Selective 1,2-hydrosilylation of terminally unsaturated 1,3-dienes using iron catalysts

Patent metadata

Field	Value
Publication number	US-9890182-B2
Application number	US-201414270661-A
Country	US
Kind code	B2
Filing date	May 6, 2014
Priority date	May 6, 2013
Publication date	Feb 13, 2018
Grant date	Feb 13, 2018

Abstract

The present invention is directed to a selective and efficient process for the hydrosilylation of compounds containing terminally unsaturated 1,3-dienes using iron-based hydrosilylation catalysts. The resulting 1,2-addition products are useful as precursors for various silicone materials or silane- or silyl/silicone-functionalized polyolefins.

First claim

What is claimed is:

1. A process for the hydrosilylation of a compound containing a terminally unsaturated 1,3-diene, the process comprising (i) contacting a composition containing a silyl hydride and a compound containing a terminally unsaturated 1,3-diene with a complex of Formula (Ia) or (Ib), optionally in the presence of a solvent, to cause the silyl hydride to react with the compound containing a terminally unsaturated 1,3-diene to produce selectively a 1,2-hydrosilylation product containing said complex, and (ii) optionally removing the complex from the 1,2-hydrosilylation product;
wherein the compound containing a terminally unsaturated 1,3-diene has the formula CH 2 ═CH—CR═CHR′ where R and R′ independently is a saturated or unsaturated alkyl or aryl group or a halogen radical, with the proviso that R′ is H for isoprene and chloroprene; and
wherein the complexes of Formula (Ia) and (Ib) are

wherein:
G is Fe;
each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is independently hydrogen, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R 2 -R 9 , other than hydrogen, optionally contain at least one heteroatom;
each occurrence of R 23 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R 23 optionally contains at least one heteroatom;
optionally any two neighboring R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 23 groups taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure.

2. The process of claim 1 , wherein R 23 is

wherein R 1 , R 2 , R 4 , R 5 and R 6 are as defined in claim 1 .

3. The process of claim 1 , wherein R 1 and R 2 are both methyl, ethyl, propyl or isopropyl groups.

4. The process of claim 1 , wherein R 3 is methyl.

5. The process of claim 1 , wherein R 1 and R 2 are both methyl, R 4 , R 5 , and R 6 are hydrogen, and R 23 is 2,6-xylyl.

6. The process of claim 1 , wherein the complex of Formula (Ia) is [( Me PDI)FeN 2 ] 2 (μ 2 -N 2 ) or the complex of Formula (Ib) is ( Me PDI)Fe(N 2 ) 2 .

7. The process of claim 1 , wherein the complex is immobilized on a support.

8. The process of claim 7 , wherein the support is selected from the group consisting of carbon, silica, alumina, MgCl 2 , zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), dendrimers, and combinations thereof.

9. The process of claim 7 , wherein at least one of R 1 -R 9 contains a functional group that covalently bonds with the support.

10. The process of claim 1 , further comprising the step of removing the complex from the hydrosilylation product by magnetic separation and/or filtration.

11. The process of claim 1 , wherein the silyl hydride is selected from the group consisting of R a SiH 4-a , (RO) a SiH 4-a , Q u T v T p H D w D H x M H y M z , and combinations thereof, wherein Q is SiO 4/2 , T is R′SiO 3/2 , T H is HSiO 3/2 , D is R′ 2 SiO 2/2 D H is R′HSiO 2/2 , M H is HR′ 2 SiO 1/2 , M is R′ 3 SiO 1/2 , each occurrence of R and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, wherein R and R′ optionally contain at least one heteroatom, each occurrence of a independently has a value of from 1 to 3, g has a value of from 0 to 3, each of p, u, v, y and z is independently from 0 to 20, w and x are independently from 0 to 500, provided that p+x+y equals 1 to 500, and the valences of the all the elements in the silyl hydride are satisfied.

12. The process of claim 11 , wherein each of p, u, v, y, and z is independently from 0 to 10, w and x are independently from 0 to 100, wherein p+x+y equals 1 to 100.

13. The process of claim 1 , wherein the silyl hydride is MD H M.

14. The process of claim 1 , wherein the compound containing the terminally unsaturated 1,3-diene is isoprene, 1,3-hexadiene, myrcene, or chloroprene.

15. The process of claim 1 , wherein the catalyst is present in an amount of from about 0.05 mol % to about 5 mol %.

16. The process of claim 1 , wherein the catalyst is present in an amount of about 0.25 mol %.

17. The process of claim 1 , wherein the reaction is conducted over a period of from about 1 hour to about 24 hours.

18. The process of claim 1 , wherein the reaction is conducted over a period of about 24 hours.

19. A 1,2-hydrosilylation product produced from the process of claim 1 , wherein the compound containing the terminally unsaturated 1,3-diene is isoprene, 1,3-hexadiene, myrcene, or chloroprene, and wherein the product comprises (i) about 5 mol % or less of a 1,4-hydrosilylation product, an internal adduct, and/or an isomerization by-product, and (ii) the complex of (Ia) or (Ib).

Assignees

• Momentive Performance Mat Inc
• Univ Princeton

Inventors

• Atienza Crisita Carmen Hojilla
• Roy Aroop Kumar
• Chirik Paul J
• Weller Keith J
• Delis Johannes G P
• Diao Tianning

Classifications

• B01J31/1815 Primary

  with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine · CPC title

• C07F7/0812 Primary

  comprising a heterocyclic ring · CPC title

• B01J2231/323

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

• B01J2531/842

  Iron · CPC title

• B01J2531/0244

  Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds · CPC title