Polymers incorporating covalently attached organoimido...

Details Polymers incorporating covalently attached organoimido... Polymers incorporating covalently attached organoimido...

2000-07-06

2004-03-16

Choi, Ling-Siu (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S346000, C526S329700, C526S274000, C526S236000

Reexamination Certificate

active

06706833

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is broadly concerned with new polyoxometalate compounds and polymers comprising recurring monomers of those compounds. More particularly, the inventive compounds comprise an organoimido group bonded to the polyoxometalate in place of at least one oxide of each starting polyoxometalate compound so as to improve certain properties (e.g., solubility in organic solvents) of the compounds.
2. Description of the Prior Art
Polyoxometalates are soluble, inorganic cluster-like compounds formed principally of an oxide anion and early transition metal cations. These discrete polymeric structures form spontaneously when simple oxides of, for example, vanadium, niobium, tantalum, molybdenum, or tungsten are combined under appropriate conditions in water. In a great majority of polyoxometalates, the transition metals are in the d
0
electronic configuration which dictates both high resistance to oxidative degradation and an ability to oxidize other materials. The principal transition metal ions that form polyoxometalates are tungsten(VI), molybdenum(VI), vanadium(V), niobium(V), and tantalum(V).
Isopolyoxometalates, the simplest of the polyoxometalates, are binary oxides of the formula [M
m
O
y
]
p−
, where m may vary over a wide range of numbers. For example, if m=8 and M=Mo, then the formula is [Mo
8
O
26
]
4−
.
Heteropolyoxometalates have the general formula [X
x
M
m
O
y
]
p−
and possess a heteroatom, X, at the center thereof. For example, in the &agr;-Keggin structure, &agr;-[PW
12
O
40
]
3−
, X is a phosphorus atom. The central phosphorus atom is surrounded by twelve WO
6
octahedra.
Polyoxometalates are characterized by a number of useful structural, electrochemical, catalytic, magnetic, medicinal, and photophysical properties (see, e.g.,
Chemical Reviews
, 98:1-389 (1998), incorporated by reference herein). Examples of applications of polyoxometalate systems include: solid state electrochromic devices; electrochemical fuel cells, precursors of oxide films for optoelectronics, recording materials, electrophotography, corrosion-resistant coatings, capacitors, and flammability control/smoke suppression. In the vast majority of these applications, the polyoxometalate species is utilized as an additive, a co-precipitant, or an ionic dopant. That is, the polyoxometalate species is present as a heterogenous additive rather than as a covalently-bonded integral component within the device. There are several disadvantages to using the polyoxometalate species as a heterogenous additive, including a non-uniform distribution of the polyoxometalate species, difficulties in varying the amount of polyoxometalate incorporation, migration and/or loss of polyoxometalate, and poor processability.
There are very few previous examples of polymers bearing covalently-incorporated polyoxometalate species. Knoth,
J. Am. Chem. Soc
., 101:2211 (1979), incorporated by reference herein, has described an all-inorganic polymer [(OC)
3
CoGe
2
W
11
SiO
40
5−
]
n
. Katsoulis et al.,
Mater. Res. Soc. Symp. Proc
., 435:589 (1996), incorporated by reference herein, have described siloxane polymers bearing polyoxometalate species. Finally, Judeinstein,
Chem. Mat
., 4:4-7 (1992), incorporated by reference herein, has described the homo-polymerization of systems such as [Bu
4
N]
4
[SiW
11
O
39
(RSiOSiR)], wherein R is vinyl, styryl, allyl, or methacryl group.
SUMMARY OF THE INVENTION
The present invention is broadly concerned with new polyoxometalate compounds as well as polymers comprising recurring monomers of these compounds. These compounds are formed by covalently bonding an organoimido group (NR, where R comprises a polymerizable moiety) to a metal site of the polyoxometalate compound in place of an oxide group.
In one embodiment polyoxometalate compounds according to the invention are represented by the formula:
[Q
x
]
+a
[X
b
M
m
M′
p
M″
z
O
n
(NR)
y
Y
c
]
−a
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;
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 Q may be the same or different, with each Q individually being a cation;
each Y is individually selected from the group consisting of H
2
O and the halides;
b is a number ranging from about 0-10, and preferably from about 1-3;
m is a number ranging from about 1-40, and preferably from about 4-18;
each of p and z is individually a number ranging from 0-6, and preferably from about 1-3, with the sum of m, p, and z ranging from 1-40;
n is a number ranging from about 1-200, preferably from about 3-62, and more preferably from about 6-39;
each a is the same number and ranges from about 1-20, and preferably from about 2-12;
each x is a number ranging from about 1-20, and preferably from about 2-12;
c is a number ranging from 0-2, and preferably from about 1-2; and
y is a number ranging from about 1-20, and preferably from about 2-6.
As used in the above formula, when b, p, z, and/or c is 0, it is intended that the substituent which b, p, z, or c is quantifying is not present in the compound. For example, if b is 0, then X is not present in the particular polyoxometalate compound.
In one embodiment, both p and z are 0, and M is Mo. In another embodiment, at least one of M and M′ is selected from the group consisting of Mo, W, and V, and M″ is selected from the group consisting of Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Ru, Rh, Ta, Re, and Os.
In embodiments where a countercation (Q) is present, each countercation is preferably not bonded to the (X
b
M
m
M′
p
M″
z
O
n
(NR)
y
Y
c
) complex, but is instead physically present therewith in order to counteract the negative charge of the complex. The presence of the countercations can be exploited in several ways such as to increase the solubility of the compounds in organic solvents or to provide for desirable properties through interaction with polyoxometalate components. Each Q is preferably 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, with bis(tetra-n-butylammonium), lithium cations, and mixtures thereof being the most preferred countercations.
In each of the foregoing embodiments, the nitrogen atom of the (NR) moiety is bonded to a metal atom of the (X
b
M
m
M′
p
M″
z
O
n
Y
c
) fragment, preferably via a triple bond. Furthermore, R is preferably a C
1
-C
8
alkyl group or a C
6
-C
12
aryl group. Even more preferably, at least one R includes a reactive portion or moiety selected from the group consisting of substituted and unsubstituted vinyl groups (e.g., such as part of an acrylate derivative), substituted and unsubstituted allyl groups, and silyl groups.
When R comprises a vinyl group, that group is represented by the formula —CR′═CH
2
, wherein R′ is selected from the group consisting of hydrogen, substituted and unsubstituted alkyls (preferably C
1
-C
6
), substituted and unsubstituted aryls (preferably C
6
-C
10
), substituted and unsubstituted silanes, substituted and unsubstituted siloxides, substituted and unsubstituted siloxanes. When R comprises an allyl group, that group is represented by the formula —CR″
2
—CR″═CH
2
, wherein each R″ is individually selected from the group consisting of hydrogen, substituted and unsubstituted alkyls (preferably C
1
-C
6
), substituted and unsubstituted aryls (preferably C
6
-C
10
), substituted and unsubstituted s

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