Preparation of organosilicon compounds with aldehyde functionality

Patent metadata

Field	Value
Publication number	US-12595339-B2
Application number	US-202118004530-A
Country	US
Kind code	B2
Filing date	Oct 11, 2021
Priority date	Oct 13, 2020
Publication date	Apr 7, 2026
Grant date	Apr 7, 2026

Abstract

A catalyzed hydroformylation process of an alkenyl-functional organosilicon compound with carbon monoxide and hydrogen produces an aldehyde-functional organosilicon compound.

First claim

The invention claimed is:

1 . A reaction product prepared by a process comprising:
1) 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 from the group consisting of hydrogen, an alkyl group, a cyano group, a halogen group, and an alkoxy group, and
R 10 R 10′ , R 11 , and R 11′ are each independently selected from the group consisting of hydrogen or and alkyl group;
wherein the reaction product comprises
the aldehyde-functional organosilicon compound, wherein
the aldehyde-functional organosilicon compound has, per molecule, at least one aldehyde-functional group covalently bonded to silicon, wherein

the aldehyde-functional group has formula

where
G is a divalent hydrocarbon group free of aliphatic unsaturation that has 2 to 8 carbon atoms; and
the rhodium/bisphosphite ligand complex catalyst; and wherein the aldehyde-functional organosilicon compound comprises
a) a first organosilicon compound comprising a linear aldehyde-functional moiety, and
b) a second organosilicon compound comprising a branched aldehyde-functional moiety; wherein
a molar ratio of the linear aldehyde-functional moiety/the branched aldehyde-functional moiety (N/I ratio)>6.

2 . The reaction product of claim 1 , where starting material (B) comprises an alkenyl-functional silane of formula (B1): R A x SiR 4 (4-x) , where each R A is vinyl; 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 reaction product of claim 1 , where the alkenyl-functional organosilicon compound comprises an alkenyl-functional polyorganosiloxane of unit formula: (R 4 3 SiO 1/2 ) a (R 4 2 R A SiO 1/2 ) b (R 4 2 SiO 2/2 ) c (R 4 R A SiO 2/2 ) d (R 4 SiO 3/2 ) e (R A SiO 3/2 ) f (SiO 4/2 ) g (ZO 1/2 ) h ; where each R A is vinyl, 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 formula (B2-1) 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, 10,000≥(a+b+c+d+e+f+g)≥2, and a quantity (b+d+f)≥1.

4 . The reaction product of claim 3 , where the alkenyl-functional polyorganosiloxane is cyclic and has a unit formula selected from the group consisting of: (R 4 R A SiO 2/2 ) d , where subscript d is 3 to 12; (R 4 2 SiO 22 ) c (R 4 R A SiO 2/2 ) d , where c is >0 to 6 and d is 3 to 12; and a combination thereof.

5 . The reaction product of claim 3 , where the alkenyl-functional polyorganosiloxane is linear and comprises unit formula (B3): (R 4 3 SiO 1/2 ) a (R 4 2 R A SiO 1/2 ) b (R 4 2 SiO 2/2 ) c (R 4 R A SiO 2/2 ) d , where a quantity (a+b)=2, a quantity (b+d)≥1, and a quantity (a+b+c+d)≥2.

6 . The reaction product of claim 3 , where the alkenyl-functional polyorganosiloxane is an alkenyl-functional polyorganosilicate resin comprising unit formula: (R 4 3 SiO 1/2 ) mm (R 4 2 R A 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.

7 . The reaction product of claim 3 , where the alkenyl-functional polyorganosiloxane is an alkenyl-functional silsesquioxane resin comprising unit formula: (R 4 3 SiO 1/2 ) a (R 4 2 R A SiO 1/2 ) b (R 4 2 SiO 2/2 ) c (R 4 R A SiO 2/2 ) d (R 4 SiO 3/2 ) e (R A 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.

8 . The reaction product of claim 3 , where each R 4 is independently selected from the group consisting of methyl and phenyl.

9 . The reaction product of claim 1 , where in the bisphosphite ligand, R 6 and R 6′ are each selected from the group consisting of a methoxy group and a t-butyl group, R 7 and R 7′ are each a t-butyl group, and R 8 , R 8′ , R 9 , R 9′ , R 10 , R 10′ , R 11 , and R 11′ are each hydrogen.

10 . The reaction product of claim 1 , where starting material (C) is present in an amount sufficient to provide 0.1 ppm to 300 ppm Rh based on weight of (B) the alkenyl-functional organosilicon compound.

11 . The reaction product of claim 1 , where starting material (C) has a molar ratio of bisphosphite ligand/Rh of 1/1 to 10/1.

12 . The reaction product of claim 1 , where the conditions in step 1) are selected from the group consisting of:
i) a temperature of 30° C. to 150° C.; ii) a pressure of 101 kPa to 6,895 kPa; iii) a molar ratio of CO/H 2 in the syngas of 3/1 to 1/3; and iv) a combination of two or more of conditions i), ii) and iii).

13 . The reaction product of claim 1 , where (C) the rhodium/bisphosphite ligand complex catalyst is formed by combining a rhodium precursor and the bisphosphite ligand to form a rhodium/bisphosphite ligand complex and combining the rhodium/bisphosphite ligand complex and starting material (A) with heating before step 1).

14 . The reaction product of claim 10 , where starting material (C) is present in an amount sufficient to provide 0.25 ppm to 20 ppm Rh.

15 . The reaction product of claim 3 , wherein the alkenyl-functional polyorganosiloxane is branched.

16 . The reaction product of claim 3 , wherein the alkenyl-functional polyorganosiloxane comprises formula: [R A R 4 2 Si—(O—SiR 4 2 ) x —O] (4-w) —Si—[O—(R 4 2 SiO) v SiR 4 3 ] w , where R A and R 4 are as described above; and subscripts v, w, and x have values such that 200≥v≥1, 2≥w≥0, and 200≥x≥1.

17 . The reaction product of claim 3 , wherein the alkenyl-functional polyorganosiloxane comprises unit formula: (R 4 3 SiO 1/2 ) aa (R A R 4 2 SiO 1/2 ) bb (R 4 2 SiO 2/2 ) cc (R A R 4 SiO 22 ) ee (R 4 SiO 3/2 ) dd , where R 4 and R A are as described above, subscript aa≥0, subscript bb>0, subscript cc is 15 to 995, subscript dd>0, and subscript ee≥0.

18 . A process for preparing an aldehyde-functional organosilicon compound, said process comprisi

Assignees

• Dow Silicones Corp
• Dow Global Tech Llc

Inventors

• Fisk Jason
• Larsen Robert
• Li Haoquan
• Tulchinsky Michael
• Wieber Gary
• Devore David
• Gohndrone John
• Ferritto Michael

Classifications

• B01J31/185

  Phosphites ((RO)3P) , their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof · CPC title

• C07F15/0073

  Rhodium compounds · CPC title

• C07F9/65746

  the molecule containing more than one cyclic phosphorus atom · CPC title

• C07F7/1892 Primary

  by reactions not provided for in C07F7/1876 - C07F7/1888 · CPC title

• C07F7/21

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