) | Method for preparing organic silicon modified propenoic ester copolymer emusion by fine emulsion polymerizing method | |
| CN103387645B (en) | Fluorinated copolymer Grafted Nano-scale TiO 2composite particles and preparation method thereof | |
| CN101875710A (en) | Siloxane-group light-initiated polyacrylic ester/silicon dioxide nanometer material and preparation method thereof | |
| CN105885419B (en) | A kind of preparation method of cadmium compound quantum dot fluorescence film | |
| CN104628923A (en) | Method for preparing aggregation-induced emission type polymer fluorescent nanoparticle through mini-emulsion polymerization initiated by oil-soluble initiator | |
| CN110128855A (en) | A kind of preparation method containing silicon dioxide hollow particle anti-reflective coating composition | |
| CN102838889B (en) | Preparation method of visible light full-waveband multilayer antireflection coating | |
| CN113088123A (en) | Micro-nano composite SiO2Particle, micro-nano composite structure super-hydrophobic coating, preparation method and application thereof | |
| CN104628924A (en) | Method for preparing aggregation-induced emission type polymer fluorescent nanoparticle through mini-emulsion polymerization initiated by water-soluble initiator | |
| CN104262531B (en) | Unmodified Ludox/polyacrylate core-shell emulsion and preparation method thereof | |
| CN110183957A (en) | A kind of environmental protection high abrasion water-based gloss oil and preparation method thereof | |
| CN109666111A (en) | A kind of Nano-meter SiO_22/ organosilicon-modified acrylate emulsion | |
| Gong et al. | Preparation of ATO-incorporated composite latex with tailored structure and controllable size for highly spectrum-selective applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170510 |
|
| RJ01 | Rejection of invention patent application after publication |