CN100396707C - Microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature and its production method - Google Patents
Microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature and its production method Download PDFInfo
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Abstract
The present invention provides a normal temperature self-crosslinked fluorine containing acrylic acid micro emulsion and a preparation method thereof. The fluorine containing acrylic acid micro emulsion comprises the following components: (methyl) acrylic alkyl radical ester, alkenyl carboxylic acid, an alkenyl crosslinking agent, an ethenyl aromatic compound, alkenyl fluorine containing alkyl ester, other alkene unsaturated monomers, an initiating agent, a buffering agent, an emulsifying agent, a neutralizing agent and water. Seed emulsion is prepared in an oxidation and reduction system, and then, semi-continuous polymerization technology is used for preparing and obtaining the fluorine containing acrylic acid micro emulsion. The fluorine containing acrylic acid micro emulsion has the advantages of good polymerization stability, small grain diameters, little surface tension of a paint film, strong adhesive force and low cost. The paint film has good hydrophobic property and has proper hydrophilicity, and the self-cleaning function of the paint film can be realized. The paint film belongs to double environmental protection type macromolecular material, and is suitable for the application in industrial production. The preparation method has the advantages of simple technology and easy industrial production.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature and preparation method thereof.
Background technology
The solvent-borne type fluoro-resin can cause environmental pollution, and harm humans is healthy, and along with the enhancing of people's environmental consciousness and the appearance of relevant laws and regulations, the application of solvent-borne type fluoro-resin and development have been subjected to certain restriction.The research of water-based fluororesin in recent years is people's attention extremely.The fluorocarbon resin emulsion belongs to novel water-based fluororesin, owing in its emulsion polymer segment, introduce the bigger carbon-fluorine bond of bond energy, greatly improved the performance such as weather resistance, contamination resistance, chemical-resistant of emulsion, had the characteristics of high-performance and environmental protection simultaneously, Application Areas is extensive.
At present mainly by fluorochemical monomer and acrylic ester monomer or other vinyl monomer are made by emulsion copolymerization, fluorochemical monomer generally adopts trifluorochloroethylene (CTEF), tetrafluoroethylene (TEF), vinyl fluoride (VF), vinylidene (VDF), (methyl) vinylformic acid fluoroalkyl ester class and alkene fluoroalkyl ethyl ethers etc. to the fluorocarbon resin emulsion.U.S. Pat 3324069, US4383075, US4557977 disclose a kind of at first under elevated pressures with alkene class fluorochemical monomers such as gasiform tetrafluoroethylene, trifluorochloroethylene, vinyl fluoride, vinylidene liquefaction, and then carry out method of emulsion polymerization; But at first these methods need under high pressure be carried out polymerization, and reaction process is difficult to control; Secondly, owing to have the chlorine atom on the polymer segment, the fluorocarbon resin emulsion that makes descends to some extent in aspect performances such as weathering resistance, chemical-resistants; Once more, because the C-F group is distributed on the main polymer chain, causing the production cost of this emulsion higher, is that the coating adhesion of paint binder can be poor with this emulsion.Also having a kind of method is to be feedstock production fluorocarbon resin emulsion with alkene fluoroalkyl ethyl ethers, because alkene fluoroalkyl ethyl ethers is in a liquid state at normal temperatures, reacting phase is controlled easily to simple and process; But same because the C-F group on the main chain of polymkeric substance, causes the production cost of this emulsion higher, be that the coating adhesion of paint binder can be poor with this emulsion.In addition, also having a kind of method is to be feedstock production fluorocarbon resin emulsion with (methyl) vinylformic acid fluoroalkyl ester class, because (methyl) vinylformic acid fluoroalkyl ester class is in a liquid state at normal temperatures, reacting phase is controlled easily to simple and process; And the bond energy of C-F key is big and stable, its perfluor side chain terminal ((CF after the film forming
2) nCF
3, n=2～11) stretch to air, occupy the interface of polymkeric substance and air, the structure that this side chain terminal coats main chain forms well " shielding protection " to the polymkeric substance interior molecules, greatly reduces the surface energy of polymkeric substance, the main chain of protection polymkeric substance; But shortcomings such as latex particle size is excessive, polymerization stability is poor, sticking power is not strong that this emulsion exists, and because (methyl) vinylformic acid fluoroalkyl ester monomer price is expensive, product cost is still higher.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, a kind of polymerization stability excellence, strong adhesion, shelf-stable, microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature that cost is low are provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature.
Purpose of the present invention is achieved through the following technical solutions:
This microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature is counted by weight, comprises following component:
20～90 parts of (methyl) acrylic acid or the like alkyl esters
1～10 part of thiazolinyl carboxylic acid
0.1～10 part of thiazolinyl linking agent
0～30 part of vinyl aromatic compounds
1～30 part of the fluorine-containing alkyl ester of thiazolinyl
0～20 part of other ethylenically unsaturated monomers
0.1～1 part of initiator
0.1～1 part of buffer reagent
2～10 parts of emulsifying agents
1～10 part of neutralizing agent
100～200 parts in water
Described (methyl) acrylic acid or the like alkyl ester, the alkyl carbon atoms number is C1～C15, can be one or more mixtures in methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, vinylformic acid n-octyl, the Isooctyl acrylate monomer; One or more mixtures in preferable methyl methyl acrylate, Isooctyl acrylate monomer, butyl methacrylate or the butyl acrylate.Preferred 30～80 weight parts of consumption of described (methyl) acrylic acid or the like alkyl ester.
Described thiazolinyl carboxylic acid, carbonatoms is C1～C15, can be one or more mixtures in vinylformic acid, methacrylic acid, the methylene-succinic acid; Preferable methyl vinylformic acid.Preferred 2～5 weight parts of the consumption of described thiazolinyl carboxylic acid.
Described thiazolinyl linking agent can be N hydroxymethyl acrylamide, Vinylstyrene, Ethylene glycol dimethacrylate, dimethacrylate triglycol ester or TriMethylolPropane(TMP) methacrylic ester; Preferred N hydroxymethyl acrylamide.Preferred 0.5～5 weight part of the consumption of described thiazolinyl linking agent.
Described vinyl aromatic compounds can be vinylbenzene, alpha-methyl styrene, 2-chlorostyrene, 3-t-butyl styrene, 3, one or more mixtures in the 4-dimethyl styrene.Preferred 5～20 weight parts of the consumption of described vinyl aromatic compounds.
The fluorine-containing alkyl ester of described thiazolinyl can be (methyl) vinylformic acid fluoroalkyl ester, (methyl) vinylformic acid contains heteroatoms fluoroalkyl ester, (methyl) vinylformic acid fultolanil ester, (methyl) vinylformic acid fluorine sulphonamide ester; Preferable methyl vinylformic acid hexafluoro butyl ester, vinylformic acid hexafluoro butyl ester, methacrylic acid (2,2, the 2-trifluoro) ethyl ester, methacrylic acid (2,2,3,3,4,4,4 seven fluorine) one or more mixtures in butyl ester, methacrylic acid perfluoro capryl ethyl ester, vinylformic acid Perfluorocaprylic Acid glycol ester, methacrylic acid β-(N-perfluor capryloyl) amino ethyl ester, propenoic acid beta-(N-ethyl, N-perfluorooctyl sulfonyl) amino ethyl ester; More preferably methacrylic acid hexafluoro butyl ester or vinylformic acid hexafluoro butyl ester.Preferred 2～20 weight parts of the consumption of the fluorine-containing alkyl ester of described thiazolinyl.
Described other ethylenically unsaturated monomers can be vinyl acetate, (methyl) vinylformic acid C5～C12 cycloalkyl ester, tertiary ethylene carbonate; Preferred vinyl acetate, (methyl) isobornyl acrylate.Preferred 0～10 weight part of the consumption of described other ethylenically unsaturated monomers.
Described initiator can be redox initiation system, preferred persulphate-mercaptan, persulphate-hydrosulphite, oxymuriate-hydrosulphite, hydrogen peroxide-ferrous salt; Also can be water-soluble ammonium persulphate, Potassium Persulphate, Sodium Persulfate; Also can be oil-soluble initiator, preferred Diisopropyl azodicarboxylate.Preferred 0.2～0.6 weight part of the consumption of described initiator.
Described buffer reagent can be sodium bicarbonate, yellow soda ash, sodium-acetate or Sodium phosphate dibasic.Preferred 0.2～0.5 weight part of the consumption of described buffer reagent.
Described emulsifying agent is the mixture of fluorine-containing emulsifier, anionic emulsifier and nonionic emulsifying agent; Wherein fluorine-containing emulsifier can be C
10F
19OC
6H
4CONHC
3H
6N
+(CH
3) I
-, C
10F
19OC
6H
4SO
3Na, C
17H
20F
17N
2O
3I, C
16H
17F
17N
2O
4, C
13H
17F
17N
2O
3, H (C
2F
4)
3COOK, C
7F
15COONa, C
6F
13COOH; Anionic emulsifier can be sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, alkyl diphenyl ether disodium sulfonate salt, oxyethyl group disodium sulfosuccinate, sodium vinyl sulfonate, oxyethyl group phenolic ether sodium sulfate, alkyl amido sodium vinyl sulfonate, allyl ethers hydroxyl sulfoacid sodium, phenolic ether phosphoric acid ester; Nonionic emulsifying agent can be fatty alcohol-polyoxyethylene ether, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, oxyethyl group propoxy-edge section Fatty Alcohol(C12-C14 and C12-C18), Isosorbide Dinitrate.The preferred C of described emulsifying agent
7F
15The mixture of COONa, sodium lauryl sulphate and polyoxyethylene octylphenol ether.Preferred 2～8 weight parts of described emulsifying agent consumption.
Described neutralizing agent can be potassium hydroxide, sodium hydroxide, ammoniacal liquor, organic amine; Described organic amine can be Trimethylamine, triethylamine, thanomin, dimethylethanolamine or trolamine.Preferred 2～8 weight parts of described neutralizing agent consumption, the pH value of regulating emulsion is 8～9.
The preparation method of above-mentioned microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature adopts redox initiation system, and the preparation seed emulsion adopts semi-continuous polymerzation technology then earlier, specifically comprises the steps:
(1) preparation of mix monomer pre-emulsion: at first (methyl) acrylic acid or the like alkyl ester of 30～80 weight parts, the thiazolinyl carboxylic acid of 1～5 weight part, the thiazolinyl linking agent of 0.5～5 weight part, the vinyl aromatic compounds of 5～20 weight parts, the fluorine-containing alkyl ester of thiazolinyl of 2～20 weight parts, other ethylenically unsaturated monomers of 0～10 weight part, the emulsifying agent of 0.2～2.0 weight part and the water of 20～60 weight parts are mixed; Stirred 10～30 minutes under 20～50 ℃ of temperature then, stirring velocity is 500～5000rpm; Carry out the pre-emulsification of ultrasonic wave 10～50 minutes again, ultrasonic oscillation device power is 50～300kW, obtains the mix monomer pre-emulsion;
(2) preparation of seed emulsion: under nitrogen protection, the above-mentioned mix monomer pre-emulsion of 5～15 weight parts, the buffer reagent of 0.2～0.5 weight part, the emulsifying agent of 0.2～2.0 weight part and the water of 60～130 weight parts are added in the reactor, be warming up to 60～90 ℃; The initiator that adds 0.05～0.5 weight part then continues reaction 10～40 minutes, is obvious blue light until emulsion, promptly gets seed emulsion;
(3) above-mentioned mix monomer pre-emulsion and the dilution with remainder is the initiator of 1% concentration, splashes into simultaneously respectively in 2～5 hours in the reactor, and temperature of reaction maintains 60～90 ℃; Be incubated 1～2 hour again after reaction finishes, add 1～10 part neutralizing agent, regulating ph value of emulsion is 8～9, makes solid content at last and be 30～50% microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature.
In this preparation method, (1) method that adopts machinery emulsification and the pre-emulsification of ultrasonic wave to combine prepares the mix monomer pre-emulsion earlier, improved the consistency of fluorochemical monomer and acrylic ester monomer, thereby improved the stability of mix monomer pre-emulsion, and then improved the stability of fluorine-containing microemulsion; (2) comprise fluorine-containing emulsifier in the selected emulsifying agent, help improving the transformation efficiency of mix monomer pre-emulsion, the microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature particle diameter is a nano level (20～80nm); (3) introduce hydroxyl, carboxyl isoreactivity group in the preparation, make the fluorine-containing microemulsion have multiple performances such as bridging property, color stuffing consistency, polarity; (4) when the preparation seed emulsion, the mix monomer pre-emulsion is carried out hunger drip, improve fluorochemical monomer and acrylate monomer copolymerization degree; (5) adopt redox initiation system, can reduce the temperature of polyreaction, also can fall the probability of cross-linkable monomer generation crosslinking reaction in the paper polymerization process simultaneously, thereby improve polymerization stability; (6) add the thiazolinyl carboxylic acid monomer, obtain the polymer segment of carboxylate-containing, improve the stable dispersion of fluorine-containing emulsion particle in water, thereby reduced the emulsifying agent consumption, improved the water tolerance of filming; (7) latex film after crosslinked improves significantly at aspects such as hardness, tensile strength, water tolerance and anti-solvents, and particularly self-crosslinking can grappling C-F group, thereby can reduce the fluorochemical monomer consumption accordingly.
The present invention compared with prior art has following advantage and effect:
(1) the polymerization stability excellence of this fluorine-containing microemulsion, particle diameter is little, film coated surface tension force is low, strong adhesion.
(2) this fluorine-containing microemulsion raw materials usedly conveniently be easy to get, low price, production cost is low.
(3) nontoxic, nonflammable, the environmental protection of this fluorine-containing microemulsion, filming both has better hydrophobic, and suitable wetting ability is arranged again, can realize the self-cleaning function of filming, and belongs to double environmental protection type macromolecular material, is adapted at using in the suitability for industrialized production.
(4) this fluorine-containing microemulsion preparation technology is simple, is easy to suitability for industrialized production.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
At first the mixture that 60g methyl methacrylate, 32g butyl methacrylate, 1g vinylformic acid hexafluoro butyl ester, 2g methacrylic acid, 6g vinylbenzene, 2gN-n-methylolacrylamide are formed adds 0.8g sodium lauryl sulphate, 2.0g polyoxyethylene octylphenol ether, 1.0gC
10F
19OC
6H
4CONHC
3H
6N
+(CH
3) I
-In the mixed aqueous solution of the composition of fluorine-containing emulsifier and 40g water, on JB90-D type powerful motor agitator, the rotating speed stirring 30min with 1000rpm obtains the mix monomer pre-emulsion then.Under nitrogen protection, 0.2g sodium bicarbonate, 0.3g sodium lauryl sulphate, 0.9g polyoxyethylene octylphenol ether, 0.3gC are being housed
10F
19OC
6H
4CONHC
3H
6N
+(CH
3) I
-Add the above-mentioned pre-emulsion of 15g in the four-hole bottle of fluorine-containing emulsifier, 70g water, be warming up to 80 ℃, add the 0.1g Potassium Persulphate, react to emulsion change basket, drip remaining pre-emulsion and 40g persulfate aqueous solution (0.34%) simultaneously, after 3.5h drips off, insulation 1h, after being cooled to room temperature, adding ammoniacal liquor and regulate pH value to 8～9, filter and promptly get microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature.
Embodiment 2
Mixture with 60g methyl methacrylate, 32g butyl methacrylate, 5g methacrylic acid hexafluoro butyl ester, 2g methacrylic acid, 2gN-n-methylolacrylamide are formed adds 0.5g sodium lauryl sulphate, 1.5g polyoxyethylene octylphenol ether, 0.8gC
10F
19OC
6H
4CONHC
3H
6N
+(CH
3) I
-In the mixed aqueous solution that fluorine-containing emulsifier and 40g water are formed, then on JB90-D type powerful motor agitator, rotating speed with 1000rpm stirs 10min, put into KQ3200DE type numerical control supersonic varnish device emulsification 20min (ultrasonic power 120kw wherein then, service temperature is controlled at 25 ± 2 ℃), promptly get the mix monomer pre-emulsion.Under nitrogen protection, 0.2g sodium bicarbonate, 0.3g sodium lauryl sulphate, 0.9g polyoxyethylene octylphenol ether, 0.3gC are being housed
10F
19OC
6H
4CONHC
3H
6N
+(CH
3) I
-Add the above-mentioned pre-emulsion of 15g in the four-hole bottle of fluorine-containing emulsifier 50g water, be warming up to 80 ℃, add the 0.1g Potassium Persulphate, react to emulsion change basket, drip remaining pre-emulsion and 40g persulfate aqueous solution (0.34%) simultaneously, after 3.5h drips off, insulation 1.5h, after being cooled to room temperature, adding ammoniacal liquor and regulate pH value to 8～9, filter and promptly get microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature.
Embodiment 3
Mixture with 60g methyl methacrylate, 32g butyl methacrylate, 5g methacrylic acid hexafluoro butyl ester, 2g methacrylic acid, 2gN-n-methylolacrylamide are formed adds 0.5g sodium lauryl sulphate, 1.5g polyoxyethylene octylphenol ether, 0.3C
10F
19OC
6H
4SO
3In the mixed aqueous solution that Na fluorine-containing emulsifier and 40g water are formed, then on JB90-D type powerful motor agitator, rotating speed with 1000rpm stirs 10min, (wherein ultrasonic power is 120kw to put into KQ3200DE type numerical control supersonic varnish device emulsification 20min then, service temperature is controlled at 25 ± 2 ℃), promptly get the mix monomer pre-emulsion.Under nitrogen protection, in four-hole bottle, add 0.2g sodium bicarbonate, 0.3g sodium lauryl sulphate, 0.9g polyoxyethylene octylphenol ether, 0.1gC
10F
19OC
6H
4SO
3Na fluorine-containing emulsifier and 50g water, stirring also is warming up to 80 ℃, drip mix monomer pre-emulsion and 45g persulfate aqueous solution (0.34%) simultaneously, 4.0h after dripping off, insulation 1.5h, after being cooled to room temperature, adding ammoniacal liquor and regulate pH value to 8～9, filter and promptly get microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature.
Embodiment 4
With the 48g methyl methacrylate, the 28g Isooctyl acrylate monomer, 10g vinylbenzene, the 2g isobornyl methacrylate, 5g methacrylic acid hexafluoro butyl ester, the 2g methacrylic acid, the mixture that the 2gN-n-methylolacrylamide is formed, add the 0.5g Sodium perfluorooctanoate, 1.5g in the mixed aqueous solution that polyoxyethylene octylphenol ether and 60g water are formed, then on JB90-D type powerful motor agitator, rotating speed with 1000rpm stirs 10min, (wherein ultrasonic power is 120kW to put into KQ3200DE type numerical control supersonic varnish device emulsification 20min then, service temperature is controlled at 25 ± 2 ℃), promptly get the mix monomer pre-emulsion.Under nitrogen protection; in the four-hole bottle that 0.2 part of sodium bicarbonate, 0.3g sodium lauryl sulphate, 0.9g polyoxyethylene octylphenol ether, 0.2g Sodium perfluorooctanoate, 50g water are housed, add the above-mentioned pre-emulsion of 15g; be warming up to 80 ℃; add the 0.2g Potassium Persulphate; react to emulsion change basket; drip remaining pre-emulsion and 40g persulfate aqueous solution (0.34%) simultaneously; 3.5h after dripping off; insulation 1h; after being cooled to room temperature; add ammoniacal liquor and regulate pH value to 8～9, filter and promptly get microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature.
Embodiment 5
With the 48g methyl methacrylate, the 28g Isooctyl acrylate monomer, 10g vinylbenzene, the 2g isobornyl methacrylate, 5g methacrylic acid hexafluoro butyl ester, the 2g methacrylic acid, the mixture that the 2gN-n-methylolacrylamide is formed, add the 0.5g Sodium perfluorooctanoate, 1.5g in the mixed aqueous solution of polyoxyethylene octylphenol ether and 60 parts of water compositions, then on JB90-D type powerful motor agitator, rotating speed with 1000rpm stirs 10min, (wherein ultrasonic power is 120kw to put into KQ3200DE type numerical control supersonic varnish device emulsification 20min then, service temperature is controlled at 25 ± 2 ℃), promptly get the mix monomer pre-emulsion.Under nitrogen protection; the 0.3g sodium bicarbonate is being housed; 0.3g sodium lauryl sulphate; 0.9g sim alkylphenol Soxylat A 25-7; 0.3g Sodium perfluorooctanoate; add the above-mentioned pre-emulsion of 15g in the container of 50g water; be warming up to 55 ℃; add 0.15g Potassium Persulphate and 0.3g sodium bisulfite; react to emulsion and become blue; after adding the 0.15g persulfate aqueous solution; drip remaining pre-emulsion in the example 3 simultaneously; 40g aqueous solution of sodium bisulfite (0.64%); 3.5h after dripping off; insulation 1.5h; after being cooled to room temperature, adding ammoniacal liquor and regulate pH value to 8～9, filter and promptly get microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature.
Claims (6)
1. microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature is characterized in that: meter by weight comprises following component:
20～90 parts of methacrylic alkyl esters
1～10 part of thiazolinyl carboxylic acid
0.1～10 part of thiazolinyl linking agent
0～30 part of vinyl aromatic compounds
1～30 part of the fluorine-containing alkyl ester of thiazolinyl
0～20 part of other ethylenically unsaturated monomers
0.1～1 part of initiator
0.1～1 part of buffer reagent
2～10 parts of emulsifying agents
1～10 part of neutralizing agent
100～200 parts in water
Described methacrylic alkyl ester is one or more mixtures in methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, vinylformic acid n-octyl, the Isooctyl acrylate monomer;
Described thiazolinyl carboxylic acid is one or more mixtures in vinylformic acid, methacrylic acid, the methylene-succinic acid;
Described thiazolinyl linking agent is N hydroxymethyl acrylamide, Vinylstyrene, Ethylene glycol dimethacrylate, dimethacrylate triglycol ester or TriMethylolPropane(TMP) methacrylic ester;
Described emulsifying agent is the mixture of fluorine-containing emulsifier, anionic emulsifier and nonionic emulsifying agent; Wherein fluorine-containing emulsifier is C
10F
19OC
6H
4CONHC
3H
6N
+(CH
3) I
-, C
10F
19OC
6H
4SO
3Na, C
17H
20F
17N
2O
3I, C
16H
17F
17N
2O
4, C
13H
17F
17N
2O
3, H (C
2F
4)
3COOK, C
7F
15COONa or C
6F
13COOH; Anionic emulsifier is sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, alkyl diphenyl ether disodium sulfonate salt, oxyethyl group disodium sulfosuccinate, sodium vinyl sulfonate, oxyethyl group phenolic ether sodium sulfate, alkyl amido sodium vinyl sulfonate, allyl ethers hydroxyl sulfoacid sodium or phenolic ether phosphoric acid ester; Nonionic emulsifying agent is fatty alcohol-polyoxyethylene ether, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether or Isosorbide Dinitrate.
2. microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature according to claim 1, it is characterized in that: described vinyl aromatic compounds is vinylbenzene, alpha-methyl styrene, 2-chlorostyrene, 3-t-butyl styrene, 3, one or more mixtures in the 4-dimethyl styrene.
3. microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature according to claim 1 is characterized in that: the fluorine-containing alkyl ester of described thiazolinyl is methacrylic acid hexafluoro butyl ester or vinylformic acid hexafluoro butyl ester.
4. microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature according to claim 1 is characterized in that: described other ethylenically unsaturated monomers is vinyl acetate, methacrylic acid C5～C12 cycloalkyl ester or tertiary ethylene carbonate.
5. microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature according to claim 1 is characterized in that:
Described initiator is persulphate-mercaptan, persulphate-hydrosulphite, oxymuriate-hydrosulphite or hydrogen peroxide-ferrous salt.
6. the fluorine-containing polyacrylic acid preparation of microemulsion of each described ambient self-crosslinking of claim 1～5 method is characterized in that comprising the steps:
(1) preparation of mix monomer pre-emulsion: at first the methacrylic alkyl ester of 30～80 weight parts, the thiazolinyl carboxylic acid of 1～5 weight part, the thiazolinyl linking agent of 0.5～5 weight part, the vinyl aromatic compounds of 5～20 weight parts, the fluorine-containing alkyl ester of thiazolinyl of 2～20 weight parts, other ethylenically unsaturated monomers of 0～10 weight part, the emulsifying agent of 0.2～2.0 weight part and the water of 20～60 weight parts are mixed; Stirred 10～30 minutes under 20～50 ℃ of temperature then, stirring velocity is 500～5000rpm; Carry out the pre-emulsification of ultrasonic wave 10～50 minutes again, ultrasonic oscillation device power is 50～300kW, obtains the mix monomer pre-emulsion;
(2) preparation of seed emulsion: under nitrogen protection, the above-mentioned mix monomer pre-emulsion of 5～15 weight parts, the buffer reagent of 0.2～0.5 weight part, the emulsifying agent of 0.2～2.0 weight part and the water of 60～130 weight parts are added in the reactor, be warming up to 60～90 ℃; The initiator that adds 0.05～0.5 weight part then continues reaction 10～40 minutes, is obvious blue light until emulsion, promptly gets seed emulsion;
(3) above-mentioned mix monomer pre-emulsion and the dilution with remainder is the initiator of 1% concentration, splashes into simultaneously respectively in 2～5 hours in the reactor, and temperature of reaction maintains 60～90 ℃; Be incubated 1～2 hour again after reaction finishes, add 1～10 part neutralizing agent, regulating ph value of emulsion is 8～9, makes solid content at last and be 30～50% microemulsion of fluorin containing crylic acid of self-crosslink in normal temperature.
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