# US 5,703,173 A · Transition metallohalopolymers

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- Number: US 5,703,173 A
- Document ID: US5703173A
- Status: Granted
- Kind: A
- Application number: 08/689,707
- Filed: 1996-08-16
- Granted: 1997-12-30
- Earliest claimed: 1996-08-16
- Assignees: Integument Technologies, Inc.
- Inventors: Timothy S. Koloski; Terrence G. Vargo
- Web page: https://patentgrep.com/patent/US5703173A

## CPC

- C08F 8/42: Introducing metal atoms or metal-containing groups
- A01N 55/02: containing metal atoms
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- A01N: PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF (preservation of food or foodstuff A23); BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES (preparations for medical, dental or toiletry purposes which kill or prevent the growth or proliferation of unwanted organisms A61K); PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS

## Abstract

Novel metallohalopolymers comprising an oxyhalopolymer and a transition metal covalently bonded to an oxygen site on the oxyhalopolymer possess desirable properties of inertness, stability, hydrophobicity and high electronegativity like fluoropolymers such as PTFE. The metallohalopolymers also possess unusual superacidic properties making oxygen-containing sites on the polymeric backbone highly nucleophilic and reactive with transition metals for synthesis of stable metallized polymers without requiring exposure to destructive calcining temperatures or intermediate chelating organosilane linking agents. The transition metals can be covalently bonded directly to the polymeric support to form metallohalopolymers for use as catalysts in the synthesis of chemicals, biocides and useful articles of manufacture, such as filtration devices containing the biocidally active metallohalopolymers.

## Claims

### Claim 1

A metallohalopolymer, which comprises a halogenated polymer having an outer surface modified with hydrogen and oxygen or oxygen-containing groups substituted for at least a portion of the halogen atoms thereon to provide an oxyhalopolymer, the oxygen or oxygen-containing groups on said oxyhalopolymer modified with an amount of covalently bonded transition metal on the outermost surface of said oxyhalopolymer and to depths of up to about 200 .ANG. to provide a surface having catalytic activity related to that of the particular transition metal, wherein the bulk characteristics of the halogenated polymer are retained below the modified outer surface region of the metallohalopolymer.

### Claim 2 (depends on 1)

The metallohalopolymer of claim 1 wherein the oxygen or oxygen-containing groups are modified by the introduction of the transition metal as covalently bonded metals in predetermined oxidation states or covalently bonded conductive metallic film.

### Claim 3 (depends on 1)

The metallohalopolymer of claim 1 wherein said oxyhalopolymer is an oxyfluoropolymer or oxychlorofluoropolymer.

### Claim 4 (depends on 2)

The metallohalopolymer of claim 2 comprising repeating non-terminal units selected from the group consisting of: ##STR2## Wherein M is a transition metal; Z is fluorine, chlorine, hydrogen, or O--R where R is hydrogen, --(CH.sub.2).sub.y --CH.sub.3 or --CH.sub.3 where y=1 to 20; X is CF.sub.2, CFCl, CCl.sub.2, CFH, CClH or CH.sub.2 ; n=10 to 1000, t=2 to 3 and m=0 to 1000.

### Claim 5 (depends on 2)

The metallohalopolymer of claim 2 wherein from about 1 to about 100 percent of the oxygen or oxygen-containing groups of the outermost surface of said oxyhalopolymer and to depths ranging from about 10 to about 200 .ANG. have covalently bonded thereto a transition metal (M) selected from the group consisting of Group IIIa, IVa, Va, VIa, VIIa, VIIIa, Ib, IIb, IIIb and IVb of the Periodic table.

### Claim 6 (depends on 2)

The metallohalopolymer of claim 2 wherein from about 1 to about 90 percent of the surface halogen atoms of said halogenated polymer are permanently substituted with hydrogen and oxygen or oxygen-containing groups from which about 30 to about 100 percent of the substituted halogens are replaced with oxygen or oxygen-containing groups and from about 0 to about 70 percent of said substituted halogens are replaced with hydrogen atoms, and where from about 1 to about 100 percent of said surface oxygen or oxygen-containing groups have covalently bonded thereto a transition metal selected from the group consisting of Group IIIa, IVa, Va, VIa, VIIa, VIIIa, Ib, IIb, IIIb and IVb of the Periodic Table.

### Claim 7 (depends on 4)

The metallohalopolymer of claim 4 wherein the transition metal is a member selected from the group consisting of Group IIIa, IVa, Va, VIa, VIIa, VIIIa, Ib, IIb, IIIb and IVb of the Periodic Table.

### Claim 8 (depends on 4)

The metallohalopolymer of claim 4 wherein the halogenated polymers are selected from the group consisting of polytetrafluoroethylene, expanded polytetrafluoroethylene, polychlorotetrafluoroethylene, polyvinylidene fluoride and polyvinyl fluoride and fluorinated ethylene-propylene copolymer.

### Claim 9 (depends on 4)

A catalytic composition comprising the metallohalopolymer of claim 4.

### Claim 10 (depends on 4)

A biocidal composition comprising the metallohalopolymer of claim 4.

### Claim 11 (depends on 10)

A filtration device comprising a biocidally effective amount of the composition of claim 10.

### Claim 12

A metallohalopolymer, which comprises an oxyhalopolymer prepared from a halogenated polymer, said oxyhalopolymer selected from the group consisting of an oxyfluoropolymer and an oxychlorofluoropolymer, said oxyhalopolymer having an outer surface modified wherein from about 1 to about 100 percent of the oxygen or oxygen-containing groups of the outermost surface and to depths ranging from about 10 to about 200 .ANG. have covalently bonded thereto a transition metal or covalently bonded conductive metallic film.

### Claim 13 (depends on 12)

The metallohalopolymer of claim 12 comprising repeating non-terminal units selected from the group consisting of: ##STR3## Wherein M is a transition metal; Z is fluorine, chlorine, hydrogen, --(CH.sub.2).sub.y --CH.sub.3, --CH.sub.3, or O--R where R is hydrogen, --(CH.sub.2).sub.y --CH.sub.3 or --CH.sub.3 where y is 1 to 20; X is CF.sub.2, CFCl, CCl.sub.2, CFH, CClH or CH.sub.2, n=10 to 1000, t=2 to 3 and m=0 to 1000.

### Claim 14 (depends on 13)

The metallohalopolymer of claim 13 wherein the transition metal (M) is a member selected from the group consisting of Group IIIa, IVa, Va, VIa, VIIa, VIIIa, Ib, IIb, IIIb and IVb of the Periodic Table.

### Claim 15 (depends on 14)

The metallohalopolymer of claim 14 wherein the perhalocarbon and halohydrocarbon polymers are selected from the group consisting polytetrafluoroethylene, expanded polytetrafluoroethylene, fluorinated ethylenepropylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride and polyvinyl fluoride, polyvinyl chloride, and polyfluoro-alkoxy polymer.

### Claim 16

A metallohalopolymer comprising a halogenated polymer with an oxyhalopolymer outer surface and a transition metal covalently bonded directly to a reactive oxygen site on said oxyhalopolymer.

### Claim 17 (depends on 16)

The metallohalopolymer of claim 16 wherein the transition metal is present as covalently bonded metals in predetermined oxidation states or a covalently bonded metallic film.

### Claim 18 (depends on 17)

The metallohalopolymer of claim 17 wherein the oxyhalopolymer is an oxyfluoropolymer or an oxychloro-fluoropolymer.

### Claim 19 (depends on 17)

The metallohalopolymer of claim 17 wherein the oxyhalopolymer is derived from a polymer selected from the group consisting of perhalocarbon polymer, a halohydrocarbon polymer, or a polyfluoroalkoxy polymer.

### Claim 20 (depends on 19)

The metallohalopolymer of claim 19 wherein perhalocarbon polymer is tetrafluoroethylene, expanded tetra-fluoroethylene, polychlorotrifluoroethylene or fluorinated ethylene-propylene copolymer, and the halohydrocarbon polymer is polyvinyl fluoride, polyvinylidene fluoride or polyvinyl chloride.

### Claim 21 (depends on 19)

The metallohalopolymer of claim 19 comprising repeating non-terminal units selected from the group consisting of: ##STR4## Wherein M is a transition metal; Z is fluorine, chlorine, hydrogen, --(CH.sub.2).sub.y --CH.sub.3, --CH.sub.3 or O--R where R is hydrogen, --(CH.sub.2).sub.y --CH.sub.3 or --CH.sub.3 where y is 1 to 20, X is CF.sub.2, CFCl, CCl.sub.2, CFH, CClH or CH.sub.2, n=10 to 1000, t=2 to 3 and m=0 to 1000.

### Claim 22 (depends on 16)

The metallohalopolymer of claim 16 wherein the halogenated polymer comprises a carbon backbone with halogen atoms and optionally one or more members selected from the group consisting of carbon, hydrogen and oxygen.

### Claim 23 (depends on 16)

The metallohalopolymer of claim 16 wherein the halogenated polymer comprises a silicon backbone with halogen atoms and optionally one or more members selected from the group consisting of carbon, hydrogen and oxygen.

### Claim 24 (depends on 16)

The metallohalopolymer of claim 16 wherein the halogenated polymer comprises a phosphorus backbone with halogen atoms and optionally one or more members selected from the group consisting of carbon, hydrogen, oxygen and nitrogen.

### Claim 25 (depends on 16)

A catalytic composition comprising the metallohalopolymer of claim 16.

### Claim 26 (depends on 16)

A biocidal composition comprising the metallohalopolymer of claim 16.

### Claim 27 (depends on 26)

A filtration device comprising a biocidally effective amount of the composition of claim 26.

### Claim 28 (depends on 16)

A sensor probe comprising the metallohalopolymer of claim 16.

### Claim 29

A method of synthesizing metallohalopolymers which comprises the steps of:
(a) providing a halogenated polymer;
(b) modifying the halogenated polymer of (a) by a method selected from the group consisting of (i) radio frequency glow discharge of hydrogen/methanol gas-vapor under vacuum, (ii) wet chemical reduction and (iii) exposing to actinic radiation in the presence of oxygen containing organic modifiers to substitute at least a portion of the halogen atoms with hydrogen and oxygen or oxygen-containing groups on the outermost surface of said halogenated polymer and to depths of up to about 200 .ANG. to provide an oxyhalopolymer, and
(c) contacting the oxyhalopolymer of (b) with a solution or gas comprising transition metal complexes for a sufficient time period to facilitate covalently bonding thereto a transition metal or covalently bonded conductive metallic film.

### Claim 30 (depends on 29)

The method of claim 29 wherein from about 1 to about 100 percent of the oxygen or oxygen-containing groups of the outermost surface of said oxyhalopolymer to depths ranging from about 10 to about 200 .ANG. have covalently bonded thereto a transition metal (M) selected from the group consisting of Group IIIa, IVa, Va, VIa, VIIa, VIIIa, Ib, IIb, IIIb and IVb of the Periodic table.

### Claim 31 (depends on 30)

The method of claim 30 wherein from about 1 to about 90 percent of the surface halogen atoms of said halopolymer including halogens to depths from about 10 to about 200 .ANG. are permanently substituted with hydrogen and oxygen or oxygen-containing groups from which about 30 to about 100 percent of the substituted halogens are replaced with oxygen or oxygen-containing groups and from about 0 to about 70 percent of said substituted halogens are replaced with hydrogen atoms, and where from about 1 to about 100 percent of said surface oxygen or oxygen-containing groups have covalently bonded thereto a transition metal selected from the group consisting of Group IIIa, IVa, Va, VIa, VIIa, VIIIa, Ib, IIb, IIIb and IVb of the Periodic table.