US4252676A
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Preparation of colloidal group VII-A transition metal dispersions by the polymer-catalyzed decomposition of carbonyl and organocarbonyl compounds thereof
Assignee: Xerox Corp
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Filing: 1979-12-04
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Granted: 1981-02-24
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Expires: 1999-12-04
Abstract
Abstract There is disclosed a method for the preparation of a homogeneous, physically stable dispersion of colloidal metal particles of a transition metal selected from the group consisting of manganese and rhenium having a size in the range of from about 10 Angstrom units to about 200 Angstrom units. The method comprises preparing a solution of a functional polymer in an inert solvent, and incrementally adding thereto a transition metal precursor, at a temperature at which the transition metal precursor will become bound to the polymer and thermally decompose to produce elemental transition metal particles, the process being carried out in an inert atmosphere. Such dispersions may be used per se as catalysts, or may be used for the preparation of supported colloidal transition metal catalysts. The dispersions may also be used for the preparation of ablative optical recording media.
Inventors
- 👤 Thomas W. Smith
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-26 18:25
CPC Classifications
B; B01; B01J; B01J23/00; B01J23/16; B01J23/32; B01J31/00; B01J31/02; B01J31/06; B01J35/00; B01J35/20; B01J35/23; B01J35/40; B01J35/45; C; C08; C08C; C08C19/00; C08C19/30; C08C19/42; C08F; C08F8/00; C08F8/42; C08J; C08J3/00; C08J3/02; C08J3/09; C08J3/11; B01J2231/00; B01J2231/50; B01J2231/52; B01J23/34; B01J23/36; Y; Y10; Y10S; Y10S430/00; Y10S430/146
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
182 words
A method for the preparation of a homogeneous, physically stable coloidal elemental dispersion of a transition metal selected from the group consisting of manganese and rhenium, comprising: (a) preparing a solution in an inert solvent of a functional polymer, the concentration of the polymer being below its critical entanglement concentration, to provide discrete reactive binding sites to which transition metal precursor molecules can become bound; (b) incrementally adding, at suitable time intervals, a labile transition metal precursor, the molecules of which rapidly become bound to the reactive sites of the polymer; (c) maintaining a temperature which is sufficiently high to decompose the polymer-bound transition metal precursor much more rapidly than any transition metal precursor which may remain unbound in the solution decomposes to metal; (d) continuing the addition of increments of transition metal precursor to yield colloidal transition metal particles of the desired size within the range of from about 10 Angstrom units to about 200 Angstrom units, the transition metal particles being bound to the polymer molecules; and (e) steps (b), (c) and (d) being carried out in an inert atmosphere.
Claim 2
Independent Claim
182 words
A method for the preparation of a homogeneous, physically stable coloidal elemental dispersion of a transition metal selected from the group consisting of manganese and rhenium, comprising: (a) preparing a solution in an inert solvent of a functional polymer, the concentration of the polymer being below its critical entanglement concentration, to provide discrete reactive binding sites to which transition metal precursor molecules can become bound; (b) incrementally adding, at suitable time intervals, a labile transition metal precursor, the molecules of which rapidly become bound to the reactive sites of the polymer; (c) maintaining a temperature which is sufficiently high to decompose the polymer-bound transition metal precursor much more rapidly than any transition metal precursor which may remain unbound in the solution decomposes to metal; (d) continuing the addition of increments of transition metal precursor to yield colloidal transition metal particles of the desired size within the range of from about 10 Angstrom units to about 200 Angstrom units, the transition metal particles being bound to the polymer molecules; and (e) steps (b), (c) and (d) being carried out in an inert atmosphere.
Claim 3
Dependent Claim
14 words
A method as set forth in claim 1 wherein the transition metal is manganese.
Claim 4
Dependent Claim
14 words
A method as set forth in claim 1 wherein the transition metal is rhenium.
Claim 5
Dependent Claim
28 words
A method as set forth in claim 1 wherein the final increment, after decomposition, yields colloidal transition metal particles having a maximum size of about 150 Angstrom units.
Claim 6
Dependent Claim
37 words
A method as set forth in claim 1 wherein the transition metal precursor increments are added in an amount of from about 5 to about 10 moles of transition metal precursor per mole of reactive binding sites.
Claim 7
Dependent Claim
27 words
A method as set forth in claim 1 wherein the transition metal precursor increments are added when only a little or no carbon monooxide is being generated.
Claim 8
Dependent Claim
24 words
A method as set forth in claim 1 wherein the transition metal precursor increments are added from about 2 to about 4 hours apart.
Claim 9
Dependent Claim
16 words
A method as set forth in claim 1 which is carried out at about atmospheric pressure.
Claim 10
Dependent Claim
34 words
A method as set forth in claim 1 wherein the addition of the transition metal precursor is continuous, at a rate sufficient to compensate for the consumption of the transition metal precursor already added.
Claim 11
Dependent Claim
16 words
A method as set forth in claim 1 wherein the sufficiently high temperature is reflux temperature.
Claim 12
Dependent Claim
26 words
A method as set forth in claim 1 wherein the sufficiently high temperature is within the range of from about 100° C. to about 200° C.
Claim 13
Dependent Claim
24 words
A method as set forth in claim 11 wherein the temperature is within the range of from about 140° C. to about 180° C.
Claim 14
Dependent Claim
31 words
A method as set forth in claim 1 wherein the sufficiently high temperature is the minimum temperature that will cause a significant rate of decomposition of the polymer-bound transition metal precursor.
Claim 15
Dependent Claim
28 words
A method as set forth in claim 1 wherein decomposition of the polymer-bound transition metal precursor to the transition metal is effected by actinic radiation instead of heat.
Claim 16
Dependent Claim
25 words
A method as set forth in claim 1 wherein the binding of the transition metal precursor to the functional polymer is effected by actinic radiation.
Claim 17
Dependent Claim
16 words
A method as set forth in claim 1 wherein additional polymer is added during the reaction.
Claim 18
Dependent Claim
18 words
A method as set forth in claim 1 wherein additional polymer is added after the reaction is complete.
Claim 19
Dependent Claim
22 words
A method as set forth in claim 1 wherein the functional polymer is soluble in the inert solvent at about ambient temperature.
Claim 20
Dependent Claim
15 words
A method as set forth in claim 1 wherein the functional polymer is a homopolymer.
Claim 21
Dependent Claim
23 words
A method as set forth in claim 1 wherein the functional polymer is a copolymer of a reactive monomer and an inert monomer.
Claim 22
Dependent Claim
19 words
A method as set forth in claim 20 wherein said copolymer is prepared by polymerization of vinyl type monomers.
Claim 23
Dependent Claim
50 words
A method as set forth in claim 20 wherein the inert monomer is selected from the group consisting of styrene, ethylene, methylmethacrylate and vinylacetate and the reactive monomer is selected from the group consisting of butadiene, isoprene, cyclopentadiene, para-styryldiphenylphosphine, isopropenylisocyanate, 2-vinylpyridine, 4-vinylpyridine, N-vinylamidazole, 4,(5)-vinylamidazole, acrylonitrile, methacrylonitrile, N-vinylphthalimide, N,N-dimethylaminoethylmethacrylate, and N-alkylacrylamides.
Claim 24
Dependent Claim
24 words
A method as set forth in claim 1 wherein said functional polymer has a molecular weight of from about 1000 to about 1 million.
Claim 25
Dependent Claim
37 words
A method as set forth in claim 23 wherein the functional polymer concentration in the solution is, respectively, from about 10 percent or more to about 0.2-0.5 percent by weight based upon the weight of the solvent.
Claim 26
Dependent Claim
23 words
A method as set forth in claim 1 wherein said functional polymer has a molecular weight of from about 10,000 to about 100,000.
Claim 27
Dependent Claim
35 words
A method as set forth in claim 25 wherein the functional polymer concentration in the solution is, respectively, from about 5 percent to about 2 percent by weight based upon the weight of the solvent.
Claim 28
Dependent Claim
19 words
A method as set forth in claim 1 wherein said inert solvent is a liquid at about ambient temperature.
Claim 29
Dependent Claim
18 words
A method as set forth in claim 1 wherein said transition metal precursor is a transition metal carbonyl.
Claim 30
Dependent Claim
15 words
A method as set forth in claim 28 wherein said transition metal carbonyl is dimanganesedecacarbonyl.
Claim 31
Dependent Claim
15 words
A method as set forth in claim 28 wherein said transition metal carbonyl is dirheniumdecacarbonyl.
Claim 32
Dependent Claim
18 words
A method as set forth in claim 1 wherein said transition metal precursor is a transition metal alkylcarbonyl.
Claim 33
Dependent Claim
18 words
A method as set forth in claim 1 wherein said transition metal precursor is a transition metal alkenylcarbonyl.
Claim 34
Dependent Claim
15 words
A method as set forth in claim 32 wherein said transition metal alkenylcarbonyl is methylcyclopentadienylmanganesetricarbonyl.
Claim 35
Dependent Claim
85 words
A homogeneous, physically stable colloidal elemental dispersion of a transition metal selected from the group consisting of manganese and rhenium, suitable for use as a catalyst, comprising colloidal transition metal particles having a particle size within the range of from about 10 Angstrom units to about 200 Angstrom units dispersed in an inert liquid and stabilized by the presence of a functional polymer to the reactive sites of which the transition metal particles are bound, said dispersion being prepared by the method of claim 1.
Claim 36
Dependent Claim
14 words
A dispersion as set forth in claim 34 wherein the transition metal is manganese.
Claim 37
Dependent Claim
14 words
A dispersion as set forth in claim 34 wherein the transition metal is rhenium.
Claim 38
Dependent Claim
21 words
A dispersion as set forth in claim 34 having a maximum colloidal transition metal particle size of about 150 Angstrom units.
Claim 39
Dependent Claim
28 words
A dispersion as set forth in claim 34 wherein the weight ratio of transition metal to polymer is within the range of from about 90:100 to about 90:10.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-02-24 | 1984-08-25 | 1985-02-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-02-24 | 1988-08-25 | 1989-02-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-02-24 | 1992-08-25 | 1993-02-24 | $7700.00 | Window Closed / Lapsed |