Isocyanide compound and hydrosilylation reaction catalyst

Patent metadata

Field	Value
Publication number	US-10829504-B2
Application number	US-201716071850-A
Country	US
Kind code	B2
Filing date	Jan 18, 2017
Priority date	Jan 22, 2016
Publication date	Nov 10, 2020
Grant date	Nov 10, 2020

Abstract

A hydrosilylation reaction catalyst prepared from a catalyst precursor comprising a transition metal compound of groups 8, 9, or 10 of the periodic table, excluding platinum, such as an iron carboxylate, cobalt carboxylate, or nickel carboxylate, and a ligand comprising an isocyanide compound having an organosiloxane group.

First claim

The invention claimed is:

1. An isocyanide compound having the formula (1) or (1)′:
R 1 —Si(R 1 ) a {[(OSi(R 1 ) 2 )] b —R 1 } c   (1)

in formula (1) or (1)′, R 1 is each independently a monovalent organic group selected from optionally substituted alkyl, alkoxy, alkenyl, alkynyl, aryl, and aralkyl groups of 1 to 30 carbon atoms which may be separated by at least one atom selected from oxygen, nitrogen, sulfur and phosphorus, and groups having the formula (2):
-A-NC  (2)

wherein A is an optionally substituted divalent organic group of 1 to 30 carbon atoms which may be separated by at least one atom selected from silicon, oxygen, nitrogen, sulfur and phosphorus, one, two or three of all R 1 groups being an organic group of formula (2),
a is 0, 1 or 2, c is 1, 2 or 3, a+c is equal to 3, b is an integer of 1 to 300, and d is an integer of 3 to 20.

2. The isocyanide compound of claim 1 wherein one of all R 1 groups in formula (1) or (1)′ is an organic group of formula (2).

3. A hydrosilylation reaction catalyst which is the reaction product of a metal salt compound having the formula (3) and an isocyanide compound having the formula (1) or (1)′,
M e (L) f (X) g   (3)

in formula (3), M is a transition metal of Group 8, 9 or 10 in the Periodic Table exclusive of platinum,
X is a halogen atom,
L is at least one monovalent organic group selected from the following formulae (4) to (6),
e is an integer of 1 or 2, f is an integer of 0 to 6, g is an integer of 0 to 3, f+g is equal to 2 or 3 when e=1, and f+g is equal to 4 to 6 when e=2,
—O—R 2   (4)

—OCO—R 2   (5)

—OSO 2 —R 2   (6)

in formulae (4) to (6), R 2 is each independently an optionally substituted monovalent organic group of 1 to 30 carbon atoms which may be separated by at least one atom selected from oxygen, nitrogen, sulfur and phosphorus, or a monovalent organic group having the formula (7):
—(B) p R 3   (7)

wherein B is an optionally substituted divalent organic group of 1 to 30 carbon atoms which may be separated by at least one atom selected from oxygen, nitrogen, sulfur and phosphorus,
p is an integer of 0 or 1, p is 0 or 1 when L is a monovalent organic group of formula (4), and p is 1 when L is a monovalent organic group of formula (5) or (6),
R 3 is a group having the formula (8):
—{Si(R 5 ) 2 —R 4 } h —Si(R 5 ) l {[(OSi(R 5 ) 2 )] m —R 5 } n   (8)

wherein R 4 is an optionally substituted divalent organic group of 1 to 10 carbon atoms which may be separated by at least one oxygen atom,
R 5 is an optionally substituted alkyl, alkoxy, aryl or aralkyl group of 1 to 30 carbon atoms which may be separated by at least one atom selected from oxygen, nitrogen, sulfur and phosphorus,
h is an integer of 0 or 1, l is an integer of 0 to 3, m is an integer of 1 to 300, n is an integer of 0 to 3, l+n is equal to 3,
R 1 —Si(R 1 ) a {[(OSi(R 1 ) 2 )] b —R 1 } c   (1)

in formula (1) or (1)′, R 1 is each independently a monovalent organic group selected from optionally substituted alkyl, alkoxy, alkenyl, alkynyl, aryl, and aralkyl groups of 1 to 30 carbon atoms which may be separated by at least one atom selected from oxygen, nitrogen, sulfur and phosphorus, and groups having the formula (2):
-A-NC  (2)

wherein A is an optionally substituted divalent organic group of 1 to 30 carbon atoms which may be separated by at least one atom selected from silicon, oxygen, nitrogen, sulfur and phosphorus, one, two or three of all R 1 groups being an organic group of formula (2),
a is 0, 1 or 2, c is 1, 2 or 3, a+c is equal to 3, b is an integer of 1 to 300, and d is an integer of 3 to 20.

4. The hydrosilylation reaction catalyst of claim 3 wherein one of all R 1 groups in formula (1) or (1)′ is an organic group of formula (2).

5. The hydrosilylation reaction catalyst of claim 3 which is prepared for effecting a hydrosilylation reaction between (i) compound having an aliphatic unsaturated bond and (ii) a hydrosilane compound or organohydro(poly)siloxane compound having a Si—H group.

6. The hydrosilylation reaction catalyst of claim 3 wherein M is Fe, Co or Ni, e is 1, f is 2, and g is 0.

7. The hydrosilylation reaction catalyst of claim 3 wherein M is Rh, e is 2, f is 4, and g is 0.

8. The hydrosilylation reaction catalyst of claim 3 wherein M is Ru, e is 2, f is 4, and g is 1.

9. The hydrosilylation reaction catalyst of claim 3 wherein L is a monovalent organic group of formula (5).

10. The hydrosilylation reaction catalyst of claim 9 wherein R 2 is an optionally halo-substituted alkyl group of 1 to 5 carbon atoms.

11. A method for preparing a hydrosilylation reaction catalyst according to claim 3 , comprising the step of reacting a metal salt compound of formula (3) with an isocyanide compound of formula (1) or (1)′, comprising (i) a compound having an aliphatic unsaturated bond and (ii) a hydrosilane compound or organohydro(poly)siloxane compound having a Si—H group.

12. A method for preparing an addition compound comprising the step of effecting hydrosilylation reaction of a compound having an aliphatic unsaturated bond with a hydrosilane compound or organohydro(poly)siloxane compound having a Si—H bond in the presence of the hydrosilylation reaction catalyst of claim 3 .

13. The method for preparing an addition compound of claim 12 wherein the compound having an aliphatic unsaturated bond is an olefin compound, or a silane compound or organo(poly)siloxane having an alkenyl group.

14. A method for preparing an addition compound comprising the steps of:
preparing a hydrosilylation reaction catalyst from a metal salt of formula (3) and an isocyanide compound of formula (1) or (1)′, as set forth in claim 3 , in a system for effecting hydrosilylation reaction between a compound having an aliphatic unsaturated bond and a hydrosilane compound or organohydro(poly)siloxane compound having a Si—H group, and
effecting the hydrosilylation reaction in the presence of the hydrosilylation reaction catalyst.

15. The method for preparing an addition compound of claim 14 wherein the compound having an aliphatic unsaturated bond is an olefin compound, or a silane compound or organo(poly)siloxane having an alkenyl group.

16. The isocyanide compound of claim 1 , wherein R 1 is each independently a monovalent organic group selected from the groups consisting of C 1 -C 30 monovalent hydrocarbon groups, alkoxy groups and groups having the formula (2).

17. The isocyanide compound of claim 1 , wherein A is an optionally substituted divalent hydrocarbon group of 1 to 30 carbon atoms.

18. The isocyanide compound of claim 1 , wherein A is a divalent hydrocarbon group selected from the groups consisting of C 1 -C 20 alkylene groups, C 6 -C 30 arylene groups and C 7 -C 30 aralkylene groups.

19. The hydrosilylation reaction catalyst of claim 3 , herein in formulae (1) and (1)′, R 1 is each independently a monovalent organic group selected from the groups consisting of C 1 -C 30 monovalent hydrocarbon groups, alkoxy groups and groups having the formula (2).

20. The hydrosilylation reaction catalyst of claim 3 , wherein in formula (2), A is an optionally substituted divalent hydrocarbon group of 1 to 30 carbon atoms.

21. The hydrosilylation reaction ca

Assignees

• Shinetsu Chemical Co
• Univ Kyushu Nat Univ Corp

Inventors

• Sakuta Koji
• Nagashima Hideo
• Sunada Yusuke
• Noda Daisuke

Classifications

• B01J2531/821

  Ruthenium · CPC title

• B01J2531/847

  Nickel · CPC title

• B01J2531/824

  Palladium · CPC title

• B01J2531/845

  Cobalt · CPC title

• B01J2231/323

  Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation · CPC title