CN101633715A - Fluorine-containing resin emulsion and preparation method thereof - Google Patents
Fluorine-containing resin emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN101633715A CN101633715A CN200910302136A CN200910302136A CN101633715A CN 101633715 A CN101633715 A CN 101633715A CN 200910302136 A CN200910302136 A CN 200910302136A CN 200910302136 A CN200910302136 A CN 200910302136A CN 101633715 A CN101633715 A CN 101633715A
- Authority
- CN
- China
- Prior art keywords
- emulsion
- monomer
- methyl
- fluorine
- class
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 84
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 33
- 239000011737 fluorine Substances 0.000 title claims abstract description 33
- 229920005989 resin Polymers 0.000 title claims abstract description 33
- 239000011347 resin Substances 0.000 title claims abstract description 33
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000004945 emulsification Methods 0.000 title claims description 6
- 239000000178 monomer Substances 0.000 claims abstract description 59
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 20
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 3
- -1 (methyl) Hydroxyethyl Chemical group 0.000 claims description 26
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000011258 core-shell material Substances 0.000 claims description 10
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 10
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- QXIQCNFSNJEMOD-UHFFFAOYSA-N 3-hydroxybutan-2-yl prop-2-enoate Chemical compound CC(O)C(C)OC(=O)C=C QXIQCNFSNJEMOD-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- QEOWFDYSNYCPRK-UHFFFAOYSA-N OCC[Na] Chemical compound OCC[Na] QEOWFDYSNYCPRK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- WINGWOKHLWWJIJ-UHFFFAOYSA-N [O].C(C(=C)C)(=O)O Chemical compound [O].C(C(=C)C)(=O)O WINGWOKHLWWJIJ-UHFFFAOYSA-N 0.000 claims description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical class CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 2
- 235000013905 glycine and its sodium salt Nutrition 0.000 claims description 2
- 239000004247 glycine and its sodium salt Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- AUCNMQYOQYTGPE-UHFFFAOYSA-N n-(hydroxymethyl)-n-methylprop-2-enamide Chemical compound OCN(C)C(=O)C=C AUCNMQYOQYTGPE-UHFFFAOYSA-N 0.000 claims description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- MRXVCTWDXRBVLW-UHFFFAOYSA-N prop-2-enoylsulfamic acid Chemical class OS(=O)(=O)NC(=O)C=C MRXVCTWDXRBVLW-UHFFFAOYSA-N 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 229920003987 resole Polymers 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical compound [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 claims description 2
- 229940029258 sodium glycinate Drugs 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000003973 paint Substances 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 239000010985 leather Substances 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract 3
- 230000002265 prevention Effects 0.000 abstract 3
- 230000007797 corrosion Effects 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 239000004160 Ammonium persulphate Substances 0.000 description 10
- 235000019395 ammonium persulphate Nutrition 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 6
- 229940119545 isobornyl methacrylate Drugs 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NHOIWQJMMMHUCV-UHFFFAOYSA-N CC(C[Na])C.C(C=C)(=O)N Chemical compound CC(C[Na])C.C(C=C)(=O)N NHOIWQJMMMHUCV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LZFMACRHJXVTIV-UHFFFAOYSA-N [F].C(=C)Cl Chemical compound [F].C(=C)Cl LZFMACRHJXVTIV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000004446 fluoropolymer coating Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical group CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a fluorine-containing resin emulsion and a preparation method thereof. The fluorine-containing monomer structures are shown in (FA1), (FA2) and (FA3), wherein Rf is a C2-C21 linear or branched fluoroalkyl or perfluoroalkyl; R1 is a hydrogen atom or C1-C8 linear or branched alkyl; and R2 is C1-C20 linear or branched alkyl. The fluorine-containing resin emulsion is prepared by using the vinyl monomer copolymer as a nucleus, using the fluorine-containing monomer copolymer as a shell and adopting the nucleus-shell emulsion copolymerization technology. The fluorine-containing resin emulsion can be widely used for anti-corrosion and anti-pollution paint, such as prevention of corrosion of bridge buildings and prevention of corrosion and pollution of ships, can also be used in fields, such as functional finishing of fiber surfaces, prevention of water and oil of leather and the like, and has significant development value and application value.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of fluorine resin emulsion and preparation method thereof.This fluorine resin emulsion can be used as the high coating of anti-the pickup, also can be used as fiber and weaving face fabric hydrophobic oleophobic treatment agent thereof.
Background technology
Fluorine resin is that fluoro-containing coating then is to be the prepared coating of one of main component with the fluorine resin with a resinoid of Fluorine containing olefine polymerization or Fluorine containing olefine and the formation of other monomer copolymerizations.Owing to have a large amount of C-F keys on the main polymer chain structure, thereby give weathering resistance, non-corrosibility, contamination resistance, thermotolerance, chemical-resistant, the hydrophobic oleophobic of polymkeric substance excellence.Fluorocarbon resin and coating have successively experienced the stages such as fusion, solvent curing and aqueous fluoropolymer coating.Fusion fluorine coating such as polytetrafluoroethylene (PTFE) and polyvinylidene difluoride (PVDF) degree of crystallinity height, fusing point height such as (PVDF), be insoluble to organic solvent, only can exist with dispersion or form of powder, need high bake ability film forming, thereby its range of application is very limited, can only be used for resistant substrates such as metal, pottery.What grow up subsequently is solvent-borne type self-vulcanizing fluorine coating.Nineteen eighty-two, Japan AGC company developed normal temperature solidified Fluorine containing olefine and the multipolymer of alkyl vinyl ether (FEVE) resin, promptly on main polymer chain, introduce other vinyl monomers, so just can reduce crystallinity of polymer effectively, improve its solvability in solvent, expanded the use range of fluorocarbon coating, indicated that the stage of ambient temperature curable fluorinated copolymer technology breaks through.After this, people improve the shortcoming of FEVE resin to color stuffing wettability difference by adjusting the group classification on the alkyl vinyl ether unit in the FEVE molecule.
But enhancing gradually along with people's environmental consciousness, the application of this coating is restricted just gradually, because a large amount of volatile organic matters that contain in the solvent type fluoric coating in use can be discharged in the atmosphere, not only cause the waste of solvent, and serious environment pollution, the directly health of harm humans.Aqueous fluoropolymer coating has technology cleaning, less energy-consumption, low emission, characteristics such as safe and harmless, advantages such as filming can be self-cleaning, anti-soil, UV resistant and good weatherability, extremely people's favor.People have carried out constantly exploring to the aqueous fluorine-containing copolymer coating, have obtained certain achievement in research.Different fluorochemical monomer, the different polymerization techniques of external in recent years employing prepared high-performance water-based fluorinated copolymer coating, has some achievements to enter the practicability stage.
Because the film forming properties of acrylic ester coating is good, the water tolerance of its paint film, photostabilization, alkali resistance, ageing resistance and tint retention might as well, and good processing characteristics is arranged, be that a class is used coating very widely, but its pollution resistance, weathering resistance etc. are unsatisfactory.Not only kept the original characteristic of paint film by the acrylic ester polymer after the modification of introducing fluoro-containing group, and improved weather resistance, the pollution resistance of paint film effectively, used more extensive.
Xu Pingxian, Lu Qingtian etc. are that fluorocarbon resin is made by fluorine vinylchlorid and alkene ester, olefin(e) acid and the copolymerization of alkene ether in its patent (CN1450091A), though product has had low surface energy, but the volatilization of organic solvent pollutes the environment, and when reaching best effect, the consumption of fluorine vinylchlorid has reached 40%, and expensive raw material certainly will increase cost.Luo Changping, the fluorine carbon emulsion and the production method thereof of HuangBing Nan etc. (CN1066588A) report, be that fluorocarbon, emulsifying agent and water ultrasonic emulsification are produced, this is a pure physical blending process, without any chemical bonding, boundary's condition such as the weathering resistance of film and weather resistance etc. outside change reduction down in the emulsion.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of fluorine resin emulsion and preparation method thereof, specifically be by chemical process with fluorochemical monomer and other vinyl monomer and the copolymerization of vinyl function monomer core-shell emulsion, preparation can be used for the novel fluorine macromolecule resin emulsion of fluorocarbon coating.
Technical scheme of the present invention is as follows:
The present invention utilizes vinyl monomer and other vinyl function monomer and fluoro-containing group monomer to adopt the nuclear-shell emulsion polymerization technology to make, the alternative linking agent that adds in the prepared resin emulsion.
Described vinyl monomer is divided into the moderate monomer of soft monomer, hard monomer and second-order transition temperature; Soft monomer comprises ethyl acrylate, butyl acrylate, isobutyl acrylate, ethyl propenoate, divinyl or chloroprene; Hard monomer comprises methyl methacrylate, (methyl) isobornyl acrylate, vinylbenzene, vinyl cyanide, vinylchlorid, Jia Jibingxisuanyizhi or vinylidene chloride; The monomer that second-order transition temperature is moderate comprises vinyl acetate, methyl acrylate or butyl methacrylate;
Described vinyl function monomer comprises (methyl) vinylformic acid, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) acrylamide, N-methylol (methyl) acrylamide, two vinylformic acid glycol ester, Vinylstyrene, (methyl) glycidyl acrylate or N-fourth oxygen methacrylic acid.
The fluoro-containing group monomer that is adopted has following structure:
R wherein
fBe C
2-C
21Straight or branched partly contain fluoroalkyl or perfluoroalkyl, R
1Be hydrogen atom or C
1-C
8The straight or branched alkyl, R
2Be C
1-C
20The straight or branched alkyl; FA
1, FA
2, FA
3Can use separately or several monomer mix to use with arbitrary proportion.
Described linking agent is diisocyanates, two amines, urea-formaldehyde resin, terpolycyantoamino-formaldehyde resin, Resins, epoxy, urethane or resol, and linking agent can selectivity add.
The preparation method of fluorine-containing resin emulsion of the present invention comprises following two key steps:
(1) nuclear pre-emulsion: add above-mentioned vinyl monomer and vinyl function monomer in being dissolved with the aqueous solution of emulsifying agent, high speed shear obtained examining pre-emulsion in 0.5～12 hour under 5 ℃～90 ℃ temperature;
(2) shell pre-emulsion: in being dissolved with the aqueous solution of emulsifying agent, add above-mentioned vinyl monomer, vinyl function monomer and fluorochemical monomer, high speed shear obtained examining pre-emulsion in 0.5～24 hour under 5 ℃～90 ℃ temperature;
(3) the sub-emulsion of nuclear species is synthetic: the aqueous solution with initiator adds in the four-hole bottle earlier, under 5 ℃～90 ℃ temperature, adds above-mentioned nuclear pre-emulsion, continues reaction and obtains examining emulsion in 0.5～24 hour;
(4) nuclear-shell emulsion is synthetic: initiator and above-mentioned shell pre-emulsion are joined in the sub-emulsion of above-mentioned nuclear species simultaneously, react under 5 ℃～90 ℃ temperature and obtained nuclear-shell emulsion in 0.5～24 hour.
(5) add linking agent in above-mentioned resin emulsion, the content of linking agent is the mass percent 0%～20% of whole polymerization single polymerization monomers.
The used emulsifying agent of above-mentioned steps is the alkylphenol polyoxyethylene class, the alkyl phenyl polyethenoxy ether class, fatty alcohol polyethenoxy ether class or styryl phenol polyethenoxy ether class, the sulfo-succinic acid salt, the alkyl diphenyl ether disulfonate class, phosphoric acid ester, the allyl ether series Sulfonates, the acrylamido Sulfonates, the salt of fluoro-containing group organic compound, the maleic acid derivatives class, XN-45S, CO-436, CO-458, CO-630, CO-858, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, lauroyl amido CAB, stearyl amido ethyl-N hydroxyethyl Sodium Glycinate, one or more mixture in the tensio-active agents such as allyl group succsinic acid alkyl ester sodium sulfonate; To add emulsifying agent be 0.5～10% of whole polymerization single polymerization monomer sum mass percents.
Described initiator is bromine-containing compound class, azo-compound class, peroxide bridge compounds, sulfocompound class, tertbutyl peroxide, sodium formaldehyde sulphoxylate, sodium bisulfite, hydrogen peroxide, Sodium Persulfate, benzoyl peroxide, 2,2,6,6 tetramethyl-s-1-piperidine oxide, Diisopropyl azodicarboxylate, cuprous salt, Ammonium Persulfate 98.5, the mixture of one or more in Potassium Persulphate, butyllithium, the alpha-brominated ethyl isobutyrate; Add-on is 0.01～5% of whole monomer sum quality percentage compositions.
The core-shell emulsion solid content that the invention has the beneficial effects as follows gained 10～60%, monomer conversion more than 90%, emulsion package stability by, freeze-thaw stability by, Calcium ion stability by, mechanical stability by, latex particle be of a size of between 50～200nm, the size distribution index is not more than 0.2000.The fluorine resin emulsion of gained, when the fluorine monomer consumption only had 5.18%, the water contact angle of film can reach 106 °, and surface energy is 15.5mN/m, is lower than the 22.0mN/m of PTFE, has had good hydrophobic oleophobic ability.The fluorine resin emulsion can be widely used in anticorrosion and antifouling coating,, naval vessel anticorrosion and antifouling anticorrosion as bridge construction, and the functional treatment and the leather water-proof that also can be used for fiber surface are prevented the wet goods field, have important development and application and are worth.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme.
Embodiment 1: the nuclear emulsion is formed
| Component | Water | Isobornyl methacrylate (IBOMA) | Butyl acrylate (BA) | Alkylphenol polyoxyethylene (OP-10) | Sodium laurylsulfonate (SDBS) |
| Quality (g) | ??40 | ??18 | ??12 | ??0.889 | ??9.44 |
The shell emulsion is formed:
| Component | Water | Methyl methacrylate (MMA) | Butyl acrylate (BA) | Fluorine monomer (FA 1) | Alkylphenol polyoxyethylene (OP-10) | Sodium laurylsulfonate (SDBS) |
| Quality (g) | ??20 | ??4 | ??11 | ?5 | ??2.44 | ??0.222 |
The preparation method: temperature of reaction is 50 ℃, earlier the part initiator is joined in the four-hole bottle, and reaction 5 hours is continued to wherein adding the nuclear pre-emulsion in the back.Initiator and shell pre-emulsion are added in the sub-emulsion of above-mentioned nuclear species simultaneously, continue reaction 0.5 hour again, make the core-shell polymer emulsion of blueing look fluorescence, can room temperature film-forming after filming, the Static Water contact angle is 109 °.
Embodiment 2: the nuclear emulsion is formed
| Component | Water | Methyl methacrylate (MMA) | Butyl acrylate (BA) | Glycidyl methacrylate (GMA) | Octyl phenyl Soxylat A 25-7 (TX-10) | Sodium laurylsulfonate (SDS) |
| Quality (g) | ??40 | ??19 | ??10 | ??1 | ?0.189 | ??8.44 |
The shell emulsion is formed:
| Component | Water | Methyl methacrylate (MMA) | Butyl acrylate (BA) | Methacrylic acid (MAA) | Fluorine monomer (FA 2) | Octyl phenyl Soxylat A 25-7 (TX-10) | Sodium laurylsulfonate (SDS) |
| Quality (g) | ??20 | ??2.5 | ??11.5 | ??1 | ??5 | ??7.84 | ??0.222 |
The preparation method: the 130ml water that will contain partial emulsifier joins in the four-hole boiling flask that agitator and thermometer are housed; 60 ℃ of temperature of reaction; stirring velocity is about 200r/min; nitrogen protection; after treating temperature equilibrium, behind the adding 9g nuclear consitution pre-emulsion (containing 0.21g ammonium persulphate and 0.17g sodium bisulfite), add 27g nuclear consitution pre-emulsion (containing ammonium persulphate 0.31g) and sodium bisulfite (0.0024g) solution 50ml again; holding temperature was reacted 60 minutes down for 60 ℃, obtained examining emulsion.Keep temperature of reaction system constant, in gained nuclear emulsion, add shell component pre-emulsion 145g (containing ammonium persulphate 0.19g) and sodium bisulfite (0.16g) solution 80ml again, 65 ℃ of isothermal reactions 30 minutes, cooled and filtered promptly gets core-shell type microfacies composite emulsion, can room-temperature self crosslinking behind this emulsion film forming, core-shell particles is closely tangled, improved the over-all properties of resin, the Static Water contact angle of film is 106 °.
Embodiment 3: the nuclear emulsion is formed
| Component | Water | Methyl methacrylate (MMA) | Methacrylic acid-2-ethylhexyl (2-EHA) | Alkylphenol polyoxyethylene (OP-10) | Sodium dodecylbenzene sulfonate (SDBS) |
| Quality (g) | ??40 | ??20 | 10 | ??8.89 | ??4.44 |
The shell emulsion is formed:
| Component | Water | Methyl methacrylate (MMA) | Fluorine monomer (FA 1) | Fluorine monomer (FA 2) | Alkylphenol polyoxyethylene (OP-10) | Sodium dodecylbenzene sulfonate (SDBS) |
| Quality (g) | ??20 | ??3 | ??3 | ?4 | ??1.92 | ??0.222 |
The preparation method: the 103ml water that will contain partial emulsifier joins in the four-hole boiling flask that agitator and thermometer are housed, and adds 0.2g sodium bicarbonate and nuclear pre-emulsion 73g (containing the 0.005g ammonium persulphate), 80 ℃ of temperature of reaction, and stirring velocity is about 200r/min.Under nitrogen protection, obtain examining emulsion after 1 hour then to wherein adding nuclear pre-emulsion 7g and Sodium Persulfate (containing 0.01g) solution 10ml, reacting.Ammonium persulphate (0.5g) is dissolved in the 20ml water, join simultaneously in the sub-emulsion of above-mentioned nuclear species with shell pre-emulsion 5g, react and made core-shell polymer emulsion in 0.5 hour, add 2 then, 4-tolylene diisocyanate (5g) promptly gets the fluorine resin emulsion of ambient crosslinking.The back Static Water contact angle of filming is 110 °.
Embodiment 4: the nuclear emulsion is formed
| Component | Water | Isobornyl methacrylate (IBOMA) | Butyl acrylate (BA) | Alkylphenol polyoxyethylene (OP-10) | Sodium laurylsulfonate (SDBS) |
| Quality (g) | ??40 | ??18 | ??12 | ??0.889 | ?6.87 |
The shell emulsion is formed:
| Component | Water | Isobornyl methacrylate (IBOMA) | Butyl acrylate (BA) | Fluorine monomer (FA 1) | Glycidyl methacrylate (GMA) | Alkylphenol polyoxyethylene (OP-10) | Sodium laurylsulfonate (SDBS) |
| Quality (g) | ??20 | ??4 | ??11 | ??3 | ??2 | ??3.98 | ??0.222 |
The preparation method: the 87ml water that will contain partial emulsifier joins in the four-hole boiling flask that agitator and thermometer are housed; 20 ℃ of temperature of reaction; stirring velocity is about 200r/min; nitrogen protection; after treating temperature equilibrium; add 14g nuclear consitution pre-emulsion (containing 5.1g ammonium persulphate and 0.07g sodium bisulfite), 27g nuclear consitution pre-emulsion (containing ammonium persulphate 0.031g) and sodium bisulfite (24g) solution 10ml, 20 ℃ of holding temperatures are reacted and were obtained examining emulsion in 60 minutes.Keep temperature of reaction system constant, add shell component pre-emulsion 45g (containing ammonium persulphate 6.9g) and sodium bisulfite (5.6g) solution 20ml again in gained nuclear emulsion, isothermal reaction 30 minutes is filtered, and promptly gets core-shell type microfacies composite emulsion.The particle surface of forming this resin contains epoxide group, can with the resin grafting of other type, to improve polymer properties.Film Static Water contact angle is 107 °.
Embodiment 5: the nuclear emulsion is formed
| Component | Water | Methyl methacrylate (MMA) | Butyl acrylate (BA) | Acrylamide-2-methyl-propyl sodium sulfonate (AMPSNa) |
| Quality (g) | ??40 | ?18 | ??12 | 10.333 |
The shell emulsion is formed:
| Component | Water | Methyl methacrylate (MMA) | Butyl acrylate (BA) | Fluorine monomer (FA) | Acrylamide-2-methyl-propyl sodium sulfonate (AMPSNa) |
| Quality (g) | ??20 | ??4 | ??11 | ?3 | 8.667 |
The preparation method: the 56ml water that will contain partial emulsifier joins in the four-hole boiling flask that agitator and thermometer are housed; add 0.2g sodium bicarbonate and nuclear pre-emulsion 3g (containing the 0.005g ammonium persulphate); 80 ℃ of temperature of reaction; stirring velocity is about 200r/min; nitrogen protection; to wherein adding nuclear pre-emulsion 7g and Sodium Persulfate (containing 0.01g) solution 10ml, insulation reaction must be examined emulsion in 1 hour.Remaining ammonium persulphate (0.25g) is dissolved in the 20ml water, join simultaneously in the sub-emulsion of above-mentioned nuclear species with shell pre-emulsion 45g, insulation reaction 15 hours, make the core-shell polymer emulsion of blueing look fluorescence, this resin is to be produced by reactive emulsifier, and with comparing of conventional emulsifier preparation, advantage is that the room temperature film-forming rear surface will not have remaining emulsifying agent, therefore surface tension will be littler, and the hydrophobic oleophobic performance is better.Can room temperature film-forming after filming, the Static Water contact angle is 122 °.
Claims (4)
1. a fluorine resin emulsion is characterized in that: by vinyl monomer and other vinyl function monomer and fluoro-containing group monomer, adopt the nuclear-shell emulsion process for copolymerization to obtain; Selectivity adds linking agent in the prepared resin emulsion;
Described vinyl monomer is divided into the moderate monomer of soft monomer, hard monomer and second-order transition temperature; Soft monomer comprises ethyl acrylate, butyl acrylate, isobutyl acrylate, ethyl propenoate, divinyl or chloroprene; Hard monomer comprises methyl methacrylate, (methyl) isobornyl acrylate, vinylbenzene, vinyl cyanide, vinylchlorid, Jia Jibingxisuanyizhi or vinylidene chloride; The monomer that second-order transition temperature is moderate comprises vinyl acetate, methyl acrylate or butyl methacrylate;
Described vinyl function monomer comprises (methyl) vinylformic acid, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) acrylamide, N-methylol (methyl) acrylamide, two vinylformic acid glycol ester, Vinylstyrene, (methyl) glycidyl acrylate or N-fourth oxygen methacrylic acid;
The fluoro-containing group monomer that described fluorine-containing latex adopted has following structure:
Wherein Rf is that the straight or branched of C2-C21 partly contains fluoroalkyl or perfluoroalkyl, and R1 is the straight or branched alkyl of hydrogen atom or C1-C8, and R2 is the straight or branched alkyl of C1-C20; FA1, FA2, FA3 use separately or several monomer mixes use with arbitrary proportion;
Described linking agent is diisocyanates, two amines, urea-formaldehyde resin, terpolycyantoamino-formaldehyde resin, Resins, epoxy, urethane or resol.
2. the preparation method of the described fluorine resin emulsion of claim 1, its feature may further comprise the steps:
(1) nuclear pre-emulsion: add described vinyl monomer of claim 1 and vinyl function monomer in being dissolved with the aqueous solution of emulsifying agent, high speed shear obtained examining pre-emulsion in 0.5～12 hour under 5 ℃～90 ℃ temperature;
(2) shell pre-emulsion: in being dissolved with the aqueous solution of emulsifying agent, add the described vinyl monomer of claim 1, vinyl function monomer and fluorochemical monomer, high speed shear obtained examining pre-emulsion in 0.5～24 hour under 5 ℃～90 ℃ temperature;
(3) the sub-emulsion of nuclear species is synthetic: the aqueous solution that will contain initiator earlier adds in the four-hole bottle, under 5 ℃～90 ℃ temperature, adds above-mentioned nuclear pre-emulsion, reacts to obtain in 0.5～24 hour;
(4) core-shell emulsion is synthetic: initiator and above-mentioned shell pre-emulsion are joined in the sub-emulsion of above-mentioned nuclear species simultaneously, react under 5 ℃～90 ℃ temperature and obtained in 0.5～24 hour;
(5) in above-mentioned resin emulsion, add the described linking agent of claim 1; The content of linking agent is 0%～20% of whole polymerization single polymerization monomer sum mass percents;
The emulsifying agent add-on is 0.5～10% of whole polymerization single polymerization monomer sum mass percents;
The initiator add-on is 0.01～5% of whole monomer sum quality percentage compositions.
3. preparation method according to claim 2 is characterized in that: emulsifying agent is the alkylphenol polyoxyethylene class, the alkyl phenyl polyethenoxy ether class, fatty alcohol polyethenoxy ether class or styryl phenol polyethenoxy ether class, the sulfo-succinic acid salt, the alkyl diphenyl ether disulfonate class, phosphoric acid ester, the allyl ether series Sulfonates, the acrylamido Sulfonates, the salt of fluoro-containing group organic compound, the maleic acid derivatives class, XN-45S, CO-436, CO-458, CO-630, CO-858, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, lauroyl amido CAB, the mixture of one or more in stearyl amido ethyl-N hydroxyethyl Sodium Glycinate and the allyl group succsinic acid alkyl ester sodium sulfonate.
4. preparation method according to claim 2, it is characterized in that: the used initiator of core-shell emulsion polymerization is bromine-containing compound class, azo-compound class, peroxide bridge compounds, sulfocompound class, tertbutyl peroxide, sodium formaldehyde sulphoxylate, sodium bisulfite, hydrogen peroxide, Sodium Persulfate, benzoyl peroxide, 2,2,6,6 tetramethyl-s-1-piperidine oxide, Diisopropyl azodicarboxylate, cuprous salt, Ammonium Persulfate 98.5, the mixture of one or more in Potassium Persulphate, butyllithium, the alpha-brominated ethyl isobutyrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910302136A CN101633715A (en) | 2009-05-07 | 2009-05-07 | Fluorine-containing resin emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910302136A CN101633715A (en) | 2009-05-07 | 2009-05-07 | Fluorine-containing resin emulsion and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101633715A true CN101633715A (en) | 2010-01-27 |
Family
ID=41593064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910302136A Pending CN101633715A (en) | 2009-05-07 | 2009-05-07 | Fluorine-containing resin emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101633715A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532436A (en) * | 2011-12-23 | 2012-07-04 | 江苏创基新材料有限公司 | Method for preparing single-component room-temperature crosslinked waterborne fluorine-containing coating |
| CN103038061A (en) * | 2010-05-06 | 2013-04-10 | Lg化学株式会社 | Multilayered sheet, and method for preparing same |
| CN103074011A (en) * | 2012-12-27 | 2013-05-01 | 广东达美新材料有限公司 | Single-component water-borne pressure sensitive adhesive for sun-proof and heat-insulating film |
| CN103160177A (en) * | 2013-03-13 | 2013-06-19 | 上海大学 | Acrylic resin coating material with superhydrophobicity and preparation method thereof |
| CN103342781A (en) * | 2013-06-20 | 2013-10-09 | 无锡洪汇新材料科技股份有限公司 | Vinyl chloride-butyl acrylate-epoxy resin copolymerization emulsion and preparation method thereof |
| CN103626912A (en) * | 2013-05-17 | 2014-03-12 | 佛山市三水灏诚合成树脂有限公司 | Aqueous acrylate emulsion adhesive for colorful metallic tiles and preparation method thereof |
| CN103757918A (en) * | 2013-12-23 | 2014-04-30 | 苏州纺友新材料有限公司 | Crease-resistant waterproof finishing agent and preparation method thereof |
| CN103864982A (en) * | 2012-12-15 | 2014-06-18 | 东莞市长安东阳光铝业研发有限公司 | Preparation method of fluorinated acrylate emulsion |
| CN105273121A (en) * | 2015-11-25 | 2016-01-27 | 浙江巨化股份有限公司电化厂 | Preparation method of fluorine-containing polyvinylidene chloride emulsion for coating |
| CN110951001A (en) * | 2019-12-26 | 2020-04-03 | 江苏智泰科技发展有限公司 | Preparation method of water-based fluorine-containing acrylic emulsion |
| CN111155310A (en) * | 2020-01-15 | 2020-05-15 | 东莞市鸿运纺织助剂有限公司 | Water-proof and oil-proof finishing agent |
| CN111154121A (en) * | 2019-12-31 | 2020-05-15 | 四川金核高分子材料有限公司 | Water-based polytetrafluoroethylene powder material and preparation method thereof |
| CN111995920A (en) * | 2020-08-24 | 2020-11-27 | 江苏华夏制漆科技有限公司 | Preparation method of low-temperature cured modified water-based acrylic amino hydrophilic coating |
| CN112142901A (en) * | 2020-09-18 | 2020-12-29 | 浙江巨化技术中心有限公司 | PVDC aqueous emulsion for water-repellent and oil-repellent coating film and preparation method thereof |
| CN112608414A (en) * | 2020-07-28 | 2021-04-06 | 杭州传化精细化工有限公司 | Fluorine-containing copolymer emulsion and preparation method and application thereof |
| CN115304704A (en) * | 2022-04-02 | 2022-11-08 | 西南石油大学 | Preparation method and application of low-permeability reservoir interface wetting regulation and control agent |
-
2009
- 2009-05-07 CN CN200910302136A patent/CN101633715A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103038061A (en) * | 2010-05-06 | 2013-04-10 | Lg化学株式会社 | Multilayered sheet, and method for preparing same |
| CN102532436B (en) * | 2011-12-23 | 2013-12-04 | 江苏创基新材料有限公司 | Method for preparing single-component room-temperature crosslinked waterborne fluorine-containing coating |
| CN102532436A (en) * | 2011-12-23 | 2012-07-04 | 江苏创基新材料有限公司 | Method for preparing single-component room-temperature crosslinked waterborne fluorine-containing coating |
| CN103864982B (en) * | 2012-12-15 | 2017-05-03 | 东莞东阳光科研发有限公司 | Preparation method of fluorinated acrylate emulsion |
| CN103864982A (en) * | 2012-12-15 | 2014-06-18 | 东莞市长安东阳光铝业研发有限公司 | Preparation method of fluorinated acrylate emulsion |
| CN103074011B (en) * | 2012-12-27 | 2015-03-18 | 广东达美新材料有限公司 | Single-component water-borne pressure sensitive adhesive for sun-proof and heat-insulating film |
| CN103074011A (en) * | 2012-12-27 | 2013-05-01 | 广东达美新材料有限公司 | Single-component water-borne pressure sensitive adhesive for sun-proof and heat-insulating film |
| CN103160177A (en) * | 2013-03-13 | 2013-06-19 | 上海大学 | Acrylic resin coating material with superhydrophobicity and preparation method thereof |
| CN103626912A (en) * | 2013-05-17 | 2014-03-12 | 佛山市三水灏诚合成树脂有限公司 | Aqueous acrylate emulsion adhesive for colorful metallic tiles and preparation method thereof |
| CN103342781B (en) * | 2013-06-20 | 2015-07-15 | 无锡洪汇新材料科技股份有限公司 | Vinyl chloride-butyl acrylate-epoxy resin copolymerization emulsion and preparation method thereof |
| CN103342781A (en) * | 2013-06-20 | 2013-10-09 | 无锡洪汇新材料科技股份有限公司 | Vinyl chloride-butyl acrylate-epoxy resin copolymerization emulsion and preparation method thereof |
| CN103757918A (en) * | 2013-12-23 | 2014-04-30 | 苏州纺友新材料有限公司 | Crease-resistant waterproof finishing agent and preparation method thereof |
| CN105273121A (en) * | 2015-11-25 | 2016-01-27 | 浙江巨化股份有限公司电化厂 | Preparation method of fluorine-containing polyvinylidene chloride emulsion for coating |
| CN110951001A (en) * | 2019-12-26 | 2020-04-03 | 江苏智泰科技发展有限公司 | Preparation method of water-based fluorine-containing acrylic emulsion |
| CN111154121A (en) * | 2019-12-31 | 2020-05-15 | 四川金核高分子材料有限公司 | Water-based polytetrafluoroethylene powder material and preparation method thereof |
| CN111155310A (en) * | 2020-01-15 | 2020-05-15 | 东莞市鸿运纺织助剂有限公司 | Water-proof and oil-proof finishing agent |
| CN112608414A (en) * | 2020-07-28 | 2021-04-06 | 杭州传化精细化工有限公司 | Fluorine-containing copolymer emulsion and preparation method and application thereof |
| CN112608414B (en) * | 2020-07-28 | 2022-09-06 | 杭州传化精细化工有限公司 | Fluorine-containing copolymer emulsion and preparation method and application thereof |
| CN111995920A (en) * | 2020-08-24 | 2020-11-27 | 江苏华夏制漆科技有限公司 | Preparation method of low-temperature cured modified water-based acrylic amino hydrophilic coating |
| CN112142901A (en) * | 2020-09-18 | 2020-12-29 | 浙江巨化技术中心有限公司 | PVDC aqueous emulsion for water-repellent and oil-repellent coating film and preparation method thereof |
| CN115304704A (en) * | 2022-04-02 | 2022-11-08 | 西南石油大学 | Preparation method and application of low-permeability reservoir interface wetting regulation and control agent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101633715A (en) | Fluorine-containing resin emulsion and preparation method thereof | |
| CN102083876B (en) | Fluoropolymer aqueous hybrid compositions with improved film formation | |
| US6833414B2 (en) | Cross-linkable aqueous fluoropolymer based dispersions containing silanes | |
| CN101475507B (en) | Fluorinated acrylate, preparation method and preparation of copolymer thereof | |
| CN1283640A (en) | Dispersion of aqueous fluorine polymer based on crosslinking | |
| CN102532436B (en) | Method for preparing single-component room-temperature crosslinked waterborne fluorine-containing coating | |
| CN101250369B (en) | Aqueous composite paint containing amphiphilic fluorine-containing acrylate blocking copolymer and preparation thereof | |
| CN101223232B (en) | Aqueous resin composition, weather resistance improver for aqueous coating material using same, weather resistance improver for thermoplastic resin, and weather resistance improver for solvent borne coating | |
| CN104231228A (en) | Waterborne fluorine-containing polyurethane resin capable of being cured by UV (Ultraviolet) and preparation method of waterborne fluorine-containing polyurethane resin | |
| CN103864982A (en) | Preparation method of fluorinated acrylate emulsion | |
| CN100404567C (en) | Preparation process of non organic solvent type fluorine-containing soapless emulsion | |
| CN105859937A (en) | Fluorine-silicon modified styrene-acrylic emulsion with hydrophobic property and preparing method thereof | |
| CN1654498A (en) | Fluoro resin/acrylic ester mixed emulsion and method for preparation thereof | |
| CN109370287B (en) | Hydrogel for slowly releasing silicone oil and application of hydrogel in marine antifouling paint | |
| CN101560278B (en) | Methyl methacrylate-styrene copolymer containing fluoro-acrylate and preparation method thereof | |
| CN101691342B (en) | Fluorine-containing acrylate monomer and preparation method and application thereof | |
| CN1670051A (en) | Fluorine-containing polyurethane emulsion and method for preparing same | |
| CN106749876A (en) | A kind of fluoroacrylic resin and preparation method thereof | |
| CN110655840A (en) | Viaduct fluorocarbon primer and preparation method thereof | |
| CN115216042B (en) | Preparation method of hydrophobic oleophobic PTFE composite membrane | |
| CN100338111C (en) | Double-phobia polyurethane-polyacrylic ester microemulsion and preparation process thereof | |
| CN103539880B (en) | Take fluorinated copolymer as seeded emulsion polymerization and its preparation method of assistant for emulsifying agent | |
| CN1337415A (en) | Prepn prolcess of polyvinylidene difluoride modified polyacrylate emulsion | |
| CN109627390A (en) | Graphene, Si modification perfluoroalkyl acrylate water-base resin and preparation method thereof | |
| CN1131250C (en) | Prepn process of fluororubber modified polyacrylate emulsion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20100127 |