US4482685A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Copolymerization of ethylene and chlorotrifluoroethylene in an aqueous emulsion
Assignee: Solvay Solexis Inc
•
Filing: 1982-09-30
•
Granted: 1984-11-13
•
Expires: 2002-09-30
Abstract
Abstract A method of emulsion copolymerization of ethylene and chlorotrifluoroethylene in the presence of a water soluble initiator and a water soluble fluorosurfactant. The fluorosurfactant having the general formula: CA3(CF2)B(C2H4)D-X wherein A is selected from H and F, B is 1 to 10, D is 1 to 6, and X is a hydrophilic group.
Inventors
- 👤 Hong B. Chin
- 👤 Swayambu Chandrasekaran
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 11:47
CPC Classifications
C; C08; C08F; C08F210/00; C08F210/02; C08F214/00; C08F214/18; C08F214/24
Claims Analysis
Total Claims: 25
Claim 1
Independent Claim
117 words
A method of copolymerizing ethylene and chlorotrifluoroethylene to form a copolymer having from 30 to 65 mol percent ethylene in an aqueous emulsion comprising the step of copolymerizing ethylene and chlorotrifluoroethylene in the presence of water, a water soluble initiator and from 0.1 to 5.0 percent by weight of water of a water soluble fluorosurfactant having the formula: CA 3 (CF 2 ) B (C 2 H 4 ) D -X wherein A is selected from the group consisting of H and F, B is 1 to 10, D is 1 to 6, and X is a hydrophilic group, wherein to be water soluble at least 0.1 percent by weight of the fluorosurfactant must dissolve in water.
Claim 2
Independent Claim
117 words
A method of copolymerizing ethylene and chlorotrifluoroethylene to form a copolymer having from 30 to 65 mol percent ethylene in an aqueous emulsion comprising the step of copolymerizing ethylene and chlorotrifluoroethylene in the presence of water, a water soluble initiator and from 0.1 to 5.0 percent by weight of water of a water soluble fluorosurfactant having the formula: CA 3 (CF 2 ) B (C 2 H 4 ) D -X wherein A is selected from the group consisting of H and F, B is 1 to 10, D is 1 to 6, and X is a hydrophilic group, wherein to be water soluble at least 0.1 percent by weight of the fluorosurfactant must dissolve in water.
Claim 3
Dependent Claim
13 words
The method as recited in claim 1 wherein B is 4 to 10.
Claim 4
Dependent Claim
68 words
The method as recited in claim 1 wherein the fluorosurfactant has the formula: CA 3 (CF 2 ) B (C 2 H 4 ) D SO 3 E wherein A is selected from H and F; E is selected from the group consisting of H + , K + , Na + and NH 4 + ; B is 6 to 10; and D is 1 to 6.
Claim 5
Dependent Claim
40 words
The method as recited in claim 1 further comprising the steps of: feeding an aqueous solution of the fluorosurfactant to a reactor; adding chlorotrifluoroethylene to the solution; feeding gaseous ethylene to the reactor; and feeding the initiator to the reactor.
Claim 6
Dependent Claim
40 words
The method as recited in claim 1 wherein X is a radical of a material selected from the group consisting of alkali metal sulfonates, alkali metal carboxylates, ammonium sulfonates, ammonium carboxylate, amine sulfonates, alkyl esters, alkyl alkoxylates, and polyoxyethylene ethanol.
Claim 7
Dependent Claim
39 words
The method as recited in claim 1 wherein the fluorosurfactant is selected from the group consisting of fluorinated alkyl alkoxylate, fluorinated alkyl polyoxyethylene ethanol, polyfluorosulfonic acid, alkali metal salt of polyfluorosulfonic acid, ethoxylated polyfluoro alcohol, and fluorinated alkyl ester.
Claim 8
Dependent Claim
22 words
The method as recited in claim 1 wherein the initiator is an oxidation-reduction system comprising an oxidizing agent and a reducing agent.
Claim 9
Dependent Claim
51 words
The method as recited in claim 4 wherein the initiator is an oxidation-reduction system comprising an oxidizing agent and a reducing agent, wherein the oxidizing agent is added to the aqueous solution of fluorosurfactant and wherein the reducing agent is fed into the reactor after the feeding of the gaseous ethylene.
Claim 10
Dependent Claim
22 words
The method as recited in claim 7 further comprising the step of adding 0.1 to 10 parts per million of cupric cation.
Claim 11
Dependent Claim
18 words
The method as recited in claim 9 wherein the cupric cation is in the form of cupric sulfate.
Claim 12
Dependent Claim
32 words
The method as recited in claim 7 wherein the oxidizing agent is a water soluble alkali metal or alkaline earth metal salt of persulfuric acid or an ammonium salt of persulfuric acid.
Claim 13
Dependent Claim
14 words
The method as recited in claim 11 wherein the oxidizing agent is potassium persulfate.
Claim 14
Dependent Claim
30 words
The method as recited in claim 7 wherein the reducing agent is selected from the group consisting of ammonium or alkali metal sulfites, thiosulfites, thiosulfates, bisulfites, hydrosulfites, and formaldehyde sulfoxylate.
Claim 15
Dependent Claim
17 words
The method as recited in claim 13 wherein the reducing agent is sodium metabisulfite or sodium bisulfite.
Claim 16
Dependent Claim
18 words
The method as recited in claim 7 wherein the pH is maintained from above 4 to about 12.
Claim 17
Dependent Claim
25 words
The method as recited in claim 1 wherein there is from 0.1 to 5.0 percent based on the weight of the water of the fluorosurfactant.
Claim 18
Dependent Claim
25 words
The method as recited in claim 16 wherein there is from 0.25 to 2.0 percent based on the weight of the water of the fluorosurfactant.
Claim 19
Independent Claim
230 words
A method of emulsion copolymerizing ethylene and chlorotrifluoroethylene to form a copolymer having from 30 to 65 mol percent ethylene, which comprises: adding to a sealed reactor a sufficient amount of water containing from 0.1 to 5.0 percent by weight of water of a fluorosurfactant to support the copolymerization, the fluorosurfactant having the formula: CA 3 (CF 2 ) B (C 2 H 4 ) D -X wherein A is selected from the group consisting of H and F, B is 1 to 10, D is 1 to 6, and X is a hydrophilic group, wherein to be water soluble at least 0.1 percent by weight of the fluorosurfactant must dissolve in water. adding an oxidizing agent which is a water salt of persulfuric acid and a buffer compound which is capable of maintaining the pH of the reaction above 4 to about 12; adding chlorotrifluoroethylene to the reactor; pressurizing said reactor with elhylene to a pressure of from about 137.8 to 10335.0 kPa (20 to about 1500 psig); adding a water soluble cupric salt and a reducing agent which is selected from the group consisting of an ammonium or alkali metal sulfite, thiosulfite, bisulfite, hydrosulfite, and formaldehyde sulfoxylate to the reactor; maintaining the temperature of the reactor in the range of from about 0° C. and 250° C.; and continuing the emulsion copolymerizing until said copolymer has been formed.
Claim 20
Independent Claim
230 words
A method of emulsion copolymerizing ethylene and chlorotrifluoroethylene to form a copolymer having from 30 to 65 mol percent ethylene, which comprises: adding to a sealed reactor a sufficient amount of water containing from 0.1 to 5.0 percent by weight of water of a fluorosurfactant to support the copolymerization, the fluorosurfactant having the formula: CA 3 (CF 2 ) B (C 2 H 4 ) D -X wherein A is selected from the group consisting of H and F, B is 1 to 10, D is 1 to 6, and X is a hydrophilic group, wherein to be water soluble at least 0.1 percent by weight of the fluorosurfactant must dissolve in water. adding an oxidizing agent which is a water salt of persulfuric acid and a buffer compound which is capable of maintaining the pH of the reaction above 4 to about 12; adding chlorotrifluoroethylene to the reactor; pressurizing said reactor with elhylene to a pressure of from about 137.8 to 10335.0 kPa (20 to about 1500 psig); adding a water soluble cupric salt and a reducing agent which is selected from the group consisting of an ammonium or alkali metal sulfite, thiosulfite, bisulfite, hydrosulfite, and formaldehyde sulfoxylate to the reactor; maintaining the temperature of the reactor in the range of from about 0° C. and 250° C.; and continuing the emulsion copolymerizing until said copolymer has been formed.
Claim 21
Dependent Claim
31 words
The method as recited in claim 18 wherein the pressure is from 1033.5 kPa to 2401.5 kPa (150 to 350 psig), and the temperature is from 5° C. to 60° C.
Claim 22
Dependent Claim
17 words
The method as recited in claim 18 wherein a cupric cation is added with the reducing agent.
Claim 23
Dependent Claim
25 words
The method as recited in claim 18 wherein there is from 0.25 to 2.0 percent based on the weight of the water of the fluorosurfactant.
Claim 24
Dependent Claim
19 words
The method as recited in claim 18 wherein the pH of the reaction is maintained from 7 to 10.
Claim 25
Dependent Claim
28 words
The method of claim 1 further comprising copolymerizing ethylene, chlorotrifluoroethylene and from 0 to 10 mol percent based on the ethylene and the chlorotrifluoroethylene of other copolymerizable monomers.
References Cited (Backward Citations)
GB767757A
Cited
US3006881A
Cited
US3043823A
Cited
US3859262A
Cited
US3720655A
Cited
US3767634A
Cited
US3857827A
Cited
US4025709A
Cited
US4225482A
Cited
US4329268A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-11-13 | 1988-05-14 | 1988-11-13 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-11-13 | 1992-05-14 | 1992-11-13 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-11-13 | 1996-05-14 | 1996-11-13 | $7700.00 | Window Closed / Lapsed |