Polymers incorporating covalently attached organoimido polyoxometalates

• US 6,706,833 B1
• Filed: 07/06/2000
• Issued: 03/16/2004
• Est. Priority Date: 07/06/2000
• Status: Expired due to Fees

• Current Assignee: Kansas State University Research Foundation
• Original Assignee: Kansas State University Research Foundation
• Inventors: Maatta, Eric A., Moore, Aaron R.
• Primary Examiner(s): CHOI, LING SIU
• Application Number:
  US09/609,863
• Time in Patent Office: 1,349 Days
• Field of Search: 526/346, 526/329.7, 526/274, 526/236, 526/240
• US Class Current: 526/240
• CPC Class Codes: C07F 11/005 compounds without a metal-carbon linkage
• CPC Class Codes: C08F 30/04 containing a metal

Abstract

New polyoxometalate compounds and polymers comprising recurring monomers of those compounds are provided. The compounds are formed by replacing at least one oxide of the starting polyoxometalate with an organoimido (NR) group bonded to the polyoxometalate via a triple bond to the nitrogen atom. The R of the (NR) group comprises a reactive functional group which renders the compound readily polymerizable, alone or with other monomers (e.g., divinylbenzene), to form the inventive polymers. Additionally, a countercation (e.g., bis(tetra-n-butylammonium)) can be mixed with the polyoxometalate compounds in order to neutralize the negative charge thereof as well as to make those compounds more soluble in organic solvents.

Claims

1. A polymer comprising recurring polyoxometalate monomers represented by the formula:

wherein;

each of M, M′

, and M″

is a metal individually selected from the group consisting of Mo, W, V, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Ru, Rh, Ta, Re, and Os;

N is bonded to one of M, M′

, or M″

;

R may be the same or different in each (NR) moiety and each R is individually selected from the group consisting of substituted and unsubstituted alkyl and aryl groups other than styrene groups;

each X is individually selected from the group consisting of Si, P, B, As, Se, S, Sn, Sb, and Bi;

each Y is individually selected from the group consisting of H₂O and the halides;

Y is bonded to one of M, M′

, or M″

;

each Q may be the same or different, with each Q individually being a cation;

b is a number ranging from about 0-10;

m is a number ranging from about 1-40;

each of p and z is individually a number ranging from 0-6, with the sum of m, p, and z ranging from 1-40;

n is a number ranging from about 1-200;

each a is the same number and ranges from about 1-20;

each x is a number ranging from about 1-20;

c is a number ranging from 0-2; and

y is a number ranging from about 1-20.

2. The polymer of claim 1, wherein at least one of M or M′

is selected from the group consisting of Mo, W, and V, and M″

selected from the group consisting of Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Ru, Rh, Ta, Re, and Os.

3. The polymer of claim 2, wherein each of M and M′

are individually selected from the group consisting of Mo, W, and V.

4. The polymer of claim 1, wherein the nitrogen atom of the (NR) moiety is bonded to one of M, M′

, or M″

via a triple bond.

5. The polymer of claim 1, said polymer further comprising recurring olefinic monomers.

6. The polymer of claim 1, said polymer further comprising recurring monomers selected from the group consisting of substituted and unsubstituted styrene monomers, olefinic monomers, acrylates, vinylic monomers, and vinylidene monomers.

7. The polymer of claim 1, said polymer further comprising recurring monomers selected from the group consisting of methacrylates, 4-methylstyrene, divinylbenzene, and mixtures thereof.

8. The polymer of claim 1, wherein each Q is individually selected from the group consisting of H⁺, alkali metal cations, alkaline earth metal cations, substituted and unsubstituted ammonium cations, substituted and unsubstituted phosphonium cations, and metal complex cations.

9. The polymer of claim 8, wherein at least one Q is selected from the group consisting of bis(tetra-n-butylammonium), lithium cation, and mixtures thereof.

10. A polymer comprising recurring polyoxometalate monomers represented by the formula:

wherein;

each of M, M′

, and M″

is a metal individually selected from the group consisting of Mo, W, V, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Ru, Rh, Ta, Re, and Os;

N is bonded to one of M, M′

, or M″

;

R may be the same or different in each (NR) moiety and each R is individually selected from the group consisting of substituted and unsubstituted alkyl and aryl groups other than styrene groups, substituted and unsubstituted vinyl groups, substituted and unsubstituted allyl groups, and silyl groups;

at least one R comprises a group selected from the group consisting of substituted and unsubstituted vinyl groups, substituted and unsubstituted allyl groups, and silyl groups;

each X is individually selected from the group consisting of Si, P, B, As, Se, S, Sn, Sb, and Bi;

each Y is individually selected from the group consisting of H₂O and the halides;

Y is bonded to one of M, M′

, or M″

;

each Q may be the same or different, with each Q individually being a cation;

b is a number ranging from about 0-10;

m is a number ranging from about 1-40;

each of p and z is individually a number ranging from 0-6, with the sum of m, p, and z ranging from 1-40;

n is a number ranging from about 1-200;

each a is the same number and ranges from about 1-20;

each x is a number ranging from about 1-20;

c is a number ranging from 0-2; and

y is a number ranging from about 1-20.

11. The polymer of claim 10, wherein said at least one R comprises a silyl group represented by the formula:

12. The polymer of claim 10, wherein said at least one R comprises a vinyl group represented by the formula:

13. The polymer of claim 10, wherein said at least one R comprises an allyl group represented by the formula:

14. A polymer comprising recurring polyoxometalate monomers represented by the formula:

wherein;

each of M, M′

, and M″

is a metal individually selected from the group consisting of Mo, W, V, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Ru, Rh, Ta, Re, and Os;

N is bonded to one of M, M′

, or M″

;

R may be the same or different in each (NR) moiety and each R is individually selected from the group consisting of substituted and unsubstituted alkyl and aryl groups;

each X is individually selected from the group consisting of Si, P, B, As, Se, S, Sn, Sb, and Bi;

each Y is individually selected from the group consisting of H₂O and the halides;

Y is bonded to one of M, M′

, or M″

;

each Q may be the same or different, with each Q individually being a cation;

b is a number ranging from about 0-10;

m is a number ranging from about 1-40;

each of p and z is individually a number ranging from 0-6, with the sum of m, p, and z ranging from 1-40;

n is a number ranging from about 1-200;

each a is the same number and ranges from about 1-20;

each x is number ranging from about 1-20;

c is a number ranging from 0-2; and

y is a number ranging from about 1-20; and

recurring monomers selected from the group consisting of substituted and unsubstituted styrene monomers, acrylates, vinylic monomers, vinylidene monomers, and mixtures thereof.

15. A polymer comprising recurring polyoxometalate monomers represented by the formula:

wherein;

each of M, M′

, and M″

is a metal individually selected from the group consisting of Mo, W, V, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Ru, Rh, Ta, Re, and Os;

N is bonded to one of M, M′

, or M″

;

R may be the same or different in each (NR) moiety and each R is individually selected from the group consisting of substituted and unsubstituted alkyl and aryl groups;

each X is individually selected from the group consisting of Si, P, B, As, Se, S, Sn, Sb, and Bi;

each Y is individually selected from the group consisting of H₂O and the halides;

Y is bonded to one of M, M′

, or M″

;

each Q may be the same or different, with each Q individually being a cation;

b is a number ranging from about 0-10;

m is a number ranging from about 1-40;

each of p and z is individually a number ranging from 0-6, with the sum of m, p, and z ranging from 1-40;

n is a number ranging from about 1-200;

each a is the same number and ranges from about 1-20;

each x is number ranging from about 1-20;

c is a number ranging from 0-2; and

y is a number ranging from about 1-20; and

recurring monomers selected from the group consisting of methacrylates, 4-methylstyrene, divinylbenzene, and mixtures thereof.

16. A polymer comprising recurring monomers of a polyoxometalate compound represented by the formula: