Composition and method for reacting an organosilicon compound and a silyl hydride catalyzed by a fluorinated arylborane Lewis acid

Patent metadata

Field	Value
Publication number	US-12398241-B2
Application number	US-202117916834-A
Country	US
Kind code	B2
Filing date	Jun 16, 2021
Priority date	Jun 24, 2020
Publication date	Aug 26, 2025
Grant date	Aug 26, 2025

Abstract

A composition and method can be used in the preparation of various siloxanes. The composition and method employ a fluorinated triarylborane Lewis acid, a hydrocarbonoxy-functional organosilicon compound, and a silyl hydride. The fluorinated triarylborane Lewis acid catalyzes reaction of a hydrocarbonoxy moiety (from the organosilicon compound) and a silicon-bonded hydrogen atom (from the silyl hydride) to form a siloxane bond.

First claim

The invention claimed is:

1. A composition comprising:
A) a fluorinated triarylborane Lewis acid selected from the group consisting of:
A1) tris(3,5-bis(trifluoromethyl)phenyl)boran 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 hydrocarbonoxy-functional organosilicon compound having an average, per molecule of at least 1 silicon-bonded group of the formula —OR 2 , wherein each R 2 is an independently selected monovalent hydrocarbon group of 1 to 6 carbon atoms; and
C) a silyl hydride having at least 1 silicon-bonded hydrogen atom per molecule.

2. The composition of claim 1 , where starting material A) is 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; and
A7) bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct.

3. The composition of claim 2 , where starting material A) is selected from the group consisting of: A1), A2), A3), A4), and A5).

4. The composition of claim 1 , where starting material A) is present in an amount of 0.1 ppm to 5 mol %, based on combined weights of B) the hydrocarbonoxy-functional organosilicon compound and C) the silyl hydride.

5. The composition of claim 4 , where starting material A) is present in an amount of 5 ppm to 6,000 ppm based on combined weights of B) the hydrocarbonoxy-functional organosilicon compound and C) the silyl hydride.

6. The composition of claim 1 , where B) the organosilicon compound is selected from the group consisting of:
B1) an alkoxysilane of formula: R 1 (4-a) SiOR 2 a , where each R 1 is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, each R 2 is a monovalent hydrocarbon group of 1 to 6 carbon atoms, and subscript a is 1 to 4; and
B2) an organosiloxane oligomer or polymer comprising a group of formula B2):

where each D independently represents an oxygen atom, a divalent hydrocarbon group, a divalent siloxane group, or a combination of a divalent hydrocarbon group and a divalent siloxane group; each R X independently represents a group of the formula —OR 2 , wherein each R 2 is as described above; each R 3 is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group; subscript c represents 0, 1, 2, or 3; subscript e represents 0, 1, or 2; and subscript d has a value of 0 or greater, with the proviso that the sum of (e+c) is at least 1, such that, on average, at least one R X is present in the formula.

7. The composition of claim 6 , where the organosiloxane oligomer or polymer comprising unit formula:
(R X R 3 2 SiO 1/2 ) o (R 3 3 SiO 1/2 ) p (R 3 2 SiO 2/2 ) q (R X R 3 SiO 2/2 ) r (R X SiO 3/2 ) s (R 3 SiO 3/2 ) t (SiO 4/2 ) u , where R X represents a group of the formula —OR 2 as described above, subscripts o, p, q, and r have values such that o≥0, p≥0, q≥0, r≥0, s≥0, t≥0, u≥0, a quantity (o+r+s) has an average value of 1 or more.

8. The composition of claim 1 , where C) the silyl hydride is selected from the group consisting of:
C1) 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; and
C2) an organohydrogensiloxane of unit formula:

(HR 4 2 SiO 1/2 ) g (R 4 3 SiO 1/2 ) h (R 4 2 SiO 2/2 ) i (HR 4 SiO 2/2 ) j , where each R 4 is an independently selected monovalent hydrocarbon group, which is free of aliphatic unsaturation; 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.

9. The composition of claim 8 , where starting material C) is a silane of formula HSiR 5 3 , where each R 5 is an alkyl group of 1 to 6 carbon atoms.

10. The composition of claim 8 , where starting material C) is a polydiorganohydrogensiloxane of formula

where subscript m is 0 or 1, each R 4 is an alkyl group, and each R 6 is independently selected from the group consisting of H and R 4 , with the proviso that at least one R 6 is a hydrogen atom.

11. A method comprising:
1) combining starting materials comprising:
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) bid(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 hydrocarbonoxy-functional organosilicon compound having an average, per molecule of at least 1 silicon-bonded group of the formula —OR 2 , wherein each R 2 is an independently selected monovalent hydrocarbon group of 1 to 6 carbon atoms; and
C) a silyl hydride having at least 1 silicon-bonded hydrogen atom per molecule; thereby forming a product of step 1) comprising a reaction product of starting materials B) and C) and a side product comprising HR 2 .

12. The method of claim 11 , where the method is performed at a temperature of 5° C. to 70° C.

13. The method of claim 11 , further comprising: neutralizing residual fluorinated triarylborane Lewis acid in the product of step 1).

14. The method of claim 11 , further comprising: during and/or after step 1), removing the side product comprising HR 2 .

15. The method of claim 11 , further comprising: recovering the reaction product.

16. The method of claim 11 , wherein starting material B) comprises tirmethylmethoxysilane.

17. The method of claim 11 , wherein starting material C) is selected from the group consisting of heptamethyltrisiloxane, pentamethyldisiloxane, and triethylsilane.

18. The composition of claim 9 , where the silane is triethylsilane.

19. The composition of claim 10 , where the polydiorganohydrogensiloxane is selected from the group consisting of heptamethyltrisiloxane and pentamethyldisiloxane.

20. The composition of claim 6 , where the alkoxysilane is trimethylmethoxysilane.

Assignees

• Dow Silicones Corp
• Dow Global Technologies Llc

Inventors

• Courtemanche Marc-Andre
• Bédard Anne-Catherine
• Spinney Heather
• Wilson David
• Raghuraman Arjun
• Mukhopadhyay Sukrit
• Sunderland Travis

Classifications

• C08G77/22

  containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen · CPC title

• C08G77/12

  containing silicon bound to hydrogen · CPC title

• C08G77/08 Primary

  characterised by the catalysts used · CPC title

• C08G77/18 Primary

  to alkoxy or aryloxy groups · CPC title