CN101250369B - Aqueous composite paint containing amphiphilic fluorine-containing acrylate blocking copolymer and preparation thereof - Google Patents
Aqueous composite paint containing amphiphilic fluorine-containing acrylate blocking copolymer and preparation thereof Download PDFInfo
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- CN101250369B CN101250369B CN2008100270240A CN200810027024A CN101250369B CN 101250369 B CN101250369 B CN 101250369B CN 2008100270240 A CN2008100270240 A CN 2008100270240A CN 200810027024 A CN200810027024 A CN 200810027024A CN 101250369 B CN101250369 B CN 101250369B
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Abstract
The invention relates to a water-based compound coating which contains amphiphilic fluorinated acrylate segmented copolymer. The water-based compound coating which contains amphiphilic fluorinated acrylate segmented copolymer is prepared by the following raw material with the following weight by parts, fluorinated acrylate segmented copolymer 0.1-100 parts, fluorinated acrylate random copolymer 0-100 parts, water 50-100 parts, inorganic salt filler 40-100 parts, defoaming agent 0.2-5 parts and dispersing agent 0.2-4 parts. The compound coating of the invention not only has the advantages of low production cost, high adhesive force, stain resistance and the like, but also has no organic solvent in the process of preparing and in end products, the coating is an environment-friendly product.
Description
Technical field
The present invention relates to chemistry painting industry, be specifically related to a kind of Water compound coating and its preparation method that contains amphiphilic fluorine-containing acrylate blocking copolymer.
Background technology
Since the nineties in 20th century, each state all successively works out rules, and the VOC of coating is limited, and in the long term, solvent based coating will be withdrawn from the market gradually, and water-borne coatings will become the favorite in market.Fluorocarbon coating " Water-borne modification " becomes the severe problem that the coating research worker is faced, and the development of environmental protection fine aqueous fluorine-containing coating is just causing the very big concern of countries in the world, is an important directions of coatings industry development from now on.At present, obtain the two big class watersoluble fluorine paints that mainly contain of application especially at home, a class is the fluorine-containing watersoluble fluorine paint of main chain, and another kind of is the fluorine-containing watersoluble fluorine paint of side chain.
Wherein the fluorine-containing watersoluble fluorine paint of main chain mainly contains three kinds:
(1) aqueous dispersions of polytetrafluoroethylhaving coating, this coating have excellent performance, but it need heat film forming, therefore make its Application Areas be subjected to certain limitation.
(2) water-based vinylidene fluoride copolymers coating, such coating can the normal temperature film forming, and artificial ageing resistance reaches 3000h.But, cause it on the high side because used base-material is the water-based fluororesin of import.
(3) water-based fluoroolefin/vinyl ether co-polymer coating, such coating comprises two kinds: a kind of is that two-pack is coating material solidified, and a kind of is single component.The former is the water-based fluororesin that adopts back emulsion process preparation earlier, is used further to prepare two-component coating, so has organic solvent inevitably in the coating; Latter's onepot coating then adopts the letex polymerization manufactured, and this coating has certain application property, but the distribution underaction.
The fluorine-containing watersoluble fluorine paint of side chain mainly is the fluoro-acrylate copolymer emulsion, and such coating has alkali resistance that the acrylic ester monomer polymerized emulsion has on the one hand, protect the look gloss retention, the characteristics such as plentiful of filming; On the other hand, owing to used fluorinated acrylate monomer, on the polymkeric substance side chain, introduced fluoro-containing group, changed the structure of molecular chain, significantly improved the surface property of acrylate copolymer, make multipolymer have low surface energy, low frictional properties, hydrophobic and oil repellent, self-cleaning property and good weathering resistance, therefore in coating, have broad application prospects.
From the present both at home and abroad flow of research of exploitation aqueous fluorine polymer coating, also there is the shortcoming of two aspects in this coating: one, because fluoro-containing coating has surface hydrophobic, oleophobic, so this ADHESION OF PAINTS power relatively a little less than; Two, mainly in the fluorine-containing ester paint rely on C-F key on the side chain to protect main chain; and the distribution of the fluoro-containing group in the fluorinated acrylate is scattered relatively; because the polymer interchain is entangled with mutually; a lot of fluoro-containing groups are difficult to arrive film coated surface after the coating film forming; weakened the modifying function of fluoro-containing group; thereby cause the cost of such coating higher relatively, this will influence the application of such coating greatly.
Summary of the invention
One of purpose of the present invention is in order to overcome the above-mentioned shortcoming and defect of prior art, and the aqueous composite paint that contains amphiphilic fluorine-containing acrylate blocking copolymer of a kind of weather-proof, resistant, corrosion-resistant, Environmental Safety is provided.
The described aqueous composite paint that contains amphiphilic fluorine-containing acrylate blocking copolymer is made by the raw material of following weight part: 0.1～100 part of fluorine-containing ester block copolymer; 0～100 part of fluorinated acrylate random copolymers; 50～100 parts in water; 40～100 parts of inorganic salt fillers; 0.2～5 part of defoamer; 0.2～4 part of dispersion agent.
The structure of described fluorine-containing ester block copolymer is as follows:
Wherein:
M is selected from the arbitrary integer between 5 to 40;
N is selected from integer arbitrary between 20 to 200;
A replaces the monomeric polymerized segment of non-perfluoroalkyl acrylate for one or more non-perfluoroalkyl acrylate monomers or non-fluorinated monomer monomer or alkyl;
B is the polymerized segment of one or more fluorinated acrylate monomers;
Described fluorine-containing ester block copolymer comprises the fluorine-containing ester block copolymer of making as follows:
In weight part, get 50～100 parts of macromole RAFT reagent; 0.1～2 part of initiator; 20～50 parts of fluorinated acrylate monomers; 40～60 parts of aqueous solvent; Above-mentioned raw materials is stirred, make to mix; Vacuum, stirring in 70～80 ℃ of reaction 12～16h, get the fluorine-containing ester block copolymer down;
Described initiator comprises Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen peroxide, isopropyl benzene hydroperoxide, 4,4 '-azo two (4-cyanopentanoic acid); Described fluorinated acrylate monomer comprises methacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate or methacrylic acid ten difluoro heptyl esters.
Described macromole RAFT reagent comprises synthetic macromole RAFT reagent as follows:
In weight part, get that non-perfluoroalkyl acrylate monomer or non-fluorinated monomer monomer or alkyl replace non-perfluoroalkyl acrylate monomer or alkyl replaces 20～40 parts of non-fluorinated monomer monomers, 0.1～2 part of initiator, 1～4 part of small molecules RAFT chain-transfer agent, 40～60 parts in water; Vacuum, stirring in 70～80 ℃ of reaction 10～12h, get macromole RAFT reagent down then;
Described non-perfluoroalkyl acrylate monomer comprises vinylformic acid; Described non-fluorinated monomer monomer comprises acrylate, Hydroxyethyl acrylate or Propylene glycol monoacrylate; Described alkyl replaces non-perfluoroalkyl acrylate monomer and comprises methacrylic acid;
Described initiator comprises Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen peroxide, isopropyl benzene hydroperoxide or 4,4 '-azo two (4-cyanopentanoic acid);
Described small molecules RAFT chain-transfer agent comprises 4-dithiobenzoic acid (4-cyanopentanoic acid) ester.
The structure of described fluorinated acrylate random copolymers is as follows:
Wherein:
P is selected from the arbitrary integer between 1 to 20;
Q is selected from the arbitrary integer between 1 to 40;
W is selected from the arbitrary integer between 5 to 100;
A replaces the monomeric polymerized segment of non-perfluoroalkyl acrylate for one or more non-perfluoroalkyl acrylate monomers or non-fluorinated monomer monomer or alkyl;
B is the polymerized segment of one or more fluorinated acrylate monomers;
Described fluorinated acrylate random copolymers comprises by following method synthetic fluorinated acrylate random copolymers:
In weight part, get 20～40 parts of fluorinated acrylate monomers, non-fluorinated monomer monomer 20-40 part, 1～4 part of initiator, emulsifying agent 1-4 part and 40～60 parts of mixing of aqueous solvent, 12～16h is reacted in vacuum, stirring down in 70～80 ℃, get the fluorinated acrylate random copolymers;
Described fluorinated acrylate monomer comprises methacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate or methacrylic acid ten difluoro heptyl esters;
Described non-perfluoroalkyl acrylate monomer comprises vinylformic acid; Described non-fluorinated monomer monomer comprises acrylate, Hydroxyethyl acrylate or Propylene glycol monoacrylate; Alkyl replaces non-perfluoroalkyl acrylate monomer and comprises methacrylic acid;
Described initiator comprises Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen peroxide, isopropyl benzene hydroperoxide or 4,4 '-azo two (4-cyanopentanoic acid);
Emulsifying agent comprises ammonium lauryl sulfate, Sodium dodecylbenzene sulfonate, Perfluorocaprylic Acid sylvite, ammonium salt of perfluorooctanoic acid, Perfluorocaprylic Acid sulfonate sodium, Perfluorocaprylic Acid sulfonic acid potassium salt or polyoxyethylene alkyl phenyl ether.
Described inorganic salt filler comprises zinc sulfide white, pure aluminium silicate, mica, titanium dioxide, talcum powder, light calcium carbonate or water-ground limestone;
Described defoamer comprises pumice wax oil base defoamer, mineral oil defoaming agent or polysiloxane defoamer;
Described dispersion agent comprises acrylate, polyacrylate, carboxylic acid sodium salt or 2-amino-2-methyl-1-propanol.
Another object of the present invention provides the described preparation method who contains the aqueous composite paint of amphiphilic fluorine-containing acrylate blocking copolymer, and described preparation method may further comprise the steps: in weight part, get 0.1～100 part of fluorine-containing ester block copolymer; 0～100 part of fluorinated acrylate random copolymers; 50～100 parts in water; 40～100 parts of inorganic salt fillers; 0.2～5 part of defoamer; 0.2～4 part of dispersion agent; Above-mentioned substance is mixed promptly.
Compared with prior art, the present invention has the following advantages:
The present invention's monomer that fluorinated acrylate and polarity is higher is as, copolymerization such as vinylformic acid, hydroxyethyl methylacrylate, thereby improves ADHESION OF PAINTS power; And by living polymerization fluoro-containing group is focused on molecular chain one end, make the multipolymer of compound with regular structure, reduce, give full play to the modifying function of fluoro-containing group owing to intermolecular being entangled with mutually causes fluoro-containing group to be difficult to arrive the probability of coatingsurface.The present invention focuses on the fluorine-containing ester block copolymer coating that in the emulsion RAFT is used for synthetic molecular weight and controllable structure, by regulating the distribution of fluoro-containing group in molecular chain, alleviate because the fluoro-containing group distribution is scattered, molecule is entangled with the surface-modifying groups of losing as far as possible; And contain by in molecular chain, introducing-OH ,-water-soluble monomer of groups such as COOH, not only can improve such ADHESION OF PAINTS power, but also make this perfluoroalkyl acrylate ester copolymer have certain surfactivity.
Coating of the present invention uses less or need not additional emulsifying agent, thereby reduced conventional emulsifier to greatest extent to coating property and to the detrimentally affect of environment; And the RAFT living polymerization that is adopted among the present invention can focus on fluoro-containing group molecular chain one end, obtain the multipolymer of compound with regular structure, thereby greatly reduce owing to intermolecular being entangled with mutually causes fluoro-containing group to be difficult to arrive the probability of coatingsurface, therefore gained coating has higher sticking power, better performances such as water tolerance, contamination resistance, abrasion resistance, thermotolerance and ageing resistance.
The every more specifically performance index of coating of the present invention is as follows:
Table 1: the performance that contains the aqueous composite paint of fluorine-containing ester block copolymer of the present invention
In the table 1:
Film adhesive: press GB/T 1720-1979 (1989) and measure.
Hardness of film: press GB/T6739-1996 (determination of pencil hardness method) and measure.
The abrasion resistance of filming: press GB/T 9266-1998 and measure.
Artificial ageing resistance: press GB/T1865-88 and measure.
With water contact angle: adopt contact angle measurement to measure the contact angle of distilled water on film coated surface, all measurements are all carried out under room temperature (25 ℃).
Raw material weight ratio when synthesizing the fluorine-containing ester block copolymer is: 10 parts of methacrylic acids, 100 parts of methacrylic acid hexafluoro butyl esters, 1 part of initiator ammonium persulfate, 200 parts of aqueous solvent, 2 parts of small molecules RAFT chain-transfer agent 4-dithiobenzoic acid (4-cyanopentanoic acid) esters.
Raw material weight ratio when synthesizing the fluorinated acrylate random copolymers is: 20 parts of Rocryl 410s, 100 parts of methacrylic acid hexafluoro butyl esters, 2 parts of initiator ammonium persulfates, 2 parts of emulsifying agent Sodium dodecylbenzene sulfonatees, 200 parts of aqueous solvent.
Other component is described in the table: organic silicone oil is 1.5 parts of 0.5 parts, sodium acrylate, 100 parts of titanium dioxide fillers.
From a kind of performance that contains fluorine-containing ester block copolymer type composite coating of table 1 prescription 1～5 the present invention who provides relatively, under identical proportioning raw materials condition, in the prescription along with the increase of the segmented copolymer emulsion components ratio of the no additional emulsifiers that aggregates into by RAFT, every performance of composite coating all improves a lot, illustrate that the raising of the molecular structure degree of order can effectively improve the utilization ratio of fluoro-containing group, the performances such as hydrophobicity of filming are strengthened, demonstrated fully technology of the present invention and improved effect.
Embodiment
The present invention below is provided some embodiment preferably, understand the present invention to help further, but protection scope of the present invention is not limited in this.
Embodiment 1
In the there-necked flask of 100ml, add 10 parts of the first monomer methacrylic acids, 1 part of initiator ammonium persulfate, 50 parts of 4 parts of RAFT reagent 4-dithiobenzoic acid (4-cyanopentanoic acid) esters and aqueous solvent.Logical nitrogen 15 minutes, freezing in ice-water bath again, by vacuumize-Tong nitrogen is repeatedly after 3 times, vacuum sealing tube.In 70 ℃ of oil baths, react 6h under the magnetic agitation and get macromole RAFT reagent.
In above-mentioned reactor, continue to add 100 parts of the second monomer trifluoroethyl methacrylates, 200 parts of 0.2 part of initiator ammonium persulfate and aqueous solvent.Logical nitrogen 15 minutes, freezing in ice-water bath again, by vacuumize-Tong nitrogen is repeatedly after 3 times, vacuum sealing tube.In 70 ℃ of oil baths, react 12h under the magnetic agitation, get fluorine-containing ester block copolymer emulsion.
Get 100 parts of above-mentioned fluorine-containing ester block copolymer emulsions, the powerful stirring down adds 0.2 part of organic silicone oil, 2 parts of sodium acrylates, mixes, and adds 100 parts talcum powder again, 50 parts water, and the powerful 1h that stirs gets composite coating.The back survey performance of filming is as follows: 1 grade of sticking power, and with 100 ° of water contact angles, pencil hardness H, abrasion resistance 〉=3000, artificial ageing resistance/600h is non-foaming not to come off.
Embodiment 2
In the there-necked flask of 100ml, add 10 parts of Propenoic acid, 2-methyl, isobutyl esters, 100 parts of methacrylic acid hexafluoro butyl esters, 2 parts of initiator potassium persulfate, 2.5 parts of 200 parts of aqueous solvent and emulsifying agent ammonium lauryl sulfates.Logical nitrogen 15 minutes, freezing in ice-water bath again, by vacuumize-Tong nitrogen is repeatedly after 3 times, vacuum sealing tube.In 70 ℃ of oil baths, react 12h under the magnetic agitation, get fluorinated acrylate random copolymers emulsion.
Get 50 parts of fluorinated acrylate random copolymers emulsions, 50 parts of the fluorine-containing ester block copolymers of embodiment 1 gained, 50 parts of titanium dioxides, 2 parts of defoamer organic silicone oils, 1 part of dispersion agent sodium acrylate, 60 parts in water; Stirring make mix composite coating.The back survey performance of filming is as follows: 1 grade of sticking power, and with 94 ° of water contact angles, pencil hardness H, abrasion resistance 〉=2500, artificial ageing resistance/600h is non-foaming not to come off.
Embodiment 3
In the there-necked flask of 100ml, add 15 parts of the first monomer hydroxyethyl methylacrylates, initiator 4,0.8 part of 4 '-azo two (4-cyanopentanoic acid), 100 parts of 4 parts of RAFT reagent 4-dithiobenzoic acid (4-cyanopentanoic acid) esters and aqueous solvent.Logical nitrogen 15 minutes, freezing in ice-water bath again, by vacuumize-Tong nitrogen is repeatedly after 3 times, vacuum sealing tube.In 70 ℃ of oil baths, react 6h under the magnetic agitation and get macromole RAFT reagent solution.
In above-mentioned reactor, continue to add 100 parts of the second monomer methacrylic acid, ten difluoro heptyl esters, initiator 4,150 parts of 0.5 part of 4 '-azo two (4-cyanopentanoic acid) and aqueous solvent.Logical nitrogen 15 minutes, freezing in ice-water bath again, by vacuumize-Tong nitrogen is repeatedly after 3 times, vacuum sealing tube.In 70 ℃ of oil baths, react 12h under the magnetic agitation and obtain the fluorinated block copolymer emulsion.
Get 100 parts of above-mentioned fluorinated block copolymers, the powerful stirring adds 0.5 part of pumice wax oil base defoamer, 1 part of 2-amino-2-methyl-1-propanol down, mixes, and adds 90 parts light calcium carbonate filler again, 100 parts water, and the powerful 1h that stirs gets composite coating.The back survey performance of filming is as follows: 1 grade of sticking power, and with 105 ° of water contact angles, pencil hardness H, abrasion resistance 〉=3000, artificial ageing resistance 600h is non-foaming not to come off.
Embodiment 4
In the there-necked flask of 100ml, add 6 parts of the first monomer Rocryl 410s, 1 part of initiator Sodium Persulfate, 80 parts of RAFT reagent 4-dithiobenzoic acid (4-cyanopentanoic acid) ester and aqueous solvent.Logical nitrogen 15 minutes, freezing in ice-water bath again, by vacuumize-Tong nitrogen is repeatedly after 3 times, vacuum sealing tube.In 70 ℃ of oil baths, react 6h under the magnetic agitation and get macromole RAFT reagent.
In above-mentioned reactor, continue to add 100 parts of the second monomer methacrylic acid hexafluoro butyl esters, 150 parts of 0.5 part of initiator Sodium Persulfate and aqueous solvent.Logical nitrogen 15 minutes, freezing in ice-water bath again, by vacuumize-Tong nitrogen is repeatedly after 3 times, vacuum sealing tube.In 70 ℃ of oil baths, react 12h under the magnetic agitation and obtain the fluorinated block copolymer emulsion.
Get 100 parts of above-mentioned fluorinated block copolymers, the powerful stirring down adds 0.3 part of organic silicone oil, 1 part of sodium acrylate, mixes, and adds 80 parts heavy calcium carbonate filling again, 80 parts water, and the powerful 1h that stirs gets composite coating.The back survey performance of filming is as follows: 1 grade of sticking power, and with 115 ° of water contact angles, pencil hardness H, abrasion resistance 〉=4000, artificial ageing resistance 600h is non-foaming not to come off.
Claims (5)
1. an aqueous composite paint that contains amphiphilic fluorine-containing acrylate blocking copolymer is characterized in that, is made by the raw material of following weight part: 0.1～100 part of fluorine-containing ester block copolymer; 0～100 part of fluorinated acrylate random copolymers; 50～100 parts in water; 40～100 parts of inorganic salt fillers; 0.2～5 part of defoamer; 0.2～4 part of dispersion agent;
The structure of described fluorine-containing ester block copolymer is as follows:
Wherein:
M is selected from the arbitrary integer between 5 to 40;
N is selected from integer arbitrary between 20 to 200;
A is that non-perfluoroalkyl acrylate monomer or non-fluorinated monomer monomer or alkyl replace the monomeric polymerized segment of non-perfluoroalkyl acrylate;
B is the polymerized segment of one or more fluorinated acrylate monomers;
Described non-perfluoroalkyl acrylate monomer comprises vinylformic acid; Described non-fluorinated monomer monomer comprises Hydroxyethyl acrylate or Propylene glycol monoacrylate; Described alkyl replaces non-perfluoroalkyl acrylate monomer and comprises methacrylic acid;
The structure of described fluorinated acrylate random copolymers is as follows:
Wherein:
P is selected from the arbitrary integer between 1 to 20;
Q is selected from the arbitrary integer between 1 to 40;
W is selected from the arbitrary integer between 5 to 100;
A is that non-perfluoroalkyl acrylate monomer or non-fluorinated monomer monomer or alkyl replace the monomeric polymerized segment of non-perfluoroalkyl acrylate;
B is the polymerized segment of one or more fluorinated acrylate monomers;
Described non-perfluoroalkyl acrylate monomer comprises vinylformic acid; Described non-fluorinated monomer monomer comprises Hydroxyethyl acrylate or Propylene glycol monoacrylate; Described alkyl replaces non-perfluoroalkyl acrylate monomer and comprises methacrylic acid.
2. the aqueous composite paint of a kind of amphiphilic fluorine-containing acrylate blocking copolymer according to claim 1 is characterized in that, described fluorine-containing ester block copolymer comprises the fluorine-containing ester block copolymer of making as follows:
In weight part, get 50～100 parts of macromole RAFT reagent; 0.1～2 part of initiator; 20～50 parts of fluorinated acrylate monomers; 40～60 parts of aqueous solvent; Above-mentioned raw materials is stirred, make to mix; Vacuum, stirring in 70～80 ℃ of reaction 12～16h, get the fluorine-containing ester block copolymer down; Described initiator comprises Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen peroxide, isopropyl benzene hydroperoxide or 4,4 '-azo two (4-cyanopentanoic acid); Described fluorinated acrylate monomer comprises methacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate or methacrylic acid ten difluoro heptyl esters.
Described macromole RAFT reagent comprises synthetic macromole RAFT reagent as follows:
In weight part, get non-perfluoroalkyl acrylate monomer or non-fluorinated monomer monomer or alkyl and replace 20～40 parts of non-perfluoroalkyl acrylate monomers, 0.1～2 part of initiator, 1～4 part of small molecules RAFT chain-transfer agent, 40～60 parts in water; Vacuum, stirring in 70～80 ℃ of reaction 10～12h, get macromole RAFT reagent down then; Described non-perfluoroalkyl acrylate monomer comprises vinylformic acid; Described non-fluorinated monomer monomer comprises Hydroxyethyl acrylate or Propylene glycol monoacrylate; Described alkyl replaces non-perfluoroalkyl acrylate monomer and comprises methacrylic acid; Described initiator comprises Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen peroxide, isopropyl benzene hydroperoxide or 4,4 '-azo two (4-cyanopentanoic acid); Described small molecules RAFT chain-transfer agent comprises 4-dithiobenzoic acid (4-cyanopentanoic acid) ester.
3. a kind of aqueous composite paint that contains amphiphilic fluorine-containing acrylate blocking copolymer according to claim 1 is characterized in that, described fluorinated acrylate random copolymers comprises by following method synthetic fluorinated acrylate random copolymers:
In weight part, get 20～40 parts of fluorinated acrylate monomers, non-fluorinated monomer monomer 20-40 part, 1～4 part of initiator, emulsifying agent 1-4 part and 40～60 parts of mixing of aqueous solvent, 12～16h is reacted in vacuum, stirring down in 70～80 ℃, get the fluorinated acrylate random copolymers;
Described fluorinated acrylate monomer comprises methacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate or methacrylic acid ten difluoro heptyl esters;
Described non-fluorinated monomer monomer comprises Hydroxyethyl acrylate or Propylene glycol monoacrylate;
Described initiator comprises Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen peroxide, isopropyl benzene hydroperoxide or 4,4 '-azo two (4-cyanopentanoic acid);
Emulsifying agent comprises ammonium lauryl sulfate, Sodium dodecylbenzene sulfonate, Perfluorocaprylic Acid sylvite, ammonium salt of perfluorooctanoic acid, Perfluorocaprylic Acid sulfonate sodium, Perfluorocaprylic Acid sulfonic acid potassium salt or polyoxyethylene alkyl phenyl ether.
4. a kind of aqueous composite paint that contains amphiphilic fluorine-containing acrylate blocking copolymer according to claim 1, it is characterized in that described inorganic salt filler comprises zinc sulfide white, pure aluminium silicate, mica, titanium dioxide, talcum powder, light calcium carbonate or water-ground limestone;
Described defoamer comprises pumice wax oil base defoamer, mineral oil defoaming agent or polysiloxane defoamer;
Described dispersion agent comprises acrylate, polyacrylate, carboxylic acid sodium salt or 2-amino-2-methyl-1-propanol.
5. the described preparation method who contains the aqueous composite paint of amphiphilic fluorine-containing acrylate blocking copolymer of claim 1 is characterized in that, may further comprise the steps: in weight part, get 0.1～100 part of fluorine-containing ester block copolymer; 0～100 part of fluorinated acrylate random copolymers; 50～100 parts in water; 40～100 parts of inorganic salt fillers; 0.2～5 part of defoamer; 0.2～4 part of dispersion agent; Above-mentioned substance is mixed promptly.
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