CN101094859A - 包含c4-燕尾状硅烷的组合物 - Google Patents
包含c4-燕尾状硅烷的组合物 Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 86
- 150000004756 silanes Chemical class 0.000 title abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- -1 perfluoro Chemical group 0.000 claims abstract description 13
- 239000007859 condensation product Substances 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims description 26
- 229910000077 silane Inorganic materials 0.000 claims description 26
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 25
- 125000001153 fluoro group Chemical group F* 0.000 claims description 16
- 229910052799 carbon Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 238000006482 condensation reaction Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical class CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000004519 grease Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003791 organic solvent mixture Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 241000252794 Sphinx Species 0.000 description 1
- BSYQEPMUPCBSBK-UHFFFAOYSA-N [F].[SiH4] Chemical compound [F].[SiH4] BSYQEPMUPCBSBK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- PIKHSCACECSNOO-UHFFFAOYSA-N fluoro hexane-1-sulfonate Chemical compound CCCCCCS(=O)(=O)OF PIKHSCACECSNOO-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical class OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical class [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
- C04B41/4933—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing halogens, i.e. organohalogen silanes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/82—Coating or impregnation with organic materials
- C04B41/84—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Abstract
本发明公开了具有两个彼此临近的全氟烷基的全氟低级烷基衍生硅烷,其在有机溶剂中适用于处理硅质基体;该组合物在混合物或缩合产物中可任选包含另外的非氟代化合物。
Description
发明领域
本发明涉及包含两个彼此邻近的全氟低级烷基或“尾部”的新型含氟硅烷,被称为“燕尾状”硅烷。该新型硅烷可易于对硅质基体的清洁处理,所述硅质基体例如陶瓷、瓷砖、玻璃、玻璃表面等。该新型硅烷在形成具有高防油和防水性的表面方面,比相同的较小分子尾部大小的单基团或单尾部硅烷更为有效。
背景技术
含氟化合物是公知的,并已在商业上用于涂覆或为各种基体提供防油和防水性能,并为其提供其它所需的性能,例如防污性和去污性。
在GB 2,218,097、US 5,274,159、US 5,702,509和更早的US3,492,394、US 3,423,234和US 3,442,664中都描述了在含氟烷基中具有至少4个碳原子的含氟磺酰氨基硅烷。
此外,在EP 1,369,453、EP 1,225,187和EP 1,225,188中描述了用于处理硬质表面(例如玻璃或陶瓷)的、在含氟烷基中具有至少4个碳原子的含氟低聚物硅烷。
尽管许多已知的含氟组合物为基体提供了抵抗性,但仍然需要发现其它可以具有改进的初始抵抗性和/或具有改进的耐久性(即甚至在磨损条件下该抵抗性仍能维持更长时间)的组合物。
因此,需要提供一种能够在基体上提供高耐久性的防水、防油和/或防污染涂层的涂覆组合物。特别地,需要提供一种耐久性涂层,其中甚至在磨损条件下该初始的抵抗性仍能基本保持。此外,该涂覆组合物优选可以以环境友好的方式涂覆和使用,能够以可靠、方便和节约成本的方式制备。此外,该涂层在暴露于UV光时理想地具有良好的耐久性,即在暴露于UV光时其抵抗性基本不会下降。此外,特别当用该组合物处理透明基体(例如玻璃)时,理想地得到光学透明的涂层。
发明内容
一方面,本发明提供了一种含氟组合物,其包含一种或多种式I的硅烷:
RfSO2-N(R)(CnH2n)CHZ(CmH2m)N(R’)SO2Rf (I)
其中Rf各自独立地为CpF2p+1,p为2~5;
R为C1~C4烷基或芳基;
m和n都是大于0的整数;
Z是式为(Cm’H2m’)X-Q-Si(Y)3的基团,其中m’为0~4,X为O、S或NH,Q为-C(O)NH-(CH2)n’-或-(CH2)n’-,R如上限定;R’为R,或者当Z为H时R’是式为-(CH2)n’-Si(Y)3的基团;n’为1~20的整数,Y为可水解的基团。
第二方面,本发明包括一种如上所述的含氟组合物,其具有含量足以溶解和/或分散所述硅烷的有机溶剂。
本发明的第三方面提供了如上所述的含氟组合物和一种或多种式II的化合物:
M(R”)q(Y)r-q (II)
其中M选自Si、Ti、Zi、Al、V、Sn和Zn;
R”为不可水解的基团;
Y为可水解的基团,例如OR、OCOCH3或Cl;
q为0、1或2,以及
r为4、3或2。
本发明的第四方面提供了一种或多种式I硅烷和一种或多种式II化合物与其含量足以溶解和/或分散这两种组分的有机溶剂的组合。
本发明还包括将含氟组合物涂覆到基体的至少一部分表面上来处理硅质基体的方法,所述含氟组合物包含在有机溶剂中的一种或多种式I硅烷以及任选的一种或多种式II化合物。
本发明的组合物是用于硅质表面的有效率和效能的防油和防水剂,所述硅质表面例如卫生陶瓷、瓷砖和玻璃。它们提供优于单尾部全氟C4硅烷的总体性能,并提供与全氟C8硅烷相当的性能。该组合物基本不含从生物活体内缓慢排出的含氟化合物,因此相对于那些基于包含更长链全氟代基团(尾部)的结构单元材料,该组合物被认为具有环境可持续性。
很多之前已知的含氟材料都包含全氟辛基部分。这些表面活性剂最终会降解为含全氟辛基的化合物。据报道某些含全氟辛基的化合物会导致在生物活体内的生物累积;这种趋势被引作关于某些含氟化合物的一种潜在担忧。例如参见US专利5,688,884(Baker等)。因此,对有效提供所需表面活性剂性能,并更有效地从体内排出(包括该组合物及其降解产物的趋向)的含氟组合物存在需求。
本发明包含全氟丁基部分的含氟材料当暴露于环境中的生物、热、氧化、水解和光解条件时,预期其将断裂为许多降解产物。例如包含全氟丁基磺酰氨基部分的组合物预期至少某种程度上会最终降解成为全氟丁基磺酸盐。令人惊奇地发现全氟丁基磺酸盐以其钾盐测试时,比全氟己基磺酸盐更有效地从体内排出,甚至比全氟辛基磺酸盐更有效排出。
发明详述
该含氟组合物包含一种或多种式I的硅烷:
RfSO2-N(R)(CnH2n)CHZ(CmH2m)N(R’)SO2Rf (I)
其中Rf各自独立地为CpF2p+1,p为2~5;
R为C1~C4烷基或芳基;
m和n都是大于0的整数;
Z是式为(Cm’H2m’)X-Q-Si(Y)3的基团,其中m’为0~4,X为O、S或NH,Q为-C(O)NH-(CH2)n’-或-(CH2)n’-,R如上限定;R’为R,或者当Z为H时R’是式为-(CH2)n’-Si(Y)3的基团;n’为1~20的整数,Y为可水解的基团。
所述全氟烷基磺酰氨基(RfSO2N-)可以相同或不同。所述全氟烷基可以各自包含2~5个碳原子,但优选各自具有4个碳原子。
在上述式I的硅烷中,一种实施方式中m为1~6的整数,n为1~6的整数。
术语“烷基”定义为具有1~4个碳原子,包括例如甲基或乙基。
术语“芳基”是指一种芳香基团,例如未取代或者可被1个或高至5个取代基取代的苯基,该取代基例如如上所述的烷基,1~4个碳原子的烷氧基,卤素例如氟、氯、溴、碘,羟基,氨基,硝基等。卤素和烷基取代基是优选的。
在上述硅烷中,一种实施方式的R限定为独立地是-CH3或-CH2CH3。
在上述式I的硅烷中,n’也可以为1~10,在一种实施方式中可以为3。
在式I的硅烷中,可水解的基团Y可以与下述式II化合物中所限定的Y相同。
代表性的本发明的含氟化合物包括但不局限于[C4F9SO2N(CH)3CH2]2CHOCH2CH2CH2Si(OCH3)3、[C4F9SO2N(CH)3CH2]2CHOCONHCH2CH2CH2Si(OCH3)3和C4F9SO2N(CH)3CH2CH2CH2N(SO2C4F9)CH2CH2CH2Si(OCH3)3。
本发明的含氟化合物可以通过已知方法制备。例如,可以通过2摩尔的C4F9SO2NH(CH)3与1,3-二氯-2-丙醇或表氯醇在碱存在下进行反应制备[C4F9SO2N(CH)3CH2]2CHOH。可通过以ClCH2CH2CH2Si(OCH3)3或以烯丙基氯对[C4F9SO2N(CH)3CH2]2CHOH进行烷基化作用,然后以HSiCl3进行硅氢化作用和甲醇分解作用,从而制备[C4F9SO2N(CH)3CH2]2CHOCH2CH2CH2Si(OCH3)3。[C4F9SO2N(CH)3CH2]2CHOH与OCNCH2CH2CH2Si(OCH3)3进行反应得到[C4F9SO2N(CH)3CH2]2CHOCONHCH2CH2CH2Si(OCH3))3。
本发明的组合物可以包含一种或多种有机溶剂。所用的有机溶剂或有机溶剂共混物必须能够溶解一种或多种式I硅烷、以及任选的与一种或多种如下所述式II化合物的混合物。
适合的有机溶剂或溶剂混合物包括脂肪醇,例如甲醇、乙醇、异丙醇;酮类,例如丙酮或甲基乙基酮;酯类,例如乙酸乙酯、甲酸甲酯;以及醚类,例如二乙醚或二丙二醇单甲醚(DPM)。
在本发明的含氟组合物中,一种或多种式I硅烷可以与一种或多种式II的化合物相结合
M(R”)q(Y)r-q (II)
其中M选自Si、Ti、Zi、Al、V、Sn和Zn;
R”为不可水解的基团;
Y为可水解的基团;
q为0、1或2,以及
r为4、3或2。
在式I硅烷和式II化合物的组合中,该组合可以是混合物,或在所述一种或多种含氟硅烷和所述一种或多种式II的非氟代化合物进行基本完全缩合反应后可得到的缩合产物。术语“基本完全缩合反应”是指该反应是完全反应或者混合物中可水解基团的至少80%消失,优选至少90%。可以通过使用红外光谱和C13-NMR对反应的完成进行监控。
在另一方面,本发明提供一种组合物,其包含在所述一种或多种含氟低聚体和所述一种或多种非氟代化合物进行部分缩合反应后可得到的缩合产物。与本发明相关的“部分缩合”和“部分缩合物”是指混合物中一些可水解的基团发生反应,但仍保留大量的可发生缩合反应的可水解基团。通常,部分缩合物是指仍存在至少20%,优选至少30%,更优选至少50%的可水解基团用于进一步的缩合反应。
与本发明相关的术语“可水解基团”是指这样的一种基团,其能在适当条件下直接进行缩合反应,或者能在适当条件下水解而产生一种能进行缩合反应的化合物。适当条件包括酸性或碱性水溶液条件,任选地在其他缩合催化剂例如Sn化合物存在下。
可水解基团Y可以相同或不同,且通常能够在适当条件下水解,例如在酸性或碱性水溶液条件下,使得该含氟低聚物可以参与缩合反应。优选地,该可水解基团水解时产生能够进行缩合反应的基团,例如硅烷醇基。
可水解基团的实例包括卤素,例如氯、溴、碘或氟;烷氧基-OR’(其中R’表示低级烷基,优选含1~6个、更优选含1~4个碳原子,可以任选地被一个或多个卤素原子取代);酰氧基-O(CO)-R”(其中R”表示低级烷基,优选含1~6个、更优选含1~4个碳原子,可以任选地被一个或多个卤素原子取代);芳氧基-OR(其中R表示芳基部分,优选含6-12个、更优选含6-10个碳原子,可以任选地被一个或多个取代基取代,该取代基独立地选自卤素以及可任选被一个或多个卤素原子取代的C1~C4烷基)。在上式中,R’、R”、R可以包括直链、支链和/或环状结构。可水解基团的特别实例包括甲氧基、乙氧基和丙氧基、氯。
不可水解基团R”可以相同或不同,通常在缩合反应条件下不能水解,所述条件例如可水解基团进行水解的酸性或碱性水溶液条件。不可水解基团R”可以独立地为烃基,例如烷基、优选为以上对R限定的1~4个碳原子的烷基,或以上对R所限定的芳基。
式(II)化合物的代表性实例包括四甲氧基硅烷、四乙氧基硅烷(TEOS)、甲基三乙氧基硅烷(MTEOS)、二甲基二乙氧基硅烷(DDS)、四乙基己基钛酸酯等。
式I硅烷和式II化合物的组合或缩合产物也可以包含如上所限定的其含量足以溶解该化合物的有机溶剂。
式(I)与(II)化合物的重量比为约100∶0~1∶99;优选的比例为50∶50~10∶90。
当式I硅烷和式II化合物的组合是缩合产物时,该反应产物可以通过各组分与任选的交联剂发生反应而制得。通常,该反应产物是部分缩合物,或者所形成的是基本完全缩合产物。
缩聚反应通常是在足以使可水解基团实现水解反应的量的水存在下,在有机溶剂中优选在室温下,将各起始组分进行混合而便利地进行的。优选地,水的量为总组合物的0.1~20重量%,更有选为1~10重量%。除水之外,应当优选使用有机或无机酸或碱催化剂。
有机酸催化剂包括乙酸、柠檬酸、甲酸、三氟甲磺酸、全氟丁酸等。无机酸的实例包括硫酸、盐酸等。适用的碱催化剂的实例包括氢氧化钠、氢氧化钾、氟化钠、氟化钾和三乙胺。酸或碱催化剂的用量通常为总组合物的0.01~10重量%,更优选为0.05~5重量%。
通常在基体上涂覆本发明的包含组分(a)、(b)和任选的交联剂和/或其部分或完全缩聚产物的组合物,其涂覆量足以形成防水和防油涂层。该涂层可以非常薄,例如1~50分子层,尽管在实际中有用的涂层可能会更厚。
可用本发明包括含氟缩合混合物的含氟组合物以特别有效的方式处理的基体包括具有硬质表面的基体,其优选具有能够与氟化的缩合物进行反应的基团。特别优选的基体包括陶瓷和玻璃。本发明的含氟组合物可以有效地处理各种制品,在其上提供防水和防油涂层。其实例包括瓷砖、浴缸或马桶、玻璃淋浴板、建筑玻璃、汽车的各种部件(例如镜子或挡风玻璃)、玻璃以及陶瓷或瓷釉陶器材料。
基体的处理会使处理过的表面对污染物具有更差的保留性以及更快速的清洁性,这是由处理过的表面的防水和防油性质所引起。不论是长期暴露或使用以及重复清洁,这些所需的性质仍能保持,因为通过本发明的组合物可以得到具有高耐久程度的处理表面。
为对基体进行有效处理,将该含氟组合物优选以如上所述的溶剂组合物的形式涂覆到基体上。涂覆到基体上的含氟组合物的量通常为足以形成防水和防油涂层的量,这种涂层在20℃时与蒸馏水的接触角至少为80℃,与正十六烷的接触角至少为40℃,上述是在涂层干燥和固化之后测定的。
优选地,该基体在用本发明的组合物涂覆之前应当是清洁的,以得到最佳的性质,特别是耐久性。也就是说,待涂覆的基体表面应当在涂覆之前基本不含有机污染物。清洁技术取决于基体的类型,包括例如用有机溶剂如丙酮或乙醇进行的溶剂清洗步骤。
根据一种优选的实施方式,涂覆到基体上的组合物是通过将包含至少25wt.%固体在有机溶剂中的溶液的浓缩物进行稀释而制备的,所述稀释通过将有机溶剂或溶剂混合物添加到该浓缩物中而实现。
各种大量的涂覆方法都可以用于涂覆本发明的组合物,例如刷涂、喷涂、浸涂、辊涂、铺展涂覆等。优选的用于涂覆含氟组合物的涂覆方法包括喷涂。通常可将待涂覆的基体与处理组合物在室温下(通常为约20℃~约25℃)接触。可选择地,该混合物可以涂覆到预先加热到例如60℃~150℃的温度下的基体上。在工业制造中对这种情况特别感兴趣,例如在生产线末端的烘箱之后立即对瓷砖进行处理。在涂覆之后,可以将处理过的基体在环境温度或升高温度(例如40℃~300℃)下进行干燥和固化足以使其干燥和固化的时间。可选择地,除了热处理,可以根据各引发器的类型和存在、通过已知方式使用辐照(例如使用UV照射器、激光等)对涂覆组合物进行固化。该方法也可需要抛光步骤来除去过剩的材料。
实施例
除非特别指出,在实施例和说明书其他部分的所有部分、百分比、比例等都以重量计,实施例中所用的所有试剂都获自或可获自普通的化学品供应商,例如Sigma-Aldrich Company,Milwaukee,Wisconsin,或者可以通过常规方法合成。
制备[C4F9SO2N(CH)3CH2]2CHOH
在装备有搅拌器、加热套、冷凝器、氮气进口、Dean-Stark分水器和温度计的三颈圆底1000mL烧瓶中,添加根据US专利6,664,354
(该专利被引入此处作为参考)中实施例1的A部分制备的C4F9SO2N(CH3)H(313.0g;1摩尔)、二甲基甲酰胺(100.0g)和庚烷(40.0g)。并在回流下加热该混合物以进行干燥。在氮气吹洗下将该混合物冷却到约30℃,添加NaOCH3(30%甲醇溶液;180.0g1摩尔)。将该混合物在50℃加热1小时,在真空下从吸气器中汽提除去甲醇。在烧瓶中添加1,3-二氯-2-丙醇(65.0g;0.5摩尔),升高温度至80℃,保持过夜。用DI水(300mL,80℃)对随后的混合物清洗三次,分离剩余的有机层,在炉中在120℃干燥1小时。对所得到的黄褐色固体的分析符合[C4F9SO2N(CH3)CH2]2CHOH。
制备FC-1:[C4F9SO2N(CH3)CH2]2CHOC(O)NH(CH2)3Si(OCH2CH3)3
在装备有搅拌器、加热套、冷凝器、氮气进口、Dean-Stark分水器和温度计的三颈圆底500mL烧瓶中,添加[C4F9SO2N(CH3)CH2]2CHOH(204.6g;0.3摩尔)和甲基乙基酮(250.0g;可获自Sigma-Aldrich,Milwaukee,WI)。将该混合物加热,使用Dean-Stark分水器去除约50g材料。将该混合物冷却到30℃,添加OCN(CH2)3Si(OCH2CH3)3(74.4g)和3滴醋酸锡(stannous actuate)。将该混合物在氮气中加热到75℃,持续16小时。结果产生一种清澈的淡黄色产品。对该产品的分析符合[C4F9SO2N(CH3)CH2]2CHOC(O)NH(CH2)3Si(OCH2CH3)3。
制备FC-2:[C4F9SO2N(CH3)CH2]2CHO(CH2)3Si(OCH2CH3)3
在装备有搅拌器、加热套、冷凝器、氮气进口、Dean-Stark分水器和温度计的三颈圆底500mL烧瓶中,添加[C4F9SO2N(CH3)CH2]2CHOH(204.6g;0.3摩尔)和二甲基甲酰胺(100.0g;可获自Sigma-Aldrich,Milwaukee,WI)和庚烷(40.0g)。将该混合物在真空抽吸下加热到100℃,使用Dean-Stark分水器除去庚烷。添加NaOCH3(54.0g;0.3摩尔;30%甲醇溶液),将得到的混合物在氮气中在50℃加热1小时。使用旋转式蒸发器汽提除去甲醇,添加ClCH2CH2CH2Si(OCH3)3(59.4g)。在氮气中将该混合物加热至75℃,保持过夜。将得到的混合物进行过滤,使用旋转式蒸发器汽提除去溶剂。在180~200℃下(在0.1mm Hg(13.3Pa))将该混合物进一步蒸馏,产生一种黄色粘性液体。对该液体的分析符合结构[C4F9SO2N(CH3)CH2]2CHO(CH2)3Si(OCH3)3。
制备测试溶液
通过将1.0g表1中列出的组合物与37%HCl(1.0g)和乙醇(98.0g)混合,制备实施例1~7和对比例C-1的测试溶液。
涂覆测试溶液
在室温下,以约40mL/分钟的速率将测试溶液喷涂到预先清洁过的白色卫生间瓷砖(可获自Sphinx,Maastricht,Netherlands)上。
接触角测量
使用Olympus TGHM测角器(Olympus Corp,Pompano Beach F1),测试处理过的基体与水和正十六烷的静态接触角。除非特别指出,在磨损之前(“初始”)、磨损之后立即(“磨损后”)和暴露于18%HCl中16小时后(“HCl处理后”),测量静态接触角。报道值为4次测量的平均值,以度为单位(表2)。
表1实施例1~7和对比例C-1的组合物
实施例号 | FC-1(g) | FC-2(g) | TEOS(g) | MTEOS(g) | DDS(g) | FC-3*(g) |
1 | 1.0 | --- | --- | --- | --- | --- |
2 | --- | 1.0 | --- | --- | --- | --- |
3 | 0.5 | --- | 0.5 | --- | --- | --- |
4 | 0.10 | --- | 0.9 | --- | --- | --- |
5 | 0.10 | --- | 0.45 | 0.45 | --- | --- |
6 | 0.10 | --- | 0.45 | --- | 0.45 | --- |
7 | --- | 0.10 | 0.90 | --- | --- | --- |
C-1 | --- | --- | --- | --- | --- | 1.0 |
---表示未添加
FC-3为C8F17SO2N(CH2CH3)CH2CH2CH2Si(OCH2CH3)3
表2实施例1~7和对比例C-1与水/十六烷的接触角(°)
实施例号 | 接触角水/十六烷(°) | ||
初始 | 磨损后 | HCl处理后 | |
1 | 108/68 | 78/53 | 99/62 |
2 | 98/66 | 72/52 | 95/60 |
3 | 105/64 | 76/53 | 95/64 |
4 | 110/67 | 80/52 | 95/60 |
5 | 108/63 | 82/50 | 98/60 |
6 | 112/61 | 75/50 | 95/55 |
7 | 105/64 | 78/54 | 92/59 |
C-1 | 105/64 | 78/46 | 95/58 |
上述说明书、实施例和数据提供了制备和使用本发明的组合物的完整描述。由于可以在不脱离本发明的精神和范围内作出本发明的很多实施方式,因此本发明在于后附的权利要求。
Claims (23)
1.一种含氟组合物,其包含:
一种或多种下式的硅烷:
RfSO2-N(R)(CnH2n)CHZ(CmH2m)N(R’)SO2Rf (I)
其中Rf各自独立地为CpF2p+1,p为2~5;
R为C1~C4烷基或芳基;
m和n都是大于0的整数;
Z是式为(Cm’H2m’)X-Q-Si(Y)3的基团,其中m’为0~4,X为O、S或NH,Q为-C(O)NH-(CH2)n’-或-(CH2)n’-,R如上限定;R’为R,或者当Z为H时R’是式为-(CH2)n’-Si(Y)3的基团;n’为1~20的整数,Y为可水解的基团。
2.根据权利要求1的组合物,其中p为4;m为1~6,n为1~6。
3.根据权利要求2的组合物,其中Z为-O-Q-Si(Y)3,其中Y独立地为-Cl或C1-C4烷氧基。
4.根据权利要求3的组合物,其中Q为-(CH2)n’-,其中n’为1~10。
5.根据权利要求3的组合物,其中Q为-C(O)NH(CH2)n’-,其中n’为1~10。
6.根据权利要求2的组合物,其中Z为氢,R’为-(CH2)n’-Si(Y),其中Y独立地为-Cl或C1-C4烷氧基。
7.根据权利要求2的组合物,其中R为-CH3或-CH2CH3。
8.根据权利要求2的组合物,其中n和m之和为2;X为O,Q为-C(O)NH-(CH2)3-。
9.根据权利要求1的组合物,其包含一种或多种如下式的硅烷:
[C4F9SO2N(CH)3CH2]2CHOCH2CH2CH2Si(OCH3)3、[C4F9SO2N(CH)3CH2]2CHOCONHCH2CH2CH2Si(OCH3)3和C4F9SO2N(CH)3CH2CH2CH2N(SO2C4F9)CH2CH2CH2Si(OCH3)3。
10.根据权利要求1的组合物,其进一步包含有机溶剂。
11.根据权利要求10的组合物,其中所述溶剂为醇类、醚类、酮类或酯类,或其混合物。
12.根据权利要求1的组合物,其进一步包含一种或多种如下式的化合物:
M(R”)q(Y)r-q (II)
其中M选自Si、Ti、Zi、Al、V、Sn和Zn;
R”为不可水解的基团;
Y为可水解的基团;
q为0、1或2,以及
r为4、3或2。
13.根据权利要求12的组合物,其中R”为R。
14.根据权利要求12的组合物,其中Y独立地为-Cl或C1-C4烷氧基。
15.根据权利要求12的组合物,其中M为Si;R”为-CH3或-CH2CH3;以及Y独立地为-Cl、-OCH3或-OCH2CH3。
16.根据权利要求12的组合物,其中式II的化合物为四甲氧基硅烷、四乙氧基硅烷、甲基三乙氧基硅烷、二甲基二乙氧基硅烷或四乙基己基钛酸酯。
17.根据权利要求12的组合物,其中化合物I与II的重量比为约100∶0~约1∶99。
18.根据权利要求12的组合物,其中化合物I与II的重量比为约50∶50~约10∶90。
19.一种含氟组合物,其包含:
(a)一种或多种如下式的硅烷:
RfSO2-N(R)(CnH2n)CHZ(CmH2m)N(R’)SO2Rf (I)
其中Rf各自独立地为CpF2p+1,p为2~5;
R为C1~C4烷基或芳基;
m和n都是大于0的整数;
Z是式为(Cm’H2m’)X-Q-Si(Y)3的基团,其中m’为0~4,X为O、S或NH,Q为-C(O)NH-(CH2)n’-或-(CH2)n’-,R如上限定;R’为R,或者当Z为H时R’是式为-(CH2)n’-Si(Y)3的基团;n’为1~20的整数,Y为可水解的基团;
(b)一种或多种如下式的化合物:
M(R”)q(Y)r-q (II)
其中M选自Si、Ti、Fi、Al、V、Sn和Zn;
R”为R;
Y独立地为-Cl或C1-C4烷氧基;
q为0、1或2,以及
r为4、3或2;以及
(c)有机溶剂。
20.根据权利要求19的组合物,其中p为4。
21.根据权利要求19的组合物,其包含组分(a)和(b)的缩合产物。
22.一种处理硅质基体的方法,包括将根据权利要求10的组合物涂覆到所述基体上。
23.一种处理硅质基体的方法,包括将根据权利要求22的组合物涂覆到所述基体上。
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US11/027,404 | 2004-12-30 | ||
US11/027,404 US7495118B2 (en) | 2004-12-30 | 2004-12-30 | Compositions containing C4-swallow tail silanes |
PCT/US2005/045326 WO2006073718A1 (en) | 2004-12-30 | 2005-12-15 | Compositions containing c4-swallow tail silanes |
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CN101094859B CN101094859B (zh) | 2010-09-29 |
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EP (1) | EP1831234B1 (zh) |
JP (1) | JP4988598B2 (zh) |
CN (1) | CN101094859B (zh) |
AT (1) | ATE524480T1 (zh) |
CA (1) | CA2592284A1 (zh) |
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-
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CA2592284A1 (en) | 2006-07-13 |
EP1831234A1 (en) | 2007-09-12 |
ATE524480T1 (de) | 2011-09-15 |
US20060147645A1 (en) | 2006-07-06 |
US7495118B2 (en) | 2009-02-24 |
WO2006073718A1 (en) | 2006-07-13 |
JP2008527079A (ja) | 2008-07-24 |
JP4988598B2 (ja) | 2012-08-01 |
EP1831234B1 (en) | 2011-09-14 |
CN101094859B (zh) | 2010-09-29 |
RU2007123147A (ru) | 2009-02-10 |
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