# US 10,501,583 B2 · Method for preparing polyhedral oligomeric silsesquioxane > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,501,583 B2 - Document ID: US10501583B2 - Status: Granted - Kind: B2 - Application number: 15/743,830 - Filed: 2017-01-26 - Published: 2018-07-19 - Granted: 2019-12-10 - Earliest claimed: 2016-01-28 - Assignees: LG Chem, Ltd. - Applicants: LG Chem, Ltd. - Inventors: Young Jee Song; Ji Young Choi; Min Hyung Lee - Web page: https://patentgrep.com/patent/US10501583B2 ## CPC - C08G 77/20: containing silicon bound to unsaturated aliphatic groups - C07F 7/21: Cyclic compounds having at least one ring containing silicon, but no carbon in the ring - C08G 77/16: to hydroxy groups - C08G 77/24: halogen-containing groups - C08G 77/70: {Siloxanes defined by use of the MDTQ nomenclature} - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22) ## Abstract The present invention relates to a method for preparing a polyhedral oligomer silsesquioxane. The preparation method includes the step of reacting a reaction mixture containing at least two types of silane compounds and a tetraalkylammonium hydroxide having 2 to 5 carbon atoms at a temperature of 5° C. or below. ## Claims ### Claim 1 A method for preparing a polyhedral oligomer silsesquioxane comprising the step of: reacting a reaction mixture containing a first silane compound represented by Chemical Formula 1 below, a second silane compound represented by Chemical Formula 2 below, and a tetraalkylammonium hydroxide having 2 to 5 carbon atoms at a temperature of 5° C. or below: R1—SiX13 [Chemical Formula 1] R2-A-SiX23 [Chemical Formula 2] wherein, in Chemical Formulae 1 and 2, A is a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 30 carbon atoms, —O—Si(R3)(R4)—, or —O—Si(R3)(R4)—R5—, R1 is a monovalent moiety derived from a hydrocarbon having 1 to 30 carbon atoms substituted with a halogen, R2 is a functional group selected from the group consisting of a (meth)acryloyl group, a (meth)acryloyloxy group, a hydroxy group, a mercapto group, a carboxyl group, an amino group, a cyano group, a glycidyl group, a glycidyloxy group, an epoxyalkyl group having 2 to 30 carbon atoms, an epoxyalkoxy group having 2 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an alkenyloxy group having 2 to 30 carbon atoms, or a monovalent moiety derived from a hydrocarbon having 1 to 30 carbon atoms substituted with at least one substituent selected from the group consisting of —OH, —NH2, —NH—R6, —NH3X3, —COON, —CONH2, —CN, —SH, a glycidyl group, a glycidyloxy group, and maleimide, X1 and X2 are each independently an alkoxy group having 1 to 5 carbon atoms, Cl, Br, or I, R3 and R4 are each independently an alkyl group having 1 to 5 carbon atoms, R5 is an alkylene group having 1 to 12 carbon atoms, R6 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkyl group having 1 to 10 carbon atoms substituted with an amino group, and X3 is a halogen. ### Claim 2 (depends on 1) The method for preparing a polyhedral oligomer silsesquioxane of claim 1, wherein, as the first silane compound, a compound in which R1 is trifluoromethyl, trifluoroethyl, trifluoropropyl, trifluorobutyl, pentafluorobutyl, trifluoropentyl, pentafluoropentyl, heptafluoropentyl, trifluorohexyl, pentafluorohexyl, heptafluorohexyl, nonafluorohexyl, trifluoroheptyl, pentafluoroheptyl, heptafluoroheptyl, nonafluoroheptyl, dodecafluoroheptyl, chloropropyl, (chloromethyl)phenyl, (chloromethyl)phenylethyl, or dibromoethyl is used. ### Claim 3 (depends on 1) The method for preparing a polyhedral oligomer silsesquioxane of claim 1, wherein, as the second silane compound, a compound in which R2 is a functional group selected from the group consisting of a (meth)acryloyl group, a (meth)acryloyloxy group, a hydroxy group, a mercapto group, a carboxyl group, an amino group, a cyano group, a glycidyl group, a glycidyloxy group, an epoxycyclohexyl group, an epoxycycloheptoxy group, a vinyl group, an allyl group, and a norbornene group, or a monovalent moiety derived from a hydrocarbon substituted with at least one substituent selected from the group consisting of cyclohexanediol, trimethylolpropane, glycerol, 3-hydroxy-3-methylbutane, aminopropyl, aniline, N-methylaminopropane, N-phenylaminopropane, N-(aminoethyl)aminopropane, propylammonium chloride, propylnitrile, propylthiol, glycidyloxypropane, N-propylmaleimide, and maleamic acid is used. ### Claim 4 (depends on 1) The method for preparing a polyhedral oligomer silsesquioxane of claim 1, wherein, as the second silane compound, a compound in which A is a single bond, methylene, ethylene, propylene, phenylene, —O—Si(CH3)(CH3)—, or —O—Si(CH3)(CH3)—CH2CH2CH2— is used. ### Claim 5 (depends on 1) The method for preparing a polyhedral oligomer silsesquioxane of claim 1, wherein, as first silane compound, at least one selected from the group consisting of (trifluoropropyl)trimethoxysilane, (trifluorobutyl)trimethoxysilane, (pentafluorobutyl)trimethoxysilane, (trifluoropentyl)trimethoxysilane, (pentafluoropentyl)trimethoxysilane, (heptafluoropentyl)trimethoxysilane, (trifluorohexyl)trimethoxysilane, (pentafluorohexyl)trimethoxysilane, (heptafluorohexyl)trimethoxysilane, (nonafluorohexyl)trimethoxysilane, (trifluoroheptyl)trimethoxysilane, (pentafluoroheptyl)trimethoxysilane, (heptafluoroheptyl)trimethoxysilane, (nonafluoroheptyl)trimethoxysilane, (dodecafluoroheptyl)trimethoxysilane, (chloropropyl)trimethoxysilane, [(chloromethyl)phenyl]trimethoxysilane, [(chloromethyl)phenylethyl]trimethoxysilane, (dibromoethyl)trimethoxysilane, and the like is used. ### Claim 6 (depends on 1) The method for preparing a polyhedral oligomer silsesquioxane of claim 1, wherein, as the second silane compound, at least one selected from the group consisting of (3-(meth)acryloxypropyl)trimethoxysilane, (2,3-dihydroxypropoxypropyl)trimethoxysilane, (3,4-dihydroxyhexylethyl)trimethoxysilane, (3-hydroxy-3-methylbutyldimethylsiloxy)trimethoxysilane (3,4-epoxyhexylpropyl)trimethoxysilane, (3,4-epoxyhexylethyldimethylsiloxy)trimethoxysilane, (3-aminopropyl)trimethoxysilane, (N-aminoethylaminopropyl)trimethoxysilane, (aminophenyl)trimethoxysilane, (N-phenylaminopropyl)trimethoxysilane, (N-methylaminopropyl)trimethoxysilane, (3-cyanopropyl)trimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, (trimethoxysilyl)norbornene, N-[3-(trimethoxysilyl)propyl]maleimide, N-[3-(trimethoxysilyl)propyl]maleamic acid, and the like is used. ### Claim 7 (depends on 1) The method for preparing a polyhedral oligomer silsesquioxane of claim 1, wherein, as the tetraalkylammonium hydroxide having 2 to 5 carbon atoms, tetrabutylammonium hydroxide is used. ### Claim 8 (depends on 1) The method for preparing a polyhedral oligomer silsesquioxane of claim 1, wherein the tetraalkylammonium hydroxide having 2 to 5 carbon atoms is used in an amount of 0.001 to 100 moles based on 100 moles of the entire silane compound. ### Claim 9 (depends on 1) The method for preparing a polyhedral oligomer silsesquioxane of claim 1, wherein the reaction mixture is reacted in the presence of an organic solvent. ### Claim 10 (depends on 9) The method for preparing a polyhedral oligomer silsesquioxane of claim 9, wherein, as the organic solvent, an ether solvent is used. ### Claim 11 (depends on 1) The method for preparing a polyhedral oligomer silsesquioxane of claim 1, wherein the reaction mixture is reacted for 5 to 128 hours. ### Claim 12 (depends on 1) The method for preparing a polyhedral oligomer silsesquioxane of claim 1, wherein the polyhedral oligomer silsesquioxane is represented by Chemical Formula 3 below: (R1SiO1.5)m(R2-A-SiO1.5)n [Chemical Formula 3] wherein, in Chemical Formula 3, A is a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 30 carbon atoms, —O—Si(R3)(R4)—, or —O—Si(R3)(R4)—R5—, R1 is a monovalent moiety derived from a hydrocarbon having 1 to 30 carbon atoms substituted with a halogen, R2 is a functional group selected from the group consisting of a (meth)acryloyl group, a (meth)acryloyloxy group, a hydroxy group, a mercapto group, a carboxyl group, an amino group, a cyano group, a glycidyl group, a glycidyloxy group, an epoxyalkyl group having 2 to 30 carbon atoms, an epoxyalkoxy group having 2 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an alkenyloxy group having 2 to 30 carbon atoms, or a monovalent moiety derived from a hydrocarbon having 1 to 30 carbon atoms substituted with at least one substituent selected from the group consisting of —OH, —NH2, —NH—R6, —NH3X3, —COOH, —CONH2, —CN, —SH, a glycidyl group, a glycidyloxy group, and maleimide, R3 and R4 are each independently an alkyl group having 1 to 5 carbon atoms, R5 is an alkylene group having 1 to 12 carbon atoms, R6 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkyl group having 1 to 10 carbon atoms substituted with an amino group, X3 is a halogen, and m and n are each independently an integer of 1 to 13, with the proviso that the sum of m and n is an integer of 6 to 14.