CN1858080A - Single component room temperature crosslinked water fluoric resin emulsion and its preparing method and use - Google Patents
Single component room temperature crosslinked water fluoric resin emulsion and its preparing method and use Download PDFInfo
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- CN1858080A CN1858080A CN 200510034406 CN200510034406A CN1858080A CN 1858080 A CN1858080 A CN 1858080A CN 200510034406 CN200510034406 CN 200510034406 CN 200510034406 A CN200510034406 A CN 200510034406A CN 1858080 A CN1858080 A CN 1858080A
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Abstract
The present invention relates to a kind of room temperature cross-linked single component water fluoric resin emulsion and its preparation method and application in paint filming material, special pressure sensitive adhesive, hydrophobic and lipophobic treater for fiber and fabric, etc. The emulsion in core-shell structure has fluoro olefin copolymer as kernel and is prepared through polymerization of fluoro olefin and (methyl) acrylate monomer or other functional monomer. The room temperature cross-linked single component water fluoric resin emulsion may be cross-linked to cure during room temperature filming process and has stable storing period over 8 months.
Description
Technical field
The present invention relates to can take place under normal temperature condition the mono-component aqueous fluorine resin emulsion of crosslinking curing, the filmogen for preparing and be applied to coating, extraordinary pressure-sensitive adhesive, fiber and weaving face fabric thereof scold water to scold oil-treatment agent etc.
Background technology
Fluoropolymer material has high thermostability and unreactiveness, low surface tension, specific inductivity, excellent weather-proof anti-, aging resistance and antioxidant property, good flame retardancy and special surface property [Sawada H., Umedo M., Kawase T., et al.; Synthesis and Properties of Fluoroalkyl End-CappedSulfobetaine Polymers.J.Appl.Polym.Sci., 2004,92:1144～1153; Smart B.E.; Properties of Fluorinated Compounds Physical and Physicochemical Properties.In:Hudlicky M., Pavlath S.E. (Eds) ' Chemistry of Organic Fluorine Compounds ' IIACS Monograph 187, American Chemistry Society, Washington DC, 1995, pp.979; Scheirs J.; Modern Fluoropolymers, Wiley, Excel Pas Victoria, Australia, 1997], thereby be widely used in surface treatment [Daikin Ind.Co., WATER-AND OIL-REPELLINGPROCESSING OF TEXTILE PRODUCT, the JP Publication No.193370 (2003) of many materials; Sumitomo Electrics Industry Ltd, fluorine resin coating material, Chinese patent publication number: CN 1038968 (1990)], surface protection engineering [Sumitomo Electrics Industry Ltd, fluororesin-coated article, Chinese patent publication number: CN 1046121 (1990) ,], multiple functional paints etc. [are appointed ring, Liang Shujun, Wang Jun, Jiang Xiaohui, Sun Youjun, a kind of fluorocarbon coating and preparation method thereof, Chinese patent publication number: CN1580154 (2005); Xu Pingxian, Lu Qingtian, Jiang Cuiping, Wang Chunmei, Li Zhuanxian, ultra-low surface energy type fluorocarbon resin, Chinese patent publication number: CN 1450091 (2003); Xu Shoubai, water fluorine-carbon nanapaint and production method thereof, Chinese patent publication number: CN1401713 (2003); Mingzhan fluorin coating stock Co., Ltd., Dalian city, water-based fluororesin, method for making and application thereof, Chinese patent publication number: CN 1362422 (2002)], thermoplastic elastomer [GA Ge Nuoweizi, based on the thermoplastic silicone elastomers of fluorocarbon resin, Chinese patent publication number: CN 1374984 (2002)], blood substitute [Luo Changping, HuangBing Nan, He Yuqing, Huang Weiyuan, fluorine carbon emulsion and production method thereof, Chinese invention patent publication number: CN1066588 (1992); Zheng Zhifeng, Xu Hong, Dong Yan, Gu Hongchen, high-concentration super-fine perfluorocarbon emulsion for injection and preparation method thereof, Chinese invention patent publication number: CN 1286081 (2001)] etc.The fluoropolymer exploitation starts from the PTFE non-viscous paint [Munekata F.Fluoropolymersas coating material.Progress in Organic Coatings, 1998,16 (2): 113～119] of E.I.Du Pont Company the earliest.Early stage fluoropolymer mainly is with PTFE, and PVF, PVDF etc. are representative fluoroolefin homopolymer, and its water-based emulsion is in autoclave, adopts directly to prepare by emulsion polymerisation process with fluoroolefin monomers.To be half hitch crystalline because this base polymer has structural regularity and polymkeric substance itself, thereby this base polymer needs the baking at high temperature could film forming; In order to improve the solvability of fluoroolefin homopolymer in solvent, reduce and be baked into film temperature, the nineteen sixties people have succeeded in developing the fluorinated copolymer based on fluoroolefin, KynarADS resin and VF/HFP copolymer [Ameduri B as Autochem, Boutevin B, Kostov G.Fluoroelastomers:Synthesis, properties and applications.Progress Polym.Sci., 2001,26:105～187].In order further to improve the solubility property of fluoropolymer, reduce the film-forming temperature of fluoro-resin, 1981, but Japan's nitre rising sun takes the lead in having developed film forming solvent type fluoric resin Lumiflon (Poly (CTFE-co-Vinylether) [Asahi Glass Co.Ltd. under the normal temperature, French Patent 81,15212].Because the consistency of this kind solvent type fluorinated polymer material and other material is not very good, smell is big, seriously polluted, construction is difficult, cost is high, thereby its application has been subjected to very big restriction.Along with the harshness day by day of development of technology and various countries' environmental requirement and use properties requirement, people have shown keen interest for film forming water fluoric resin emulsion under the energy room temperature.The researchist is by the direct letex polymerization of emulsion [Yamaguchi Seitaro for this reason, Ogita Koichiro.Fluoropolymer-basedaqueous dispersion composition and coating composition.JP Publication NO.2001-261908] or solution polymerization in conjunction with phase conversion techniques [Li Tongxin, Liu Fei, Yu Yongjun etc., water-based fluororesin, method for making and contain the watersoluble fluorine paint of water-based fluororesin, the open CN 1322775 (2001) of Chinese invention patent application] or core-shell emulsion polymerization [Kato; Minoru; Hiraharu; Teruo; Nishiwaki; Koichi.Aqueousfluorine-containing polymer dispersion and aqueous dispersion containingfluorine-containing polymer and water-soluble resin and/or water dispersible resin.U.S.Pat.5349003] etc. method general-OH and-functional groups such as COOH are incorporated in the fluoropolymer chain structure, prepare crosslinked water-based fluoropolymer emulsion to take place with amine substance etc.Outstanding advantage of core-shell emulsion polymerization is exactly can be according to the molecular designing requirement, synthetic needed polymer chain structure and the particle shape structure of obtaining.In existing water-dispersion fluoro-resin emulsion product, the film forming fluorine resin of single-component room-temperature is a thermoplastic resin, during its cross-linking and curing reaction occurs under the hot conditions (more than 50 ℃), and can normal temperature crosslinked be bicomponent system.Although at present the research and development of bi-component waterborne fluorine resin have obtained remarkable progress, its pot-life is short, and need be mixed at the use scene, thereby makes troubles and problem such as quality instability to construction.Problem at above-mentioned existence, the present invention adopts the seeded emulsion polymerization method, and the modification by (methyl) Acrylic Acid Monomer and other special function monomer has prepared good stability and the single component fluorine resin emulsion of crosslinking reaction can take place in the room temperature film-forming process.
Summary of the invention
In order to improve the deficiency that existing procucts exist, the invention provides a kind of single component and can in the room temperature film-forming process, realize water fluoric resin emulsion of crosslinking curing and preparation method thereof, this emulsion can be used as coating filmogen etc.This emulsion is to adopt the vinyl fluoride carbon resin to be nuclear, and (methyl) Acrylic Acid Monomer and some specific function monomers are shell, prepare by the seeded emulsion polymerization method, and its composition characteristic is:
(1) monomer such as (methyl) vinylformic acid and ester class thereof is selected from (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid hexafluoro butyl ester, (methyl) 2-EHA, acrylamide, vinylbenzene, vinyl acetate, the vinyl cyanide etc. 2～4 kinds, the quality percentage composition is 25.0～65.0%, and wherein the quality percentage composition of each component is 0.3～64.1%;
(2) function monomer is selected from (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) glycidyl acrylate, n-methylolacrylamide, acrylamide, diacetone acrylamide, two amido ethyl-methyl acrylate, γ-(methacryloxypropyl) propyl trimethoxy silicane etc. 1～3 kind, the quality percentage composition is 0.5～3.1%, and wherein the quality percentage composition of each component is 0.01～2.5%.
(3) the used emulsifying agent of emulsified monomer is selected from the zwitter-ion Surfactants such as polyoxyethylene octylphenol ether (OP) series, polyoxyethylene nonylphenol ether (NP) series, XN-45S, CO-436, CO-458, CO-630, CO-858, sulfo-succinic acid salt (A-102, A-103 or A-501), alkyl diphenyl ether disulfonate class, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or phosphoric acid ester tensio-active agent and lauroyl amido CAB, stearyl amido ethyl-N hydroxyethyl Sodium Glycinate 1～3 kind, and the quality percentage composition is 0.2～8%;
(4) composition of nuclear emulsion comprises emulsifying agent, pH regulator agent, defoamer and fluoroolefin multipolymer etc.Wherein the composition of emulsifying agent is by ionic or nonionic emulsifier, as XN-45S, CO-436, CO-458, CO-630 or CO-858, sulfo-succinic acid salt (A-102, A-103 or A-501), the alkyl diphenyl ether disulfonate class, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or phosphoric acid ester, polyoxyethylene octylphenol ether (OP) series, in the tensio-active agents such as polyoxyethylene nonylphenol ether (NP) series one or more are composited, the quality percentage composition is 0.5～5.5%, the mass ratio of anionic emulsifier and nonionic emulsifying agent is between 0.2～4.0, other adds plain tensio-active agent of a certain amount of fluorine such as Fluorad FC-4430, FC-4432, one or more among the Zonyl FSJ etc.; PH value conditioning agent is selected from AMP-95, SODIUM PHOSPHATE, MONOBASIC, primary ammonium phosphate, sodium bicarbonate or bicarbonate of ammonia, and the quality percentage composition is 0.1～1%; Defoamer is selected from Foamaster series, and as 50,111, NXZ, 8034 etc., the quality percentage composition is 0.01～0.8%; The constitutional features of fluoropolymer nuclear is as follows:
X=Cl or F
R
1Be C
1～C
8Alkyl, wherein ideal C atom number is 4～6, and is preferably branched structure
R
2Be C
1～C
6Alkyl
M=8～20, wherein optimal value is 12～18
(5) used initiator system is selected from tertbutyl peroxide, benzoyl peroxide, AIBN, and sodium formaldehyde sulphoxylate, hydrogen peroxide, Sodium Persulfate, Potassium Persulphate or ammonium persulphate, quality percentage composition are 0.1～2%.
(6) in the emulsion polymerization process there be used other component: crosslinking accelerator be selected from acid amides and other aminated compounds such as succinic diamide, adipamide,, black tropine, ethylenediamine tetraacetic acid (EDTA) (EDTA), succinyl hydrazine, in the adipic dihydrazide etc. 1～3 kind; PH value conditioning agent is selected from SODIUM PHOSPHATE, MONOBASIC, primary ammonium phosphate, sodium bicarbonate or bicarbonate of ammonia, and the quality percentage composition is 0.1～1%; The quality percentage composition of deionized water or distilled water is 30.0～70.0%; Ammoniacal liquor quality percentage composition is 0.45～0.85%.
But a kind of preparation method of the water-based fluororesin emulsion of self-cross linking type under the single component normal temperature room temperature condition is characterized in that comprising following step:
A. pre-emulsification: in being dissolved with the aqueous solution of emulsifying agent, add (methyl) vinylformic acid and esters monomer thereof, lauryl mercaptan successively, under the room temperature high speed shear, obtain pre-emulsified monomer milk sap.
B. the sub-emulsion of nuclear species: under the vacuum of 50～75 ℃ and 20～500mmHg, employing phase conversion techniques is 3000～50000 fluoroolefin copolymer resin lipoprotein solution with molecular weight, distill out organic solvent on one side, add the aqueous solution that contains emulsifying agent and the plain emulsifying agent of fluorine on one side, determine to add the amount of water according to the polymer content of material that finally distills out and requirement, under the shearing condition of room temperature and 600～1500rpm, its dispersion is prepared into the stable emulsion of certain size and distribution again.The emulsion solids content that makes is 45 ± 2%, and the mean sizes of latex particle is about 150nm, and the size distribution index is not more than 0.0100.
C. nuclear-shell emulsion is synthetic: under certain temperature and shearing condition, earlier an amount of initiator is joined among the sub-emulsion B of nuclear species, in 2～4 hours above-mentioned pre-emulsified monomer emulsion is splashed into wherein then, be incubated 1～2 hour again.The temperature of entire reaction course must not be above 85 ℃.
D. aftertreatment: add tertbutyl peroxide and sodium formaldehyde sulphoxylate, be incubated 30 minutes, be cooled to about 40 ℃ after pH value with the ammoniacal liquor regulation system is 8～10, the promotor of adding 0.01～3.0% (based on monomer mass) gets final product discharging.
The water-based fluororesin emulsion of single-component room-temperature self-cross linking type can be used for the filmogen of coating etc.The testing method of coating property is measured by national standard " exterior wall coating material of synthetic resin emulsion standard " GB/T9755-2001; The particle size of emulsion analysis is measured with 1000HSA Zetasizer particle-size analyzer (Malvern company), and surface contact angle is measured with JY-82 contact angle instrument (Chengde trier company limited).
Specific embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1
Prescription (by mass percentage)
The nuclear emulsion is formed
Commercially available Lumiflon resin (in PFEVE, Mn=30000～50000) 100 deionized waters 120, NaHCO
30.5 NP-40 0.5, CO-436 (50-Wt%) 2.2, MgSO
47H
2O 0.6 ZONYLFSJ 0.2
The dropping monomer emulsion is formed
Methyl methacrylate (MMA) 100, butyl acrylate (BA) 200, methacrylic acid (MAA) 3.5, n-methylolacrylamide 3.5, diacetone-acryloamide(DAA) 2.5, deionized water 350, NP-40 0.7CO-436 (50-Wt%) 2.5
The preparation method:
1) preparation of fluoro-resin nuclear emulsion: the Lumiflon fluoro-resin that in four-hole bottle, adds metering, be warmed up to 50～60 ℃, add 80% of emulsifying agent Zonyl FSJ, NP-40 and CO-436 total amount under stirring successively, after stirring 10～20min, be warmed up to 65 ℃, at 50mmHg with under stirring, underpressure distillation on one side, on one side in flask make up water, after the solvent distillation finishes, remove heating unit, supply the water yield and the MgSO of adding according to the solid content that steams quantity of solvent and requirement
47H
2The emulsifying agent of O and remainder 20%, under the shearing condition of 600～1500rpm, can prepare required fluoropolymer emulsion after 1～2 hour powerful the dispersion.
2) drip monomeric emulsification: with the metering NP-40 and CO-436 with the metering water in flask, dissolve after, add BA successively, MMA, MAA, n-methylolacrylamide, diacetone-acryloamide(DAA), powerful emulsification got final product in 1 hour under the shearing condition of 700rpm.
3) dripping: with 1) resin emulsion that makes is as nuclear, and it is transferred in the reactor, under stirring, 100～200rpm is warmed up to 75 ℃, adding (NH
4)
2S
2O
8Initiator solution continue to stir 15min, begins to drip by 2) monomer emulsion that makes, dropwised in 2～4 hours, then 80 ℃ of insulations 1～2 hour down.
One of 4) aftertreatment: add tertbutyl peroxide and sodium formaldehyde sulphoxylate, be incubated 30 minutes, be cooled to pH value to 8～9 of using the ammoniacal liquor regulation system about 40 ℃, add an amount of black tropine and adipic dihydrazide, or the two, drop to the room temperature discharging again.
Emulsion property
Wherein PF-1# is the fluorine resin emulsion of the present invention's preparation, and A601 is that the water-based fluorine silicon resin emulsion that good fluorine chemistry of silicones company limited produces is avenged in Harbin, and FCS031031 is that the Dalian nation of shaking produces the aqueous fluorocarbon coating resin emulsion
The emulsion fundamental property
| PF-1# | A601 | FCS031031 | |
| Solid content (%) | 46.21 | 45.3 | 49.17 |
| The pH value | 8.2 | 7.5 | 6.8 |
| Viscosity, mPaS | 110 | 119 | 125 |
| Median size, nm | 230.2 | 190.5 | 157.6 |
The emulsion film forming performance
| PF-1# | A601 | FCS031031 | |
| Minimum film-forming temperature ℃ | 8 | 18 | 30 |
| 25 ℃/24h of water-intake rate | 6.62％ | 12.43％ | 15.64％ |
| Contact angle (H 2O) | 57° | 42° | 45° |
| Solvent resistance | In toluene, N-BUTYL ACETATE, do not dissolve and swelling | In toluene, N-BUTYL ACETATE, be partly dissolved and swelling | In toluene, N-BUTYL ACETATE, be partly dissolved and epidermis wrinkling |
| Outward appearance and feel | Smooth transparent, softness | Smooth translucent, crisp firmly | Smooth transparent, stiff |
Embodiment 2
Prescription (by mass percentage)
With the Lumiflon resin among the F100 of the nation fluorocarbon resin replacement embodiment 1 that shakes, all the other components are identical with embodiment 1 with consumption
The preparation method
The preparation method is identical with embodiment 1, just with the Lumiflon resin in the F100 of nation fluorocarbon resin equivalent substitution embodiment 1 working method of shaking.
Emulsion property
Wherein PF-2# is the fluorine resin emulsion of the present invention's preparation, and A601 is that the water-based fluorine silicon resin emulsion that good fluorine chemistry of silicones company limited produces is avenged in Harbin, and FCS031031 is that the Dalian nation of shaking produces aqueous fluorocarbon coating with resin emulsion emulsion fundamental property
The emulsion film forming performance
Embodiment 3
| PF-2# | A601 | FCS031031 | |
| Solid content (%) | 44.21 | 45.3 | 49.17 |
| The pH value | 8.0 | 7.5 | 6.8 |
| Viscosity, mPa.s | 107 | 119 | 125 |
| Median size, nm | 250.7 | 190.5 | 157.6 |
| PF-2# | A601 | FCS031031 | |
| Minimum film-forming temperature ℃ | 13 | 18 | 30 |
| 25 ℃/24h of water-intake rate | 9.48％ | 12.43％ | 15.64％ |
| Contact angle (H 2O) | 48° | 42° | 45° |
| Solvent resistance | In toluene, N-BUTYL ACETATE, do not dissolve and swelling | In toluene, N-BUTYL ACETATE, be partly dissolved and swelling | In toluene, N-BUTYL ACETATE, be partly dissolved and epidermis wrinkling |
| Outward appearance and feel | Smooth transparent, softness | Smooth translucent, crisp firmly | Smooth transparent, stiff |
Prescription (by mass percentage)
Replace the Lumiflon resin among the embodiment 1 with JF-2 fluorocarbon resin (sky produces among the 3F), all the other components are identical with embodiment 1 with consumption
The preparation method
The preparation method is identical with embodiment 1, just with the Lumiflon resin in JF-2 fluorocarbon resin (sky produces in 3F Changshu) equivalent substitution embodiment 1 working method.
Emulsion property
The emulsion fundamental property
| PF-3# | A601 | FCS031031 | |
| Solid content (%) | 48.34 | 45.30 | 49.17 |
| The pH value | 8.0 | 7.5 | 6.8 |
| Viscosity, mPa.s | 106 | 119 | 125 |
| Median size, nm | 275.7 | 190.5 | 157.6 |
Wherein PF-3# is the fluorine resin emulsion of the present invention's preparation, and A601 is that the water-based fluorine silicon resin emulsion that good fluorine chemistry of silicones company limited produces is avenged in Harbin, and FCS031031 is that the Dalian nation of shaking produces the aqueous fluorocarbon coating resin emulsion
The emulsion film performance
| PF-3# | A601 | FCS031031 | |
| Minimum film-forming temperature ℃ | 15 | 18 | 30 |
| 25 ℃/24h of water-intake rate | 9.65％ | 12.43％ | 15.64％ |
| Contact angle (H 2O) | 48° | 42° | 45° |
| Solvent resistance | In toluene, N-BUTYL ACETATE, do not dissolve and swelling | In toluene, N-BUTYL ACETATE, be partly dissolved and swelling | In toluene, N-BUTYL ACETATE, be partly dissolved and epidermis wrinkling |
| Outward appearance and feel | Smooth transparent, softness | Smooth translucent, crisp firmly | Smooth transparent, stiff |
Embodiment 4
Prescription (by mass percentage)
Replace the Lumiflon resin among the embodiment 1 with JF-3 fluorocarbon resin (sky produces among the 3F) fat, all the other components are identical with embodiment 1 with consumption
The preparation method
The preparation method is identical with embodiment 1, just with the Lumiflon resin in JF-3 fluorocarbon resin (sky produces among the 3F) equivalent substitution embodiment 1 working method.
Emulsion property
Wherein PF-4# is the fluorine resin emulsion of the present invention's preparation, and A601 is that the water-based fluorine silicon resin emulsion that good fluorine chemistry of silicones company limited produces is avenged in Harbin, and FCS031031 is that the Dalian nation of shaking produces the aqueous fluorocarbon coating resin emulsion
The emulsion fundamental property
| PF-4# | A601 | FCS031031 | |
| Solid content (%) | 48.25 | 45.3 | 49.17 |
| The pH value | 8.5 | 7.5 | 6.8 |
| Viscosity, mPa.s | 107 | 119 | 125 |
| Median size, nm | 245.7 | 190.5 | 157.6 |
The emulsion film performance
| PF-4# | A601 | FCS031031 | |
| Minimum film-forming temperature ℃ | 15 | 18 | 30 |
| 25 ℃/24h of water-intake rate | 8.52％ | 12.43％ | 15.64％ |
| Contact angle (H 2O) | 47.5° | 42° | 45° |
| Solvent resistance | In toluene, N-BUTYL ACETATE, do not dissolve and swelling | In toluene, N-BUTYL ACETATE, be partly dissolved and swelling | In toluene, N-BUTYL ACETATE, be partly dissolved and epidermis wrinkling |
| Outward appearance and feel | Smooth transparent, tough firmly | Smooth translucent, crisp firmly | Smooth transparent, stiff |
Embodiment 5 single component normal temperature cold curing watersoluble fluoro-resin are used for the preparation of white inferior light exterior coating:
In the Enamel jar container, add following goods and materials on one side, stir on one side, stirring velocity is 1000～1800 rev/mins, the composition quality that feeds intake is divided as follows:
Water 24.9, ethylene glycol 2.94, defoamer 8034L 0.3, dispersion agent H100 0.7, mould inhibitor LXZ0.38, wetting agent PE100 0.24, pH regulator agent AMP-95 0.3, rutile titanium white powder 41.6, coarse whiting 9.0, kaolin 7.2, talcum powder 4.0, nanometer SiO
20.8 the above-mentioned material that mixes is carried out powerful emulsification pretreatment, make fineness at 40～60um, viscosity is 20～25 seconds slurries.
Regulate stirring velocity to 300～500 rev/min, and divide by quality successively and add following goods and materials:
PF-1# fluoro-resin emulsion 90, defoamer 0.4, alkali swelling type thickening material H660 6.2, associative thickener L663 2.1, dipropylene glycol butyl ether 3.2, ethylene glycol 1.0, AMP-95 0.4
After disperseing to finish, with 100 order net filtrations, the viscosity of coating products 40～50 seconds.Measure as follows with the coating products basic mechanical design feature that aforesaid method obtains according to national standard " exterior wall coating material of synthetic resin emulsion GB/T9755-2001 ":
13390 alkali resistance＞=300 of abrasion resistance are hour no abnormal
150 hours water tolerance＞=300 of acid resistance (30% sulfuric acid) are hour no abnormal
2400 hours VOC values of artificial weathering ageing resistance 80g/L
These major technology indexs have all surpassed the premium grads technical indicator.
Claims (6)
1. but the water-based fluororesin emulsion of self-cross linking type under the single component room temperature condition prepares with fluoroolefin copolymer emulsion employing nuclear-shell emulsion polymerization technology with emulsive (methyl) vinylformic acid and esters monomer thereof and other function monomer.Its composition characteristic is as follows:
(1) monomer such as (methyl) vinylformic acid and ester class thereof is selected from (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid hexafluoro butyl ester, (methyl) 2-EHA, acrylamide, vinylbenzene, vinyl acetate, the vinyl cyanide etc. 2～4 kinds, the quality percentage composition is 25.0～65.0%, and wherein the quality percentage composition of each component is 0.3～64.1%.
(2) function monomer is selected from (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) glycidyl acrylate, N hydroxymethyl acrylamide, acrylamide, diacetone acrylamide, two amido ethyl-methyl acrylate, γ-(methacryloxypropyl) propyl trimethoxy silicane etc. 1～3 kind, the quality percentage composition is 0.5～3.1%, and wherein the quality percentage composition of each component is 0.01～2.5%.
(3) the used emulsifying agent of emulsified monomer is selected from the zwitter-ion Surfactants such as polyoxyethylene octylphenol ether (OP) series, polyoxyethylene nonylphenol ether (NP) series, XN-45S, CO-436, CO-458, CO-630 or CO-858, sulfo-succinic acid salt (A-102, A-103 or A-501), alkyl diphenyl ether disulfonate class, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or phosphoric acid ester tensio-active agent and lauroyl amido CAB, stearyl amido ethyl-N hydroxyethyl Sodium Glycinate 1～3 kind, and the quality percentage composition is 0.2～8%.
(4) composition of nuclear emulsion comprises emulsifying agent, pH regulator agent, defoamer and fluoroolefin multipolymer etc.Wherein the composition of emulsifying agent is by anionic or nonionic emulsifier, as XN-45S, CO-436, CO-458, CO-630 or CO-858, sulfo-succinic acid salt (A-102, A-103 or A-501), the alkyl diphenyl ether disulfonate class, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or phosphoric acid ester, OP series, in the NP series etc. one or more are composited, the quality percentage composition is 0.5～5.5%, the mass ratio of anionic emulsifier and nonionic emulsifying agent is between 0.2～4.0, other adds plain tensio-active agent of a certain amount of fluorine such as Fluorad FC-4430, FC-4432, one or more among the Zonyl FSJ etc.; PH value conditioning agent is selected from AMP-95, SODIUM PHOSPHATE, MONOBASIC, primary ammonium phosphate, sodium bicarbonate or bicarbonate of ammonia, and the quality percentage composition is 0.1～1%; Defoamer is selected from Foamaster series, and as 50,111, NXZ, 8034 etc., the quality percentage composition is 0.01～0.8%; The constitutional features of fluoropolymer nuclear is as follows:
X=Cl or F
R
1Be C
1～C
8Alkyl, wherein ideal C atom number is 4～6, and is preferably branched structure
R
2Be C
1～C
6Alkyl
M=8～20, wherein optimal value is 12～18
(5) used initiator system is selected from tertbutyl peroxide, benzoyl peroxide, AIBN, sodium formaldehyde sulphoxylate, hydrogen peroxide, Sodium Persulfate, Potassium Persulphate or ammonium persulphate, and the quality percentage composition is 0.1～2%.
(6) in the emulsion polymerization process there be used other component: crosslinking accelerator is selected from 1～3 kind in amine and the amides, as succinic diamide, adipamide,, black tropine, ethylenediamine tetraacetic acid (EDTA) (EDTA), succinyl hydrazine, adipic dihydrazide and dimer thereof etc.; PH value conditioning agent is selected from SODIUM PHOSPHATE, MONOBASIC, primary ammonium phosphate, sodium bicarbonate or bicarbonate of ammonia, and the quality percentage composition is 0.1～1%; The quality percentage composition of deionized water or distilled water is 30.0～70.0%; Ammoniacal liquor quality percentage composition is 0.45～0.85%.
2. claims 1 described emulsive (methyl) vinylformic acid and esters monomer thereof and other function monomer are to be prepared under shear conditions by emulsifying agent, water, pH regulator agent, (methyl) vinylformic acid and esters monomer, other function monomer etc. that single emulsifying agent or numerous emulsifiers are composited.
3. claims 1 described monocomponent self-cross-linking water-based fluororesin emulsion can be stablized between 0～45 ℃ and deposits more than 8 months, and do not adding under other any additives situation, at room temperature can form even, transparent, glossiness is high, the film of good toughness, and self-crosslinking reaction can take place between polymer molecule in the film process realize crosslinking curing.
4. according to claim 1,2,3 requirement, but a kind of preparation method of the water-based fluororesin emulsion of self-cross linking type under a kind of single component room temperature condition is characterized in that comprising following step:
A. pre-emulsification: in being dissolved with the aqueous solution of emulsifying agent, add (methyl) vinylformic acid and esters monomer thereof, lauryl mercaptan successively, under the room temperature high speed shear, obtain pre-emulsified monomer milk sap.
B. the sub-emulsion of nuclear species: under 50～75 ℃, the vacuum of 20～500mmHg, employing phase conversion techniques is 3000～50000 fluoroolefin copolymer resin lipoprotein solution with molecular weight, distill organic solvent on one side, add the aqueous solution that contains emulsifying agent and the plain emulsifying agent of fluorine on one side, adding the total amount of water determines according to the material that finally distills out and the polymer content of requirement, under the shearing condition of room temperature and 600～1500rpm, its dispersion is prepared into the stable emulsion of certain size and distribution again.
C. nuclear-shell emulsion is synthetic: under certain temperature and shearing condition, earlier an amount of initiator is joined in the sub-emulsion of nuclear species, in 2～4 hours above-mentioned pre-emulsified monomer emulsion is added drop-wise in the seed emulsion then, be incubated 1～2 hour again.The temperature of whole process is no more than 85 ℃.
D. aftertreatment: add tertbutyl peroxide and sodium formaldehyde sulphoxylate and also be incubated 30 minutes, be cooled to about 40 ℃ after pH value with the ammoniacal liquor regulation system is 8～10, adding 0.01～3.0% (based on monomer mass) promotor gets final product discharging.
5. in claims 1 and the described nuclear-shell emulsion polymerization of 4B, 45 ± 2%, latex particle is of a size of about 150nm as the solids content of the polymer emulsion of nuclear species, and the size distribution index is not more than 0.0100; Its composition comprises emulsifying agent, pH regulator agent, defoamer and fluoroolefin copolymer resin etc.
But 6. solidified water-based fluororesin emulsion under the single component room temperature condition for preparing of claims 1 and 4 described employing nuclear-shell emulsion polymerization means, its latex particle size range is between 160～300nm, and the size distribution index is not more than 0.2000.
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