US 12,441,844 B2
Methods for making polyfunctional organosiloxanes and compositions containing same
Marc-Andre Courtemanche, Midland, MI (US); Anne-Catherine Bedard, Midland, MI (US); Heather Spinney, Midland, MI (US); David Wilson, Midland, MI (US); Arjun Raghuraman, Pearland, TX (US); Sukrit Mukhopadhyay, Midland, MI (US); and Travis Sunderland, Midland, MI (US)
Assigned to Dow Global Technologies LLC, Midland, MI (US); and Dow Silicones Corporation, Midland, MI (US)
Appl. No. 17/916,827
Filed by Dow Silicones Corporation, Midland, MI (US); and Dow Global Technologies LLC, Midland, MI (US)
PCT Filed Jun. 16, 2021, PCT No. PCT/US2021/037540
§ 371(c)(1), (2) Date Oct. 4, 2022,
PCT Pub. No. WO2021/262494, PCT Pub. Date Dec. 30, 2021.
Claims priority of provisional application 63/043,152, filed on Jun. 24, 2020.
Prior Publication US 2023/0151156 A1, May 18, 2023
Int. Cl. C08G 77/12 (2006.01); C08G 77/08 (2006.01); C08G 77/16 (2006.01)
CPC C08G 77/12 (2013.01) [C08G 77/08 (2013.01); C08G 77/16 (2013.01)] 19 Claims
 
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

OG Complex Work Unit Chemistry
 where each of Ro1, Ro2, Ro3, Ro4, Ro5, Ro6, Rm1, Rm2, Rm3, Rm4, Rm5, Rm6, Rp1, Rp2, and Rp3 is independently selected from the group consisting of H, F, and CF3; R2 includes a functional group or a functional polymer group; and subscript x is 0 or 1; with the provisos that:
not all of Ro1, Ro2, Ro3, Ro4, Ro5, Ro6, Rm1, Rm2, Rm3, Rm4, Rm5, Rm6, Rp1, Rp2, and Rp3 can be F simultaneously;
not all of Ro1-6, Rm1-6, and Rp1-3 can be H simultaneously; and
when two or more of Ro1, Ro2, Ro3, and Ro4 are CF3, then Ro5 and Ro6 are each selected from H or F;
B) a hydroxyl-functional organosilicon compound of formula

OG Complex Work Unit Chemistry
 where subscript n is 1 to 2,000, and each R1 is independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups; and
C) a cyclic polyorganohydrogensiloxane of formula (RHSiO2/2)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 H2;
optionally 2) during and/or after step 1), removing the H2 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):

OG Complex Work Unit Chemistry
 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 R1 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):

OG Complex Work Unit Chemistry
 where each of subscript n, subscript v, R and R1 are independently selected and described above.