Methods for making polyfunctional organosiloxanes and compositions containing same

Patent metadata

Field	Value
Publication number	US-12441844-B2
Application number	US-202117916827-A
Country	US
Kind code	B2
Filing date	Jun 16, 2021
Priority date	Jun 24, 2020
Publication date	Oct 14, 2025
Grant date	Oct 14, 2025

Abstract

A polyfunctional organohydrogensiloxane is prepared using a fluorinated triarylborane Lewis acid as catalyst. The polyfunctional organohydrogensiloxane may be formulated into release coating compositions. Alternatively, the polyfunctional organohydrogensiloxane may be further functionalized with a curable group to form a clustered functional organosiloxane. The clustered functional organosiloxane may be formulated into thermal radical cure adhesive compositions.

First claim

The invention claimed is:

1. A method for preparing a product comprising a polyfunctional organohydrogensiloxane, where the method comprises:
1) Combining starting materials comprising
A) a fluorinated triarylborane Lewis acid of formula

 where each of R o1 , R o2 , R o3 , R o4 , R o5 , R o6 , R m1 , R m2 , R m3 , R m4 , R m5 , R m6 , R p1 , R p2 , and R p3 is independently selected from the group consisting of H, F, and CF 3 ; R 2 includes a functional group or a functional polymer group; and subscript x is 0 or 1; with the provisos that:
not all of R o1 , R o2 , R o3 , R o4 , R o5 , R o6 , R m1 , R m2 , R m3 , R m4 , R m5 , R m6 , R p1 , R p2 , and R p3 can be F simultaneously;
not all of R o1-6 , R m1-6 , and R p1-3 can be H simultaneously; and
when two or more of R o1 , R o2 , R o3 , and R o4 are CF 3 , then R o5 and R o6 are each selected from H or F;

B) a hydroxyl-functional organosilicon compound of formula

 where subscript n is 1 to 2,000, and each R 1 is independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups; and
C) a cyclic polyorganohydrogensiloxane of formula (RHSiO 2/2 ) v , where subscript v is 3 to 12; and each R is an independently selected monovalent hydrocarbon group; thereby preparing the product comprising a polyfunctional organohydrogensiloxane and a by-product comprising H 2 ;
optionally 2) during and/or after step 1), removing the H 2 generated during formation of the polyfunctional organohydrogensiloxane; and
3) neutralizing residual fluorinated triarylborane compound in the polyfunctional organohydrogensiloxane, wherein where the polyfunctional organohydrogensiloxane has formula a-1):

 where
each subscript v is independently 3 to 12;
each subscript n is independently 1 to 1,000;
each R is an independently selected monovalent hydrocarbon group; and
each R 1 is independently selected from monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, with the proviso that one or more hydrogen atoms in formula a-1) may be replaced by a group of formula a-2):

 where each of subscript n, subscript v, R and R 1 are independently selected and described above.

2. The method of claim 1 , where the fluorinated triarylborane is selected from the group consisting of tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct; bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct; and bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane.

3. The method of claim 1 , where starting material B) comprises a hydroxyl-terminated polydiorganosiloxane, subscript n is 2 to 1,000, and each R 1 is selected from the group consisting of an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, and a halogenated alkyl group of 1 to 20 carbon atoms.

4. The method of claim 1 , where in the cyclic polyorganohydrogensiloxane, subscript v is 4 to 10, and each R is an alkyl group of 1 to 6 carbon atoms.

5. The method of claim 1 , where step 2) is present.

6. The method of claim 1 , where the polyfunctional organohydrogensiloxane has one or more hydrogen atoms in formula a-1) is replaced by a group of formula a-2):

 where each of subscript n, subscript v, R and R 1 are independently selected and described above.

7. The method of claim 1 , where the polyfunctional organohydrogensiloxane has formula:

8. The method of claim 1 , further comprising recovering the polyfunctional organohydrogensiloxane from the product.

9. A method for preparing a clustered functional organopolysiloxane comprising:
1) preparing a) the product by the method of claim 1 , and
2) Combining starting materials comprising
a) the product,
b) a hydrosilylation reaction catalyst, and
c) a reactive species having an average, per molecule at least one aliphatically unsaturated group capable of undergoing an addition reaction with a silicon-bonded hydrogen atom of starting material a) and further comprising one or more curable groups per molecule, where the clustered functional organopolysiloxane has formula a′-1):

 where
each subscript v is independently 3 to 12;
each subscript n is independently 1 to 1,000;
each R is an independently selected monovalent hydrocarbon group;
each R 1 is independently selected from monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups; and
each R 8 is independently selected from the group consisting of H and a curable group, and with the proviso that one or more of R 8 may be replaced with a group of formula a′-2);

 where subscript n, subscript v, R, R 1 , and R 8 are as described above; with the proviso that at least one R 8 per molecule is the curable group.

10. The method of claim 9 , where the reactive species is selected from the group consisting of:
i) a silane of formula R 4 y SiR 5 (4-y) , where subscript y is 1 to 3, each R 4 is the aliphatically unsaturated group capable of undergoing an addition reaction, and each R 5 is the curable group; thereby preparing a product comprising a clustered functional organosiloxane; and
ii) an organic compound of formula R 6 R 7 , where each R 6 is the aliphatically unsaturated group capable of undergoing an addition reaction, and each R/is the curable group.

11. The method of claim 9 , where the clustered functional organopolysiloxane has one or more of R 8 is replaced with a group of formula a′-2):

 where subscript n, subscript v, R, R 1 , and R 8 are as described above.

12. The method of claim 9 , where the clustered functional organopolysiloxane has formula:

13. A curable composition comprising:
(I) the product prepared by the method of claim 1 , and
(II) a curing agent.

14. The method of claim 10 , where the each R 5 is independently selected from the group consisting of an organic group containing an acrylate group, an organic group containing an alcohol group, an organic group containing an alkoxy group, an organic group containing an epoxy group, an organic group containing an isocyanate group, an organic group containing a methacrylate group, and an organic group containing a urethane group; and each R 7 is independently selected from the group consisting of an organic group containing an acrylate group, an organic group containing an alcohol group, an organic group containing an alkoxy group, an organic group containing an epoxy group, an organic group containi

Assignees

• Dow Silicones Corp
• Dow Global Technologies Llc

Inventors

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

Classifications

• C08G77/16 Primary

  to hydroxy groups · CPC title

• C08G77/08 Primary

  characterised by the catalysts used · CPC title

• C08L83/04

  Polysiloxanes · CPC title

• C08G77/12 Primary

  containing silicon bound to hydrogen · CPC title