CN100369923C - 氟化膦酸 - Google Patents
氟化膦酸 Download PDFInfo
- Publication number
- CN100369923C CN100369923C CNB038123363A CN03812336A CN100369923C CN 100369923 C CN100369923 C CN 100369923C CN B038123363 A CNB038123363 A CN B038123363A CN 03812336 A CN03812336 A CN 03812336A CN 100369923 C CN100369923 C CN 100369923C
- Authority
- CN
- China
- Prior art keywords
- gram
- phosphonic acids
- mixture
- fluorinated phosphonic
- base material
- 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.)
- Expired - Fee Related
Links
- 150000003009 phosphonic acids Chemical class 0.000 title abstract description 18
- -1 alkali metal cation Chemical class 0.000 claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 238000011282 treatment Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 55
- 229910052799 carbon Inorganic materials 0.000 claims description 34
- 239000002585 base Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 125000002947 alkylene group Chemical group 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 73
- 229910052731 fluorine Inorganic materials 0.000 description 54
- 239000011737 fluorine Substances 0.000 description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- 239000000243 solution Substances 0.000 description 47
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 46
- 239000007788 liquid Substances 0.000 description 35
- 150000001721 carbon Chemical group 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 27
- 238000003756 stirring Methods 0.000 description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 239000007787 solid Substances 0.000 description 24
- 238000009835 boiling Methods 0.000 description 20
- 239000012043 crude product Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 18
- 239000012141 concentrate Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000004821 distillation Methods 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 15
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical class CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 14
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 description 10
- 238000001338 self-assembly Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000031709 bromination Effects 0.000 description 8
- 238000005893 bromination reaction Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical class C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- PGRFXXCKHGIFSV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-iodobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)I PGRFXXCKHGIFSV-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 230000001476 alcoholic effect Effects 0.000 description 7
- 229960004756 ethanol Drugs 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical class OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 241000534944 Thia Species 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 235000012721 chromium Nutrition 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000001273 butane Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229960004624 perflexane Drugs 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- OUEFENYULDYAFC-UHFFFAOYSA-N dioxosilane hexane Chemical compound CCCCCC.[Si](=O)=O OUEFENYULDYAFC-UHFFFAOYSA-N 0.000 description 3
- YJCXKNNURGCXFQ-UHFFFAOYSA-N ethoxy(ethyl)phosphinic acid Chemical compound CCOP(O)(=O)CC YJCXKNNURGCXFQ-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000011928 denatured alcohol Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- APBCNLYLPJQPGB-UHFFFAOYSA-N docos-21-enoic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCC=C APBCNLYLPJQPGB-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- WXPWPYISTQCNDP-UHFFFAOYSA-N oct-7-en-1-ol Chemical compound OCCCCCCC=C WXPWPYISTQCNDP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- XVKJSLBVVRCOIT-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-10-iododecane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCI XVKJSLBVVRCOIT-UHFFFAOYSA-N 0.000 description 1
- KWXGJTSJUKTDQU-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-8-iodooctane Chemical class FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I KWXGJTSJUKTDQU-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 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 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000006344 nonafluoro n-butyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 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 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 229940094989 trimethylsilane Drugs 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
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Abstract
氟化膦酸化合物,用该化合物对基材表面处理的方法,该化合物具有化学式(I),其中,R1是含3-21个碳原子的直链亚烷基,含2-20个碳原子的氧杂取代的直链亚烷基,或者含2-20个碳原子的硫杂取代的直链亚烷基;R2是含4-10个碳原子的全氟烷基;R3是氢、碱金属阳离子或者含1-6个碳原子的烷基;M是氢或碱金属阳离子,条件是若R1是未取代的直链亚烷基,则R1和R2中碳原子数总和至少是10。
Description
技术领域
本发明涉及自装配(self-assemble)形成单层的氟化有机化合物,尤其是氟化膦酸。
背景技术
自装配材料,正如它名字所暗示的,当与另一种物质接触时自发形成一种结构(例如胶束或单层)。单层的形成在发生在固体基材(例如金属片)表面时特别有用。如果形成单层的材料赋予该基材表面低表面能,那么就能够赋予该表面一种或多种有用的性能,例如斥水性、耐腐蚀性、润滑性和粘合剂剥离性。若该表面能足够低,则可以获得拒油性和耐污性。一般来说,通过使用碳氟化合物材料可以获得如此低的表面能。
氟化的自装配单层已经用于防污涂层、抗反射玻璃涂层和剥离涂层。通常的自装配材料由极性的头部基团连接在疏水的尾部组成。具有氟化尾部的自装配材料尽管成本较高,但在工业上已被广泛接受。这是因为这些材料与其他替换材料(如具有烃尾部或聚硅氧烷尾部的材料)相比,在粘合剥离性能和防污性方面显示优越得多的性能。这一领域的商用产品通常使用带有7个和8个碳的全氟烷基的材料。近年来,工业上为寻找这些基团的替代材料作了大量努力。
希望有这样的新型材料,它们能在范围广泛的基材上自装配形成低表面能的单层,尤其希望能有不含7个和8个碳的全氟烷基的材料。
发明概述
本发明的一个方面提供了一种氟化膦酸化合物,它具有以下化学式:
其中:
R1是含3-21个碳原子的直链亚烷基,含2-20个碳原子的氧杂取代的直链亚烷基,或者含2-20个碳原子的硫杂取代的直链亚烷基;
R2是含4-10个碳原子的全氟烷基;
R3是氢、碱金属阳离子或者含1-6个碳原子的烷基;
M是氢或碱金属阳离子,
条件是若R1是未取代的直链亚烷基,则R1和R2中碳原子数总和至少是10。
本发明的另一个方面提供了一种处理制品表面的方法,该方法包括:
提供具有表面的基材;
向所述基材的所述表面施用具有以下化学式的氟化膦酸化合物:
其中:
R1是含3-21个碳原子的直链亚烷基,含2-20个碳原子的氧杂取代的直链亚烷基,或者含2-20个碳原子的硫杂取代的直链亚烷基;
R2是含4-10个碳原子的全氟烷基;
R3是氢、碱金属阳离子或者含1-6个碳原子的烷基;
M是氢或碱金属阳离子,
条件是若R1是未取代的直链亚烷基,则R1和R2中碳原子数总和至少是10。
本发明的另一个方面提供了一种制品,它包括具有表面的基材,所述表面与具有以下化学式的氟化膦酸化合物单层的至少一部分紧密接触:
其中:
R1是含3-21个碳原子的直链亚烷基,含2-20个碳原子的氧杂取代的直链亚烷基,或者含2-20个碳原子的硫杂取代的直链亚烷基;
R2是含4-10个碳原子的全氟烷基;
R3是氢、碱金属阳离子或者含1-6个碳原子的烷基;
M是氢或碱金属阳离子,
条件是若R1是未取代的直链亚烷基,则R1和R2中碳原子数总和至少是10。
本发明的另一个方面提供了一种制品,它由下述方法制得,该方法包括:
提供具有表面的基材;
向所述基材的所述表面施用具有以下化学式的氟化膦酸化合物:
其中:
R1是含3-21个碳原子的直链亚烷基,含2-20个碳原子的氧杂取代的直链亚烷基,或者含2-20个碳原子的硫杂取代的直链亚烷基;
R2是含4-10个碳原子的全氟烷基;
R3是氢、碱金属阳离子或者含1-6个碳原子的烷基;
M是氢或碱金属阳离子,
条件是若R1是未取代的直链亚烷基,则R1和R2中碳原子数总和至少是10。
本发明的氟化膦酸在应用于各种基材时都能自装配(例如形成单层膜),在这些基材上产生涂层,显示低表面能、粘合剥离性能、润滑性、斥水性和/或防污性中的至少一种性能。
本文所用“全氟”的含义是所指的基团或分子中氢被氟彻底取代。
详细说明
本发明的氟化膦酸具有以下化学式:
其中:
R1是含3-21个碳原子的直链亚烷基,含2-20个碳原子的氧杂取代的直链亚烷基,或者含2-20个碳原子的硫杂取代的直链亚烷基。R1较好是含5-21个碳原子的直链亚烷基,更好是含10-21个碳原子的直链亚烷基。两种有用的直链亚烷基是癸烷-1,10-二基和二十一烷-1,21-二基。不希望受理论的束缚,据信氧原子和/或硫原子具有与亚甲基(即-CH2-)相似的空间尺寸,可以取代亚烷基链中的亚甲基而不会明显破坏本发明氟化膦酸的自装配性质和/或性能特征。因此,亚烷基链可以在一个部位或多个部位发生氧杂或硫杂取代(即用氧原子或硫原子代替亚甲基),这不会产生不利影响,这些技术方案包括在本发明内。
R2是含4-10个碳原子的全氟烷基,条件是若R1是未取代的直链亚烷基,则R1和R2中碳原子数总和至少是10。全氟烷基例如包括全氟丁基、全氟戊基、全氟己基的异构体,以及它们的混合物。R2优选是全氟正丁基。
R3是氢、碱金属阳离子(例如锂、钠、钾),或者含1-6个碳原子的烷基(例如甲基、乙基、丁基、己基)。R3优选是氢或碱金属。
M是氢或碱金属阳离子。
尽管R1和R2的选择范围宽,优选是整个链长应足够长以获得所需性能。因此,较好是R1和R2中碳原子数总和至少为10。
本发明的氟化膦酸可以用多种已知方法制备:例如在相应的烷基氯、烷基溴或烷基碘上进行Michaelis-Arbuzov反应,然后进行水解,该方法记述于Bhatacharya等的Chemical Reviews(1981),卷81,第415-430页;又如向结构为CH2=CH(CH2)mPO3H2的烯烃或其酯中加入全氟化烷基碘,然后进行还原,该方法记述于Rong等的Tetrahedron Letters(1990),卷31,第5615-5616页)。
本发明的氟化膦酸可有利地用于多种基材,这些氟化膦酸可以在基材的至少一部分表面上形成单层覆盖层。所述单层通常是取向的,膦酰基与基材表面接触,全氟烷基由接触表面向外伸出。本发明的氟化膦酸可以有利地应用于各种金属基材天然的氧化物表面层,尽管也可应用于其他基材。金属的例子包括铬、铝、铜、镍、钛、银和它们的合金和混合物。其他材料的例子包括金属氧化物以及金属氧化物和氮化物的混合物,包括氧化铝、氧化钛、氮化钛和氧化铟锡。较好的是,基材包括铬、铝、铜和/或镍。
将本发明的氟化膦酸施用于基材的方法例如包括:喷涂、浸涂、刷涂和旋涂氟化膦酸在有机溶剂(如乙醇或异丙醇)中的稀溶液(如0.1重量%)。根据采用的精确涂覆条件,上述方法中有一些可能会施涂超过一单层量的氟化膦酸。这种情况下,过量的物料最多只是很弱地结合,通常可以用合适溶剂冲洗来容易地除去。一般来说,本发明的氟化膦酸作为一层施用到待处理的基材表面的至少一部分上,优选是全部表面上。较好的是,氟化膦酸在基材表面上形成一单层(例如自装配单层)。氟化膦酸层可以是任何厚度,但是在冲洗除去过量的未结合物料并干燥之后,厚度通常在0.5-10纳米(nm)的范围内,优选是1-5nm,更优选是1-2.5nm。
本发明的氟化膦酸具有实用性,例如作为脱模剂、防污涂层、润滑涂层、防水涂层和/或制造微流体和/或微型机电设备。
本发明的目的和优点将进一步说明于以下实施例中,但是这些实施例中所记述的具体材料和用量以及其他条件和细节不应被解释为对本发明造成不恰当的限制。
实施例
以下制备例和实施例中的所有份数、百分数和比率除非另有说明,均是重量计。
1-碘代-1H,1H,2H,2H-全氟癸烷和1-碘代-1H,1H,2H,2H-全氟己烷得自Lancaster Synthesis,Windham,New Hampshire。
7-辛烯-1-醇得自TCI America,Portland,Oregon。
21-二十二烯酸是根据Mirviss,S.B.在The Journal of Organic Chemistry(1989),第54卷,第1948-1951页所述制备的。
以下制备例和实施例中的“室温”是指约20-24℃。
以下制备例和实施例中的“过夜”指约14-16个小时(hr)。
以下制备例中的“九氟丁基”指线型异构结构-CF2CF2CF2CF3。
除非另外指出,以下制备例和实施例中所用的所有试剂均得自或购自普通的化学供应商,例如Aldrich Chemical Co.,Milwaukee,Wisconsin,或者也可以用已知方法合成得到。
制备CF3(CF2)7CH2CH2PO3H2
将42.8克1-碘-1H,1H,2H,2H-全氟癸烷和37.4克亚磷酸三乙酯的混合物于150℃加热40小时。通过蒸馏从混合物中除去乙膦酸二乙酯和其它挥发物,0.05乇(7Pa)的沸点为30-50℃。对余下的浓缩混合物进行蒸馏,得到23.1克73∶16∶11的1-(二乙基膦酰基)-1H,1H,2H,2H-全氟癸烷、乙膦酸乙酯·1H,1H,2H,2H-全氟癸基酯和乙膦酸乙酯的混合物,0.05乇(7Pa)的沸点为102-109℃。
向17.5克上述混合物在100毫升二氯甲烷的溶液中加入10.7克溴化三甲基硅烷。于室温24小时后,该溶液浓缩至浅黄色液体,将中间体膦酸甲硅烷基酯(silylphosphonate ester)溶解在200毫升甲醇中。所得溶液于室温搅拌30分钟(min),然后浓缩得到灰白色固体。如上再溶解于甲醇中然后浓缩,再重复两次。将粗产品化合物用水研磨,将7.3克物料在乙酸乙酯中重结晶,得到3.1克1-膦酰基-1H,1H,2H,2H-全氟癸烷(CF3(CF2)7CH2CH2PO3H2)白色晶体,熔点为170-178℃。
制备CF3(CF2)3CH2CH2PO3H2
将37.4克1-碘-1H,1H,2H,2H-全氟己烷和50.0克亚磷酸三乙酯的混合物于150℃加热。16个小时之后,加入额外的50.0克亚磷酸三乙酯,继续加热。2小时之后,再加入额外的50.0克亚磷酸三乙酯,继续再加热24小时。用12英寸(30cm)真空夹套填充柱蒸馏除去乙膦酸二乙酯和其它挥发物,0.05乇(7Pa)的沸点为34-38℃。蒸馏浓缩物,得到22.3克90∶2∶7的1-二乙基膦酰基-1H,1H,2H,2H-全氟己烷、磷酸三乙酯和乙膦酸乙酯·1H,1H,2H,2H-全氟己基酯的混合物,是透明无色液体,0.05乇(7Pa)的沸点为47-51℃。
向15.37克上述混合物在100毫升二氯甲烷的溶液中加入15.31克溴化三甲基硅烷。于室温24小时后,该溶液浓缩至浅黄色液体,将中间体膦酸甲硅烷基酯溶解在200毫升甲醇中。所得溶液于室温搅拌30分钟(min),然后浓缩得到白色固体。如上再溶解于甲醇中然后浓缩,再重复两次。将粗产品化合物在乙腈中重结晶,得到8.89克1-膦酰基-1H,1H,2H,2H-全氟己烷(CF3(CF2)3CH2CH2PO3H2)无色片状体,熔点为160-162℃。
制备CF3(CF2)3(CH2)6PO3H2
向187.4克全氟丁基碘和100.2克5-己烯-1-醇溶解于1.4升乙腈和0.6升水的混合溶剂的溶液中,边搅拌边分批加入100.8克碳酸氢钠和200.2克连二亚硫酸钠的混合物。于室温搅拌反应混合物过夜,用1N盐酸酸化。用二乙醚萃取混合物,用饱和的碳酸氢钠水溶液洗涤混合有机相,然后用盐水洗涤,再然后在无水硫酸镁上干燥。对溶液进行浓缩,对浓缩物进行1H NMR分析(即1H核磁共振谱),表明该浓缩物大致为3∶1的5-己烯-1-醇和5-碘-6-(九氟丁基)-1-己醇的混合物。将该浓缩物与100毫升乙酸乙酯、100.0克全氟丁基碘和0.82克2,2′-偶氮二异丁腈混合,对所得溶液脱气,并于70℃加热。24小时后,对浓缩部分的1H NMR分析表明大致是5-己烯-1-醇和5-碘-6-(九氟丁基)1-己醇的2∶1混合物。再加入50.0克全氟丁基碘和0.82克2,2′-偶氮二异丁腈,于70℃继续加热24小时。对混合物进行浓缩,得到146.1克5-碘-6-(九氟丁基)-1-己醇粗产物,其形式是与5-己烯-1-醇的大致8∶1混合物,呈橙色液体。粗产物不进行进一步提纯而直接使用。
向165.0克锌粉末在1升乙醇的浆液中加入10.0克乙酸。边搅拌边滴加上述粗产物混合物在100毫升乙醇中的溶液,持续1小时,于50℃加热反应混合物4小时。过滤该混合物,浓缩滤液。将浓缩物溶解在氯仿中,过滤溶液并浓缩得到149.0克淡黄色粘性液体。对65.0克的一部分浓缩物进行连续蒸馏球(bulb-to-bulb)蒸馏,得到18.1克6-(九氟丁基)-1-己醇的微黄色液体,0.05乇(7Pa)的沸点为130-140℃。
向18.00克6-(九氟丁基)-1-己醇和225毫升48重量%氢溴酸的混合物中缓慢加入23毫升浓硫酸。于100℃加热反应混合物12小时,倒入1升水中。用己烷萃取该混合物,然后用饱和的碳酸氢钠水溶液洗涤混合有机相,在无水硫酸镁上干燥。将己烷溶液浓缩至淡琥珀色液体,通过2英寸(5cm)二氧化硅用己烷洗脱。将洗脱液浓缩,得到淡琥珀色液体,经过连续蒸馏球蒸馏得到18.29克1-溴-6-(九氟丁基)己烷透明无色液体,0.05乇(7Pa)的沸点是70-80℃。
将18.04克1-溴-6-(九氟丁基)己烷和19.6克亚磷酸三乙酯的混合物于150℃加热。18小时后,再加入10.0克亚磷酸三乙酯,再继续加热8小时。蒸馏除去乙膦酸二乙酯和其它挥发物,0.05乇(7Pa)的沸点是30-50℃,对浓缩物进行连续蒸馏球蒸馏,得到18.88克1-(二乙基膦酰基)-6-(九氟丁基)己烷透明无色液体,0.05乇(7Pa)的沸点是120-130℃。
向18.63克1-(二乙基膦酰基)-6-(九氟丁基)己烷在100毫升二氯甲烷的溶液中加入16.8克溴化三甲基硅烷。于室温18小时后,将溶液浓缩成接近无色的液体,将中间体膦酸甲硅烷基酯溶解在250毫升甲醇中。于室温搅拌所得溶液30分钟,浓缩至得到白色固体。再溶解在甲醇中然后浓缩,重复两次,将粗产物在庚烷和2-丙醇的99∶1的混合物中两次重结晶,得到12.50克1-膦酰基-6-(九氟丁基)己烷(CF3(CF2)3(CH2)6PO3H2)无色叶状物,熔点为107-108℃。
制备CF3(CF2)3(CH2)4PO3H2
向190.3克全氟丁基碘和36.1克3-丁烯-1-醇溶解于560毫升乙腈和240毫升水的混合溶剂的溶液中,边搅拌边分批加入48.3克碳酸氢钠和95.8克连二亚硫酸钠的混合物。于室温搅拌反应混合物过夜,用1N盐酸酸化。用二乙醚萃取混合物,用饱和的碳酸氢钠水溶液洗涤混合有机相,然后用盐水洗涤,再然后在无水硫酸镁上干燥。浓缩得到38.5克橙色液体,将其溶解在50毫升乙醇中。将该溶液加入搅拌的29.42克锌粉末在400毫升乙醇的浆液中,于50℃加热4小时,然后过滤,浓缩滤液得到39.15克透明的淡橙色液体。对10.0克的一部分物料进行连续蒸馏球蒸馏,得到5.20克4-(九氟丁基)-1-丁醇的透明无色液体,0.10乇(14Pa)的沸点为105-115℃。
向12.50克4-(九氟丁基)-1-丁醇和150毫升48重量%氢溴酸的混合物中缓慢加入15毫升浓硫酸。于100℃加热反应混合物18小时,然后倒入500毫升水中。用己烷萃取该混合物,然后用饱和的碳酸氢钠水溶液洗涤混合有机相,在无水硫酸镁上干燥。过滤并浓缩,得到12.50克粗产物1-溴-4-(九氟丁基)丁烷透明淡琥珀色液体,不进行进一步纯化即使用。
将12.40克1-溴-4-(九氟丁基)丁烷和21.00克亚磷酸三乙酯的混合物于150℃加热。18小时后,蒸馏从混合物中除去乙膦酸二乙酯和其它挥发物,0.05乇(7Pa)的沸点是30-50℃,对余下的浓缩混合物进行连续蒸馏球蒸馏,得到13.0克1-(二乙基膦酰基)-4-(九氟丁基)丁烷透明无色液体,0.05乇(7Pa)的沸点是105-110℃。
向11.54克1-(二乙基膦酰基)-4-(九氟丁基)丁烷在50毫升二氯甲烷的溶液中加入10.7克溴化三甲基硅烷。于室温18小时后,将溶液浓缩成接近无色的液体,将中间体膦酸甲硅烷基酯溶解在250毫升甲醇中。于室温搅拌所得溶液1小时,浓缩至得到白色固体。再溶解在甲醇中然后浓缩,重复两次,将粗产物从乙腈中重结晶,得到8.39克1-膦酰基-4-(九氟丁基)丁烷(CF3(CF2)3(CH2)4PO3H2)无色针状物,熔点为123-124℃。
实施例1
本实施例说明制备CF3(CF2)3(CH2)8PO3H2。
向190.70克全氟丁基碘和38.47克7-辛烯-1-醇溶解于480毫升乙腈和180毫升水的混合溶剂的溶液中,边搅拌边分批加入29.40克碳酸氢钠和58.33克连二亚硫酸钠的混合物。于室温搅拌反应混合物过夜,用1N盐酸酸化。混合物用400毫升水洗涤,用3份200毫升二乙醚萃取,用2份200毫升饱和的碳酸氢钠水溶液和1份200毫升盐水洗涤混合有机相,在无水硫酸镁上干燥。浓缩得到粗产物7-碘-8-(九氟丁基)-1-辛醇淡黄色液体,不进行进一步提纯即使用。
向98.0克锌粉末在600毫升乙醇的浆液中加入3.0克乙酸。边搅拌边滴加如上制得的粗产物7-碘-8-(九氟丁基)-1-辛醇在100毫升乙醇中的溶液,持续15分钟,于50℃加热反应混合物3小时。过滤该混合物,浓缩滤液,得到100.0克淡黄色粘性液体。将79.6克的一部分物料与300毫升己烷搅拌,用硅藻土(商品名″CELITE″,Johns-Manville Corporation,Enver,Colorado)过滤上层清液,浓缩得到44.24克8-(九氟丁基)-1-辛醇透明无色油状物,不进行进一步提纯即使用。
向15.22克8-(九氟丁基)-1-辛醇和200毫升48重量%氢溴酸的混合物中缓慢加入20毫升浓硫酸。于100℃加热反应混合物18小时,倒入800毫升水中。用2份200毫升己烷萃取该混合物,然后用2份200毫升饱和的碳酸氢钠水溶液、2份200毫升3克式浓度的硫代硫酸钠水溶液和1份100毫升盐水洗涤混合有机相,然后在无水硫酸镁上干燥。该溶液被浓缩成黑色液体,通过2英寸(5cm)二氧化硅用500毫升己烷洗脱。将洗脱液浓缩,得到透明的淡黄色液体,经过连续蒸馏球蒸馏得到9.14克1-溴-8-(九氟丁基)辛烷透明淡黄色液体,0.05乇(7Pa)的沸点是105-110℃。
将8.24克1-溴-8-(九氟丁基)辛烷和8.31克亚磷酸三乙酯的混合物于150℃加热。15小时后,再加入4.30克亚磷酸三乙酯,继续加热4小时。蒸馏除去乙膦酸二乙酯和其它挥发物,0.05乇(7Pa)的沸点是30-50℃,对浓缩物进行连续蒸馏球蒸馏,得到8.72克1-(二乙基膦酰基)-8-(九氟丁基)辛烷透明无色液体,0.08乇(11Pa)的沸点是115-125℃。
向7.03克1-(二乙基膦酰基)-8-(九氟丁基)辛烷在30毫升二氯甲烷的溶液中加入6.12克溴化三甲基硅烷。于室温18小时后,将溶液浓缩成浅黄色液体,将中间体膦酸甲硅烷基酯溶解在150毫升甲醇中。于室温搅拌所得溶液30分钟,浓缩至得到白色固体。再溶解在甲醇中然后浓缩,重复两次,将粗产物从乙腈中两次重结晶,得到4.68克1-膦酰基-8-(九氟丁基)辛烷(CF3(CF2)3(CH2)8PO3H2)白色晶体,熔点为87-89℃。
实施例2
本实施例说明制备CF3(CF2)3(CH2)11PO3H2。
向199.7克全氟丁基碘和93.7克10-十一碳烯-1-醇溶解于700毫升乙腈和300毫升水的混合溶剂的溶液中,边搅拌边分小批加入53.8克碳酸氢钠和106.2克连二亚硫酸钠的混合物。于室温搅拌反应混合物过夜,用1N盐酸酸化。混合物用二乙醚萃取,然后用饱和的碳酸氢钠水溶液和盐水依次洗涤混合有机相,再在无水硫酸镁上干燥。浓缩醚溶液,得到234.4克粗产物10-碘-11-(九氟丁基)-1-十一烷醇的淡琥珀色粘性液体,不进行进一步提纯即使用。
向130.0克锌粉末在500毫升乙醇的浆液中加入5.0克乙酸。边搅拌边滴加230.0克如上制得的粗产物10-碘-11-(九氟丁基)-1-十一烷醇在100毫升乙醇中的溶液,持续1小时。然后,于50℃加热反应混合物4小时。过滤该混合物,浓缩滤液,得到淡黄色粘性液体。将液体以7份进行连续蒸馏球蒸馏,得到97.3克11-(九氟丁基)-1-十一烷醇无色固体,0.05乇(7Pa)的沸点是160-200℃。
向19.52克11-(九氟丁基)-1-十一烷醇和200毫升48重量%氢溴酸的混合物中缓慢加入20毫升浓硫酸。于100℃加热反应混合物24小时,倒入1升水中。用己烷萃取该混合物,然后用饱和的碳酸氢钠水溶液洗涤混合有机相,再在无水硫酸镁上干燥。该溶液被浓缩成琥珀色液体,通过3英寸二氧化硅用己烷洗脱。将洗脱液浓缩,得到淡琥珀色液体,经过连续蒸馏球蒸馏得到19.82克1-溴-11-(九氟丁基)十一烷透明无色液体,0.06乇(8Pa)的沸点是120-170℃。
将15.03克1-溴-11-(九氟丁基)十一烷和15.00克亚磷酸三乙酯的混合物于150℃加热。18小时后,再加入9.00克亚磷酸三乙酯,继续加热24小时。蒸馏除去乙膦酸二乙酯和其它挥发物,0.05乇(7Pa)的沸点是30-50℃,对浓缩物进行连续蒸馏球蒸馏,得到16.07克1-(二乙基膦酰基)-11-(九氟丁基)十一烷透明无色液体,0.05乇(7Pa)的沸点是170-200℃。
向15.23克1-(二乙基膦酰基)-11-(九氟丁基)十一烷在40毫升二氯甲烷的溶液中加入11.50克溴化三甲基硅烷。于室温24小时后,将溶液浓缩成浅黄色液体,将中间体膦酸甲硅烷基酯溶解在200毫升甲醇中。于室温搅拌所得溶液30分钟,浓缩至得到白色固体。再溶解在甲醇中然后浓缩,重复两次,将粗产物从庚烷中两次重结晶,得到10.85克1-膦酰基-11-(九氟丁基)十一烷(CF3(CF2)3(CH2)11PO3H2)无色片状物,熔点为93-96℃。
实施例3
本实施例说明制备CF3(CF2)7(CH2)11PO3H2。
向41.10克全氟辛基碘和11.92克10-十一碳烯-1-醇溶解于100毫升乙腈和40毫升水的混合溶剂的溶液中,边搅拌边分小批加入6.89克碳酸氢钠和13.58克连二亚硫酸钠的混合物。于室温搅拌反应混合物过夜,用1N盐酸酸化。混合物用二乙醚萃取,然后用饱和的碳酸氢钠水溶液和盐水洗涤混合有机相,再在无水硫酸镁上干燥。浓缩得到43.2克粗产物10-碘-11-(十七氟辛基)-1-十一烷醇白色固体,不进行进一步提纯即使用。
向19.6克锌粉末在150毫升乙醇的浆液中加入4.0克乙酸。边搅拌边滴加如上制得的粗产物10-碘-11-(十七氟辛基)-1-十一烷醇在50毫升乙醇中的溶液,持续1小时。然后,于50℃加热反应混合物4小时。过滤该混合物,浓缩滤液,得到大约45克柔软的白色固体,即粗产物11-(十七氟辛基)-1-十一烷醇,不进行进一步提纯即使用。
向29.0克11-(十七氟辛基)-1-十一烷醇粗产物和250毫升48重量%氢溴酸的混合物中缓慢加入25毫升浓硫酸。于100℃加热反应混合物18小时,倒入1升水中。用己烷萃取该混合物,然后用饱和的碳酸氢钠水溶液洗涤混合有机相,再在无水硫酸镁上干燥。该溶液被浓缩成黑色液体,通过3英寸二氧化硅用己烷洗脱。将洗脱液浓缩,得到20.2克粗产物1-溴-11-(十七氟辛基)十一烷接近白色的固体,不进行进一步提纯即使用。
将5.23克1-溴-11-(十七氟辛基)十一烷和4.2克亚磷酸三乙酯的混合物于150℃加热。18小时后,从反应混合物中蒸馏出乙膦酸二乙酯和其它挥发物,0.05乇(7Pa)的沸点是30-50℃。将浓缩物与额外的2.0克亚磷酸三乙酯混合,于150℃加热混合物。3小时之后,再此蒸馏出挥发物,将粗产物1-(二乙基膦酰基)-11-(十七氟辛基)十一烷溶解在10毫升二氯甲烷中。向该溶液中加入3.1克溴化三甲基硅烷。于室温18小时后,将溶液浓缩成接近无色的液体,将中间体膦酸甲硅烷基酯溶解在200毫升甲醇中。于室温搅拌所得溶液3小时,冷却至0℃。过滤收集粗产物,从甲醇中重结晶得到2.32克1-膦酰基-11-(十七氟辛基)十一烷(CF3(CF2)7(CH2)11PO3H2)白色晶体,熔点为115-117℃。
实施例4
本实施例说明制备CF3(CF2)3(CH2)22PO3H2。
边搅拌边将5.08克21-二十二烯酸在50毫升四氢呋喃中的溶液滴加入0℃的0.90克氢化铝锂在100毫升四氢呋喃中的浆液。于室温搅拌反应混合物过夜。
通过加入5毫升乙酸乙酯接着加入30毫升2N碳酸氢钠水溶液来使过量的氢化铝锂淬火。分离出白色粘性物质-锂盐,将上层清液转移至分液漏斗中。用两份50毫升的二乙醚萃取沉淀的盐,用100毫升水洗涤混合有机溶液。将浑浊的水相用1N盐酸水溶液进行酸化,再用两份50毫升二乙醚进行萃取。用盐水洗涤混合有机相,在无水硫酸镁上干燥。过滤并浓缩,得到4.40克21-二十二碳烯-1-醇白色固体,熔点为62-64℃,不进行进一步提纯即使用。
将4.00克21-二十二碳烯-1-醇、10.0克全氟丁基碘和0.10克2,2′-偶氮二异丁腈的混合物脱气,于70℃在氮气气氛下加热18小时。浓缩该混合物得到浅棕褐色固体,将其溶解在20毫升乙醇中。将该溶液加入搅拌的5.0克锌粉在含10滴乙酸的50毫升乙醇的浆液中。于50℃加热该混合物3小时,然后过滤。浓缩滤液得到白色固体。将粗产物从庚烷中重结晶,得到6.96克米白色固体。通过在二氧化硅上的柱色谱法进行进一步提纯,用1∶1的己烷和二乙醚的混合溶剂进行洗脱,得到1.73克白色固体。该产物的1H NMR谱表明,它是22-(九氟丁基)-1-二十二烷醇和22-(九氟丁基)-21-二十二碳烯-1-醇大致9∶1的混合物。将该产物溶解在己烷和乙醇的1∶1混合溶剂中,加入100毫克5重量%碳载钯,在帕尔氢化器上保持该混合物处于50psi(350kPa)压力的氢气中18小时。过滤并浓缩,得到1.69克22-(九氟丁基)-1-二十二烷醇白色固体,不进行进一步提纯即使用。
向1.00克22-(九氟丁基)-1-二十二烷醇和30毫升48重量%氢溴酸的混合物中缓慢加入3毫升浓硫酸。于100℃加热反应混合物24小时。将该混合物冷却至室温,过滤收集固体产物,溶解在己烷中。用己烷萃取滤液一次,用饱和的碳酸氢钠水溶液和盐水洗涤混合有机相,再在无水硫酸镁上干燥。过滤并浓缩,得到1.03克1-溴-22-(九氟丁基)二十二烷米白色固体,不进行进一步提纯即使用。
将0.98克1-溴-22-(九氟丁基)二十二烷和4.00克亚磷酸三乙酯的混合物于150℃加热。18小时后,蒸馏出乙膦酸二乙酯和其它挥发物,0.05乇(7Pa)的沸点是30-50℃,留下1.09克1-(二乙基膦酰基)-22-(九氟丁基)二十二烷米白色固体,不进行进一步提纯即使用。
向1.05克1-(二乙基膦酰基)-22-(九氟丁基)二十二烷在10毫升二氯甲烷的溶液中加入0.61克溴化三甲基硅烷。于室温18小时后,将溶液浓缩成米色油脂,向其中加入30毫升甲醇,形成白色固体。所得混合物于室温搅拌30分钟。减压除去溶剂,留下白色固体,用另外20毫升甲醇将该固体浆液化30分钟。再次除去溶剂,留下白色固体,将粗产物从甲醇中重结晶,得到0.61克1-膦酰基-22-(九氟丁基)二十二烷(CF3(CF2)3(CH2)22PO3H2)白色晶体,熔点为106-108℃。
实施例5
本实施例说明在基材上自装配膜的制备和检测。
涂有真空淀积的500纳米厚铬、铝、铜和镍膜的直径为4英寸的硅晶片得自WaferNet,San Jose,California。这些晶片被切割成四分之一份,各小片在一个装置中处于紫外线和臭氧中5分钟,该装置是将一个紫外线灯(5英寸×5英寸见方(12.5cm×12.5cm)紫外线灯,商品名为″UV GRID LAMP″,得自BHK,Claremont,California,型号88-9102-02)装入一个金属片小盒(13cm宽×14cm深×15cm高),以使得该紫外线灯悬挂于盒子底部上方8cm处。用一个小型的实验室千斤顶将待清洁的各小片硅片放置在尽可能靠近紫外线灯但又不与其物理接触的位置。盒子前方是扇门,在顶部装以铰链,以便插入和取出样品。在盒子的一面上有一个小孔,该孔与氧气源连接,氧气以大约1-5标准升/分钟的流量流入盒子内。
对经紫外线灯/臭氧清洁的涂有铜、镍和铝的硅晶片的四分之一小片如下进行涂覆:将这些小片浸入示出的氟化膦酸在变性乙醇中的0.1重量%溶液1小时,然后在新鲜的无水乙醇中漂洗,在氮气气流下干燥。用得自AST Products,Billerica,Massachusetts的商品名为″VCA-2500XE″的视频接触角分析仪测量经涂覆晶片样品涂有金属那面上对于水和十六烷的静止接触角、前进接触角和后退接触角。
对经紫外线/臭氧清洁的涂有铬的硅晶片的四分之一小片如下进行涂覆:用示出的氟化膦酸在变性乙醇中的0.1重量%溶液对晶片进行旋涂(即以300转/秒涂覆5秒,然后再以2000转/分钟涂覆15秒),于150℃在真空热板上加热经涂覆的晶片3分钟,然后在新鲜的无水乙醇中漂洗,在氮气气流下干燥。
用5微升液滴测量水的静止接触角,用1-2微升液滴测量前进接触角和后退接触角。下表1-4中报道的接触角测量值表示至少三滴液滴在相背两面上的测量平均值。接触角测量值的偏差,对于静止测量值和前进测量值用+/-1度来估计,对于后退测量值用+/-2度来估计。去离子水(电阻≥18.2兆欧)和无水十六烷用于接触角测量。结果示于下表1-4。
表1报道了涂铬的硅片上水和十六烷的接触角测量值。
表1
涂铬的硅片上的接触角 | ||
材料 | 水静止/前进/后退(度/度/度) | 十六烷前进/后退(度/度) |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>2</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 120/132/90 | 68/28 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>7</sub>(CH<sub>2</sub>)<sub>2</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 126/137/101 | 81/43 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>4</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 124/131/92 | 70/30 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>6</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 128/135/95 | 78/34 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>8</sub>PO<sub>3</sub>H<sub>2</sub> | 126/135/96 | 76/38 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>11</sub>PO<sub>3</sub>H<sub>2</sub> | 132/139/99 | 81/41 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>22</sub>PO<sub>3</sub>H<sub>2</sub> | 132/143/109 | 85/50 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>7</sub>(CH<sub>2</sub>)<sub>11</sub>PO<sub>3</sub>H<sub>2</sub> | 135/143/112 | 90/54 |
表2报道了涂铝的硅片上水和十六烷的接触角测量值。
表2
涂铝的硅片上的接触角 | ||
材料 | 水静止/前进/后退(度/度/度) | 十六烷前进/后退(度/度) |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>2</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 103/108/79 | 64/44 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>7</sub>(CH<sub>2</sub>)<sub>2</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 114/119/108 | 75/58 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>4</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 106/114/92 | 68/46 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>6</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 110/116/100 | 69/52 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>8</sub>PO<sub>3</sub>H<sub>2</sub> | 111/118/109 | 73/53 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>11</sub>PO<sub>3</sub>H<sub>2</sub> | 114/120/110 | 73/56 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>22</sub>PO<sub>3</sub>H<sub>2</sub> | 120/123/116 | 74/63 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>7</sub>(CH<sub>2</sub>)<sub>11</sub>PO<sub>3</sub>H<sub>2</sub> | 122/125/118 | 80/70 |
表3报道了涂铜的硅片上水和十六烷的接触角测量值。
表3
涂铜的硅片上的接触角 | ||
材料 | 水静止/前进/后退(度/度/度) | 十六烷前进/后退(度/度) |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>2</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 103/111/83 | 67/42 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>7</sub>(CH<sub>2</sub>)<sub>2</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 115/119/106 | 76/54 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>4</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 103/111/93 | 69/34 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>6</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 104/114/93 | 71/37 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>8</sub>PO<sub>3</sub>H<sub>2</sub> | 109/117/102 | 72/49 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>11</sub>PO<sub>3</sub>H<sub>2</sub> | 112/116/100 | 73/53 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>22</sub>PO<sub>3</sub>H<sub>2</sub> | 117/119/108 | 74/58 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>7</sub>(CH<sub>2</sub>)<sub>11</sub>PO<sub>3</sub>H<sub>2</sub> | 115/121/105 | 79/64 |
表4报道了涂镍的硅片上水和十六烷的接触角测量值。
表4
涂镍的硅片上的接触角 | ||
材料 | 水静止/前进/后退(度/度/度) | 十六烷前进/后退(度/度) |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>2</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 93/107/32 | 62/33 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>7</sub>(CH<sub>2</sub>)<sub>2</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 118/131/95 | 78/55 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>4</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 106/120/64 | 68/40 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>6</sub>PO<sub>3</sub>H<sub>2</sub>(比较例) | 111/125/81 | 71/44 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>8</sub>PO<sub>3</sub>H<sub>2</sub> | 115/128/100 | 76/49 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>11</sub>PO<sub>3</sub>H<sub>2</sub> | 117/130/102 | 75/50 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>3</sub>(CH<sub>2</sub>)<sub>22</sub>PO<sub>3</sub>H<sub>2</sub> | 123/135/110 | 78/50 |
CF<sub>3</sub>(CF<sub>2</sub>)<sub>7</sub>(CH<sub>2</sub>)<sub>11</sub>PO<sub>3</sub>H<sub>2</sub> | 126/136/111 | 85/57 |
Claims (12)
2.如权利要求1所述的氟化膦酸化合物,其特征在于,R3或M的至少一个是氢。
3.如权利要求1所述的氟化膦酸化合物,其特征在于,R1是含10-21个碳原子的直链亚烷基。
4.如权利要求1所述的氟化膦酸化合物,其特征在于,R1是癸烷-1,10-二基或二十一烷-1,21-二基。
5.如权利要求1所述的氟化膦酸化合物,其特征在于,R2是全氟正丁基。
6.如权利要求1所述的氟化膦酸化合物,其特征在于,M是氢或碱金属阳离子,R1是癸烷-1,10-二基或二十一烷-1,21-二基,R2是全氟正丁基。
7.一种处理制品表面的方法,该方法包括:
提供具有表面的基材;
向所述基材的所述表面施用权利要求1-5中任一项的氟化膦酸化合物。
8.如权利要求7所述的方法,其特征在于,所述基材是金属。
9.一种制品,它包括具有表面的基材,所述表面与权利要求1-5中任一项的氟化膦酸化合物单层的至少一部分紧密接触。
10.如权利要求9所述的制品,其特征在于,所述基材是金属。
11.一种制品,它由下述方法制得,该方法包括:
提供具有表面的基材;
向所述基材的所述表面施用权利要求1-5中任一项的氟化膦酸化合物。
12.如权利要求11所述的制品,其特征在于,所述基材是金属。
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- 2003-05-20 KR KR1020047019311A patent/KR100966660B1/ko not_active IP Right Cessation
- 2003-05-20 AU AU2003248533A patent/AU2003248533A1/en not_active Abandoned
- 2003-05-20 DE DE60322889T patent/DE60322889D1/de not_active Expired - Lifetime
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Also Published As
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JP2005528446A (ja) | 2005-09-22 |
AU2003248533A1 (en) | 2003-12-19 |
EP1509536B1 (en) | 2008-08-13 |
CA2486165A1 (en) | 2003-12-11 |
ATE404572T1 (de) | 2008-08-15 |
JP4317125B2 (ja) | 2009-08-19 |
WO2003102003A1 (en) | 2003-12-11 |
DE60322889D1 (de) | 2008-09-25 |
KR20050004254A (ko) | 2005-01-12 |
EP1509536A1 (en) | 2005-03-02 |
KR100966660B1 (ko) | 2010-06-30 |
US20030228469A1 (en) | 2003-12-11 |
CN1656108A (zh) | 2005-08-17 |
US6824882B2 (en) | 2004-11-30 |
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