Composition and method for silyl hydride reaction catalyzed by fluorinated arylborane Lewis acids

Patent metadata

Field	Value
Publication number	US-12473404-B2
Application number	US-202117915656-A
Country	US
Kind code	B2
Filing date	Jun 16, 2021
Priority date	Jun 24, 2020
Publication date	Nov 18, 2025
Grant date	Nov 18, 2025

Abstract

A composition includes a silyl hydride (having at least one silicon-bonded hydrogen atom per molecule) and a fluorinated triarylborane Lewis acid. In the method, the Lewis acid catalyzes reaction of silicon bonded hydrogen atoms from the silyl hydride and water, thereby forming a siloxane bond in the resulting product. The composition and method can be used to form siloxane intermediates and cured networks.

First claim

The invention claimed is:

1 . A composition for silyl hydride reaction, wherein the composition comprises:
A) a fluorinated triarylborane Lewis acid selected from the group consisting of:
A1) tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct;
A2) bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct;
A3) bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct;
A4) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct;
A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane;
A6) (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane;
A7) bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct; and
A8) a combination of two or more of A1) to A7); and
B) a silyl hydride having at least one silicon-bonded hydrogen atom per molecule.

2 . The composition of claim 1 , where starting material A) is selected from the group consisting of:
A4) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct; A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane; and A6) (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane.

3 . The composition of claim 1 , where B) the silyl hydride is selected from the group consisting of:
B1) a silane of formula H k SiR 5 (4-k) , where each R 5 is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, and subscript k is 1 to 3; B2) a polyorganohydrogensiloxane comprising two or more siloxane units selected from the group consisting of HR 4 2 SiO 1/2 , R 4 3 SiO 1/2 , HR 4 SiO 2/2 , R 4 2 SiO 2/2 , R 4 SiO 3/2 , HSiO 3/2 and SiO 4/2 , where each R 4 is an independently selected monovalent hydrocarbon group, which is free of aliphatic unsaturation; and B3) a polyolefin having a silicon-bonded hydrogen functional group of formula (B3-1):

where each R 1 is an independently selected monovalent hydrocarbon group and each subscript a is independently 1 or 2.

4 . The composition of claim 3 , where
starting material B1) is a silane of formula HSiR 5 3 , where each R 5 is an alkyl group of 1 to 6 carbon atoms; starting material B2) is a polydiorganohydrogensiloxane of unit formula: (HR 4 2 SiO 1/2 ) g (R 4 3 SiO 1/2 ) h (R 4 2 SiO 2/2 )(HR 4 SiO 2/2 ) j , where R 4 is as described above, and subscripts g, h, i, and j have values such that g≥0, h≥0, a quantity (g+h) has an average value of 2, i≥0, j≥0, and a quantity (g+j)≥1, and a quantity (i+j) ranges from 0 to 1000; and starting material B3) is an SiH-functional polyolefin selected from the group consisting of unit formula (B3-2):

where R 1 and subscript a are as described above, each D 1 is independently a divalent hydrocarbon group of 2 to 50 carbon atoms, each R 25 is independently H, a monovalent hydrocarbon group of 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms, and subscripts M and N have values such that 1≤M≤10, and 10≤N≤20,000,
unit formula (B3-3):

where subscript a and R 1 are as described above, subscript f is 0 or 1, subscripts t and u are fractions with relative values such that 0<t≤1, 0≤u≤1, subscript g is 1 or more, each R et represents an ethylene unit, and each R O represents an olefin unit other than ethylene; and
unit formula (B3-4):

where subscripts a, f, g, t, and u, and R 1 are as described above; and each R 7 is independently a monovalent hydrocarbon group of 1 to 20 carbon atoms.

5 . A method for forming product with a siloxane bond, the method comprising:
1. Combining starting materials comprising A) a fluorinated triarylborane Lewis acid selected from the group consisting of:
A1) tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct;
A2) bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct;
A3) bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct;
A4) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct;
A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane;
A6) (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane;
A7) bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct; and
A8) a combination of two or more of A1) to A7);
B) a silyl hydride having at least one silicon-bonded hydrogen atom per molecule, and C) water; thereby reacting the silicon-bonded hydrogen atom to form the siloxane bond and a by-product comprising hydrogen.

6 . The method of claim 5 , where starting material A) is selected from the group consisting of:
A4) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct; A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane; and A6) (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane.

7 . The method of claim 5 , where B) the silyl hydride is selected from the group consisting of:
B1) a silane of formula H k SiR 5 (4-k) , where each R 5 is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, and subscript k is 1 to 3; B2) a polyorganohydrogensiloxane comprising two or more siloxane units selected from the group consisting of HR 4 2 SiO 1/2 , R 4 3 SiO 1/2 , HR 4 SiO 2/2 , R 4 2 SiO 2/2 , R 4 SiO 3/2 , HSiO 3/2 and SiO 4/2 , where each R 4 is an independently selected monovalent hydrocarbon group, which is free of aliphatic unsaturation; and B3) a polyolefin having a silicon-bonded hydrogen functional group of formula (B3-1):

where each R 1 is an independently selected monovalent hydrocarbon group and each subscript a is independently 1 or 2.

8 . The method of claim 7 , where:
starting material B1) is a silane of formula HSiR 5 3 , where each R 5 is an alkyl group of 1 to 6 carbon atoms; starting material B2) is a polydiorganohydrogensiloxane of unit formula: (HR 4 2 SiO 1/2 ) g (R 4 3 SiO 1/2 ) h (R 4 2 SiO 2/2 )(HR 4 SiO 2/2 ) j , where R 4 is as described above, and subscripts g, h, i, and j have values such that g≥0, h≥0, a quantity (g+h) has an average value of 2, i≥0, j≥0, and a quantity (g+j)≥1, and a quantity (i+j) ranges from 0 to 1000; and starting material B3) is an SiH-functional polyolefin copolymer selected from the group consisting of
unit formula (B3-2):

where R 1 and subscript a are as described above, each R 25 is independently H, a monovalent hydrocarbon group of 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms, 1≤M≤10, and 10≤N≤20,000;
unit formula (B3-3):

where subscript a and R 1 are as described above, subscript f is 0 to 1, subscripts t and u have relative values such that 0<t≤1, 0≤u≤1, subscript g is 1 or more, each R et represents an ethylene unit, and each R O

Assignees

• Dow Silicones Corp
• Dow Global Technologies Llc

Inventors

• Courtemanche Marc-Andre
• Bedard Anne-Catherine
• Spinney Heather
• Wilson David
• Raghuraman Arjun
• Mukhopadhyay Sukrit
• Shah Andrew
• Devore David
• Laitar David
• Reddel Jordan
• Lai Shuqi

Classifications

• C08G77/44 Primary

  containing only polysiloxane sequences · CPC title

• C08G77/08

  characterised by the catalysts used · CPC title

• C08G77/12 Primary

  containing silicon bound to hydrogen · CPC title