US5496901A
Expired / Lapsed
US
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Method of making fluoropolymers
Assignee: University of North Carolina at Chapel Hill
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Filing: 1993-02-26
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Granted: 1996-03-05
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Expires: 2013-02-26
Abstract
Abstract PCT No. PCT/US93/01626 Sec. 371 Date Sep. 27, 1994 Sec. 102(e) Date Sep. 27, 1994 PCT Filed Feb. 26, 1993 PCT Pub. No. WO93/20116 PCT Pub. Date Oct. 14, 1993.A process for making a fluoropolymer is disclosed. The process comprises solubilizing a fluoromonomer in solvent comprising a carbon dioxide fluid, and then polymerizing the fluoromonomer to produce the fluoropolymer. A preferred solvent for carrying out the process is supercritical carbon dioxide; preferred fluoromonomers for carrying out the process are fluoroacrylate monomers such as 1,1-dihydroperfluorooctyl acrylate. The polymerization step is preferably carried out in the presence of an initiator such as azobisisobutyronitrile.
Inventors
- 👤 Joseph M. DeSimone
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 08:24
CPC Classifications
C; C08; C08J; C08J3/00; C08J3/02; B; B05; B05D; B05D1/00; B05D1/02; B05D1/025; B05D5/00; B05D5/08; B05D5/083; C08F; C08F12/00; C08F12/02; C08F12/04; C08F12/14; C08F12/16; C08F12/20; C08F14/00; C08F14/18; C08F16/00; C08F16/12; C08F16/14; C08F16/16; C08F16/22; C08F16/24; C08F20/00; C08F20/02; C08F20/10; C08F20/22; C08J2327/00; C08J2327/02; C08J2327/12; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/54; Y10; Y10S; Y10S526/00; Y10S526/942
Claims Analysis
Total Claims: 31
Claim 1
Independent Claim
44 words
A process for making a fluoroacrylate polymer, comprising: solubilizing a fluoroacrylate monomer in a solvent, the solvent comprising carbon dioxide fluid; and then polymerizing the fluoroacrylate monomer in said solvent to produce said fluoroacrylate polymer, wherein said polymerizing step is a solution polymerization step.
Claim 2
Dependent Claim
44 words
A process for making a fluoroacrylate polymer, comprising: solubilizing a fluoroacrylate monomer in a solvent, the solvent comprising carbon dioxide fluid; and then polymerizing the fluoroacrylate monomer in said solvent to produce said fluoroacrylate polymer, wherein said polymerizing step is a solution polymerization step.
Claim 3
Dependent Claim
21 words
A process according to claim 1, wherein said polymerizing step is carried out in the presence of a chain transfer agent.
Claim 4
Dependent Claim
82 words
A process for making a fluoroacrylate polymer, comprising: solubilizing a fluoroacrylate monomer in a solvent, the solvent comprising carbon dioxide fluid wherein said fluoroacrylate monomer comprises a monomer of formula (I): H.sub.2 C═CR.sup.1 COO(CH.sub.2).sub.n R.sup.2 (I) wherein: n is 1 or 2; R 1 is hydrogen or methyl; and R 2 is a perfluorinated aliphatic or perfluorinated aromatic group; and then polymerizing the fluoroacrylate monomer in said solvent to produce said fluoroacrylate polymer, wherein said polymerizing step is a solution polymerization step.
Claim 5
Dependent Claim
82 words
A process for making a fluoroacrylate polymer, comprising: solubilizing a fluoroacrylate monomer in a solvent, the solvent comprising carbon dioxide fluid wherein said fluoroacrylate monomer comprises a monomer of formula (I): H.sub.2 C═CR.sup.1 COO(CH.sub.2).sub.n R.sup.2 (I) wherein: n is 1 or 2; R 1 is hydrogen or methyl; and R 2 is a perfluorinated aliphatic or perfluorinated aromatic group; and then polymerizing the fluoroacrylate monomer in said solvent to produce said fluoroacrylate polymer, wherein said polymerizing step is a solution polymerization step.
Claim 6
Dependent Claim
39 words
A process according to claim 3, wherein R 2 is a C1 to C8 perfluoroalkyl or --CH 2 NR 3 SO 2 R 4 , wherein R 3 is C1-C2 alkyl and R 4 is C1 to C8 perfluoroalkyl.
Claim 7
Dependent Claim
34 words
A process according to claim 3, wherein said fluoroacrylate monomer is selected from the group consisting of: 2-(N-ethylperfluorooctanesulfonamido) ethyl acrylate; 2-(N-ethylperflooctanesulfonamido) ethyl methacrylate; 2-(N-methylperfluorooctanesulfonamido) ethyl acrylate; 2-(N-methylperflooctanesulfonamido) ethyl methacrylate; 1,1-Dihydroperfluorooctyl acrylate; and 1,1-Dihydroperfluorooctyl methacrylate.
Claim 8
Dependent Claim
21 words
A process according to claim 3, wherein said polymerizing step is carried out in the presence of a chain transfer agent.
Claim 9
Dependent Claim
46 words
A process for making a fluoroalkylene oxide polymer, comprising: solubilizing a fluoroalkylene oxide monomer in a solvent comprising carbon dioxide fluid; and then polymerizing the fluoroalkylene oxide monomer in said solvent to produce said fluoroalkylene oxide polymer, wherein said polymerizing step is a solution polymerization step.
Claim 10
Dependent Claim
46 words
A process for making a fluoroalkylene oxide polymer, comprising: solubilizing a fluoroalkylene oxide monomer in a solvent comprising carbon dioxide fluid; and then polymerizing the fluoroalkylene oxide monomer in said solvent to produce said fluoroalkylene oxide polymer, wherein said polymerizing step is a solution polymerization step.
Claim 11
Dependent Claim
23 words
A process according to claim 7 wherein said fluoroalkylene oxide monomer is selected from the group consisting of perfluoropropylene oxide and perfluorocyclohexene oxide.
Claim 12
Dependent Claim
42 words
A process for making a fluorostyrene polymer, comprising: solubilizing a fluorostyrene monomer in a solvent comprising carbon dioxide fluid; and then polymerizing the fluorostyrene monomer in said solvent to produce said fluorostyrene polymer, wherein said polymerizing step is a solution polymerization step.
Claim 13
Dependent Claim
42 words
A process for making a fluorostyrene polymer, comprising: solubilizing a fluorostyrene monomer in a solvent comprising carbon dioxide fluid; and then polymerizing the fluorostyrene monomer in said solvent to produce said fluorostyrene polymer, wherein said polymerizing step is a solution polymerization step.
Claim 14
Dependent Claim
68 words
A process according to claim 9, wherein said fluorostyrene monomer comprises a monomer of Formula (VI): ##STR20## wherein: R 1 and R 2 are each independently hydrogen, fluorine, or methyl; R 3 is hydrogen, fluorine, methyl or perfluoromethyl; R 4 is hydrogen, fluorine, or C1-C12 perfluorinated aliphatic group; and wherein the 2, 3, 5, and 6 positions of the aromatic styrene ring are each independently hydrogen or fluorine.
Claim 15
Dependent Claim
50 words
A process for making a fluorinated vinyl ether polymer comprising: solubilizing a fluorinated vinyl ether monomer in a solvent comprising carbon dioxide fluid; and then polymerizing the fluorinated vinyl ether monomer in said solvent to produce said fluorinated vinyl ether polymer, wherein said polymerizing step is a solution polymerization step.
Claim 16
Dependent Claim
50 words
A process for making a fluorinated vinyl ether polymer comprising: solubilizing a fluorinated vinyl ether monomer in a solvent comprising carbon dioxide fluid; and then polymerizing the fluorinated vinyl ether monomer in said solvent to produce said fluorinated vinyl ether polymer, wherein said polymerizing step is a solution polymerization step.
Claim 17
Dependent Claim
54 words
A process according to claim 11, wherein said fluorinated vinyl ether monomer comprises a monomer of Formula (IV): R.sup.1 R.sup.2 C═CR.sup.3 O(CH.sub.2).sub.n R (IV) wherein: n is 0, 1 or 2; R 1 , R 2 and R 3 are each independently hydrogen or fluorine; and R is perfluorinated aliphatic or perfluorinated aromatic group.
Claim 18
Dependent Claim
54 words
A process for making a fluoroolefin copolymer comprising: solubilizing a fluoroolefin monomer and a comonomer in a solvent comprising carbon dioxide fluid; and then polymerizing said monomers in said solvent to produce said fluoroolefin copolymer; wherein said polymerizing step is a solution polymerization step; and wherein said fluoroolefin copolymer is an amorphous fluoroolefin copolymer.
Claim 19
Dependent Claim
54 words
A process for making a fluoroolefin copolymer comprising: solubilizing a fluoroolefin monomer and a comonomer in a solvent comprising carbon dioxide fluid; and then polymerizing said monomers in said solvent to produce said fluoroolefin copolymer; wherein said polymerizing step is a solution polymerization step; and wherein said fluoroolefin copolymer is an amorphous fluoroolefin copolymer.
Claim 20
Dependent Claim
28 words
A process according to claim 13, wherein said fluoroolefin monomer is selected from the group consisting of difluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoro-2, 2 dimethyl-1, 3-dioxole and mixtures thereof.
Claim 21
Dependent Claim
58 words
A process for making a fluoroolefin polymer comprising: solubilizing a fluoroolefin monomer in a solvent comprising carbon dioxide fluid; and then polymerizing the fluoroolefin monomer in said solvent to produce said fluoroolefin polymer; wherein said polymerizing step is a solution polymerization step; and wherein said polymerizing step is carried out in the presence of a chain transfer agent.
Claim 22
Dependent Claim
58 words
A process for making a fluoroolefin polymer comprising: solubilizing a fluoroolefin monomer in a solvent comprising carbon dioxide fluid; and then polymerizing the fluoroolefin monomer in said solvent to produce said fluoroolefin polymer; wherein said polymerizing step is a solution polymerization step; and wherein said polymerizing step is carried out in the presence of a chain transfer agent.
Claim 23
Dependent Claim
20 words
A process according to claim 13, wherein said fluoroolefin polymer is an amorphous fluoroolefin polymer which is a fluorocarbon elastomer.
Claim 24
Dependent Claim
22 words
A process according to claim 1, 3, 7, 9, 11, 13, or 15, wherein said carbon dioxide fluid is liquid carbon dioxide.
Claim 25
Dependent Claim
22 words
A process according to claim 1, 3, 7, 9, 11, 13 or 15, wherein said carbon dioxide fluid is supercritical carbon dioxide.
Claim 26
Dependent Claim
29 words
A process according to claim 1, 3, 7, 9, 11, 13 or 15, further comprising the step of separating said polymer from said carbon dioxide and collecting said polymer.
Claim 27
Dependent Claim
21 words
A process according to claim 19, wherein said separating step is carried out by venting said carbon dioxide to the atmosphere.
Claim 28
Dependent Claim
35 words
A process according to claim 1, 3, 7, 9, 11, 13 or 15, further comprising: solubilizing a comonomer in said carbon dioxide fluid, and wherein said polymerizing step comprises copolymerizing said fluoromonomer with said comonomer.
Claim 29
Dependent Claim
26 words
A process according to claim 1, 3, 7, 9, 11, 13 or 15, wherein said polymerizing step is carried out in the presence of an initiator.
Claim 30
Dependent Claim
20 words
A process according to claim 1, 3, 7, 9, 11, 13 or 15, wherein said solvent further comprises a cosolvent.
Claim 31
Dependent Claim
25 words
A process according to claim 15, wherein said fluoroolefin monomer is selected from the group consisting of difluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoro-2,2-dimethyl-1,3-dioxole and mixtures thereof.
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