Preparation of organosilicon compounds with carboxy functionality

Patent metadata

Field	Value
Publication number	US-2025051524-A1
Application number	US-202318715165-A
Country	US
Kind code	A1
Filing date	Feb 16, 2023
Priority date	Mar 21, 2022
Publication date	Feb 13, 2025
Grant date	—

Abstract

An organosilicon compound with carboxy-functional groups is prepared. An oxidation process in which an aldehyde-functional organosilicon compound and an oxygen source are combined produces the carboxy-functional organosilicon compound.

First claim

1 . A process for preparing a carboxy-functional organosilicon compound, the process comprising:
forming an aldehyde-functional organosilicon compound before step I) by a process comprising combining, under conditions to catalyze hydroformylation reaction, starting materials comprising,
(A) a gas comprising hydrogen and carbon monoxide,
(B) an alkenyl-functional organosilicon compound, and
(C) a rhodium/bisphosphite ligand complex catalyst, where the bisphosphite ligand has formula

where
R 6 and R 6′ are each independently selected from the group consisting of hydrogen, an alkyl group of 1 to 20 carbon atoms, a cyano group, a halogen group, and an alkoxy group of 1 to 20 carbon atoms;
R 7 and R 7′ are each independently selected from the group consisting of an alkyl group of 3 to 20 carbon atoms, and a group of formula —SiR 17 3 , where each R 17 is an independently selected monovalent hydrocarbon group of 1 to 20 carbon atoms;
R 8 , R 8′ , R 9, and R 9′ are each independently selected form the group consisting of hydrogen, an alkyl group, a cyano group, a halogen group, and an alkoxy group, and
R 10′ , R 11 , and R 11 ′ are each independently selected from the group consisting of hydrogen or and alkyl group; thereby forming a hydroformylation reaction product comprising the aldehyde-functional organosilicon compound; and thereafter

I) combining, under conditions to conduct oxidation reaction, starting materials comprising the aldehyde-functional organosilicon compound and an oxygen source, thereby forming an oxidation reaction product comprising the carboxy-functional organosilicon compound.

2 . The process of claim 1 , where the aldehyde-functional organosilicon compound comprises an aldehyde-functional silane of formula: R Ald x SiR 4 (4-x) , where each R Ald is an independently selected aldehyde group of 3 to 9 carbon atom having formula

where G is a linear or branched divalent hydrocarbon group of 2 to 8 carbon atoms that is free of aliphatic unsaturation; each R 4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbon atoms, and an hydrocarbonoxy-functional group of 1 to 18 carbon atoms; and subscript x is 1 to 4.

3 . The process of claim 1 , where the aldehyde-functional organosilicon compound comprises an aldehyde-functional polyorganosiloxane of unit formula: (R 4 3 SiO 1/2 ) a (R 4 2 R Ald SiO 1/2 ) b (R 4 2 SiO 2/2 ) c (R 4 R Ald SiO 2/2 ) d (R 4 SiO 3/2 ) c (R Ald SiO 3/2 ) f (SiO 4/2 ) g (ZO 1/2 ) h ; where each R Ald is an independently selected aldehyde group of 3 to 9 carbon atoms, and each R 4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and an hydrocarbonoxy group of 1 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R 5 , where each R 5 is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms; subscripts a, b, c, d, e, f, and g represent numbers of each unit in the unit formula and have values such that subscript a≥0, subscript b≥0, subscript c≥0, subscript d≥0, subscript e≥0, subscript f≥0, subscript g≥0; and subscript h has a value such that 0≤h/(e+f+g)≤1.5, with the proviso that when e=f=g=0, then h≥0; 10,000≥(a+b+c+d+e+f+g)≥2, and a quantity (b+d+f)≥1.

4 . The process of claim 3 , where the aldehyde-functional polyorganosiloxane is selected from the group consisting of:
i) a cyclic aldehyde-functional polyorganosiloxane having a unit formula selected from the group consisting of (R 4 R Ald SiO 2/2 ) d , where subscript d is 3 to 12; (R 4 2 SiO 2/2 ) c (R 4 R Ald SiO 2/2 ) d , where c is >0 to 6 and d is 3 to 12; and a combination thereof; ii) a linear aldehyde-functional polyorganosiloxane comprising unit formula: (R 4 3 SiO 1/2 ) a (R 4 2 R Ald SiO 1/2 ) b (R 4 2 SiO 2/2 ) c (R 4 R Ald SiO 2/2 ) d , where a quantity (a+b)=2, a quantity (b+d)≥1, and a quantity (a+b+c+d)≥2; iii) an aldehyde-functional polyorganosilicate resin comprising unit formula: (R 4 3 SiO 1/2 ) mm (R 4 2 R Ald SiO 1/2 ) nn (SiO 4/2 ) oo (ZO 1/2 ) h , where subscripts mm, nn, and oo represent mole percentages of each unit in the polyorganosilicate resin; and subscripts mm, nn and oo have average values such that mm≥0, nn≥0, oo>0, and 0.5≤(mm+nn)/oo≤4; iv) an aldehyde-functional silsesquioxane resin comprising unit formula: (R 4 3 SiO 1/2 ) a (R 4 2 R Ald SiO 1/2 ) b (R 4 2 SiO 2/2 ) c (R 4 R Ald SiO 2/2 ) d (R 4 SiO 3/2 ) c (R Ald SiO 3/2 ) f (ZO 1/2 ) h ; where f>1, 2<(e+f)<10,000; 0<(a+b)/(e+f)<3; 0<(c+d)/(e+f)<3; and 0<h/(e+f)<1.5; v) a branched aldehyde-functional polyorganosiloxane comprising unit formula: R Ald SiR 12 3 , where each R 12 is selected from R 13 and —OSi(R 14 ) 3 ; where each R 13 is a monovalent hydrocarbon group; where each R 14 is selected from R 13 , —OSi(R 15 ) 3 , and —[OSiR 13 2 ] ii OSiR 13 3 ; where each R 15 is selected from R 13 , —OSi(R 16 ) 3 , and —[OSiR 13 2 ] ii OSiR 13 3 ; where each R 16 is selected from R 13 and —[OSiR 13 2 ] ii OSiR 13 3 ; and where subscript ii has a value such that 0≤ii≤100, with the proviso that at least two of R 12 are —OSi(R 14 ) 3; vi) a Q branched aldehyde-functional polyorganosiloxane oligomer comprising unit formula: (R 4 3 SiO 1/2 ) q (R 4 2 R Ald SiO 1/2 ) r (R 4 2 SiO 2/2 ) s (SiO 4/2 ) t , where subscripts q, r, s, and t have average values such that 2≥q≥0, 4≥r≥0, 995≥s≥4, t=1, (q+r)=4, and (q+r+s+t) has a value sufficient to impart a viscosity>170 mPa·s measured by rotational viscometry (as described below with the test methods) to the Q branched polyorganosiloxane; and vii) a T branched aldehyde-functional polyorganosiloxane comprising unit formula: (R 4 3 SiO 1/2 ) aa (R Ald R 4 2 SiO 1/2 ) bb (R 4 2 SiO 2/2 ) cc (R Ald R 4 SiO 2/2 ) ee (R 4 SiO 3/2 ) dd , where subscript aa≥0, subscript bb>0, subscript cc is 15 to 995, subscript dd>0, and subscript ee≥0.

5 . The process of claim 2 , where each R Ald is independently selected from the group consisting of propyl aldehyde, butyl aldehyde, and heptyl aldehyde.

6 . The process of a claim 2 , where each R 4 is independently selected from the group consisting of methyl and phenyl.

7 . The process of claim 1 , further comprising: II) equilibrating the carboxy-functional organosilicon compound with a cyclic polydiorganosiloxane in the presence of an equilibration catalyst.

8 . The process of claim 1 , further comprising
recovering the aldehyde-functional organosilicon compound before step I).

9 . The process of claim 1 , were the oxygen source is selected from the group consisting of air, oxygen gas, and a peroxide compound.

10 . The process of claim 9 , where the oxygen source is used at a partial pressure from 3 psia (20 kPa) to 100 psia (690 kPa).

11 . The process of claim 1 , where the starting materials in step I) further comprise an additional material selected from the group consisting of an oxidation reaction catalyst, a solvent, and both the oxidation reaction catalyst and the solvent.

12 . The process of claim 11 , where the oxidation reaction catalyst is present and comprises a transition metal complex comprising a metal selected from the group consisting of Co, Cu, Mn, Ni, Rh, and a combination of two or more

Assignees

• Dow Silicones Corp
• Dow Global Technologies Llc

Inventors

• Molitor Erich
• Fisk Jason
• Maar Ryan
• Larsen Robert
• Devore David

Classifications

• C08G77/70

  Siloxanes defined by use of the MDTQ nomenclature · CPC title

• C08G77/08

  characterised by the catalysts used · CPC title

• C07F7/21

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

• C07F7/0889

  Reactions not involving the Si atom of the Si-O-Si sequence · CPC title

• C08G77/14

  containing silicon bound to oxygen-containing groups · CPC title