Single component room temperature crosslinked water fluoric resin emulsion and its production and application
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 ofFluoroalkyl End-Capped Sulfobetaine Polymers.J.Appl.Polym.Sci., 2004,92:1144~1153; Smart B.E.; Properties of Fluorinated Compounds Physical andPhysicochemical Properties.In:Hudlicky M., Pavlath S.E. (Eds) ' Chemistryof Organic Fluorine Compounds ' II.ACS Monograph 187, AmericanChemistry Society, Washington DC, 1995, pp.979; Scheirs J.; ModernFluoropolymers, 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: CN1362422 (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: CN 1066588 (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.Fluoropolymers as 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.Sei., 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-based aqueous dispersioncomposition 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 dispersibleresin.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.
But the water-based fluororesin emulsion of self-cross linking type under a kind of single component room temperature condition, this emulsion is to adopt the vinyl fluoride carbon resin to be nuclear, (methyl) Acrylic Acid Monomer and some specific function monomers are shell, prepare by the seeded emulsion polymerization method, it is by methacrylic acid and esters monomer thereof, function monomer, emulsifying agent, the pre-emulsified monomer milk sap and the fluoroolefin multipolymer nuclear emulsion of preparation adopt the nuclear-shell emulsion polymerization technology to prepare down through shear conditions for water and pH regulator agent, wherein
(1) methacrylic acid and esters monomer thereof are selected from methacrylic acid, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, trifluoroethyl methacrylate, methacrylic acid hexafluoro butyl ester, methacrylic acid 2-ethylhexyl, acrylamide, vinylbenzene, vinyl acetate or the vinyl cyanide 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 hydroxyethyl methylacrylate, Rocryl 410, glycidyl methacrylate, N hydroxymethyl acrylamide, acrylamide, diacetone acrylamide, two amido ethyl-methyl acrylate or the gamma-methyl allyl acyloxypropyl trimethoxysilane 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 aforementioned two class monomers is 1~3 kind in the zwitter-ion Surfactant that is selected from sulfo-succinic acid salt, alkyl diphenyl ether disulfonate class, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or the phosphoric acid ester tensio-active agent of polyoxyethylene octylphenol ether OP series, polyoxyethylene nonylphenol ether (NP) series, XN-45S, CO-436, CO-458, CO-630 or CO-858, A-102, A-103 or A-50 and lauroyl amido CAB, stearyl amido ethyl-N hydroxyethyl Sodium Glycinate, and the quality percentage composition is 0.2~8%;
(4) comprise emulsifying agent in the composition of nuclear emulsion, the pH regulator agent, defoamer and fluoroolefin multipolymer, its center emulsion is selected from XN-45S with emulsifying agent, CO-436, CO-458, CO-630 or CO-858, A-102, the sulfo-succinic acid salt of A-103 or A-501, the alkyl diphenyl ether disulfonate class, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or phosphoric acid ester, in OP series or NP series anionic type or the nonionic emulsifier 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, select for use simultaneously and be selected from FluoradFC-4430, in the plain tensio-active agent of FC-4432 or Zonyl FSJ fluorine one or more, mass ratio is 0.2%; 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 be selected from Foamaster series 50,111, NXZ or 8034, the quality percentage composition is 0.01~0.8%; Fluoropolymer nuclear is 3000~50000 fluoroolefin copolymer resin for molecular weight, and its constitutional features is as follows:
X=C1 or F;
R
1Be C
1~C
8Alkyl, and be branched structure;
R
2Be C
1~C
6Alkyl;
m=8~20;
(5) used initiator is selected from tertbutyl peroxide, benzoyl peroxide, AIRN, 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 1~3 kind that is selected from succinic diamide, adipamide, black tropine, edta edta, succinyl hydrazine or adipic dihydrazide and dimeric amine and the amides; 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 methacrylic 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 on one side and contain the aqueous solution of nuclear emulsion with emulsifying agent and the plain tensio-active agent of fluorine, 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 the pre-emulsified monomer emulsion in the above-mentioned A step is added drop-wise in the sub-emulsion of nuclear species 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 gets final product discharging based on the promotor of monomer mass 0.01~3.0%.
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 water 120, NaHCO
30.5 NP-40 0.5, CO-436 (50-Wt%) 2.2, MgSO
47H
2O 0.6 ZONYL FSJ 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 0.7, CO-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
The emulsion film forming performance
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 the aqueous fluorocarbon coating resin emulsion
The emulsion fundamental property
The emulsion film forming performance
Embodiment 3
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
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
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
The emulsion film performance
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 LXZ 0.38, 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.