CN102172491A - Fluorine-contained surfactant and preparation method thereof - Google Patents
Fluorine-contained surfactant and preparation method thereof Download PDFInfo
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- CN102172491A CN102172491A CN2011100561375A CN201110056137A CN102172491A CN 102172491 A CN102172491 A CN 102172491A CN 2011100561375 A CN2011100561375 A CN 2011100561375A CN 201110056137 A CN201110056137 A CN 201110056137A CN 102172491 A CN102172491 A CN 102172491A
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- fluorine
- ester
- methacrylic acid
- containing surfactant
- monomer
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 36
- -1 acrylic ester Chemical class 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 67
- 239000011737 fluorine Substances 0.000 claims description 67
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 65
- 229920000642 polymer Polymers 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 229920001400 block copolymer Polymers 0.000 claims description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229920001567 vinyl ester resin Polymers 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 239000004793 Polystyrene Substances 0.000 claims description 4
- LXYIXJJWHUOJBY-UHFFFAOYSA-N [Li]CCCOC(C)OCC Chemical compound [Li]CCCOC(C)OCC LXYIXJJWHUOJBY-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- 229940074391 gallic acid Drugs 0.000 claims description 4
- 235000004515 gallic acid Nutrition 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- QZTSARXNYCUCRQ-UHFFFAOYSA-N (4-cyanophenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=C(C#N)C=C1 QZTSARXNYCUCRQ-UHFFFAOYSA-N 0.000 claims description 3
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 3
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical class CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 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
- OGVIMBVPFAEZDF-UHFFFAOYSA-N (4-cyanophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(C#N)C=C1 OGVIMBVPFAEZDF-UHFFFAOYSA-N 0.000 claims description 2
- SJWKGDGUQTWDRV-UHFFFAOYSA-N 2-Propenyl heptanoate Chemical compound CCCCCCC(=O)OCC=C SJWKGDGUQTWDRV-UHFFFAOYSA-N 0.000 claims description 2
- PZGMUSDNQDCNAG-UHFFFAOYSA-N 2-Propenyl octanoate Chemical compound CCCCCCCC(=O)OCC=C PZGMUSDNQDCNAG-UHFFFAOYSA-N 0.000 claims description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical group CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 claims description 2
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 claims description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002221 fluorine Chemical class 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000006344 nonafluoro n-butyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 claims description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 33
- 238000000576 coating method Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 3
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical class C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 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
- 239000003863 metallic catalyst Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000006000 trichloroethyl group Chemical group 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a fluorine-contained surfactant and a preparation method thereof. The fluorine-contained surfactant is characterized in that a fluorine-contained monomer and a non fluorine-contained monomer, such as acrylic ester are processed by an anion polymerization technology to obtain a segmented copolymer. Compared with the prior art, the fluorine-contained surfactant has a segmented structure, has the advantages of excellent surface activity, pure product, low polymerization temperature, high polymerization speed, wide application prospect and excellent efficacy in the field of leveling; and no active groups or catalysts are introduced in.
Description
Technical field
The invention belongs to chemical field, relate to a kind of fluorine-containing surfactant and preparation method thereof, be specifically related to a kind of block polymer that constitutes by the monomer of fluorochemical monomer and non-contain fluorine atoms.
Background technology
Fluorine-containing surfactant is a kind of fluoropolymer.Because the special physics and the chemical property of fluorine, therefore than traditional surfactant, fluorine-containing surfactant has more advantage, for example: high surface, high heat-resistant stability and high chemical stability, its fluorine-containing alkyl is hydrophobic but also hate oil not only, so fluorine-containing surfactant is the highest a kind of of surface-active in all surface activating agent up to now.The very low fluorine-containing surfactant of interpolation consumption just can greatly reduce the surface tension of water.Solve some owing to can be low or surperficial greasy dirt be arranged in the surface, be difficult to wetting and spreading, phenomenons such as the cissing that causes, shrinkage cavity, volcanic crater.The fluorine-containing surfactant that adds in the lacquer can make coating surface cover the fluorine carbon molecule of one deck hydrophobic oleophobic, and hydrone can't permeate.Because fluorocarbon chain also oleophobic in hydrophobic so have certain solvent resistance, has improved the resistance to water of lacquer.Simultaneously, the general hydrophilic non-watertight property of paint film spot, and hydrophobic paint film grease proofness spot not can be in case various spots and added the paint film of fluorocarbon surfactant.Fluorocarbon surfactant has good temperature tolerance, even baking temperature reaches 150 ℃ to 200 ℃, still keeps stable, and plays a role.
This type of fluorine-containing surfactant is because its unique character can be widely used in industrial various aspects, for example: paint of coating, paper apply agent, cosmetic industry etc.The levelling that is specially adapted to microthin coating improves, as employed photoresist paintability improvement in the panel of LCD production process.
LCD becomes the leading role of panel TV set and display gradually.For enhancing productivity, the glass substrate size of liquid crystal panel manufacturer processing is increasing, and the liquid crystal panel production line is divided into different generations.The 1st generation liquid crystal glass base size only be 300mm * 400mm, present main product is 8 generation of the 6th generation to the product, wherein the 6th generation liquid crystal glass base be of a size of 1,500mm * 1,800mm, and the 8th generation liquid crystal glass base size reach 2,200mm * 2,600mm.In order to regulate luminous flux according to correct rule by colored filter, need on glass substrate, make tft array, this is that very complicated circuit multilayer is scribed engineering.Wherein mainly contain film (metal, dielectric or electro-conductive glass) and form, spray operations such as photoresist, partly shielding effect exposure, development and etching, because need repeatedly make different film patterns, so the coating performance of photoresist plays crucial effects.The interpolation of surfactant can keep photoresist homogeneity, improve coating etc.Particularly when being coated on photoresist on the base material, can produce the flakey texture on the surface, and, can suppress this scale spot, eliminate the defective (Mura) in the coating process by using surfactant.
In recent years, for the research of fluorine-containing block polymer, domestic and international research work concentrates on structural design, the synthetic method of fluoropolymer in a large number.In the prior art, fluoropolymer mainly is to utilize free radical polymerisation process to implement.For example: Jean-Marc C. etc. utilizes radical polymerization, has synthesized random copolymer (the Jean-Marc C. of trifluoroethyl methacrylate and a-fluoropropenes acid trichloro ethyl ester; Veronique M.; Bruno A.; Journal of Polymer Science:Part A:Polymer Chemistry, Vol.48,2154-2161 (2010)).Yet the polymer phase with Narrow Molecular Weight Distribution and compound with regular structure demonstrates significantly different behavior and performances for the copolymer of usual manner preparation.Controlled free radical polymerization provides to have can expect and maximum control that the polymer of definite structure is synthetic.Recently, discovered the possible technique of utilizing active free radical polymerization to prepare various block copolymer.For example: active atomic transferring free-radical polymerization (ATRP) and reversible addition-fracture chain shifts (RAFT) polymerization.Chinese patent application numbers 200780049949.9 discloses polymethylacrylic acid trifluoro ethyl ester and the methacrylic acid diethylin ethyl ester block copolymer that employing ATRP (ATRP) and reversible addition-fracture chain shift (RAFT) polymerization preparation.The ATRP method has its unique advantage, but its maximum shortcoming is to contain metallic catalyst in the final product, is difficult to remove, and product is impure.Fangping Yi then utilizes the RAFT polymerization to prepare fluorine-containing bi-block copolymer, and has studied its self-assembly property (FangpingYi; Sixun Zheng.; J.Phys.Chem.B 2009,113,1857-1868).Though the RAFT polymerization has characteristics such as reaction condition gentleness, the RAFT reagent that is added in polymerization process (sulfur-bearing thing) can remain in the final polymer, is difficult to remove, and polymer properties is produced certain influence.Simultaneously, RAFT reagent preparation process complexity, the suitability for industrialized production difficulty is bigger.It is many that active anionic polymerization then has suitable monomers, and the activated centre is stable, and polymerization speed is fast, and the solvent range of choice is big, the polymerization temperature wide ranges, and can carry out advantages such as the design of multiple molecular structure is synthetic.Be used widely in industrial quarters, for example, Chinese invention patent application number 200810117321.4 discloses and has utilized organo-lithium compound to use conjugated diolefin homopolymerization as anionic polymerization initiator in organic hydrocarbon solvent or use conjugated diene and carry out copolymerization and prepare polymer with monovinylarene.
Therefore, a kind of novel block type fluorine-containing surfactant is provided, and the preparation method that can obtain pure polymerizate, to help to improve the overall performance of fluorine-containing surfactant, enrich the fluorine-containing surfactant kind, can be coating, printing ink etc., particularly photoresist provides the surface-active of function admirable.
Summary of the invention
The object of the invention provides a kind of fluorine-containing surfactant with block structure and excellent surface activity, has and is intended to be applied to the photoresist field, solves the defect problem in the photoresist film forming procedure.
For achieving the above object, the technical solution used in the present invention is:
A kind of fluorine-containing surfactant is characterized in that this fluorine-containing surfactant is the block copolymer that first fluorine-containing monomer and the second not fluorine-containing monomer polymerization by following general formula (I) expression obtain;
Wherein, X is that hydrogen, fluorine, chlorine, bromine, iodine, cyano group or carbon number are 1～20 straight or branched fluoro-alkyl; Or carbon number is 1～20 straight or branched alkyl; Phenyl replacement or non-replacement, wherein, substituting group is that carbon number is 1～4 straight or branched alkyl, the substituting group number is 1～2; X is preferably hydrogen, fluorine, chlorine, methyl or phenyl.
Y is that carbon number is 1～10 aliphatic group; Or carbon number is 6～10 cyclic aliphatic group; Or carbon number is 6～10 aromatic group; The Y structure optimization is :-CH
2-,-CH
2CH
2-,-CH
2CH
2CH
2-,-C (CH
3)
2-,-CH
2CH
2CH
2CH
2-,-CH
2C (CH
3)
2-,-(CH
2)
2C (CH
3)
2-,-CH
2C (CH
3)
2-,-CH (CH
3) CH
2CH
2CH
2-,-(CH
2)
8CH
2-,
The Rf group is that carbon number is 1～6 perfluoroalkyl or part fluoro-alkyl; The Rf group is preferably-CF
3,-CF
2CF
3,-CF
2CF
2CF
3,-CF (CF
3)
2,-CF
2CF
2CF
2CF
3,-CF
2CF (CF
3)
2,-C (CF
3)
3,-(CF
2)
4CF
3,-(CF
2)
2CF (CF
3)
2,-CF
2C (CF
3)
3,-CF (CF
3) CF
2CF
2CF
3Or-(CF
2)
5CF
3
The described second not fluorine-containing monomer is: vinyl ester, polystyrene compound or the acrylic amide of acrylic or methacrylic esters of gallic acid, aliphatic olefin propyl ester class, aliphatic acid.
Wherein, described acrylic or methacrylic esters of gallic acid is preferably methyl acrylate, the acrylic acid ethyl ester, butyl acrylate cores, the acrylic acid isobutyl, the acrylic acid tertiary butyl ester, the acrylic acid propyl diester, the 2-EHA base, the acrylic acid decyl ester, acrylic acid isodecyl ester, the acrylic acid Lauryl Ester, stearyl acrylate base ester, acrylic acid iso stearyl ester, isobornyl acrylate, glycidyl acrylate base ester, phenyl acrylate, the acrylic acid benzyl ester, acrylic acid 4-cyano-phenyl ester, the acrylic acid dimethylamino ethyl ester, acrylic acid diethyl amino ethyl ester;
Perhaps methyl methacrylate, the methacrylic acid ethyl ester, the methacrylic acid butyl ester, the methacrylic acid isobutyl, the methacrylic acid tertiary butyl ester, the methacrylic acid propyl diester, methacrylic acid 2-ethylhexyl, the methacrylic acid decyl ester, methacrylic acid isodecyl ester, the methacrylic acid Lauryl Ester, the methacrylic acid stearyl, methacrylic acid iso stearyl ester, IBOMA, GMA base ester, the methacrylic acid phenylester, the methacrylic acid benzyl ester, methacrylic acid 4-cyano-phenyl ester, dimethylaminoethyl acrylate methyl base ammonia ethyl ester, methacrylic acid diethyl amino ethyl ester;
Described aliphatic olefin propyl ester class is preferably allyl heptanoate, allyl octanoate, allyl acetate;
The vinyl ester of described aliphatic acid is preferably vinyl-acetic ester, vinyl propionate base ester, sad vinyl esters, laurate vinyl esters, vinyl stearate base ester;
Described polystyrene compound is preferably styrene or p-methylstyrene;
Described acrylic amide is preferably N methacrylamide or N hydroxymethyl acrylamide.
In the fluorine-containing surfactant of the present invention, the percentage that first monomer accounts for total polymer weight is 10%～90%, preferred 40%～60%; The percentage that second monomer accounts for total polymer weight is 90%～10%, preferred 40%～60%.
The preparation method of fluorine-containing surfactant of the present invention obtains block copolymer by fluorine-containing first monomer of following general formula (I) expression and the second not fluorine-containing monomer by the anion initiated polymerization:
Described anion initiated polymerization is for carrying out discontinuously, be specially: in the high vacuum polyplant, add polymerization solvent, simultaneously or one after the other add after initator causes, add first monomer polymerization, polymerization time is 0.5～15 hour, is preferably 1～3 hour, adds second monomer polymerization again 0.5～3 hour, preferred polymeric 0.5～1 hour, polymerization adds terminator, reaction terminating, purifying polymer after finishing.
Described polymerization solvent is preferably cyclohexane, n-hexane or oxolane, oxolane more preferably, and solvent quality is 0.5: 1～5: 1 with first monomer mass ratio, is preferably 1: 1～3: 1; Described initiators for polymerization is preferably (1 '-ethoxy ethoxy) propyl lithium or Ph
3CLi, the consumption and first monomer mole ratio are 1: 1～1.5, preferred 1: 1.2.Described polymeric reaction temperature is-100 ℃～150 ℃, is preferably-100 ℃～110 ℃, most preferably is-78 ℃～30 ℃.Described terminator is preferably water, methyl alcohol or isopropyl alcohol, and the mol ratio of terminator and initator is 0.1～1.1.The weight ratio that first monomer and second monomer are taken is 10～90: 90～10, and preferred weight ratio is 40～60: 60～40.
Beneficial effect of the present invention compared with the prior art: fluorine-containing surfactant of the present invention has block structure and excellent surface activity, product is pure, do not introduce active group or catalyst, and polymerization temperature is lower, polymerization speed is fast, the prospect that will be widely used especially has very outstanding effectiveness in the levelling field.Particularly be applied to the photoresist field, solved the defect problem in the photoresist film forming procedure.
The performance test methods of above-mentioned fluorine-containing surfactant:, control the wherein content of fluorine-containing surfactant, and be coated with test by common technique formulated positive photoresist.After the cleaning of base plate glass sheet, oven dry, with 2000 rev/mins of rotating speeds, the condition of 30 seconds whirl coating time institute's preparation photoresist is spin-coated on glass baseplate surface with photoresist spinner, form photoresist film, baking is 90 seconds before carrying out on 100 ℃ of hot plates.The cooling back is observed and the test thickness.
Foregoing description also is not used in qualification, but is used for the explanation effect.Below part provide special and by way of example mode embodiments of the invention are described.Provide these embodiment as the explanation of the invention effect, and do not mean that limitation of the invention.
Description of drawings
Fig. 1 has shown gel permeation chromatography (GPC) figure according to the fluorine-containing surfactant of embodiment 1 preparation.Wherein a is first block GPC figure, and b continues polymerization gained bi-block copolymer GPC figure on the first block basis.
Fig. 2 has shown the coating design sketch of the photoresist that does not add embodiment 1 described fluorine-containing surfactant.
Fig. 3 shows the coating design sketch of the photoresist that has added embodiment 1 described fluorine-containing surfactant.
Fig. 4 has shown the photoresist that has added embodiment 13 described fluorine-containing surfactants, and surface-active contents is 1000ppm.
Fig. 5 shows the photoresist that has added embodiment 13 described fluorine-containing surfactants, and surface-active contents is 1500ppm.
Fig. 6 shows the photoresist that has added embodiment 13 described fluorine-containing surfactants, and surface-active contents is 2000ppm.
The specific embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment 1:
With the ether is solvent, in high-vacuum installation, make 1 '-ethoxy ethoxy) propyl chloride and lithium metal generation lithium be for reaction, preparation (1 '-ethoxy ethoxy) propyl lithium.
High vacuum (＜10 is all adopted in polymerization
-3Pa) with seal the anionic polymerisation experimental technique and carry out. in the high vacuum polyplant, be polymer solvent with 100～150mL THF, 1.0mL 0.5mol/L
3(1 '-ethoxy ethoxy) propyl lithium is an initator, initator and C
3F
7CH
2CH
2CH
2OCOCH=CH
2(mol ratio 1: 1.2) polymerisation was cooled to-78 ℃ with liquid nitrogen/isopropanol bath rapidly after 1～3 hour, slowly added 5.0～15.0g methyl styrene thereupon, added 0.02 gram CH behind polymerase 10 .5～1 hour
3The OH cessation reaction.Reacted polymer under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and carries out deposition and purification with n-hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, recording productive rate is 96%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum (
1H NMR,
19F NMR) detects the structure of its molecular weight, molecular weight distribution and copolymer, prove to have obtained target product that number-average molecular weight is 8780g/mol.
Embodiment 2～4:
The fluorochemical monomer kind in changing embodiment 1, initator, solvent, second monomer, polymerization temperature are equal to described in the embodiment 1 identical.Wherein the fluorochemical monomer that uses respectively is: (CF
3)
2CF (CF
2)
2C (CH
3)
2OCOCH=CH
2, (CF
3)
3CCF
2CH
2C (CH
3)
2OCOCH=CH
2, CF
3CF
2CF
2(CF
3) CFCH
2CH
2CH
2CH
2OCOCH=CH
2Obtaining the polymer number-average molecular weight is 9000～10000.
Embodiment 5～8:
The fluorochemical monomer kind and second monomer in changing embodiment 1, initator, solvent, polymerization temperature are equal to described in the embodiment 1 identical.Wherein use second monomer to be acrylic acid 4-cyano-phenyl ester, the first fluorine-containing monomer is respectively:
Obtaining the polymer number-average molecular weight is 1000～100000.
Embodiment 9:
With the ether is solvent, makes Ph in high-vacuum installation
3CCl and lithium metal generation lithium prepare Ph for reaction
3CLi.
High vacuum (＜10 is all adopted in polymerization
-3Pa) with seal the anionic polymerisation experimental technique and carry out.In the high vacuum polyplant, be polymer solvent with 100～150mL oxolane (THF), 1.0mL 0.5mol/L
3Ph
3CLi is an initator, initator and (CF
3)
3CCH
2CH
2CH
2OCOCH=CH
2(mol ratio 1: 1.2) reaction back is cooled to-78 ℃ with liquid nitrogen/isopropanol bath rapidly, slowly adds 5.0～15.0g styrene thereupon, adds 0.01 gram deionized water cessation reaction behind polymerase 10 .5～1h.Reacted polymer under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and carries out deposition and purification with n-hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, recording productive rate is 90%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum (
1H NMR,
19F NMR) detects the structure of its molecular weight, molecular weight distribution and copolymer, prove to have obtained target product.Obtaining the polymer number-average molecular weight is 93520g/mol.
Embodiment 10～15:
Second monomeric species in changing embodiment 9, initator, solvent, fluorochemical monomer, polymerization temperature are equal to described in the embodiment 9 identical.Wherein use second monomer respectively to be: laurate vinyl esters, p-methylstyrene, isobutyl methacrylate, N methacrylamide, acrylic acid dimethylamino ethyl ester, methacrylic acid diethyl amino ethyl ester.Obtaining the polymer number-average molecular weight is 10000～100000.
Embodiment 16～18:
Remove the fluorochemical monomer kind and second monomer that change among the embodiment 9, be cooled to outside-100 ℃ with liquid nitrogen/isopropanol bath, initator, solvent, polymerization temperature are equal to described in the embodiment 9 identical.Wherein use second monomer to be stearyl acrylate base ester, the first fluorine-containing monomer respectively is:
Embodiment 19:
By common technique formulated positive photoresist, wherein (number-average molecular weight is respectively 2100,4248 to phenolic resins, weight ratio is 1.5: 1), emulsion 2,3,4,4 '-tetrahydroxybenzophenone and 1, the carboxylate of 2-naphthoquinones two nitrine-5-sulfonic acid chloride, solvent 1-Methoxy-2-propyl acetate content are respectively 20%, 3%, 77%.Add embodiment 1 described fluorine-containing surfactant, content is respectively 0ppm and 4500ppm and is coated with test.After the cleaning of base plate glass sheet, oven dry, with 2000 rev/mins of rotating speeds, the condition of 30 seconds whirl coating time institute's preparation photoresist is spin-coated on glass baseplate surface with photoresist spinner, form photoresist film, baking is 90 seconds before carrying out on 100 ℃ of hot plates.The cooling back is observed and the test thickness.As a result shown in the accompanying drawing 3, added fluorine-containing surfactant after, than not adding surfactant (referring to accompanying drawing 2), the photoresist coating performance obviously improves, defective (Mura) disappears.
Embodiment 20:
By common technique formulated positive photoresist, wherein (number-average molecular weight is respectively 2100,4248 to phenolic resins, weight ratio is 1.5: 1), emulsion 2,3,4,4 '-tetrahydroxybenzophenone and 1, the carboxylate of 2-naphthoquinones two nitrine-5-sulfonic acid chloride, solvent 1-Methoxy-2-propyl acetate content are respectively 20%, 3%, 77%.Add embodiment 3 described surfactants, content is 4500ppm and is coated with test.After the cleaning of base plate glass sheet, oven dry, with 5000 rev/mins of rotating speeds, the condition of 20 seconds whirl coating time institute's preparation photoresist is spin-coated on glass baseplate surface with photoresist spinner, form photoresist film, baking is 90 seconds before carrying out on 100 ℃ of hot plates.The cooling back is observed and the test thickness.
Embodiment 21:
By common technique formulated positive photoresist, wherein (number-average molecular weight is respectively 1200,3899 to phenolic resins, weight ratio is 2: 1), emulsion 2,3,4,4 '-tetrahydroxybenzophenone and 1, the carboxylate of 2-naphthoquinones two nitrine-5-sulfonic acid chloride, solvent 1-Methoxy-2-propyl acetate content are respectively 25%, 4.5%, 70.5%.Control the wherein content of fluorine-containing surfactant, and be coated with test, used fluorine-containing surfactant is described in the embodiment 13.After silicon chip cleaning, oven dry, with 4000 rev/mins of rotating speeds, the condition of 25 seconds whirl coating time institute's preparation photoresist is spin-coated on silicon chip surface with photoresist spinner, form photoresist film, baking is 90 seconds before carrying out on 110 ℃ of hot plates.The cooling back is observed and the test thickness.Shown in accompanying drawing 4～6, its fluorine-containing surfactant content is respectively 1000ppm (accompanying drawing 4), 1500ppm (accompanying drawing 5), 2000ppm (accompanying drawing 6).When fluorine-containing surfactant content was increased to 2000ppm, filming performance obviously improved, and defective (Mura) disappears.
Embodiment 22～24:
The fluorine-containing surfactant kind in changing embodiment 21, photoresist resin, emulsion, solvent, coating method are equal to described in the embodiment 11 identical.The surfactant that uses wherein, it is described respectively to be embodiment 7,9,18.
Claims (12)
1. fluorine-containing surfactant is characterized in that this fluorine-containing surfactant is the block copolymer that first fluorine-containing monomer and the second not fluorine-containing monomer polymerization by following general formula (I) expression obtain;
Wherein, X is that hydrogen, fluorine, chlorine, bromine, iodine, cyano group or carbon number are 1～20 straight or branched fluoro-alkyl; Or carbon number is 1～20 straight or branched alkyl; Phenyl replacement or non-replacement, wherein, substituting group is that carbon number is 1～4 straight or branched alkyl, the substituting group number is 1～2;
Y is that carbon number is 1～10 aliphatic group; Or carbon number is 6～10 cyclic aliphatic group; Or carbon number is 6～10 aromatic group;
The Rf group is that carbon number is 1～6 perfluoroalkyl or part fluoro-alkyl;
The described second not fluorine-containing monomer is: vinyl ester, polystyrene compound or the acrylic amide of acrylic or methacrylic esters of gallic acid, aliphatic olefin propyl ester class, aliphatic acid.
2. fluorine-containing surfactant as claimed in claim 1 is characterized in that X is hydrogen, fluorine, chlorine, methyl or phenyl.
3. fluorine-containing surfactant as claimed in claim 1 is characterized in that described Y structure is :-CH
2-,-CH
2CH
2-,-CH
2CH
2CH
2-,-C (CH
3)
2-,-CH
2CH
2CH
2CH
2-,-CH
2C (CH
3)
2-,-(CH
2)
2C (CH
3)
2-,-CH
2C (CH
3)
2-,-CH (CH
3) CH
2CH
2CH
2-,-(CH
2)
8CH
2-,
4. fluorine-containing surfactant as claimed in claim 1, described Rf group is-CF
3,-CF
2CF
3,-CF
2CF
2CF
3,-CF (CF
3)
2,-CF
2CF
2CF
2CF
3,-CF
2CF (CF
3)
2,-C (CF
3)
3,-(CF
2)
4CF
3,-(CF
2)
2CF (CF
3)
2,-CF
2C (CF
3)
3,-CF (CF
3) CF
2CF
2CF
3Or-(CF
2)
5CF
3
5. fluorine-containing surfactant as claimed in claim 1 is characterized in that described acrylic or methacrylic esters of gallic acid is a methyl acrylate, the acrylic acid ethyl ester, butyl acrylate cores, the acrylic acid isobutyl, the acrylic acid tertiary butyl ester, the acrylic acid propyl diester, the 2-EHA base, the acrylic acid decyl ester, acrylic acid isodecyl ester, the acrylic acid Lauryl Ester, stearyl acrylate base ester, acrylic acid iso stearyl ester, isobornyl acrylate, glycidyl acrylate base ester, phenyl acrylate, the acrylic acid benzyl ester, acrylic acid 4-cyano-phenyl ester, the acrylic acid dimethylamino ethyl ester, acrylic acid diethyl amino ethyl ester;
Perhaps methyl methacrylate, the methacrylic acid ethyl ester, the methacrylic acid butyl ester, the methacrylic acid isobutyl, the methacrylic acid tertiary butyl ester, the methacrylic acid propyl diester, methacrylic acid 2-ethylhexyl, the methacrylic acid decyl ester, methacrylic acid isodecyl ester, the methacrylic acid Lauryl Ester, the methacrylic acid stearyl, methacrylic acid iso stearyl ester, IBOMA, GMA base ester, the methacrylic acid phenylester, the methacrylic acid benzyl ester, methacrylic acid 4-cyano-phenyl ester, dimethylaminoethyl acrylate methyl base ammonia ethyl ester, methacrylic acid diethyl amino ethyl ester;
Described aliphatic olefin propyl ester class is allyl heptanoate, allyl octanoate, allyl acetate;
The vinyl ester of described aliphatic acid is vinyl-acetic ester, vinyl propionate base ester, sad vinyl esters, laurate vinyl esters, vinyl stearate base ester;
Described polystyrene compound is styrene or p-methylstyrene;
Described acrylic amide is N methacrylamide or N hydroxymethyl acrylamide.
6. fluorine-containing surfactant as claimed in claim 1 is characterized in that the percentage that first monomer accounts for total polymer weight is 10%～90%; The percentage that second monomer accounts for total polymer weight is 90%～10%.
7. fluorine-containing surfactant as claimed in claim 6 is characterized in that the percentage that first monomer accounts for total polymer weight is 40%～60%; The percentage that second monomer accounts for total polymer weight is 40%～60%.
8. the preparation method of the described fluorine-containing surfactant of claim 1 is characterized in that this method is to obtain block copolymer by the first fluorine-containing monomer of following general formula (I) expression and the second not fluorine-containing monomer by the anion initiated polymerization:
9. the preparation method of fluorine-containing surfactant according to claim 8, it is characterized in that described anion initiated polymerization is for carrying out discontinuously, be specially: in the high vacuum polyplant, add polymerization solvent, simultaneously or one after the other add initator, add first monomer polymerization, polymerization time is 0.5～15 hour, is preferably 1～3 hour; Added second monomer polymerization again 0.5～3 hour, polymerization adds terminator, reaction terminating, purifying polymer after finishing.
10. the preparation method of fluorine-containing surfactant according to claim 9, wherein said polymerization solvent is cyclohexane, n-hexane or oxolane, is preferably oxolane; Described initiators for polymerization is (1 '-ethoxy ethoxy) propyl lithium or Ph
3CLi, the consumption and first monomer mole ratio are 1: 1～1.5, preferred 1: 1.2.
11. the preparation method of fluorine-containing surfactant according to claim 9, wherein said polymeric reaction temperature is-100 ℃～150 ℃, is preferably-100 ℃～110 ℃, most preferably is-78 ℃～30 ℃.
12. the preparation method of fluorine-containing surfactant according to claim 9 is characterized in that described terminator is water, methyl alcohol or isopropyl alcohol, the mol ratio of terminator and initator is 0.1～1.1.
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