WO2016052262A1 - 含フッ素アルキルシラン化合物およびその製造法 - Google Patents
含フッ素アルキルシラン化合物およびその製造法 Download PDFInfo
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- WO2016052262A1 WO2016052262A1 PCT/JP2015/076699 JP2015076699W WO2016052262A1 WO 2016052262 A1 WO2016052262 A1 WO 2016052262A1 JP 2015076699 W JP2015076699 W JP 2015076699W WO 2016052262 A1 WO2016052262 A1 WO 2016052262A1
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- integer
- reaction
- fluorine
- compound
- fluorinated alkyl
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- -1 alkyl silane compound Chemical class 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 150000003624 transition metals Chemical class 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 6
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 229910052731 fluorine Inorganic materials 0.000 claims description 20
- 239000011737 fluorine Substances 0.000 claims description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 239000004480 active ingredient Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000012756 surface treatment agent Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 229910052740 iodine Inorganic materials 0.000 abstract description 5
- 239000011630 iodine Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 3
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 abstract 1
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 4
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- 239000005052 trichlorosilane Substances 0.000 description 3
- 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
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 231100000693 bioaccumulation Toxicity 0.000 description 2
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- PVCVRLMCLUQGBT-UHFFFAOYSA-N (1-tert-butylcyclohexyl) (1-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CCCCC1(C(C)(C)C)OC(=O)OOC(=O)OC1(C(C)(C)C)CCCCC1 PVCVRLMCLUQGBT-UHFFFAOYSA-N 0.000 description 1
- CJVROGOPKLYNSX-UHFFFAOYSA-N (4-tert-butylcyclohexyl) carboxyoxy carbonate Chemical compound CC(C)(C)C1CCC(OC(=O)OOC(O)=O)CC1 CJVROGOPKLYNSX-UHFFFAOYSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- CSUFEOXMCRPQBB-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropan-1-ol Chemical compound CC(F)(F)C(O)(F)F CSUFEOXMCRPQBB-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- HIILRBRZMJQLRP-UHFFFAOYSA-N 2-ethoxyhexoxycarbonyloxy 2-ethoxyhexyl carbonate Chemical compound CCCCC(OCC)COC(=O)OOC(=O)OCC(OCC)CCCC HIILRBRZMJQLRP-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- FBQZJBMRDNLFQO-UWVGGRQHSA-N bis[(3S)-3-methoxybutyl] ethanediperoxoate Chemical compound CO[C@@H](C)CCOOC(=O)C(=O)OOCC[C@H](C)OC FBQZJBMRDNLFQO-UWVGGRQHSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 238000005831 deiodination reaction Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- DQEUYIQDSMINEY-UHFFFAOYSA-M magnesium;prop-1-ene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C=C DQEUYIQDSMINEY-UHFFFAOYSA-M 0.000 description 1
- CYSFUFRXDOAOMP-UHFFFAOYSA-M magnesium;prop-1-ene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C=C CYSFUFRXDOAOMP-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical group Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000011995 wilkinson's catalyst Substances 0.000 description 1
- UTODFRQBVUVYOB-UHFFFAOYSA-P wilkinson's catalyst Chemical compound [Cl-].C1=CC=CC=C1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)[Rh+](P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 UTODFRQBVUVYOB-UHFFFAOYSA-P 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
-
- 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 Table
- 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
-
- 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 Table
- 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
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
Definitions
- the present invention relates to a fluorine-containing alkylsilane compound and a method for producing the same. More specifically, the present invention relates to a fluorine-containing alkylsilane compound having a large contact angle with water and a method for producing the same.
- a compound having a perfluoroalkyl group as a structural unit is obtained by chemically treating the surface of various substrates such as fiber, metal, glass, rubber, resin, etc., thereby improving surface modification, water / oil repellency, and mold release properties. It is known to improve antifouling properties and leveling properties.
- telomer compounds having a perfluoroalkyl group having 8 to 12 carbon atoms are most likely to exhibit these performances, and telomer compounds having 8 carbon atoms are preferably used.
- a fluorine-containing alkylsilane compound having a perfluoroalkyl group having 6 or less carbon atoms and a large contact angle with water is also known.
- a method is described in which a fluorine-containing alkylsilane compound having a terminal —CH 2 CH 2 Si (R 1 ) 3-n Xn is obtained by reducing the above compound with a reducing agent.
- the target compound may be colored by iodine, and that tributyltin hydride having a high environmental load is used in the deiodination reaction. Be looked at.
- a compound having a CH 2 group between a CF 2 group and a CF 2 group is weak under basic conditions, and the reaction conditions (synthesis route) are limited.
- Patent Document 2 a silane coupling agent Rf (C 6 H 4 -C 6 H 4 ) CH 2 CH 2 CH 2 Si (OCH) 3 having a biphenylalkyl group is exposed to a high temperature atmosphere of 350 ° C. or higher. Also, it is described that these compounds have excellent heat resistance, durability, releasability, and antifouling properties, such as no decrease in the contact angle of the modified surface due to these compounds.
- Patent Document 3 describes the fluorine-containing alkylsilane compound having a bifunctional organosiloxane group.
- An object of the present invention is to use a fluorine-containing alkylsilane compound that can remove free iodine derived from a raw material compound before carrying out a hydrosilylation reaction without using a metal reagent having a high environmental load, and also has good handling properties. And providing a manufacturing method thereof.
- a transition metal catalyst such as a Pt-based catalyst, it is possible to remove free iodine derived from a raw material compound before performing a hydrosilylation reaction, and a fluorine-containing alkylsilane compound having good handling properties is obtained.
- the fluorine-containing alkylsilane compound of the present invention to which an appropriate hydrosilylating agent is added in the presence of a transition metal catalyst imparts water and oil repellency, antifouling properties, etc. thereto by chemical bonding to the surface of various substrates. Therefore, it is used as an active ingredient of the surface treatment agent.
- the fluorine-containing alkylsilane compound according to the present invention is produced through the following series of steps. (1) CF 3 (CF 2 ) n (CH 2 CF 2 ) a (CF 2 CF 2 ) b I (IV) And carboxylic acid allyl ester R′COOCH 2 CH ⁇ CH 2 is reacted. (2) Generated CF 3 (CF 2 ) n (CH 2 CF 2 ) a (CF 2 CF 2 ) b CH 2 CHICH 2 OCOR ⁇ [III] And a transition metal is reacted.
- examples of the lower alcohol having 1 to 3 carbon atoms include fluorine-free alcohols such as methanol, ethanol, propanol, and isopropanol, and fluorine-containing alcohols such as trifluoroethanol, tetrafluoropropanol, and hexafluoroisopropanol.
- fluorine-free alcohols such as methanol, ethanol, propanol, and isopropanol
- fluorine-containing alcohols such as trifluoroethanol, tetrafluoropropanol, and hexafluoroisopropanol.
- metal alkenyl include allylmagnesium chloride and allylmagnesium bromide.
- Polyfluoroalkyl iodide [IV] used as a raw material compound in the above step (1) is a known compound, and is described in Patent Document 4, for example.
- polyfluoroalkyl iodides include the following compounds. CF 3 (CF 2 ) (CH 2 CF 2 ) I CF 3 (CF 2 ) (CH 2 CF 2 ) 2 I CF 3 (CF 2 ) 2 (CH 2 CF 2 ) I CF 3 (CF 2 ) 2 (CH 2 CF 2 ) 2 I CF 3 (CF 2 ) 3 (CH 2 CF 2 ) I CF 3 (CF 2 ) 3 (CH 2 CF 2 ) 2 I CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) I CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) I CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 2 I CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 2 I CF 3 (CF 2 ) 2 (CH 2 CF 2 ) (CF 2 CF 2 ) I
- Carboxylic acid allyl ester in a small excess molar number that reacts with these polyfluoroalkyl iodides includes R ′ having an alkyl group having 1 to 3 carbon atoms, preferably allyl acetate. Used. This reaction is carried out at a temperature of about 70-120 ° C.
- a radical initiator relative to the polyfluoroalkyl iodide, such as di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, (4-tert-butylcyclohexyl) peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, di (2-ethoxyhexyl) peroxydicarbonate, di (3-methoxybutyl) peroxydicarbonate, di
- a radical initiator relative to the polyfluoroalkyl iodide, such as di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, (4-tert-butylcyclohexyl) peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, di (2-ethoxyhexyl) peroxydicarbonate, di (3-methoxybutyl) peroxydicarbonate, di
- the produced allyl carboxylate adduct [III] is subjected to iodine reduction and olefination reaction using a transition metal, for example, a simple metal such as Zn, Mg, Mn, or Cu or a reagent thereof, preferably Zn.
- a transition metal for example, a simple metal such as Zn, Mg, Mn, or Cu or a reagent thereof, preferably Zn.
- the carboxylic acid allyl adduct and the transition metal are used together with a solvent such as methanol and ethanol, respectively. Further, the transition metal is used in a molar excess with respect to the carboxylic acid allyl adduct.
- alkoxysilane those having a lower alkoxy group having 1 to 3 carbon atoms such as trimethoxysilane, triethoxysilane, and tripropoxysilane are used.
- Alkoxysilane is used in a small excess molar ratio with respect to the terminal allyl compound.
- the reaction is carried out in the presence of a transition metal catalyst at a reaction temperature of about 25-100 ° C.
- a transition metal catalyst preferably Pt-based or Rh-based catalyst
- the catalyst is used in an amount of about 0.001 to 10 mol% with respect to the polyfluoroalkylallyl compound.
- the polyfluoroalkylallyl compound [II] can also be obtained by reacting with a small excess molar ratio of chlorosilane and then with a lower alcohol or metal alkenyl having 1 to 3 carbon atoms.
- the reaction with chlorosilane is performed at a reaction temperature of about 25 to 100 ° C., using the transition metal catalyst as described above at a ratio of about 0.001 to 10 mol% with respect to the polyfluoroalkylallyl compound, and the terminal group is —SiCl 3.
- the lower alcohol or metal alkenyl having 1 to 3 carbon atoms is reacted at a reaction temperature of about 25 to 120 ° C.
- halogen can be left in the terminal group by reacting less than 3 equivalents of lower alcohol or metal alkenyl with respect to the terminal —SiCl 3 group.
- the obtained fluorine-containing alkylsilane compound has a large contact angle with water, that is, indicates that the surface free energy is low, indicating that the releasability and antifouling property are high.
- Reference example 1 In the presence of inert nitrogen gas, a dropping funnel and a Dim funnel are attached to a 1000 ml three-necked flask, and polyfluoroalkyl iodide CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) is placed in the three-necked flask.
- Reference example 2 In the presence of inert nitrogen gas, a dropping funnel and a Dim funnel were attached to a three-neck flask having a volume of 500 ml. Put 180 ml of methanol and 20.1 g (0.33 mol) of Zn in the flask, and add 200 g (0.28 mol) of allyl acetate adduct obtained in Reference Example 1 and 20 ml of methanol to the dropping funnel. When starting, dropping from the dropping funnel was started to start the reaction. After dropping, the mixture was stirred for 2 hours and then cooled to room temperature to stop the reaction.
- Example 1 In the presence of inert nitrogen gas, a septum and a Dimroth were attached to a 100 ml three-necked flask.
- 20.0 g (0.04 mol) of the terminal allyl compound obtained in Reference Example 2 and 5.8 ml (0.05 mol) of triethoxysilane were added, and the inside of the three-necked flask was stirred and heated to 80 ° C.
- 20 mg of chloroplatinic acid H 2 PtCl 16 ⁇ 6H 2 O (0.05 mol% with respect to the terminal allyl compound) was added to initiate the reaction. After stirring for a whole day and night, the reaction was stopped by cooling to room temperature.
- Reference example 3 Base material: Matsunami Glass (Preclin water edge polish S7213) Solution: Vertrel 100g, sample 0.1g, 0.05M hydrochloric acid 40mg, methanol 5ml Application condition: Spin coating, 0.5g, 1000rpm, 30 seconds Drying condition: 23 °C, 50% RH The contact angle measurement results for each sample under the above conditions are shown in the following table. Front contact angle (°) No. Sample H 2 O Hexadecane 1 Example 1 108 69 2 ⁇ 2 108 69 3 C 6 F 13 CH 2 CH 2 Si (OEt) 3 106 63 4 Comparative Example 106 73 5 C 8 F 17 CH 2 CH 2 Si (OEt) 3 109 69 69
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Abstract
Description
CF3(CF2)n(CH2CF2)a(CF2CF2)b(CH2)3SiR3-dXd 〔I〕
(ここで、nは0~5の整数であり、aは1または2、bは0~3の整数であり、Rは炭素数1~3のアルコキシ基、含フッ素アルコキシ基またはアルケニル基であり、Xはハロゲンであり、dは0~3の整数である)で表される含フッ素アルキルシラン化合物が提供される。
CF3(CF2)n(CH2CF2)a(CF2CF2)bCH2CH=CH2 〔II〕
(ここで、n、a、bは上記定義と同じである)で表されるポリフルオロアルキルアリル化合物を、遷移金属触媒の存在下で、
・アルコキシシランと反応させ、
または
・クロロシランと反応させた後、低級アルコールまたは金属アルケニルと反応させる
ことにより製造される。
(1) CF3(CF2)n(CH2CF2)a(CF2CF2)bI 〔IV〕
に、カルボン酸アリルエステル R´COOCH2CH=CH2を反応させる。
(2) 生成した
CF3(CF2)n(CH2CF2)a(CF2CF2)bCH2CHICH2OCOR´ 〔III〕
に、遷移金属を反応させる。
(3) 生成した
CF3(CF2)n(CH2CF2)a(CF2CF2)bCH2CH=CH2 〔II〕
に、アルコキシシランを反応させ、
またはクロロシランを反応させた後、炭素数1~3の低級アルコールまたは金属アルケニルと反応させ、
CF3(CF2)n(CH2CF2)a(CF2CF2)b(CH2)3SiR3-dXd 〔I〕
を得る。ここで、炭素数1~3の低級アルコールとしては、メタノール、エタノール、プロパノール、イソプロパノール等のフッ素非含有アルコールまたはトリフルオロエタノール、テトラフルオロプロパノール、ヘキサフルオロイソプロパノール等の含フッ素アルコールが挙げられる。また、金属アルケニルとしては、アリルマグネシウムクロリド、アリルマグネシウムブロミド等が挙げられる。
CF3(CF2)(CH2CF2)I
CF3(CF2)(CH2CF2)2I
CF3(CF2)2(CH2CF2)I
CF3(CF2)2(CH2CF2)2I
CF3(CF2)3(CH2CF2)I
CF3(CF2)3(CH2CF2)2I
CF3(CF2)(CH2CF2)(CF2CF2)I
CF3(CF2)(CH2CF2)(CF2CF2)2I
CF3(CF2)2(CH2CF2)(CF2CF2)I
CF3(CF2)2(CH2CF2)(CF2CF2)2I
CF3(CF2)3(CH2CF2)2(CF2CF2)I
CF3(CF2)3(CH2CF2)2(CF2CF2)2I
CF3(CF2)n(CH2CF2)a(CF2CF2)bCH2CH=CH2
は、アルコキシシランと反応させることにより、目的化合物である
CF3(CF2)n(CH2CF2)a(CF2CF2)b(CH2)3SiR3-dXd 〔I〕
を与える。
不活性窒素ガスの存在下で、容量1000mlの三口フラスコに滴下ロートおよびジムロートを取り付け、三口フラスコ中にポリフルオロアルキルアイオダイドCF3(CF2)3(CH2CF2)(CF2CF2)2I 400g(0.66モル)を、また滴下ロートに酢酸アリルCH2=CHCH2OCOCH3 74.0ml(0.69モル)およびラジカル開始剤P-16〔ジ(第3ブチルシクロヘキシル) パーオキシジカーボネート〕2.61g(6.5ミリモル)をそれぞれ入れ、三口フラスコ内を攪拌し、その温度が90℃になったところで滴下ロートからの滴下を開始し、反応を開始させた。反応後半で、発熱が弱くなってきたので、P-16 0.09gを追加して反応を継続させた。
CF3CF2CF2CF2CH2CF2CF2CF2CF2CF2CH2CHICH2OCOCH3
19F-NMR(d-アセトン,282.65Hz):
-80.2:CF 3 CF2CF2CF2CH2CF2CF2CF2CF2CF2CH2-
-110.3:CF3CF2CF2CF 2 CH2CF 2 CF2CF2CF2CF2CH2-
-112.2:CF3CF2CF2CF2CH2CF2CF2CF2CF2CF 2 CH2-
-120.2:CF3CF2CF2CF2CH2CF2CF 2 CF2CF2CF2CH2-
-121.9:CF3CF2CF2CF2CH2CF2CF2CF 2 CF2CF2CH2-
-122.5:CF3CF2CF 2 CF2CH2CF2CF2CF2CF 2 CF2CH2-
-124.9:CF3CF 2 CF2CF2CH2CF2CF2CF2CF2CF2CH2-
不活性窒素ガスの存在下で、容量500mlの三口フラスコに滴下ロートおよびジムロートを取り付けた。フラスコ中にメタノール180mlおよびZn 20.1g(0.33モル)を、また滴下ロートに参考例1で得られた酢酸アリル付加体200g(0.28モル)およびメタノール20mlをそれぞれ入れ、三口フラスコ内を攪拌し、還流し始めたところで滴下ロートからの滴下を開始し、反応を開始させた。滴下後2時間攪拌した後室温まで冷却し、反応を停止させた。
CF3CF2CF2CF2CH2CF2CF2CF2CF2CF2CH2CH=CH2
1H-NMR(d-アセトン,300.4Hz):
δ5.9~5.7:-CF2CH2CH=CH2(m)
5.4:-CF2CH2CH=CH 2 (m)
3.6:-CF2CH 2 CF2-(quin)
3.0:-CF2CH 2 CH=CH2(dt)
19F-NMR(d-アセトン,282.65Hz):
-80.2:CF 3 CF2CF2CF2CH2CF2CF2CF2CF2CF2CH2-
-110.2:CF3CF2CF2CF 2 CH2CF 2 CF2CF2CF2CF2CH2-
-111.9:CF3CF2CF2CF2CH2CF2CF2CF2CF2CF 2 CH2-
-120.3:CF3CF2CF2CF2CH2CF2CF 2 CF2CF2CF2CH2-
-121.9:CF3CF2CF2CF2CH2CF2CF2CF 2 CF2CF2CH2-
-122.1:CF3CF2CF2CF2CH2CF2CF2CF2CF 2 CF2CH2-
-122.5:CF3CF2CF 2 CF2CH2CF2CF2CF2CF2CF2CH2-
-124.9:CF3CF 2 CF2CF2CH2CF2CF2CF2CF2CF2CH2-
不活性窒素ガスの存在下で、容量100mlの三口フラスコにセプタムおよびジムロートを取り付けた。三口フラスコ中に、参考例2で得られた末端アリル化合物20.0g(0.04モル)およびトリエトキシシラン5.8ml(0.05モル)を入れ、三口フラスコ内を攪拌し、80℃まで昇温させた。昇温後、塩化白金酸 H2PtCl16・6H2O 20mg(末端アリル化合物に対して0.05モル%)を加えて、反応を開始させた。一昼夜攪拌した後、室温まで冷却して反応を停止させた。
CF3CF2CF2CF2CH2CF2CF2CF2CF2CF2CH2CH2CH2Si(OCH2CH3)3
1H-NMR(CDCl3,300.4Hz):
δ3.83:-Si(OCH 2 CH3)3(q)
2.92:-CF2CH 2 CF2-(quin)
2.13:-CH 2 CH2CH2-(tt)
1.75:-CH2CH 2 CH2-(m)
1.21:-Si(OCH2CH 3 )3(t)
0.70:-CH2CH2CH 2 -(t)
19F-NMR(CDCl3,282.65Hz):
-82.2:CF 3 CF2CF2CF2CH2CF2CF2CF2CF2CF2CH2-
-113.2:CF3CF2CF2CF 2 CH2CF 2 CF2CF2CF2CF2CH2-
-115.6:CF3CF2CF2CF2CH2CF2CF2CF2CF2CF 2 CH2-
-122.5:CF3CF2CF2CF2CH2CF2CF 2 CF2CF2CF2CH2-
-124.0~-126.0:CF3CF2CF 2 CF2CH2CF2CF2CF 2 CF 2 CF2CH2-
-127.0:CF3CF 2 CF2CF2CH2CF2CF2CF2CF2CF2CH2-
不活性窒素ガスの存在下で、容量100mlの三口フラスコにセプタムおよびジムロートを取り付けた。三口フラスコ中に、参考例2で得られた末端アリル化合物20.0g(0.04モル)およびトリクロロシランSiHCl3 4.8ml (0.05ミリモル)を入れ、三口フラスコ内を攪拌し、40℃まで昇温させた。昇温後、カルステッド触媒(Pt・CH2=CHSiMe2OMe2SiCH=CH2)14.5mg(末端アリル化合物に対して0.1モル%)を加えて、反応を開始させた。油浴温度を徐々に上げて行き、100℃となったところで温度を一定とし、一昼夜攪拌した。NMRによって原料の消失を確認した後、室温に冷却して反応を停止させた。
CF3CF2CF2CF2CH2CF2CF2CF2CF2CF2CH2CH2CH2Si(OCH3)3
1H-NMR(CDCl3,300.4Hz):
δ3.58:-Si(OCH 3)3(s)
2.92:-CF2CH 2 CF2-(quin)
2.12:-CH 2 CH2CH2-(tt)
1.74:-CH2CH 2 CH2-(m)
0.72:-CH2CH2CH 2 -(t)
19F-NMR(CDCl3,282.65Hz):
-82.1:CF 3 CF2CF2CF2CH2CF2CF2CF2CF2CF2CH2-
-113.2:CF3CF2CF2CF 2 CH2CF 2 CF2CF2CF2CF2CH2-
-115.6:CF3CF2CF2CF2CH2CF2CF2CF2CF2CF 2 CH2-
-122.5:CF3CF2CF2CF2CH2CF2CF 2 CF2CF2CF2CH2-
-124.0~-126.0:CF3CF2CF 2 CF2CH2CF2CF2CF 2 CF 2 CF2CH2-
-127.0:CF3CF 2 CF2CF2CH2CF2CF2CF2CF2CF2CH2-
実施例2において、末端アリル化合物の代りにC6F13CH2CH=CH2 30g(0.08モル)を用い、またカルステッド触媒量を31.6g(末端アリル化合物に対して0.1モル%)に、トリクロロシラン量を10.1ml(0.105モル)に、メタノール量を12ml(0.30モル)に、オルトギ酸メチル量を7.7ml(0.1モル)に、トリクロロシランとの反応温度を60℃にそれぞれ変更して用い、透明な液状の末端トリメトキシシリルプロピル誘導体を31.66g(収率79%)を得た。
CF3CF2CF2CF2CF2CF2CH2CH2CH2-Si(OCH3)3
1H-NMR(CDCl3,300.4Hz):
δ3.63:-Si(OCH 3 )3(s)
2.10:-CH 2 CH2CH2-(quin)
1.81:-CH2CH 2 CH2-(m)
1.74:-CH2CH2CH 2 -(t)
19F-NMR(CDCl3,282.65Hz):
-82.0:CF 3 CF2CF2CF2CF2CF2CH2-
-115.6:CF3CF2CF2CF2CF2CF 2 CH2-
-123.1:CF3CF2CF2CF2CF 2 CF2CH2-
-124.0:CF3CF2CF 2 CF2CF2CF2CH2-
-124.8:CF3CF2CF2CF 2 CF2CF2CH2-
-127.3:CF3CF 2 CF2CF2CF2CF2CH2-
基材:松浪硝子(プレクリン水縁磨きS7213)
溶液:バートレル100g、試料0.1g、0.05M塩酸40mg、メタノール5ml
塗布条件:スピンコート、0.5g、1000rpm、30秒間
乾燥条件:23℃、50%RH
上記条件下での各試料の接触角測定結果は、次の表に示される。
表
接触角(°)
No. 試料 H 2 O ヘキサデカン
1 実施例1 108 69
2 〃 2 108 69
3 C6F13CH2CH2Si(OEt)3 106 63
4 比較例 106 73
5 C8F17CH2CH2Si(OEt)3 109 69
Claims (5)
- 一般式
CF3(CF2)n(CH2CF2)a(CF2CF2)b(CH2)3SiR3-dXd 〔I〕
(ここで、nは0~5の整数であり、aは1または2、bは0~3の整数であり、Rは炭素数1~3のアルコキシ基、含フッ素アルコキシ基またはアルケニル基であり、Xはハロゲンであり、dは0~3の整数である)で表される含フッ素アルキルシラン化合物。 - 一般式
CF3(CF2)n(CH2CF2)a(CF2CF2)bCH2CH=CH2 〔II〕
(ここで、nは0~5の整数であり、aは1または2、bは0~3の整数である)で表されるポリフルオロアルキルアリル化合物を、遷移金属触媒の存在下で、炭素数1~3の低級アルキル基を有するアルコキシシランと反応させることを特徴とする請求項1記載の含フッ素アルキルシラン化合物の製造法。 - 一般式
CF3(CF2)n(CH2CF2)a(CF2CF2)bCH2CH=CH2 〔II〕
(ここで、nは0~5の整数であり、aは1または2、bは0~3の整数である)で表されるポリフルオロアルキルアリル化合物を、遷移金属触媒の存在下で、クロロシランと反応させた後、炭素数1~3の低級アルコールまたは金属アルケニルと反応させることを特徴とする請求項1記載の含フッ素アルキルシラン化合物の製造法。 - 遷移金属触媒がPt系またはRh系触媒である請求項2または3記載の含フッ素アルキルシラン化合物の製造法。
- 請求項1記載の含フッ素アルキルシラン化合物を有効成分とする表面処理剤。
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US10125154B2 (en) | 2018-11-13 |
CN106715447A (zh) | 2017-05-24 |
US20170305938A1 (en) | 2017-10-26 |
KR20170066379A (ko) | 2017-06-14 |
KR102444487B1 (ko) | 2022-09-19 |
JPWO2016052262A1 (ja) | 2017-04-27 |
JP5979332B1 (ja) | 2016-08-24 |
EP3202768B1 (en) | 2020-05-27 |
EP3202768A1 (en) | 2017-08-09 |
EP3202768A4 (en) | 2018-02-21 |
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