CN102585073B - Fluorine silicon-modified acrylic ester emulsion and preparation method thereof - Google Patents
Fluorine silicon-modified acrylic ester emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fluorine silicon-modified acrylic ester emulsion and a preparation method thereof. The fluorine silicon-modified acrylic ester emulsion is a shell-core emulsion mainly prepared from a fluorine monomer, vinyl triisopropoxysilane, nano silica sol, a vinyl monomer, a long carbon chain monomer, an emulsifier, a pH buffer, an initiator, deionized water and the like. The fluorine monomer is delayed to be dripped during polymerization, so that the fluorine element is enriched on the surfaces of emulsion particles, the hydrophobic and oleophobic properties of fluorine elusion is given full play to, the use of the fluorine monomer is reduced, and the cost is reduced. The composition of inorganic silicon oxide particles and an organic polymer keeps the good film forming property of the polymer and has the weather resistance, high hardness and other characteristics of the inorganic matter, so as to improve the stain resistance of a varnish film.
Description
Technical field
The present invention can be used for the application of inner wall of building, relates to a kind of hud typed fluorine silicon-modified acrylic ester emulsion and preparation method thereof.
Background technology
The fluorine reforming polymer surface free energy that contains perfluoro alkyl group is low, can give hydrophobic oleophobic, the anti-stain characteristic energy of material surface excellence, at aspects such as building external paint, antifouling paint, anti-fog coatings, important potential application is arranged.Zisman side chain perfluoro MU (methylene unit) in 1962 report (methyl) perfluoroalkyl acrylate homopolymer just have while surpassing 7 extremely low surface can (10～11mN/m) (and JPhys Chem, 1962,66:1207-1208).
The method of introducing fluoro-containing group mainly contains three kinds: the one, and adopt trifluorochloroethylene, tetrafluoroethylene and vinyl ethers/vinyl acetate between to for plastic class copolymerization to form (as the Chinese invention patent 200510135388.7 of application), multiplex this method of fluorocarbon resin of selling in the market; The 2nd, add fluorochemical additive, as (as Chinese invention patent ZL200710090028.9) such as Perfluorocaprylic Acid, fluorocarbon surfactants; The 3rd, use fluorinated acrylate monomer, this is present a kind of most widely used method, is equally also the most popular research direction.But the perfluoroalkyl acrylate monomer is expensive, and its homopolymer cost is too high, is difficult to widespread use.Utilize the reaction enthalpy of perfluorinated acrylate, Q-e value and acrylate are close, and itself and acrylic ester copolymer can be reduced costs, and are beneficial to and realize industrialization.
SiO in Nano silica sol
2Penetrating power is very strong, can be attached to the surface of base material and filler particles, evaporation along with moisture, between particle, dehydration forms the firmly solid netted skeleton of siloxane bond, but this filming lacks continuity and spreadability, and fluorinated acrylate polymer has good film-forming properties, and both recombination energies can be overcome the film shortcoming of easy embrittlement efflorescence of silicon sol.Because inorganics and organism are the materials of two kinds of different in kinds, both interfaces lack enough affinities, and the interface affinity that therefore improves both is the key of composite emulsion preparation.
Interior wall coating can be divided into high-gloss paint, mercerising coating, flat paint and low luster coating according to the glossiness of paint film.Due to reflective more serious after the hard-gloss paint film forming, harmful to people's eyes; Human consumer's aesthetic standards more and more tend to have the coatings with low gloss finish of soft outward appearance in addition, so the demand of low luster coating sharply increases.Present low luster coating is mainly to make coating surface coarse by adding the flatting silicas such as superfine silicon dioxide, talcum powder, to reach low gloss effect.Generally, the median size of flatting silica is larger, and porosity is higher, and extinction effect is better.But large particle size filler makes coating surface coarse, and high porosity reduces paint film compactness, causes stain easily to infiltrate paint film and be difficult to remove, and the coating resistance to soiling descends.
Summary of the invention
The emulsion that the purpose of this invention is to provide a kind of fluorinated silicone modified acrylate, this fluorine silicon-modified acrylic ester emulsion can be used for preparing the good low luster coating of resistance to soiling.
The technical scheme that realizes above-mentioned purpose is as follows:
A kind of fluorine silicon-modified acrylic ester emulsion, the raw material that it includes following weight part forms:
The stratum nucleare pre-emulsion that is formed by following weight part raw material:
1) Nano silica sol 17-45 part
2) vinyl monomer 85-150 part
3) grow carbochain monomer 7-42 part
4) fluorochemical monomer is 0 part
5) vinyl silane triisopropoxide 2-15 part
6) emulsifying agent 2-7 part
7) deionized water 75-90 part;
The shell pre-emulsion that is formed by following weight part raw material:
1) vinyl monomer 20-65 part
2) grow carbochain monomer 8-43 part
3) fluorochemical monomer 15-85 part
4) vinyl silane triisopropoxide 5-18 part
5) emulsifying agent 3-10 part
6) deionized water 70-80 part; And
150-165 part deionized water, 0.9-1.3 part emulsifying agent, 0.5-3.0 part pH buffer reagent, 1.0-3.0 part initiator; Described fluorochemical monomer is perfluoroalkyl acrylate; Described long carbochain monomer is long carbon chain acrylate monomer.
Preferably, described vinyl monomer is one or more the mixture in methyl methacrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, vinylbenzene, vinylformic acid, methacrylic acid.
Described perfluoroalkyl acrylate is preferably trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl esters, methacrylic acid 17 fluorine monooctyl esters.Perfluorinated acrylate is to introduce full-fluorine group on the side chain of original copolymer, because the perfluor side chain is orientated outwardly, main chain and interior molecules is shielded, and makes the polymer physics stable performance, weathering resistance and good endurance.The low surface energy of perfluorinated acrylate provides good hydrophobic oleophobic performance for emulsion again, makes water-based or oiliness stain be not easy to adhere to.
Long carbochain has excellent hydrophobic performance, can produce synergistic effect with fluorochemical monomer, improves hydrophobic nature and does not reduce oil repellency.Long carbochain monomer of the present invention is long carbon chain acrylate monomer, is preferably one or more mixtures in dodecylacrylate, aliphatic acrylate, vinylformic acid stearyl, lauryl methacrylate, methacrylic acid cetyl ester, methacrylic acid stearyl.
The vinyl silane triisopropoxide that adopts in the present invention is easy to copolymerization and enters the main chain of vinyl and acrylic latex, at aqueous based systems, has extraordinary stability, and can not react before the coating cohesion or crosslinked.General silane coupling agent, as A-174, A-1100 etc., add and namely have on a small quantity gel to produce, limited the further raising of emulsion degree of crosslinking, and the addition of vinyl silane triisopropoxide can reach 10%, thereby improve significantly the degree of crosslinking of paint film, can obtain hard and highly cross-linked coating after curing, thereby improve the sticking power of solvent resistance, water tolerance, anti-scratch and scrub resistance, hygrometric state and the dry state of paint film.The water borne coating formulation that contains this silane after 1 year aging, still keeps stability and validity.
The Nano silica sol that the present invention adopts is alkaline silica sol, and solid content is 30 ± 1%.Because the silanol base is contained on the silica sol particle surface, can generate covalent linkage with the alcoxyl cardinal extremity reaction of vinyl silane triisopropoxide, and the vinyl terminal of vinyl silane triisopropoxide can generate covalent linkage with resin, thereby makes inorganic silicon oxide and organic polymer coupling.The structure of inorganic Si-O key belongs to ionic, has conductivity preferably, can not produce charge accumulated, does not namely produce static, and dust is difficult to adhere to.During the coating film forming, merge mutually by jam-packed and distortion along with the moisture evaporation for latex particle, and dehydrating condensation between silica sol particle, form the Si-O reticulation, fill film forming by organism, form fine and close structure, make fine dust particle be difficult for invading its gap, thereby coating has good stain resistance.The high rigidity of inorganics also has very large contribution at the coating high temperature resistance aspect after-tacking.
Emulsifying agent of the present invention comprises anionic emulsifier and nonionic emulsifier, and described anionic emulsifier is one or more the composition in allyloxy hydroxypropyl azochlorosulfonate acid sodium (COPS-1), ethoxylated alkylphenol ammonium sulfate (CO436), alkyl polyoxyethylene acyl sodium sulfonate (073), disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate (2A1), 1-propenyloxy group-2-hydroxypropanesulfonic acid sodium (AOPS-1); Described nonionic emulsifier be alkylphenol polyoxyethylene class (as polyoxyethylene nonylphenol ether NP-10, polyoxyethylene nonylphenol ether NP-40, alkylphenol polyoxyethylene OP-10, alkylphenol polyoxyethylene OP-40), non-ionic type fluorocarbon surfactant (as
The composition of one or more FSO).In the shell pre-emulsion, be preferably the mixture of anionic emulsifier and fluorocarbon surfactant because fluorocarbon surfactant have with fluorochemical monomer and polymer phase like fluoroalkyl, the more general emulsifying agent of emulsifying effectiveness will be got well.
Described pH buffer reagent is sodium bicarbonate, sodium carbonate, sodium-acetate.
Described initiator is Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
Another object of the present invention is to provide the preparation method of above-mentioned fluorine silicon-modified acrylic ester emulsion.
The technical scheme that realizes above-mentioned purpose is as follows:
The preparation method of fluorine silicon-modified acrylic ester emulsion comprises the following steps:
(1) stratum nucleare pre-emulsion, shell pre-emulsion are pressed respectively above-mentioned composition, mixing stirs well even, standby;
(2) in reactor, add the 10-20% of 90-105 part deionized water, 0.9-1.3 part emulsifying agent, 0.5-3.0 part pH buffer reagent and stratum nucleare pre-emulsion total amount as seed emulsion, be warming up to 74-76 ℃, after being dissolved in deionized water, the 20-40% of initiator total amount adds, question response system blueing light, drip successively remaining stratum nucleare pre-emulsion, shell pre-emulsion while being warming up to 79-81 ℃, and dripping remaining initiator when dripping remaining stratum nucleare pre-emulsion, shell pre-emulsion, the time that drips remaining stratum nucleare pre-emulsion and shell pre-emulsion is 4-6 hour; Postpone half an hour and drip initiator;
(3) dropwise when initiator, be warmed up to 83-86 ℃ of slaking 0.8-1.2 hour, then cool to below 45 ℃, regulating pH with ammoniacal liquor is 7, discharging.
In emulsion polymerization process, adopt to postpone drip the method for fluorochemical monomer, make fluorine element be enriched in the emulsion particle surface, can not only give full play to the excellent properties such as hydro-oleophobicity, weathering resistance of fluorine emulsion, can reduce again the consumption of fluorochemical monomer, reduce the emulsion cost.
The present invention prepares a kind of dumb light antifouling paint with above-mentioned fluorine silicon-modified acrylic ester emulsion, by the raw material of following weight part, is prepared from:
(1) above-mentioned fluorine silicon-modified acrylic ester emulsion 25-50 part;
(2) titanium dioxide slurry 30-45 part;
(3) polyaminoester emulsion 14-30 part;
(4) wax dispersion 1-5 part of emulsifier-free;
(5) defoamer 0.2-0.3 part;
And the weight part ratio of described fluorine silicon-modified acrylic ester emulsion and polyaminoester emulsion is 1～3.5: 1.
The present invention has the distribution of the monomer of different glass temperature at the two-layer pre-emulsion of nucleocapsid by adjusting, emulsion particle is designed to stone soft shell type.For stone soft shell type emulsion, because softer shell is wrapped in the emulsion particle surface, so emulsion is easy to film forming; , because in soft shell, the molecular chain rotation is easier to, be conducive to the carrying out of crosslinking reaction again, increase the paint film density, improve resistance to soiling; Wrapped stone has given emulsion particle certain hardness, can prevent that paint film high temperature from after-tacking.
The present invention uses fluorine carbon emulsion and polyaminoester emulsion blend, utilizes both larger surface energy differentials different, thereby increases the nano and micro relief of coatingsurface, reduces coatingsurface to the reflection of light ability, makes coating reach the dumb light effect.
Compared with prior art, the present invention has following beneficial effect:
The present invention adopts the core-shell emulsion polymerization method, and the organic fluorine of hydrophobic oleophobic is enriched in the latex surface, reduces the emulsion cost when not affecting the fluorochemical monomer excellent properties, and long carbochain monomer and fluorochemical monomer synergy, strengthen the emulsion hydrophobicity.
The present invention adopts vinyl silane triisopropoxide in synthetic, its good stability, can not react before coating cohesion or crosslinked, ambient temperature curable, can obtain hard and highly cross-linked coating after curing, the molecular structure that is designed to the stone soft shell is conducive to emulsion film forming and self-crosslinking reaction carries out, and improves the compactness of paint film, thereby improves anti-pollution characteristic.
The present invention is compound with inorganic silicon oxide particle and organic polymer, and the siloxane bond reticulation of utilizing the good film-forming properties of polymkeric substance and silicon sol dehydrating condensation to form forms fine and close paint film, further improves contamination resistance.
The present invention adopts fluorine carbon emulsion and polyaminoester emulsion blend to reach low gloss effect, has overcome traditional flatting silica because particle diameter is large, the high paint film density that causes of porosity descends, thus the difficulty that causes stain easily to permeate and be difficult to remove.
Embodiment
Titanium dioxide slurry in the present invention is bought in Longkou wheat Brian Goodell chemistry company limited, and wherein in titanium dioxide slurry, the mass content of titanium dioxide is 68-69wt%.The wax dispersion of described emulsifier-free is a kind of low-molecular-weight polyolefin aqueous dispersion of not using any emulsifying agent, and its size distribution is narrow, and particle is spherical in shape.In following examples, Nano silica sol used is alkaline silica sol, and its solid content is 30 ± 1%, buys the N-30 in chemical industry company limited of Shanghai Hang Seng.
Embodiment 1
One, the chief component of described fluorine silicon-modified acrylic ester emulsion is as follows:
The raw material consumption of the two-layer pre-emulsion of table 1 nucleocapsid
Stratum nucleare pre-emulsion, shell pre-emulsion are pressed respectively above-mentioned composition, mix and blend 20-30min, rotating speed 500～600rpm, standby.
Table 2 initiator solution
| The material title | Initial initiator/g | Drip initiator/g |
| Sodium Persulfate | 0.35 | 1.00 |
| Deionized water | 6 | 48 |
Emulsion viscosity is measured with NDJ-1 type Rotary Viscosimeter.Condition determination is as follows: probe temperature is 25 ℃; Use No. 1 rotor; Rotating speed is 60r/min, sees GB/T1723-1993.Lower same.
Two, being prepared as follows of described fluorine silicon-modified acrylic ester emulsion:
After stirring in 100 gram deionized waters, 0.4 gram allyloxy hydroxypropyl azochlorosulfonate acid sodium, 0.3 gram ethoxylated alkylphenol ammonium sulfate, 0.6 gram NP-10 and 0.9g sodium bicarbonate input reactor, add 27g stratum nucleare pre-emulsion, be warming up to 75 ℃, add initial initiator, question response system blueing light, drip simultaneously the residue pre-emulsion and drip initiator, wherein while being warmed up to 80 ℃, the dropping of residue pre-emulsion is sequentially: first drip residue stratum nucleare pre-emulsion, rear dropping shell pre-emulsion.With dripping off the residue pre-emulsion in 4 hours, with dripping off initiator in 4.5 hours.Be warmed up to 85 ℃ of slakings 1 hour, then cool to below 45 ℃, with discharging after ammoniacal liquor adjusting pH=7.
Gained emulsion white blueing light, solid content is that 45%, 25 ℃ of lower viscosity is 1040mpas.
Three, the described dumb light antifouling paint of this enforcement is composed as follows:
Table 3 dumb light antifouling paint formula
Four, being prepared as follows of described dumb light antifouling paint:
Take quantitative fluorine silicon-modified acrylic ester emulsion and drop in titanium dioxide slurry, then add polyaminoester emulsion, wax dispersion and defoamer, stir and can make the dumb light antifouling paint that is applicable to inner wall of building, coating is specifically filled a prescription in Table 3.
With 200 μ m blade applicators knifing on high-density plate, under room temperature, (25 ℃) maintenance is 7 days with the dumb light antifouling paint of above-mentioned preparation.Measure 60 ° of gloss of paint film with the glossiness determinator.Selected pollutent is applied to coating surface, after naturally placing 1h, with the cotton that is soaked with 5% washing powder water, cleans back and forth 100 times, rinse well and dry, the range estimation stain is removed degree.Testing method following examples are identical therewith.
60 ° of gloss of the paint film of gained dumb light antifouling paint are 8, and anti-pollution characteristic is in Table 13.
Embodiment 2
One, the chief component of described fluorine silicon-modified acrylic ester emulsion is as follows:
The raw material consumption of the two-layer pre-emulsion of table 4 nucleocapsid
Stratum nucleare pre-emulsion, shell pre-emulsion are pressed respectively above-mentioned composition, mix and blend 20-30min, rotating speed 500～600rpm, stir standby.
Table 5 initiator solution
| The material title | Initial initiator/g | Drip initiator/g |
| Potassium Persulphate | 0.8 | 2.2 |
| Deionized water | 10 | 50 |
Two, being prepared as follows of described fluorine silicon-modified acrylic ester emulsion:
After stirring in 90 gram deionized waters, 0.5 gram alkyl polyoxyethylene acyl sodium sulfonate, 0.5 gram NP-40 and 3.0g sodium bicarbonate input reactor; add 44g stratum nucleare pre-emulsion; be warming up to 75 ℃; add initial initiator; question response system blueing light; being warmed up to 80 ℃ drips simultaneously the residue pre-emulsion and drips initiator (, as embodiment 1, press the stratum nucleare pre-emulsion first, the order after the shell pre-emulsion drips).With dripping off pre-emulsion in 6 hours, with dripping off initiator in 6.5 hours.Be warmed up to 86 ℃ of slakings 1.0 hours, then cool to below 45 ℃, with discharging after ammoniacal liquor adjusting pH=7.
Gained emulsion white blueing light, solid content is that 46%, 25 ℃ of lower viscosity is 1350mpas.
Three, described antifouling paint is composed as follows:
Table 6 antifouling paint formula
Then take quantitative fluorine silicon-modified acrylic ester emulsion and drop in titanium dioxide slurry, then add polyaminoester emulsion, wax dispersion and defoamer, stir and can make the dumb light antifouling paint that is applicable to inner wall of building, antifouling paint is specifically filled a prescription in Table 6.
60 ° of gloss of the paint film of gained dumb light antifouling paint are 5, and anti-pollution characteristic is in Table 13.
Embodiment 3
One, the chief component of described fluorine silicon-modified acrylic ester emulsion is as follows:
The raw material consumption of the two-layer pre-emulsion of table 7 nucleocapsid
Stratum nucleare pre-emulsion, shell pre-emulsion are pressed respectively above-mentioned composition, mix and blend 20-30min, rotating speed 500～600rpm, standby.
Table 8 initiator solution
| The material title | Initial initiator/g | Drip initiator/g |
| Ammonium persulphate | 0.6 | 1.4 |
| Deionized water | 10 | 50 |
Two, the chief component of described fluorine silicon-modified acrylic ester emulsion is as follows:
After stirring in 105 gram deionized waters, 0.5 gram 1-propenyloxy group-2-hydroxypropanesulfonic acid sodium, 0.6 gram OP-10 and 1.5g sodium carbonate input reactor, add 37g stratum nucleare pre-emulsion, be warming up to 75 ℃, add initial initiator, question response system blueing light, being warmed up to 80 ℃ drips simultaneously residue pre-emulsion (press the stratum nucleare pre-emulsion first, the order after the shell pre-emulsion drips) and drips initiator.With dripping off pre-emulsion in 5.5 hours, with dripping off initiator in 6.0 hours.Be warmed up to 83 ℃ of slakings 1.2 hours, then cool to below 45 ℃, with discharging after ammoniacal liquor adjusting pH=7.
Gained emulsion white blueing light, solid content is 46%, under room temperature, viscosity is 3370mpas.
Table 9 antifouling paint formula
Then take quantitative fluorine silicon-modified acrylic ester emulsion and drop in titanium dioxide slurry, then add polyaminoester emulsion, wax dispersion and defoamer, stir and can make the dumb light antifouling paint that is applicable to inner wall of building, antifouling paint is specifically filled a prescription in Table 9.
60 ° of gloss of the paint film of gained dumb light antifouling paint are 7, and anti-pollution characteristic is in Table 13.
Embodiment 4
One, the chief component of described fluorine silicon-modified acrylic ester emulsion is as follows:
The raw material consumption of the two-layer pre-emulsion of table 10 nucleocapsid
Stratum nucleare pre-emulsion, shell pre-emulsion are pressed respectively above-mentioned composition, mix and blend 20-30min, rotating speed 500～600rpm, stir standby.
Table 11 initiator solution
| The material title | Initial initiator/g | Drip initiator/g |
| Sodium Persulfate | 0.4 | 0.8 |
| Deionized water | 15 | 45 |
Two, being prepared as follows of described fluorine silicon-modified acrylic ester emulsion:
After stirring in 95 gram deionized waters, 0.5 gram disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, 0.4 gram OP-40 and 0.5g sodium-acetate input reactor, add 45g stratum nucleare pre-emulsion, be warming up to 75 ℃, add initial initiator, question response system blueing light, being warmed up to 80 ℃ drips simultaneously residue pre-emulsion (press the stratum nucleare pre-emulsion first, the order after the shell pre-emulsion drips) and drips initiator.With dripping off pre-emulsion in 5 hours, with dripping off initiator in 5.5 hours.Be warmed up to 86 ℃ of slakings 0.8 hour, then cool to below 45 ℃, with discharging after ammoniacal liquor adjusting pH=7.
Gained emulsion white blueing light, solid content is 45%, under room temperature, viscosity is 510mpas.
Three, described antifouling paint is composed as follows:
Table 12 antifouling paint formula
Then take quantitative fluorine silicon-modified acrylic ester emulsion and drop in titanium dioxide slurry, then add polyaminoester emulsion, wax dispersion and defoamer, stir and can make the dumb light antifouling paint that is applicable to inner wall of building, antifouling paint is specifically filled a prescription in Table 13.
60 ° of gloss of the paint film of gained dumb light antifouling paint are 6, and anti-pollution characteristic is in Table 15.
Table 13 resistant test result
| The stain title | Embodiment 1 coating | Embodiment 2 coating | Embodiment 3 coating | Embodiment 4 coating |
| China's pencil | ○ | □ | □ | ○ |
| Pencil is red | ○ | ○ | ○ | ○ |
| Wax crayon is red | □ | □ | □ | □ |
| Wax crayon is blue | ○ | ○ | ○ | ○ |
| Watercolor is red | ◇ | □ | ○ | □ |
| Watercolor is green | ◇ | □ | □ | ◇ |
| Watercolor is blue | □ | ○ | □ | ○ |
| The oil pen | △ | ◇ | △ | △ |
| Tomato juice | ○ | ○ | ○ | ○ |
| Coffee | ○ | ○ | ○ | ○ |
Annotate: zero cleans substantially; is residual more shallow; ◇ is medium; △ is residual darker; * residual profound.
These are only specific embodiments of the invention, with this, do not limit protection scope of the present invention; Any replacement and the improvement done on the basis of not violating the present invention's design, all belong to protection scope of the present invention.
Claims (9)
1. a fluorine silicon-modified acrylic ester emulsion, is characterized in that, it mainly is prepared from by the raw material of following weight part:
(A) the stratum nucleare pre-emulsion that is formed by following weight part raw material:
(B) the shell pre-emulsion that is formed by following weight part raw material:
(C) 0.9-1.3 part emulsifying agent, 0.5-3.0 part pH buffer reagent, 1.0-3.0 part initiator; 150-165 part deionized water, described fluorochemical monomer are perfluoroalkyl acrylate; Described long carbochain monomer is long carbon chain acrylate monomer;
Described vinyl monomer is one or more the mixture in methyl methacrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, vinylbenzene, vinylformic acid, methacrylic acid.
2. fluorine silicon-modified acrylic ester emulsion according to claim 1, is characterized in that, described perfluoroalkyl acrylate is methacrylic acid 17 fluorine monooctyl esters.
3. fluorine silicon-modified acrylic ester emulsion according to claim 1, it is characterized in that, described long carbon chain acrylate monomer is one or both mixtures in dodecylacrylate, aliphatic acrylate, vinylformic acid stearyl, lauryl methacrylate, methacrylic acid cetyl ester, methacrylic acid stearyl.
4. fluorine silicon-modified acrylic ester emulsion according to claim 1, is characterized in that, described Nano silica sol is alkaline silica sol, and its solid content is 30 ± 1%.
5. fluorine silicon-modified acrylic ester emulsion according to claim 1, it is characterized in that, described emulsifying agent comprises anionic emulsifier and nonionic emulsifier, and described anionic emulsifier is one or more the composition in allyloxy hydroxypropyl azochlorosulfonate acid sodium, ethoxylated alkylphenol ammonium sulfate, alkyl polyoxyethylene acyl sodium sulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, 1-propenyloxy group-2-hydroxypropanesulfonic acid sodium; Described nonionic emulsifier is one or more the composition in polyoxyethylene nonylphenol ether NP-10, polyoxyethylene nonylphenol ether NP-40, alkylphenol polyoxyethylene OP-10, alkylphenol polyoxyethylene OP-40, non-ionic type fluorocarbon surfactant.
6. fluorine silicon-modified acrylic ester emulsion according to claim 5, is characterized in that, in described shell pre-emulsion, described emulsifying agent is the mixture of anionic emulsifier and fluorocarbon surfactant.
7. fluorine silicon-modified acrylic ester emulsion according to claim 1, is characterized in that, described pH buffer reagent is sodium bicarbonate, sodium carbonate, sodium-acetate; Described initiator is Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
8. a method for preparing the described fluorine silicon-modified acrylic ester emulsion of claim 1-7 any one, is characterized in that, comprises the following steps:
(1) stratum nucleare pre-emulsion, shell pre-emulsion are formed by the described raw material of claim 1 respectively, mixing and stirring, standby;
(2) in reactor, add the 10-20% of 90-105 part deionized water, 0.9-1.3 part emulsifying agent, 0.5-3.0 part pH buffer reagent and stratum nucleare pre-emulsion total amount as seed emulsion, be warming up to 74-76 ℃, after being dissolved in deionized water, the 20-40% of initiator total amount adds, question response system blueing light, drip successively remaining stratum nucleare pre-emulsion, shell pre-emulsion while being warming up to 79-81 ℃, and drip the remaining initiator with deionized water dissolving when dripping remaining stratum nucleare pre-emulsion, shell pre-emulsion;
(3) dropwise when initiator, be warmed up to 83-86 ℃ of slaking 0.8-1.2 hour, then be cooled to below 45 ℃, regulating pH with ammoniacal liquor is 7, and discharging, obtain described fluorine silicon-modified acrylic ester emulsion.
9. preparation method according to claim 8, is characterized in that, in step (2), the time that drips remaining stratum nucleare pre-emulsion and shell pre-emulsion is 4-6 hour; Remaining initiator drips off in 0.5 hour after remaining stratum nucleare pre-emulsion, shell pre-emulsion dropwise.
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