# US 5,350,805 A · Epoxide-direct grafted halogenated vinyl polymers

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- Number: US 5,350,805 A
- Document ID: US5350805A
- Status: Granted
- Kind: A
- Application number: 08/075,229
- Filed: 1993-06-10
- Granted: 1994-09-27
- Earliest claimed: 1993-06-10
- Assignees: Koch Membrane Systems, Inc.
- Inventors: Juchui R. Lin
- Web page: https://patentgrep.com/patent/US5350805A

## CPC

- B01D 67/0011: {Casting solutions therefor}
- B01D 71/34: Polyvinylidene fluoride
- B01D 71/78: Graft polymers
- C08F 8/08: Epoxidation
- C08L 63/00: Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- B01D 2323/38: Graft polymerization
- Y10T 428/249953: Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T 428/31511: Of epoxy ether
- Y10T 428/3154: Of fluorinated addition polymer from unsaturated monomers
- Y10T 428/31935: Ester, halide or nitrile of addition polymer
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

An epoxy or trimethylene ether-direct grafted halogeneated vinyl polymer is prepared by the reaction of an epoxide such as a 5-ethyl, 5'-methyl-hydantoin/epichlorogydrin condensation product with a halogenated vinyl polymer such as polyvinylidene fluoride in the presence of a metal halide catalyst. The ether residue of the epoxide is grafted directly to the first carbon-chain carbon of the halogenated vinyl polymer. The graft polymer compositions are utilized as ultrafiltration and reverse osmosis membranes.

## Claims

### Claim 1

A polymer comprising an epoxy-direct grafted halogenated vinyl polymer, in which an ether moiety of an epoxy-direct grafted group is bonded directly to a first carbon-chain carbon of a halogenated vinyl polymer, said first carbon adjacent a second carbon-chain carbon of the halogenated vinyl polymer, said second carbon having bonded directly thereto generally two moieties selected from the group consisting of fluoro, chloro, bromo, iodo, methyl and hydro, provided that said second carbon has bonded directly thereby at least one fluoro, chloro, bromo or iodo moiety.

### Claim 2 (depends on 1)

The polymer of claim 1, wherein said epoxy-direct grafted halogenated vinyl polymer comprises a terminal epoxy-direct grafted halogenated vinyl polymer.

### Claim 3

A polymer comprising a halogenated vinyl trimethylene ether copolymer, in which an ether moiety of a trimethylene containing group is bonded directly to a first carbon-chain carbon of a halogenated vinyl polymer, said first carbon adjacent a second carbon-chain carbon of the halogenated vinyl polymer said second carbon having bonded directly thereto generally two moieties selected from the group consisting of fluoro, chloro, bromo, iodo, methyl and hydro, provided that said second carbon has bonded directly thereto at least one fluoro, chloro, bromo or iodo moiety.

### Claim 4

A polymer comprising a fluorinated vinyl trimethylene ether copolymer, in which an ether moiety of a trimethylene containing group is bonded directly to a first carbon-chain carbon of a fluorinated vinyl polymer, said first carbon adjacent a second carbon-chain carbon of the fluorinated vinyl polymer, said second carbon having bonded directly thereto generally two moieties selected from the group consisting of fluoro, chloro, bromo, iodo, methyl and hydro, provided that said second carbon has bonded directly thereto at least one fluoro moiety.

### Claim 5

A polymer of the general formula: ##STR9## wherein E is ##STR10## and A is selected from the group consisting of: ##STR11## wherein X is --F, --C1, --Br, or --I;
Y is X, --CX.sub.3, or --H;
n.sub.1 is an integer between 1 and 5,000;
x is an integer between 1 and 10;
q is an integer between 1 and 30; and
z is an integer between 1 and 20; provided that when the value of x is less than the number of --O and N-- moieties for a given A group, the --O or N-- moieties not bonded to E are OH or NH groups, respectively.

### Claim 6

A polymer comprising an epoxide modified fluorinated vinyl polymer, wherein said epoxide modified fluorinated vinyl polymer comprises an epoxy-direct grafted fluorinated vinyl polymer, in which an ether moiety of an epoxy-direct grafted group is bonded directly to a first carbon-chain carbon of a fluorinated vinyl polymer, said first carbon adjacent a second carbon-chain carbon of the fluorinated vinyl polymer, said second carbon having bonded directly thereto generally two moieties selected from the group consisting of fluoro, chloro, bromo, iodo, methyl and hydro, provided that said second carbon had bonded directly thereto at least one fluoro moiety.

### Claim 7 (depends on 6)

The polymer of claim 6, wherein said second carbon has bonded directly thereto two fluoro moieties.

### Claim 8 (depends on 6)

The polymer of claim 6, wherein said epoxy-direct grafted fluorinated vinyl polymer comprises a terminal epoxide epoxy-direct grafted fluorinated vinyl polymer.

### Claim 9

A polymer having a formula: ##STR12## wherein E is ##STR13## and A is ##STR14## and wherein X is --F, --C1, --Br, or --I;
Y is X, --CX.sub.3, or --H;
n.sub.1 is an integer between 1 and 5,000; and
x is an integer between 1 and 10; provided that when X is 1, A is ##STR15##

### Claim 10 (depends on 9)

The polymer of claim 9, wherein X is --F or --C1.

### Claim 11 (depends on 9)

The polymer of claim 9, wherein X is --F.

### Claim 12

A polymer having a formula: ##STR16## wherein E is ##STR17## and A is ##STR18## and wherein X is --F, --C1, --Br, or --I;
Y is X, --CX.sub.3, or --H;
n.sub.1 is an integer between 1 and 5,000; and
x is an integer between 1 and 10.

### Claim 13 (depends on 12)

The polymer of claim 12, wherein X is --F or --C1.

### Claim 14 (depends on 12)

The polymer of claim 12, wherein X is --F; provided that when x is 1, A is ##STR19##

### Claim 15

A polymer having a formula: ##STR20## wherein E is ##STR21## and A is ##STR22## and wherein X is --F, --C1, --Br, or --I;
Y is X, --CX.sub.3, or --H;
n.sub.1 is an integer between 1 and 5,000; and
x is an integer between 1 and 10; provided that when x is 1, A is ##STR23##

### Claim 16 (depends on 15)

The polymer of claim 15, wherein X is --F or --C1.

### Claim 17 (depends on 15)

The polymer of claim 15, wherein X is --F.

### Claim 18

A method of making an epoxide modified halogenated vinyl polymer reaction product comprising contacting an epoxide with a halogenated vinyl polymer in the presence of a catalyst of an inorganic salt of at least one Group IA or IIA metal.

### Claim 19 (depends on 18)

The method of claim 18, wherein said epoxide is a condensation product of bisphenol A and epichlorohydrin.

### Claim 20 (depends on 19)

The method of claim 19, wherein said halogenated vinyl polymer is selected from the group consisting of polyvinylidene fluoride, polyvinylidene chloride, polyvinyl chloride and copolymers of polyvinylidene fluoride.

### Claim 21 (depends on 19)

The method of claim 19, wherein said halogenated vinyl polymer is polyvinylidene fluoride.

### Claim 22 (depends on 18)

The method of claim 18, wherein said epoxide is a condensation product of bisphenol F and epichlorohydrin.

### Claim 23 (depends on 22)

The method of claim 22, wherein said halogenated vinyl polymer is selected from the group consisting of polyvinylidene fluoride, polyvinylidene chloride, polyvinyl chloride and copolymers of polyvinylidene fluoride.

### Claim 24 (depends on 22)

The method of claim 22, wherein said halogenated vinyl polymer is polyvinylidene fluoride.

### Claim 25 (depends on 18)

The method of claim 18, wherein said epoxide is a condensation product of 5-ethyl,5'-methyl-hydantoin with epichlorohydrin.

### Claim 26 (depends on 25)

The method of claim 25, wherein said halogenated vinyl polymer is selected from the group consisting of polyvinylidene fluoride, polyvinylidene chloride, polyvinyl chloride and copolymers of polyvinylidene fluoride.

### Claim 27 (depends on 25)

The method of claim 25, wherein said halogenated vinyl polymer is polyvinylidene fluoride.

### Claim 28 (depends on 18)

The method of claim 18, wherein said halogenated vinyl polymer is selected from the group consisting of polyvinylidene fluoride, polyvinylidene chloride, polyvinyl chloride, copolymers of polyvinylidene fluoride, halogenated polyethylene, and halogenated polypropylene having an equivalent gram epoxy weight of between approximately 260 and 15,000.

### Claim 29 (depends on 18)

The method of claim 18, wherein said halogenated vinyl polymer is a copolymer of hexafluoropropylene and vinylidene fluoride.

### Claim 30 (depends on 18)

The method of claim 18, wherein said epoxide is present in an amount within the range of approximately 0.1 to 100 parts by weight and said halogenated vinyl polymer is present in an amount within the range of approximately 5 to 40 parts by weight.

### Claim 31 (depends on 18)

The method of claim 18, wherein said catalyst is solubilized in an organic solvent, then the halogenated vinyl polymer is added to thereto and dissolved therein, and then the epoxide is added thereto and a homogeneous mixture is formed, a color change thereto occurring thereafter.

### Claim 32 (depends on 31)

The method of claim 31, wherein said inorganic salt catalyst is selected from the group consisting of lithium chloride, lithium iodide, lithium fluoride, calcium chloride, magnesium chloride, and sodium fluoride.

### Claim 33 (depends on 31)

The method of claim 31, wherein said inorganic salt catalyst is a fluoride, chloride, bromide or iodide of a Group IA metal.

### Claim 34 (depends on 18)

The method of claim 18, wherein said catalyst is an added catalyst.

### Claim 35 (depends on 1)

The polymer of claim 1, which can be solubilized.

### Claim 36 (depends on 6)

The polymer of claim 6, which can be solubilized.

### Claim 37 (depends on 7)

The polymer of claim 7, wherein the epoxy-direct grafted group is a residue of a condensation product of 5-ethyl, 5'-methyl-hydantoin with an epoxy.

### Claim 38 (depends on 36)

The polymer of claim 36, wherein the epoxy is epichlorohydrin.

### Claim 39 (depends on 31)

The method of claim 31, wherein the halogenated vinyl polymer is present in an amount from 5 to 40 parts by weight (pbw), the epoxide is present in an amount from 0.1 to 100 pbw, the organic solvent is present in an amount from 0.1 to 100 pbw, and the inorganic salt catalyst is present in an amount from 0.1 to 10 pbw.

### Claim 40 (depends on 39)

The method of claim 39, which is conducted at ambient pressure and at a temperature below 130 degrees C.

### Claim 41 (depends on 40)

The method of claim 40, which is conducted at a temperature below 90 degrees C. Z