Method for preparing polyhedral oligomeric silsesquioxane

Patent metadata

Field	Value
Publication number	US-10501583-B2
Application number	US-201715743830-A
Country	US
Kind code	B2
Filing date	Jan 26, 2017
Priority date	Jan 28, 2016
Publication date	Dec 10, 2019
Grant date	Dec 10, 2019

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.

First claim

The invention claimed is:

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:
R 1 —SiX 1 3   [Chemical Formula 1]

R 2 -A-SiX 2 3   [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(R 3 )(R 4 )—, or —O—Si(R 3 )(R 4 )—R 5 —,
R 1 is a monovalent moiety derived from a hydrocarbon having 1 to 30 carbon atoms substituted with a halogen,
R 2 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, —NH 2 , —NH—R 6 , —NH 3 X 3 , —COON, —CONH 2 , —CN, —SH, a glycidyl group, a glycidyloxy group, and maleimide,
X 1 and X 2 are each independently an alkoxy group having 1 to 5 carbon atoms, Cl, Br, or I,
R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms, R 5 is an alkylene group having 1 to 12 carbon atoms,
R 6 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 X 3 is a halogen.

2. The method for preparing a polyhedral oligomer silsesquioxane of claim 1 , wherein, as the first silane compound, a compound in which R 1 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.

3. The method for preparing a polyhedral oligomer silsesquioxane of claim 1 , wherein, as the second silane compound, a compound in which R 2 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.

4. 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(CH 3 )(CH 3 )—, or —O—Si(CH 3 )(CH 3 )—CH 2 CH 2 CH 2 — is used.

5. 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.

6. 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.

7. 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.

8. 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.

9. The method for preparing a polyhedral oligomer silsesquioxane of claim 1 , wherein the reaction mixture is reacted in the presence of an organic solvent.

10. The method for preparing a polyhedral oligomer silsesquioxane of claim 9 , wherein, as the organic solvent, an ether solvent is used.

11. The method for preparing a polyhedral oligomer silsesquioxane of claim 1 , wherein the reaction mixture is reacted for 5 to 128 hours.

12. The method for preparing a polyhedral oligomer silsesquioxane of claim 1 , wherein the polyhedral oligomer silsesquioxane is represented by Chemical Formula 3 below:
(R 1 SiO 1.5 ) m (R 2 -A-SiO 1.5 ) 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(R 3 )(R 4 )—, or —O—Si(R 3 )(R 4 )—R 5 —,
R 1 is a monovalent moiety derived from a hydrocarbon having 1 to 30 carbon atoms substituted with a halogen,
R 2 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, —NH 2 , —NH—R 6 , —NH 3 X 3 , —COOH, —CONH 2 , —CN, —SH, a glycidyl group, a glycidyloxy group, and maleimide,
R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms, R 5 is an alkylene group having 1 to 12 carbon atoms,
R 6 is an alkyl group having 1 to 10 carbon atoms, an aryl grou

Assignees

• Lg Chemical Ltd

Inventors

• Song Young Jee
• Choi Ji Young
• Lee Min Hyung

Classifications

• C08G77/16

  to hydroxy groups · CPC title

• C08G77/24 Primary

  halogen-containing groups · CPC title

• C07F7/21

  Cyclic compounds having at least one ring containing silicon, but no carbon in the ring · CPC title

• C08G77/70

  Siloxanes defined by use of the MDTQ nomenclature · CPC title

• C08G77/20 Primary

  containing silicon bound to unsaturated aliphatic groups · CPC title