Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

Patent metadata

Field	Value
Publication number	US-9562118-B2
Application number	US-201514824955-A
Country	US
Kind code	B2
Filing date	Aug 12, 2015
Priority date	Aug 12, 2014
Publication date	Feb 7, 2017
Grant date	Feb 7, 2017

Abstract

A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

First claim

What is claimed is:

1. A compound comprising a reaction product of a hafnium-based metal-organic framework and a single-site zirconium-benzyl derivative.

2. The compound of claim 1 wherein the hafnium-based metal-organic framework has an organic portion comprising 1,3,6,8-tetrakis(p-benzoate)pyrene (TBAPy).

3. The compound of claim 2 wherein the single-site zirconium-benzyl derivative is tetrabenzylzirconium (ZrBn 4 ).

4. The compound of claim 3 wherein the hafnium-based metal-organic framework has a formula Hf 6 (OH) 16 (TBAPy) 2 .

5. The compound of claim 4 wherein the compound has on average 2.4 Zr per Hf 6 .

6. The compound of claim 4 wherein the compound has three Zr—O bonds and one Zr—Bn bonds.

7. The compound of claim 1 wherein the compound is crystalline.

8. A method of using a metal-organic framework for alkene polymerization, the method comprising:
providing a compound of claim 1 ;
contacting the compound with an alkene under at least one of a pressure and temperature sufficient to polymerize the alkene.

9. The method of claim 8 wherein the alkene is 1-hexene.

10. The method of claim 8 wherein the compound remains crystalline after the alkene is polymerized.

11. The method of claim 9 wherein the polymerized 1-hexene is stereoregular.

12. The method of claim 8 wherein the hafnium-based metal-organic framework has an organic portion comprising 1,3,6,8-tetrakis(p-benzoate)pyrene (TBAPy).

13. The method of claim 12 wherein the single-site zirconium-benzyl derivative is tetrabenzylzirconium (ZrBn 4 ).

14. The method of claim 13 wherein the hafnium-based metal-organic framework has a formula Hf 6 (OH) 16 (TBAPy) 2 .

15. The method of claim 14 wherein the compound has on average 2.4 Zr per Hf 6 .

16. The method of to claim 14 wherein the compound has three Zr—O bonds and one Zr—Bn bonds.

17. The method of claim 9 wherein the compound is crystalline.

18. The method of claim 17 wherein the compound remains crystalline after the alkene is polymerized.

Assignees

• Univ Northwestern

Inventors

• Farha Omar K
• Hupp Joseph T
• Delferro Massimiliano
• Klet Rachel C

Classifications

• C07F7/003

  without C-Metal linkages · CPC title

• C07F7/00

  Compounds containing elements of Groups 4 or 14 of the Periodic Table · CPC title

• C08F10/14 Primary

  Monomers containing five or more carbon atoms · CPC title

• C07F7/006

  Chemistry & Metallurgy · mapped topic

• C08F4/64

  Titanium, zirconium, hafnium or compounds thereof · CPC title