CA1173199A

CA1173199A - Polyfluoroallyloxy compounds, their preparation and copolymers therefrom

Info

Publication number: CA1173199A
Application number: CA000435394A
Authority: CA
Inventors: Carl G. Krespan
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1979-12-20
Filing date: 1983-08-25
Publication date: 1984-08-21

Abstract

ABSTRACT OF THE DISCLOSURE
The reaction of a polyfluoxocarbonyl compound such as a polyfluoroketone or polyfluorocarboxylic acid fluoride with fluoride ion and a polyfluoroallyl chloride, bromide or fluorosulfate produces a polyfluoroallyloxy compound, e.g., CF2=CFCF2OCF2CF2SO2F. The polyfluoroallyloxy compounds copolymerize with ethylenically unsaturated monomers such as terrafluoroethylene, chlorotrifluoroethylene or vinylidene fluoride to form polymers which are moldable, and in some cases electrically conducting or are water-wettable and dyeable.

Description

1~73199 BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to polyfluoroallyloxy compounds, processes for their preparation and copolymers prepared therefrom.
Relation to the Prior Art 1. U.S. Patent 2,856,435 to E. S. Lo discloses the preparation of perfluoroallyloxy-l,l-dihydroperfluoro-alkanes from 3-chloropentafluoropropene and a l,l-dihydroperfluoroalkanol in alkaline medium, e.g.

CF2=CFCF2Cl + HOCH2CF3 K ~ CF2=CFCF2OCH2CF3

2. U.S. Patent 2,671,799 to W. T. Miller discloses a process for replacing the chlorine in perfluoroallyl chloride (3-chloropentafluoropropene) with methoxy, cyano, iodo and nitrate groups, e.g.
CF2=CFCF2Cl + NaOCH3 ~ CF2=cFcF2ocH3

3. M. E. Redwood and C. J. Willis, _anad. J. Chem., 45, 389 (1967) describe the reaction of allyl bromide with cesium heptafluoro-2-propoxide to form 2-allyloxyhepta-fluoropropane:
CH2=CHCH2Br + (CF3)2CFO Cs ~
CH2=CHCH2OCF(CF3)2 + CsBr

4. J. A. Young, Fluorine Chemistry Reviews, 1, 389-393 (1967) surveys the formation of perfluoroalkoxide anions by the action of alkali metal fluorides on perfluoro-ketones, perfluoroalkyloxiranes, perfluorocarboxylic acid fluorides and perfluoroalkyl fluorosulfates.
References 5-9 which follow are examples of the nucleophilic reactions of perfluoroalkoxide anions.

5. U.S. Patent 3,450,684 to R. A. Darby discloses the '.~
X `~

l 173199 preparation of fluorocarbon polyethers and their polymers by reaction of perfluoroalkanoyl fluorides with potassium or quaternary ammonium fluoride and hexafluoropropene epoxide.

i.e. RfCOF + CF3-CF - CF2 RfCF2OCFCOF

6. U.S. Patent 3,674,820 to A. G. Pittman and W. L. Wasley discloses the reaction of fluoroketones with an alkali metal fluoride and an omega-haloalkanoic acid ester to form an omega-(perfluoroalkoxy) alkanoic acid ester, e.g.
(CF3)2CO + KF + Br(CH2)4CO2CH3 >
(CF3)2CFO(CH2)4CO2CH3

7. U.S. Patent 3,795,684 to E. Domba also discloses the reaction of hexafluoroacetone with potassium fluoride and an omega-haloalkanoic acid ester.

8. U.S. 3,527,742 to A. G. Pittman and W. L. Wasley, discloses the reduction of the compounds of Reference 6 to the corresponding alcohols and their esterification to polymerizable acrylates.

9. U.S. 3,799,992 to A. G. Pittman and W. L. Wasley discloses the preparation of (perfluoroalkoxy)vinyl compounds by reaction of a perfluoroketone with an alkali metal fluoride and a 1,2-dihaloethane, followed by dehydrohalogenation of the intermediate 2-perfluoro-alkoxyhaloethane.
e-g- (CF3)2CO + KF + BrCH2CH2Br ~
(CF3)2CFOCH2CH2Br HBr ~ (CF3)2cFcH=cH2

10. U.S. Patent 3,321,532 to C. E. Lorenz discloses the rearrangement of perfluoro-2-alkoxyalkanoyl fluorides X

11731g~
to perfluoroalkoxyolefins by passage over a metal oxide at 100-400C, e.g.,

11. U. S. Patent 3,467,638 to D. B. Pattison discloses polyfluorovinyl ethers of the formula CF2=cFfocF2cF~oc6F5 ~ CF3J n where n is 1 or 2 and copolymers containing said ethers.

12. L. S. Kobrina, Fluorine Chemistry Reviews, vol. 7, p. 67, Marcel Dekker, Inc., N. Y. (1974), discloses the substitution of hydroxyl into -OC6F5 groups to form -OC6F40H .

13, U. S. Patent 4,131,740 to D. C. England discloses the compound ROOC-CF2-COF, hexafluoropropene oxide adducts with the formula O O , vinyl ethers ROCCF2 fcF2ocF ~ { :F
~ CF3J n prepared from same, of the formula RCCF2 ~ F2CF ~ F20CF=CF2 , and copolymers prepared ~ CF3J n-l from said vinyl ethers; n is 1 to 6, and R is CH3 or C2H5 .

14. Canadian Patent Application Serial No. 301,618, filed 1978 April 18 to D. C. England discloses the nitrile NCCF2 ~ F2OCF ~ F2OCF=CF2 where n is 1 to 6.

CF3 n-l 2~ SUMMARY OF THE INVENTION
According to the present invention there is provided a polyfluoroallyloxy compound having the formula ~7319~
CF2=C-CF2 ORF
x wherein X is -Cl or -F;
Rl R is -CF or -CF(R )2;

Y is -F or -CF3;
Rl is a linear or branched perfluoroalkyl group of 1 to 14 carbon atoms, 0 to 1 of which is a keto group, interruptable no more frequently than every second carbon atom by from 1 to 4 oxygen atoms, having 0 to 2 functional groups selected from the class consisting of -SO2F, -COF, -CO2H, -Cl, -Br, -I, -CN, -CF=F2, -OC6F5 and -CO R3 where R is -CH3 or -C2H5; and R2 is -F, -CF2Cl, -CF2CN, -CF2COF, -CF2CO2H, -CF2OCF(CF3)2, or -CF2Co2R3 where R3 is as defined above.
There is also provided a process for preparing a polyfluoroallyloxy compound which comprises:
(1) mixing and reacting (a) a carbonyl compound having the formula:
o A - C -B
wherein A is a linear or branched perfluoroalkyl of 1 to 14 carbon atoms, 0 to 1 of which is a keto group, interruptable no more frequently than every second carbon atom by from 1 to 4 oxygen atoms, having 0 to 2 functional groups selected from the class consisting of -SO2F, ~73~99 -S020CF2CH3. -COF, -Cl, -Br, -I, -CN, -OC6F5, -CF=CF2, and -Co2R3 where R3 18 -CR3 or -C2H5; and B 18 -~ or -CF3; or (~) a carbonyl compound havine the ~ormula:
o R2 _ C - R2 wherein R is -F, -CF2Cl, -CF2CN, -CF2COF, -CF20CF(CF3)2~ or CF2C 2 where R3 i8 as defined aboYer with a metal ~luorlde of the formula MF where M
is K-, Rb-, Cs-, or R4N- where each -R, allke or di~ferent, is alkyl of 1 to 6 carbon atoms;
and (2) mlxlng the mixture from (l) with a per~luoroallyl compound Or the fo mu~a 2 ~ ~ 2 X Z
wherein X i8 -Cl or -F; and Z i8 -Cl, -Br or -OS02~.
Also provided i8 a copolymer o~ the afores~id polyfluoroallyloxy compound with at least one ethylenically un~aturated monomer.

D~TAIL~ OF THE INVENTION
Thl8 ln~ention relates to compounds of formu~ae 4 and 7 prepared ~rom startlng mater~als l, 2, 3 and 6 accordlng to the fo~lowing equations:

~731~9 O R
2 ,C ,CF2 + MF + A-C-B ~ CF2=C-CF20CF + MZ
X Z , X Y

and o CF2=C-CF2 + ~5F + R-C--R2 > CF2-C-CF20CF (R ) 2 + MZ
X Z X

In the above equations, starting materials 1, 2, and 3 or 6 react to give products 4 or 7, respectively, and a metal salt 5. The symbols A, B, Rl, R2, M, X, Y and z are -as given in the Summary. Products represented by general structures 4 and 7 can be converted into useful copolymers especially with tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, and chlorotrifluoroethylene.
Preferred polyfluoroallyloxy compounds of formula 4 are those in which Rl is a linear or branched perfluoro-alkyl group of 1 to 11 carbon atoms, interruptable with 1 to 3 oxy~en atoms, having 0 to 1 functional group selected from the class consisting of -SO2F, -COF, -Cl, -Br, -CN, -OC6F5, -CF=CF2, -CO2H and -CO2R where R3 is -CH3 or -C2H5; and X is -F.
Especially preferred polyfluoroallyloxy compounds of formula 4 are those in which R1 is ~ CF2 ~x R4, -CFOCF2CF2R or -CF2OCF2R , where R is -SO2F, -COF, -CO2H, -CN or Co2R3; R5 is -COF, -CO2H or -Co2R3, x is 1 to 6i and X is -F.

X

1173~99 Preferred polyfluoroallyloxy compounds of formula 7 are those in which R2 is -CF2COF, -CF2Cl, -CF2CO2H or -CF2CO2R : and X is -F.
The polyfluoroallyl group of the produc-ts 4 and 7 is derived from the corresponding polyfluoroallyl chloride, bro-mide or fluorosulfate 1 by nucleophilic displacement of the chloride, bromide or fluorosulfate group with a preformed poly-fluoroalkoxide anion derived from the metal fluoride 2 and the carbonyl compound 3 or 6. The synthesis is thus a one-vessel sequential addition of reagents 3 or 6 and 1 to a suspension or solution of 2 in a suitable solvent.
Polyfluoroallyl fluorosulfates are the preferred reagents for this displacement, and they can he prepared conveniently by treatment of polyfluoroalkenes with sulfur trioxide. Such reactions are typically carried out in sealed Cariu5 tubes at temperatures of 25-95C for periods of 16 hours to 4 days, and the product fluorosulfates are purified by fractional distillation. A preparation of the preferred perfluoroallyl fluorosulfate ~pentafluoro-2-propenyl fluoro-sulfate) is given in Example 2.
Stable metal polyfluoroalkoxides are formed by thereaction of certain metal fluorides with polyfluorinated ketones and acid fluorides (J. A. Young, loc. cit.), thus:

,CF3 (CF3)2CO + KF ~ CF3-C-O K
F

~ `3~ 9 9 CF3COF + KF ~ ' ~ +
F
The usefulness of such intermediate polyfluoroalkoxides is determined by their stability, as measured by their ease of thermal decomposition. Because their formation is reversible, the equilibrium concentrations of various species in a given reaction mixture are important quan-tities which determine whether or not the subsequent displacement will occur to form product 4 or 7. Solutions in which the equilibrium lies towards the right lhigh concentration of anion) will be more effective than those in which it lies towards the left (high concentration of carbonyl compound).
Polyfluoroalkoxide anion formation and chemistry is dependent upon the following four conditions, discussed in further detail by J. A. Young, loc. cit., F. W. Evans, M. H. Litt, A. M. Weidler-Kubanek and F. P. Avonda, J.
Org. Chem., 33, 1837, 1839 (1968), and M. A. Redwood and _ ~
C. J. Willis, Canad. J. Chem., 45, 389 (1967).
(1) Stable polyfluoroalkoxide anions are formed when the carbonyl compound is highly fluorinated because the electron-withdrawing effect of the fluorine atoms distributes the negative charge over the entire anion.
Substitution of some of the fluorine by chlorine, other fluoroalkyl groups or hydrogen destablizes the anion because these groups are less electron-withdrawing and the negative charge is not as readily accommodated. (2) Large cations such as K , Rb , Cs and R4N favor the ~ 173~99 formation of stable polyfluoroalkoxides more than small cations such as Li and Na because the lattice energy of metallic fluorides is inversely proportional to cation size.
In other words, large cation siæe and small lattice energy favours disruption of the metallic fluoride crystal structure to form the anion. (3) Solvents which have a high heat of solution for the polyfluoroalkoxide favor its formation.
Aprotic polar solvents such as N,N-dimethylformamide (DMF), acetonitrile, and 1,2-dimethoxyethane (glyme) are very effective for this purpose. (4) When there are fluorine atoms alpha to - the oxygen atom in the anion, loss of fluoride ion may compete with the desired reactions, e.g., ' has no ~-fluorine to lose and O -- C -- C -- O
' forms many stable derivatives.

CF3 requires a reactive compound CF3 - C - 0 such as allyl bromide for nucleo-F philic substitution.

CF30 usually eliminates F ; nucleophilic substitution is shown with per-fluoroallyl fluorosulfate in Example 20.

In the practice of this invention, the polyfluoro-alkoxide anion is preferably preformed by the addition of the carbonyl compound to a stirred mixture of the metal fluoride in a suitable aprotic solvent. The completeness of forma-tion of the anion is generally signalled by the extent to which the metal fluoride dissolves in the solvent as the . 1~7319~
reaction progresses. The stoichiometry of polyfluoroalkoxide anion formation requires one molar equivalent of metal fluoride for each carbonyl group which is converted to its anion, e.g.:

(CF ) CO + KFCF - C - O K

O O F F
FC(CF2)4CF + 2KFK ~ C(CF2)4C ~ K
F F
The presence of up to a twice-molar excess of metal fluoride is generally not detrimental. Two side effects of excess metal fluoride are: (1) to hinder the observation of the reaction endpoint because of the presence of undissolved solid in the reaction mixture, and (2) excess fluoride ion in solution may react directly with perfluoroallyl fluorosulfate to form hexafluoropropene.
Because of the limited thermal stability of polyfluoroalkoxides, their formation is usually accom-plished between -20C and +60C, preferably with external cooling to maintain the temperature between 0C and 10C.
The time required to complete polyfluoroalkoxide formation varies with the carbonyl component, but it is preferably from 0.5 to 2 hours, each individual case being usually determined by how long it takes the reaction mixture to become homogeneous.
N,N-Dimethylformamide (DMF), acetonitrile, N,N-dimethylacetamide (D~AC), y-butyrolactone, 1,2-dimethoxyethane (glyme), 1-(2-methoxyethoxy)-2-methoxy-ethane (diglyme), 2,5,8,11-tetraoxadodecane (triglyme), ~' 1~731g9.
dioxane, sulfolane, nitrobenzene and benzonitrile are suitable, illustrative aprotic polar solvents for the preparation of polyfluoroalkoxides and their subsequent reaction with the polyfluoroallyl chloride, bromide or fluorosulfate. DMF, diglyme, triglyme and acetonitrile are preferred solvents for these reactions.
The apparatus, reactants and solvents should be adequately dried for use in the process of the invention because the presence of water hydrolyzes polyfluoroalkoxides:
(RF)2CFO + H2O > (RF)2C(OH2) + F

-- > RFC02H + HF2 Metal fluorides which are useful in this invention are potassium fluoride (KF)/ rubidium fluoride (RbF), cesium fluoride (CsF) and tetraalkylammonium fluorides (R4NF) such as tetraethylammonium fluoride ((C2H5)4NF) and tetrabutylammonium fluoride ((C4Hg)4NF).
R, alike or different, is alkyl of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Potassium fluoride is preferred because of its availability, economic advantage, and ease of handling.
Polyfluorinated carbonyl compounds which are useful in this invention are ketones and carboxylic acid fluorides. Ketones give branched fluorocarbon products, whereas acid fluorides give primary fluorocarbon products in which the new ether linkage is at the primary or secondary center:
(RF)2CO > (RF)2C-O-CF2CF=CF2 (ketone) RFCOF > RFCF2OCF2CF=CF2 (acid fluoride) X

` ~ ~73~gg Polyfluorinated ketones w~ich are useful include hexafluoroactone, chloropentafluoroacetone, 1,3-dichloro-tetrafluoroacetone, l,l-difluoroethyl 2-oxopentafluoro-propanesulfonate, dimethyltetrafluoroacetone-1,3-dicarboxy-late, 1,3-bis(2-heptafluoropropoxy)tetrafluoropropanone, octafluorobu~anone, decafluoro-2-pentanone, dodecalfluoro-2-hexanone, tetradecafluoro-2-heptanone, hexadecafluoro-2-octanone, octadecafluoro-2-nonanone, eicosafluoro-2-decanone, and 3-ketotetrafluoroglutaroyl fluoride.
Polyfluoroinated acid fluorides which are useful include carbonyl fluoride, trifluoroacetyl fluoride, penta-fluoropropionyl fluoride, heptafluorobutyroyl fluoride, nonafluoropentanoyl fluoride, tetrafluorodiglycolyl di-O O
fluoride FCCF2OCF2CF, 3-ketotetrafluoroglutaroyl fluoride O O O
.. .. ..
FCCF2CCF2CF, undecafluorohexanoyl fluoride, tridecafluoro-heptanoyl fluoride, pentadecafluorooctanoyl fluoride, hepta-decafluorononanoyl fluoride, nonadecafluorodecanoyl fluoride, difluoromalonyl difluoride, tetrafluorosuccinyl difluoride, hexafluoropropane-1,3-dioyl difluoride (hexafluoroglutaryl difluoride), octafluorobutane-1,4-dioyl difluoxide tocta-fluoroadipoyl difluoride), decafluoropentane-1,5-dioyl difluoride ldecafluoropimelyl difluoride), dodecafluoro-hexane-1,6-dioyl d$fluoride (dodecafluorosuberyl difluoride), fluorosulfonyldifluoroacetyl fluoride, 2-(fluorosulfonyl)-tetrafluoropropionyl fluoride, 2-(1-heptafluoropropoxy)-tetrafluoropropionyl fluoride, 2-~2-tl-heptafluoropropoxy) hexafluoropropoxy~tetrafluoropropionyl fluoride, 2-~2-~2-(l-heptafluoropropoxy)hexafluoropropoxy~hexafluoropropoxy~-tetrafluoropropionyl fluoride, CF3CF2 4CF2oCF ~ F2OCFCOF, ~ CF3J 0-5 CF3 FS2CF2 4 F2OCF ~ F2OCFCOF, C~3OOCCF2 fCF2OCF ~ F2OCFCOF, CF3~ 0_5 CF3 ~ C~3/ 0_5 CF3 ~.73199 NC ~CF2 ~ F20CF ~ cF20cFcoF~ NC ~CF2)1_12COF, \ ~ 0_5 CF3 carbomethoxydifluoroacetyl fluoride, cyanodifluoroacetyl fluoride, 5-carbomethoxyperfluoro~2-methyl-3-oxavaleroyl)-fluoride and 2-(pentafluorophenoxy)tetrafluoropropionyl fluoride.
The ketone l,l-difluoroethyl 2-oxopentafluoro-propanesulfonate (Example 3) is a special case as a starting material because it is an in situ source of 2-oxopenta-fluoropropanesulfonyl fluoride since the latter has not been isolated.
CF3COCF2S020CF2CH3 ~ ~rCF3COCF2S02F;~ `~
,CF3 Many of the above starting materials are com-mercially a~ailable, e.g., PCR, Gainesville, Florida, is a supplier o~ fluorinated ketones and carboxylic acids.
Examples 2, 3, 4, 5, 7, 9, 10, 11, 12, 13, 16, 19, 23 and 24 give ~ources and methods of preparation of some compounds which are not commercially available. Generally, perfluoro-ketones can be prepared from esters of perfluoro-alkanecarboxylic acids and from the reaction of carbonyl fluoride with perfluoroalkenes (W. A. Sheppard and C. M.
Sharts, "Organic Fluorine Chemistry", p. 365-368, W. A.
8enjamin, New York, 1969, H. P. Braendlin and E. T. McBee, Advances in Fluorine ChemistrY~ 3, 1 (1963)). Perfluoro-alkane carboxylic acid fluorides and perfluoroalkane-~,~-dicarboxylic acid difluorides are prepared by treat-ment of the corresponding acids with sulfur tetrafluoride, by the addition of carbonyl fluoride to perfluoroalkenes (F. S. Fawcett, C. W. Tullock and D. D. Coffman, J. Amer.
Chem. Soc., 84 4275, 4285 (1962)) and by electrolysis of _ ~

11731g~
alkanecarboxylic acids in hydrogen fluoride (~. Hudlicky, "Chemistry of Fluorine Compounds", p~ 86, MacMillan Co., New York, 1962). Perfluoroalkanedicarboxylic acids are prepared by oxidation of fluorinated ~ dialkenes or fluorinated cycloalkenes (Hudlicky, loc. cit., p. 150-152). Perfluoroalkyl polyethers with a terminal acid fluoride group can be made from hexafluoropropene oxide and its fluoride ion induced oligomers, as described by R. A. Darby, U.S. Patent 3,450,684 (1969) and by P. Tarrant, C. G. Allison, K. P. Barthold and E. C. Stump, Jr., fluorine Chem. Rev., 5, 88 (1971).
The stoichiometry of the displacement with polyfluoroallyl chloride, bromide or fluorosulfate requires one molar equivalent of this reagent for each reactive center in the polyfluoroalkoxide anion.
With a difunctional polyfluoroalkoxide, however, the stoichiometry can be adjusted to give either the mono-or the di-substitution product, thus:
O O O
.. .. ..
FCCF2CF + KF + CF2=CFCF2OSO2F > FCCF2CF2OCF2CF=CF2 (Example 5) O O
.. ..
FCCF2CF + 2KF + 2CF2=CFCF2OSO2F ~ (CF2=cFcF2cF2)2cF2 (Example 17) FCO(CF2)4COF ~ KF + CF2 = CFCF2OSO2F ~ CF2 = CFCF2O(CF2)5COF

(Examples 21, 22) FCO(CF2)4COF +2KF +2CF2 = CFCF2OSO2F ~ (CF2=CFCF2OCF2CF2CF2)2 (Example 13) The formation of the polyfluoroalkoxide and its subsequent reaction with the polyfluoroallyl chloride, ; - -llt73199 bromide or fluorosulfate can be carried out sequentiallywithout isolation of intermediates in glass apparatus at atmospheric pressure using the normal precautions to exclude moisture. The use of cooling baths and low temperature condensers (e.g. those packed with dry ice and acetone mixtures) serves to moderate the reactions and facilitate the retention of volatile reagents and products. The progress of the displacement reaction is conveniently followed by the appearance of a precipitate of the salt MZ (5), by gas liquid partition chromatography (glpc) and by fluorine nuclear magnetic resonance spectroscopy ( F NMR).
The displacement reaction can be carried out between -20C and +80C, and is preferably between 0C and 30C. Typically, the reaction mixture is cooled externally to 0C to 15C during the addition of the polyfluoroallyl chloride, bromide or fluorosulfate, and is then allowed to warm up to 25C to 30C for the remainder of the reaction time.
The time re~uired to complete the displacement reaction varies from one to 24 hours, and is preferably from 2 to 4 hours. Typically, the reaction mixture is externally cooled for 5 to 45 min while the polyfluoroallyl chloride, bromide or fluorosulfate is being added, and is then stirred at room temperature for 2 to 3 hours.
The products of the reaction are isolated by standard procedures. In some cases, the reaction product is appreciably more volatile than the high-boiling solvent used (diglyme bp 162C, DMF bp 153C) and can be distilled into a trap cooled to -80C by warming the reaction vessel X

1~73199 to 30C to 50C under a reduced pressure of 1 to 200 mm of Hg. Alternatively, the reaction mixture can be poured into five to ten times its volume of water; the insoluble lower layer of fluorinated product is separated, washed free of solvent with more water, dried and fractionally distilled from phosphorus pentoxide or concentrated sulfuric acid.
The polyfluoroallyloxy compounds of this invention are unsaturated monomers which can be converted to new and useful polymers. Polyfluoroallyloxy monomers can be homopolymerized under high pressure to oligomeric compositions of matter. ~he economic factors of a costly monomer and the necessity for high pressure operation, however, make it preferable to incorporate these monomers into copolymers formed with less expensive ethylenically unsaturated monomers, e.g., olefins such as ethylene or propylene; halogenated olefins such as tetrafluoroethylene, trifluoroethylene, hexafluoropropylene, vinylidene fluoride, vinylidene chloride, trifluoromethyl trifluorovinyl ether and chlorotrifluoroethylene; and acrylic acid or methacrylic acid esters. Halogenated olefins are preferred, especially tetrafluoroethylene, chlorotrifluoroethylene, trifluoromethyl trifluorovinyl ether, hexafluoropropylene and vinylidene fluoride. Such copolymers have either more desirable or entirely new properties not possessed by e.g., poly(tetra-fluoroethylene), poly(trifluoroethylene), poly(vinylidene fluoride), poly(chlorotrifluoroethylene) or polyethylene.
Copolymerization may be defined as any process whereby two or more monomers are incorporated as integral parts of a high polymer. A copolymer is the product resulting from X

such a process. It is not necessary that the relative numbers of the different types of unit be the same in different molecules of the copolymer or even in different portions of a single molecule.
Copolymers which contain from about 5-55 weight percent (about 1-25 mole percent) of polyfluoroallyloxy comonomer have lower melting points than the corresponding polyfluoroolefins, and consequently are more readily molded and shaped into useful objects. Copolymers which contain from about 0.1-10 weight percent, preferably about 1-10 percent (about 0.3-5 mole percent) of a polyfluoroallyloxy comonomer with pendant -SO2F or -COF groups can be partially hydrolyzed to a copolymer bearing -SO2OH or -CO2H groups which have an affinity for cationic dye molecules. Thus, it is possible to dye fluorocarbon polymers in a variety of colors.
~his cannot be done with polyfluoroolefins which do not have incorporated comonomer of this type. Copolymers which con-tain from about 5 to 35 weight percent (about 1.0 to 10 mole percent) o~ a polyfluoroallyloxy comonomer with pendant -S02F, -OC6F5, or -COF groups can also be partially or essen-tially completely hydrolyzed to a copolymer bearing hydro-philic -SO2OH, -OC6F4OH and -CO2H groups. Such a copolymer has an affinity for water and is water-wettable. Poly-fluoroolefins which do not have incorporated a comonomer of this type are not wetted and are impermeable to water. A
second important feature of copolymers which contain about 1.0 to 10 mole percent of a polyfluoroallyloxy comonomer bearing -SO2OH or -CO2H groups or ionized forms thereof;
e.g., -SO2O Na or -CO2 Na , is their capacity for ion exchange. A specific use for such polymers is in a chloroalkali cell, such as disclosed in German Patent Application 2,251,660, published April 26, 1973, and Netherlands Patent Application 72.17598, published June 29, 1973, wherein an ion-exchange polymer in the form of a film membrane or diaphragm is used to separate the anode and cathode portion of the cell from which chlorine and sodium hydroxide are respectively produced from brine flowing within the anode portion of the cell.
The properties of each copolymer depend upon the distribution of monomer units along the polymer chain since a copolymer is not a physical mixture of two or more polymers each derived from the respective monomers but a new material incorporating each monomer. It is well known that the composition of such a copolymer may also be quite different from that of the monomer mixture (feed) from which it is formed. Furthermore, "the relative tendencies of monomers to be incorporated into polymer chains do not correspond at all to their rel~tive rates of polymerization alone..... the reactive properties of a growing polymer chain depend primarily upon the monomer unit at the growing end, and not upon the length and composition of the chain as a whole.", C. Walling, "Free Radicals In Solution", pages 99-100, John Wiley &
Sons, Inc., New York (1957).
The copolymerization reaction to prepare the present copolymers can be carried out either in a nonaqueous or an aqueous medium with the reactants and initiator in solution, suspension, or emulsion form in a closed vessel with agitation. This type of reaction is well known to those skilled in the art.

~1731~9 The copolymerization is initiated by a free radical type initiator which is generally present at a concentration of from 0.001 to 5 percent by weight of the reaction mixture, and is preferably from 0.01 to 1.0 percent by weight. Such free radical initiator systems are preferably operable at or below 25C, and are exemplified by, but not restricted to pentafluoropropionyl peroxide (C2F5COO)2, dinitrogen difluoride (N2F2), azobisisobutyronitrile, ultraviolet irradiation and ammonium or potassium persulfate; mixtures of iron (II) sulfate with hydrogen peroxide, ammonium or potassium persulfate, cumene hydroperoxide, t-butyl hydroperoxide; mixtures of silver nitrate and ammonium or potassium persulfate;
mixtures of trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid or pentadecafluorooctanoic acid with ammonium or potassium persulfate. The peroxide systems may contain additionally sodium sulfite, sodium metabisulfite, or sodium thiosulfate.
When aqueous emulsion systems are used for copolymerization they contain emulsifying agents in the form of the sodium or potassium salts of saturated aliphatic acids of between about 14 and 20 carbon atoms or of perfluoroalkanoic acids and perfluoroalkanesulfonic acids of between 6 and 20 carbon atoms, e.g., potassium stearate or potassium pentadecafluorooctanoate. These emulsifiers may constitute between 0.1 and 10.0 weight percent of the reaction mixture and preferably constitute between 0.5 and 5 parts by weight percent.
Aqueous emulsion systems are customarily buffered to pH 7 or above by the addition of reagents ,,~

1173~99 such as disodium hydrogen phosphate, sodium metaborate, or ammonium metaborate to the amount of àbout 1 to 4 weight percen-t of the reaction mixture.
The following three types of copolymerization systems are preferred in preparing the preferred copolymers of this invention:
1) Solutions of two or more comonomers in 1,1,2-trichloro-1,2,2-trifluoroethane (Freon~ 113) solvent containing pentafluoropropionyl peroxide are shaken in an autoclave at about 25C for about 20 hours. The crude polymer is isolated by evaporation of the solvent and freed from monomers and lower oligomers by washing with more solvent.
2) An aqueous emulsion of two or more comonomers containing an emulsifier such as potassium perfluorooctanesulfonate and an initiator such as ammonium persulfate is shaken in an autoclave at about 70C and internal pressures of 30-200 p.s.i.g. for 0.75 to 8 hours. The polymer is isolated by filtration or centrifugation.
3) The polyfluoroallyloxy comonomer may be used as the solvent in place of 1,1,2-trichloro-1,2,2-trifluoro-ethane in method (1) when it i8 desired to incorporate a large proportion ~up to 25 mole percent) of the polyfluoroallyloxy component in the polymer.

SPECIFIC EMBODIMENTS OF THE INVENTION
The following illustrative examples demonstrate ways of carrying out the invention. All parts and percentages are by weight unless otherwise stated. ~or structure confirmation analyses, fluorine nuclear magnetic resonance chemical shifts are in parts per million from 1 ~7319~
internal fluorotrichloromethane, and proton nuclear magnetic resonance chemical shifts are in parts per million from internal tetramethylsilane. Infrared and nuclear magnetic resonance spectra were recorde~ on undiluted liquid samples unless otherwise stated.

l-(Heptafluoro-2-propoxy)-1,1,3,3-tetrafluoro-2-chloro-2-propene (CF3)2CO + KF + CF2=CClCF2Cl ~ (CF3)2CFOCF2CCl=CF2 Hexafluoroacetone (16.6 g, 0.10 mol) was distilled into a stirred mixture of potassium fluoride (5.80 g, 0.10 mol) and l-(2-methoxyethoxy)-2-methoxyethane (hereinafter referred to as diglyme) (100 ml) to give a homogeneous solution. This mixture was mai~tained at 25-30C and treated with 1,2-dichloro-1,1,3,3-tetrafluoropropene (18.3 g, 0.10 mol, prepared according to J. E. Bissey, H. Goldwhite and D. G. Rowsell, J. Org. Chem., 32, 1542 (1967)). The mixture was stirred overnight and then it was poured into water (500 ml). The lower layer was washed with water (250 ml), dried, and distilled to give 1-(heptafluoro-2-propoxy)-1,1,3,3-tetrafluoro-2-chloro-propene (13.0 g, 0.039 mol, 39~), bp 82-83C whose structure was confirmed by the following: ~max 5.72 (CCl=CF2) and 7.5-10 ~m (CF, C-O); 19F NMR, -64.9 (m) 2F, -OCF2C=C; -76.0 (2nd order m) 2F, C=CF2; -81.2 (t J = 5.7 Hz, each member d J = 2.2 Hz) 6F, CF3; and -146.7 ppm (t J = 22.9 Hz each member septet J = 2.2 Hz) lF, CFO.
Anal- Calcd for C6ClF11O C, 21-67; Cl, 10-66 Found: C, 21.43; Cl, 10.89 .~

1-(1,1,1,2,3,3-Hexafluoro-3-chloro-2-propoxy)-pentafluoro-2-propene .
A. Pentafluoro-2-propenyl fluorosulfate (Perfluoroallyl fluorosulfate) CF3cF = CF2 + S03 ~ 4 3 + CF2=CF-CF20S02F
A mixture of commercial liquid sulfur trioxide (10 ml) and hexafluoropropene (45 g, 0.30 mol) was sealed in a Carius tube at liquid nitrogen temperature, mixed well at 25C, allowed to stand for 4 days at 25C, and finally heated in a steam bath for 6 hours. From two such tubes, there was obtained by distillation, 3-(trifluoro-methyl)-3,4,4-trifluoro-1-oxa-2-thiacyclobutane 2,2-dioxide (2-hydroxy-1-trifluoromethyl-1,2,2-trifluoroethane sulfonic acid sultone, D. C. England, M. A. Dietrich and R. V. Lindsey, Jr., J. Amer. Chem. Soc., 82, 6181 (1960)) (25 g, 22%) bp 44C, and pentafluoro-2-propenyl fluoro-sulfate (hereinafter referred to as perfluoroallyl fluorosulfate) (73 g, 63~), bp 58-60C.
Perfluoroallyl fluorosulfate is characterized by: ~max 5-55 (C=C) and 6.75 ~m (SO2); 19F NMR, 46.1 (t J = 8.5 Hz, each member d J = 1.8 Hz) lF, SO2F, -74.0 (d J = 28.2 Hz, each member d J = 13.9 Hz, d J =
8.5 Hz, d J = 7.8 Hz) 2F, -91.2 (d J = 50 Hz, each member d J = 40.5 Hz, t J = 7.8 Hz) lF, -104.7 (d J = 119.4 Hz, each member d J = 50 Hz, d J = 28.2 Hz) lF, and -192.4 ppm (d J = 119.4 Hz, each member d J = 40.5 Hz, t J =
13.9 Hz, d J = 1.8 Hz) lF.

~ 173199 B. 1-(1,1,1,2,3,3-Hexafluoro-3-chloro-2-propoxy)-pentafluoro-2-propene CF3COCF2Cl + KF + CF2=CFCF20S02F--7 CF3CFOCF2CF=CF2 A suspension of potassium fluoride (5.80 g, 0.10 mol) and diglyme (100 ml) was stirred at 20C in a cooling bath while chloropentafluoroacetone (18.3 g, 0.10 mol) was distilled in. After the potassium fluoride had dissolved, perfluoroallyl fluorosulfate (23.0 g, 0.10 mol) was added rapidly with cooling of the reaction mixture. The resulting exothermic reaction was accompanied by the precipitation of solid. The mixture was stirred at 25C for one hour, and then the volatile components were transferred to a trap cooled to -80C by heating the reaction mixture at 42C (5 mm Hg). The volatile product was distilled from phosphorus pentoxide to give 1-(1,1,1,2,3,3-hexafluoro-3-chloro-2-propoxy)-penta1uoro-2-propene, (19.6 g, 0.059 mol, 59%) bp 85-86C which was characterized by: ~max 5.55 (CF = CF2) and 7-10 ~m 20 (CF, C-O); 19F NMR, -68.6 (m) 2F, CF2Cl, -69.1 (m) 2F, CF2O, -78.8 (m) 3F, CF3, -93.2 (d J = 54.7 Hz, each member d J = 39.8 Hz, t J = 7.5 Hz), lF, cis-CF~-CF=CF, -105.9 (d J = 116.7 Hz, each member, d J = 54.7 Hz, t J = 24.0 Hz) lF, trans-CF2-CF=CF, -141.2 (t J = 22.8 ~

Hz, each member m) lF, CF, and -190.4 ppm (d J = 116.7 Hz, each member d J = 39.8 Hz, t J = 13.4 Hz) lF, -CF2CF=C .
-Anal. Calcd for C6ClFl10: C, 21.67; Cl, 10.66 Found: C, 21.34; Cl, 10.21 1~7~19g EXA:MPLE 3 2~ Pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl fluoride (2-Perfluoroallyloxypropane-l-sulfonyl fluoride-) _ A. 2-Oxopentafluoropropanesulfonic Acid OC H O o , 2 5 " "
CF3C=CF2 + SO3 > CF3CCF2S2C2H5 + CF3CCF2S2H

O O
ll ll CF3ccF2so2oc2H5 + CF3C2 ~ C 3CC 2 2 (i) Dropwise addition of sulfur trioxide (12.8, 0.16 mol) to 2-ethoxy-1,1,3,3,3-pentafluoropropene (D. W. Wiley and H. E. Simmons, J. Org. Chem., 29, 1876 (1964)) (29.0 g, 0.165 mol) produced an ~_ exothermic reaction. The black reaction mixture was distilled to give recovered 2-ethoxy-1,1,3,3,3-pentafluoropropene (6.3 g, 0.036 mol, 22%, identified by ir) and ethyl 2-oxopentafluoropropanesulfonate (20.2 g, 0.078 mol, 49% conversion and 63% yield) bp 47-48C (12 mm Hg): ~max 3.34 and 3.41 (saturated CH), 5.60 (C = O), 7.09 (SO2O), and 7.6-8.5 ~m (C-F, SO2); 1H NMR, ~ 4.59 (q J = 7.2 Hz) 2H, OCH2 and 1.51 ppm (t J = 7.2 Hz) 3H, CH3; 19F
NMR, -75.0 (t J = 8.3 Hz) 3F, CF3, and -107.4 ppm (q J = 8.3 Hz) 2F, CF2.
(ii) The above reaction was repeated at 0-5C with sulfur trioxide (88 g, 1.1 mol) and 2-ethoxy-1,1,3,3,3-pentafluoropropene (176 g, 1.0 mol). The colorless X

~1731gg reaction mixture, which darkened on standing over-night, was distilled to give recovered 2-ethoxy-1, 1,3,3,3-pentafluoropropene (28.6 g, 0.16 mol, 16%) bp 46 48C, ethyl 2-oxopentafluoropropanesulfonate (145.1 g, 0.57 mol, 57~ conversion and 68~ yield) bp 48-52C (12 mm Hg), and a higher boiling fraction composed mainly of 2-oxopentafluoropropanesulfonic acid. The crude acid was redistilled at 81-82C
(6.2 mm Hg), yield 35.6 g (0.16 mol, 16% conversion and 19% yield) of pure acid: ~max (CC14, CaF2 plates) 3.3 and 4.2 (broad) (SOH), 5.58 (C=O), 7.13 (SO2O~ and 7.5 - 9 ~m (CF, SO2); lH NMR ~ 10.2 ppm (s) SO2OH; 19F NMR, -76.2 (t J = 7.5 Hz) 3F, CF3, and -108 ppm (q J = 7.5 Hz) 2F, CF2.
Anal. Calcd for C HF5O S: C, 15.80; H, 0.44;
3 4 F, 41.65; S, 14.06 Found: C, 15.95; H, 0.55;
F, 41.55; S, 13.89 (iii) Ethyl 2-oxopentafluoropropanesulfonate (25.6 g, 0.10 mol) was stirred at 25C and treated with trifluoroacetic acid (17.1 g, 0.15 mol). The mixture was allowed to stand overnight, and then it was heated to reflux (60C) in a spinning band still. Fractional distillation of the mixture at a pot temperature below 100C gave 2-oxopenta-fluoropropanesulfonic acid (18.4 g, 0.081 mol, 81%) bp 73C (2.6 mm Hg).
B. l,l-Difluoroethyl 2-oxopentafluoropropanesulfonate O O
CF3ccF2so2oH + CF2 CH2 > CF3CCF2S020CF2CH3 ~173199 A m~tal tube containing 2-oxopentafluoropropane-sulfonic acid (23.8 g, 0.10 mol) was cooled below -40C and vinylidene fluoride (l,l-difluoroethane) (13 g, 0.20 mol) was added. The mixture was shaken and warmed to 25C where it was kept for 4 hours.
Distillation of the liquid product gave 20.4 g (0.07 mol, 70~) of l,l-difluoroethyl 2-oxopentafluoropro-panesulfonate, bp 62-63C (50 mm Hg): ~max (CC14) 5.54 (C=0), 6.96 (SO2O) and 7.5 - 9 ~m (CF, SO2);
1H NMR, ~ 2.06 ppm (t J = 14.3 Hz) CH3; 19F NMR, - 58.3 (q J = 14.3 Hz, each member t J = 7.1 Hz) 2F, OCF2, -75.0 (t J = 8.0 Hz) 3F, CF3 and -106.1 ppm (q J = 8.0 Hz, each member t J = 7.1 Hz) 2F, CF2SO2.
Anal. Calcd for C5H3F704S: C, 20 56; H, 1-03;

Found: C, 20.73; H, 1.03;
F, 45.72 A similar experiment on a 0.8-mol scale gave an 86% yield of product bp 60C (50 mm Hg). This material was stored in polytetrafluoroethylene bottles to avoid degradation.

C. 2-(1-Pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl fluoride o CF3CCF2SO20CF2CH3 + KF + CF2=CFCF2OSO2F

CF3-CFOCF2CF=CF2 + CH8CO~ + XOS02F

A suspension of dry potassium fluoride (5.80 g;

0.10 mol) in 2, 5, 8, ll-tetraoxadodecane (triglyme) (100 ml) was stirred and cooled at 0C while ~.

l,l-difluoroethyl 2-oxopentafluoropropanesulfonate prepared as in Example 3B (29.2 g, 0.10 mol) was added. When the potassium fluoride had nearly all dissolved, perfluoroallyl fluorosulfate prepared as in Example 2A (23.0 g, 0.10 mol) was added at 0C, and the resulting mixtura was stirred at 20-26C
for 3 hours. Volatile components were removed by distillation at a flask temperature of 25C and 1 mm Hg pressure. The distillate was washed with cold dilute ammonium hydroxide, dried and distilled to give 2 (1-pentafluoro-2-propenyloxy)hexafluoropropane-l-sulfonyl fluoride (13.0 g, 0.034 mol, 34%), bp 47-48C (60 mm Hg) whose structure was confirmed by:
~max 5-59 (CF=CF2), 6.80 (SO2F) and 7.5 - 10 ~m (C-F, C-O, SO2); 19F NMR, + 45.4 (m) lF, SO2F, -70.0 (m) 2F, OCF2, -78.0 (quintet J = 10.7 Hz) 3F, CF3, -91.5 (d J = 51.5 Hz, each member d J = 39.5 Hz, t J = 7.5 Hz) lF, cis-CF2CF = CF, -104.8 (d J = 117.0 Hz, each member d J = 51.5 Hz, t J = 25.5 Hz) lF, trans-CF2CF
= CF, -107.0 and -108.4 (AB J = 255 Hz, each member q J = 10.7 Hz, m) 2F, CF2SO2F, -138.7 (t J = 20.2 Hz, each member m) lF, CF, and -190.8 ppm (d J = 117.0 Hz, each member d J = 39.5 Hz, t J = 13.0 Hz) lF, CF2C~ C.
Anal. Calcd for C6F12O3S: C, 18.96; F, 59.98; S, 8.43 Found: C, 19.24i F, 60.06; S, 8.26 In a similar reaction to Example 3C, it was shown by ir that the gases generated were composed mainly of acetyl fluoride and small amounts of hexafluoropropene and sulfuryl fluoride.

., 1-{1,3-bis(2-Heptafluoropropoxy)-2-pentafluoropropoxy}-pentafluoro-2-propene A. 1~3-bis(2-Heptafluoropropoxy)tetrafluoropropanone O O
2(CF3)2CO + KF + ClF2CCCF2Cl ~ (CF3)2C~X~2CCF2OCF(CF3)2 A mixture of dry potassium fluoride (21.0 g, 0.36 mol), dry N,N-dimethylformamide (DMF) (150 ml), hexafluoroacetone (59.8 g, 0.36 mol) and 1,3-dichloro-tetrafluoroacetone (35.8 g, 0.18 mol) was heated at reflux (40-60C) for 3 days. Distillation into a trap cooled to -80C gave recovered hexafluoroacetone (16.5 ml, 46~) and a 63 g of liquid bp 30-145C. The higher-boiling material was redistilled from sulfuric acid to give 1,3-bis(2-heptafluoropropoxy)tetrAfluoropropanone (18.7 g, 0.037 m~l, 21% conversion, 39~ yield based on hexafluoroacetone), bp 117-118C: ~max (CC14) 5.51 (C=O) and 7.5-9 ~m (CF, C-O-C); MS m/e 479 (M-F) , 313 (M-F-CF3COCF3) , 263 (M-F-CF3COCF3-CF2) , 235 [(CF3)2CFOCF2~ , 169 (C3F7) , 147 (CF3COCF2) , 97 (CF3CO) and 69 (CF3) ; 19F NMR, -75.0 (d J = 21.5 Hz, each member septet J = 5.5 Hz) 2F, OCF2, -81.4 (m) 6F, CF3, and -145.3 ppm (t J = 21.5 Hz, each member septet J = 2.1 Hz) lF, CF.
Anal. Calcd for C9F1803: C, 21.70; F, 68.66 Found: C, 21.60; F, 68.59 B. 1-{1,3-bis(2-Heptafluoropropoxy)-2-pentafluoropropoxy}-pentafluoro-2-propene o (CF3)2CFOCF2CCF2OCF(CF3)2 + KF + CF2 = CFCF2OSO2F

CF2 = CFCF2OCF[CF2OCF(CF3)2]2 ~r A mixture of 1,3-bis(2-heptafluoropropoxy)-tetrafluoropropanone (20.0 g, 0.04 mol), diglyme (100 ml) and potassium fluoride ~2.32 g, 0.04 mol) was stirred ana warmed to 55C. The two liquid phases and solid originally present became homogeneous and stayed so upon cooling. Perfluoroallyl fluorosulfate prepared as in Example 2A (10.0 g, 0.043 mol) was added rapidly at 10~C
and the mixture was allowed to warm. The slight exothermic reaction was accompanied by precipitation of solid and the appearance of a second liquid phase. The mixture was stirred for 2 hours and then poured into water (350 ml).
The lower layer was washed with water (75 ml), dried over phosphorus pentoxide and distilled to give l-~1,3-bis(2-heptafluoropropoxy)-2-pentafluoropropoxy}-pentafluoro-2-propene ~16.1 g, 0.024 mol, 62%) bp 64-67C (25 ~ Hg) whose structure was confirmed by: ~max 5.57 (CF2 = CF) and 7.5-9 ~m (CF, C-O); 19F NMR, -69.4 (m) 2F, OCF2C=C;
-80.3 ~broad) 4F, CFOC~2 -81.5 (s) 12F, CF3, -93.7 (d J = 54.0 Hz, each member d J = 39.6 T~z, t J = 7.8 llz) lF, cis-CF2 - CF = CF , -106.3 (d J = 117.4 Hz, each member d J = 54.0 Hz, t J = 23.7 Hz) lF, trans-CF2CF =
C~ , -145.8 (m) 3F, OCF, and -190.9 ppm (d J = 117.4 Hz, each member d J = 39.6 Hz, t J = 16.6 Hz) lF, CF2CF - C.
Anal- Calcd for C12F243 C~ 22-24; F~ 70-35 Found: C, 22.66; F, 70.27 3-(1-Pentafluoro-2-propenyloxy)tetrafluoropropionyl_fluoride A. Difluoromalonyl difluoride SO3 ,, CH30CF2CF2CF ~ FccF2cF
3-Methoxytetrafluoropropionyl fluoride (F. S. Fawcett, C. W. Tullock and D. D. Coffman, J. Amer.
Chem. Soc., 84, 4275 (1962)) (81 g, 0.45 mol) was slowly added to sulfur trioxide (80 g, 1.0 mol) at 40C, and the product difluoromalonyl difluoride, bp -9C, was continu-ously removed by distillation through a low ~emperature still, yield 58 g (0.40 mol, 90~). The product structure was confirmed by: ~max 1860 cm 1 (COF), F NMR (no solvent), 17.1 ppm (t J = 10 Hz) 2F, COF and -114.2 ppm (t J = 10 Hz) 2F, CF2.

B. 3-(1-Pentafluoro-2-propenyloxy)tetrafluoropropionyl fluoride O O O
ll ll ll FCCF2CF + KF + CF2=cFcF2oso2F ~ FCCF2CF20CF2CF=CF2 A mixture of dry potassium fluoride (7.5 g, 0.13 mol) and diglyme (100 ml) was stirred at 10C and difluoro-malonyl difluoride from part A (18.5 g, 0.13 mol) was distilled into it. After 20 min. the potassium fluoride was nearly all dissolved, and perfluoroallyl fluorosulfate prepared as in Example 2A (29.9 g, 0.13 mol) was added dropwise at 10-15C. The mixture was stirred for 3 hours, then the volatile components were removed at a pot temper-ature of 32C and 4.8 mm Hg pressure. Fractionation of the distillate gave 3-(1-pentafluoro-2-propenyloxy)tetrafluoro-30 propionyl fluoride (14.9 g, 0.051 mol, 39%) bp 70-71C and a *~

small amount of higher bp material. The product structure was confirmed by: ~max 5.33 (COF), 5-60 (CF = CF2) and 7.5-10 ~m (CF, C-O); 19F NMR 23.7 (apparent quintet, J 7.5 Hz) lF, COF, -71.9 (d J = 24.6 Hz, each member t J = 13.9 Hz, d J = 13.9 Hz, d J ~ 7.4 Hz) 2F, OCF2C=C, -86.7 (m) 2F, CF2O, -91.6 (d J = 51.8 Hz, each member d J = 39.4 Hz, t J = 7.4 Hz) lF, cis-CF2CF = CF, -105.1 (d J = 117.1 Hz, each member d J = 51.8 Hz, t J = 24.6 Hz) lF, trans-CF2-CF=CF, -122.0 (d J = 8.2 Hz, each member t J = 3.1 Hz) 2F, FCOCF2, and -191.0 ppm (d, J = 117.1 Hzt ~

each member d, J = 39.4 Hz, t J = 13.9 Hz, t J % 1.6 Hz) lF, CF2-CF=C.

Anal. Calcd for C6F10O2: C, 24.51 Found: C, 24.56 .

Perfluoro-3~6-dioxanon-8-enoyl Fluoride A. Tetrafluorodiglycolyl Chloride Cl Cl 2 ~ F KMnO4 -H2S4 HO2CCF2OCF2CO2H-O O ~
,. ..
ClCCF20CF2CCl A mixture of 307.6 g (1.46 mol) of dichlorotetra-fluorodihydrofuran, 157.8 g (3.9 mol) of NaOH, 312 g (1.97 mol) of potassium permanganate and 1500 ml of water was refluxed for 17 hours. A brief (steam) distillation gave 10.6 g (3~) of recovered dihydrofuran. The reaction mixture was filtered and the filter cake triturated with 2 x 400 ml of water. The combined aqueous solutions were evaporated to 1500 ml, treated cold with 300 ml of conc. H2SO4 and extracted continuously with ether for a day. The extracts were evaporated until ether was no longer evolved at 25C
(0.5 mm Hg). To the crude solid diacid, 279 g (up to 93%
yield), was added 5 g (0.06 mol) of pyridine and 416.5 g (3.5 mol) of thionyl chloride. ~ittle gas evolution occurred at this stage, but considerable gas evolved as the mixture was stirred and warmed past 40C. Evolved gases were passed through a 0 trap; after 4 hours at ca. 40C, gassing slowed and trap contents (10 ml) were returned to the pot. The mixture was then refluxed, with occasional return of cold trap contents to the reaction, until the head temperature reached 81C and no gas was being evolved.
Fractionation afforded 215.2 g (61% from dihydrofuran) of tetrafluorodigylcolyl chloride, bp 94-97C. Structure was confirmed by NMR: 19F -77.0 ppm (s, -CF2O-).
Tetrafluorodigycolyl chloride, bp 96.5C, has previously been prepared by a different route by R. E. Banks, E. D. Burling, B. A. Dodd, and K. Mullen, J. Chem. Soc. (C), 1706 (1969).
B. Tetrafluorodigylcolyl Fluoride O O O O
ClCCF2OCF2CCl NaF > FCCF2OCF2CF

Conversion of the diacid chloride to the corresponding fluoride, bp 32-33C, was accomplished by a scale-up of the procedure of R. E. Banks, E. D. Burling, B. A. Dodd, and K. Mullen, J. Chem. Soc. (c), 1706 (1969).
A mixture of 215 g (0.885 mol) of tetrafluorodiglycolyl 30 dichloride, 140.5 g (3.35 mol) of NaF, and 1200 ml of ~p ~1731g9 anhydrous acetonitrile was stirred overnight, then distilled to give a fraction collected at 35-79C. The distillate was treated with 20 g of NaF and distilled to give 105 g of tetrafluorodiglycolyl difluoride, bp 32-33C.
Addition of another 100 g (2.38 mol) of NaF to the reaction mixture and slow distillation afforded another fraction, bp 35-81C. Treatment with 10 g of NaF and fractionation gave another 37.0 g of difluoride product, bp 32-33C, for a total of 142 g (76%).
C. Perfluoro-3,6-dioxanon-8-enoyl Fluoride O O
FCCF2OCF2CF ~ KF + CF2=CFCF2OSO2F
o CF2=CFCF20CF2CF20CF2CF
A mixture of 38.9 g (0.67 mol) of KF, 141.5 g (0.67 mol) of tetrafluorodiglycolyl difluoride, and 500 ml of dry diglyme was stirred for 30 minutes at 5C, during which time nearly all of the KF dissolved. Then 154.1 g (0.67 mol) of perfluoroallyl fluorosulfate was added rapidly at 5C and the mixture was stirred at 0-5C for 3 hours, at 25C for 2 hours, and allowed to stand overnight.
Volatiles were evaporated to diglyme reflux at 38C (3 mm Hg). Distillation of volatiles from 20 g of NaF gave 28.2 g (20%) of recovered diacid fluoride, bp 32-33C, and 125.0 g (52~) of monoacid fluoride, almost all of it bp 93-94C.
Structure was confirmed by:
ir (CC14): 5.30 (COF), 5.59 (C=C), 8-9 ~ (CF, C-O). NMR: F 13.3 (m, lF, COF), -72.0 (d of d of t of d, JFF 25, 13, 13, 7.7 Hz, 2F, =CFCF2), -77.5 (t of d, JFF 11.5, 2.7 Hz, 2F, CF2CO2F), -88.8 (t, JFF 11.5 Hz, 2F, CF2OCF2COF), -89.4 (t, JFF 12.7 Bz, 2 F, =CFCF2OCF2), -91.9 (d of d of t~
JFF S2.7, 39.3, 7.7 Hz, lF, c -CF2CF=CF), -105.3 (d of d of t, JFF 117.6, 52.7, 24.6 Hz, 1 F, trans-CF2CF=CF~, and -190.8 ppm (d of d of t of t, JFF 117.6, 39.39 13.7, 1.6 Hz, 1 F, CF2CF=).

2-(1-Pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluoride FSO2CF2CF ~ KF + CF2=cFcF2Oso2~ ~ FSO2CF2CF2OCF2CF=CF2 A suspension of potassium fluoride (5.8 g, 0.10 mol) in diglyme (100 ml) was stirred and cooled while fluorosulfonyldifluoroacetyl fluoride tl8.0 g, 0.10 mol) ~D. C. England, M. A. Dietrich and R. V. Lindsey, Jr., J.
Amer. Chem. Soc., 82 6181 (1960)) was added rapidly. The mixture was stirred for 15 min at 20-30C during which time the potassium fluoride dissolved, and then it was treated with perfluoroallyl fluorosulfate prepared as in Example 2A
(25.0 g, 0.11 mol) at 20-25C over 5 min. The mixture was stirred for 2 hours, during which time solid precipitated, and the temperature rose to 28C and fell again. The volatile components were transferred to a trap cooled to -80C by warming the solution to reflux at 38C ~5 mm Hg).
The distillate was treated with concentrated sulfuric acid (10 ml) to remove diglyme, then distilled to give 2~ pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluoride (19.9 g, 0.06 mol, 60~) bp 55-56C (150 mm Hg).
The product structure was confirmed by: ~max 5-53 (CF2=CF), 6.79 (SO2F) and 7-10 ~m (CF,C-O,SO~); 19F NMR, ~44.9 (t J = 6 Hz, each member t J = 6 ~z) lF, FSO2, -71.8 (d J - 25.3 Hz, each member t J = 13.8 Hz, d J = 13.8 Hz, d J = 7.3 Hz) 2F, OCF2C=C, -83.0 (m) 2F, CF2CF2O, -90.9 (d J = 50.6 Hz, each member d J = 39.5 Hz, t J = 7.3 Hz) lF, cis-CF2CF=CF, -104.5 (d J = 117.6 Hz, each member d J = 50.6 Hz, t J = 25.3 Hz) lE, trans-CF2CF=CF, -113.0 (d J = 5.6 Hz, each member t J = 2.9 Hz) 2E', FS02CF2, and -190.9 ppm (d J =

117.6 Hz, each member d J = 39.S Hz, t J = 13.8 Hz, t J =
3.2 Hz) lF, CF2CF=C.

Anal. Calcd for C5F10O3S: C, 18.19; F, 57.55; S, 9.71 Found: C, 18.35; F, 57.40; S, 9.69 2-(1-Pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluoride_ __ O
FS02CF2CF + KF + CE~2 = CFCF2OSO2F------~FSO2CF2CF2OCF2CF=CF2 The procedure of Example 7 was followed, substituting acetonitrile for digylme as the solvent. The acetonitrile was not rigorously purified, and the yields of 2-(1-pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluoride, pb 54-55C (150 mm Hg) ranged from 40-50%.

1-[1-(Pentafluoro-2-propenyloxy)]hexafluoropropane-2-sulfonyl fluoride FSO2CFCOF + KF + CF2=CFCF2OSO2F ~ FSO2CFcF2OcF2cF=cF2 A mixture of potassium fluoride (5.80 g, 0.10 mol) and dyglyme (100 ml) was stirred at 10C while 2-fluoro-sulfonyltetrafluoropropionyl fluoride (23.0 g, 0.10 mol) (D. C. England, M. A. Dietrich and R. V. Lindsey, Jr., J.
Amer. Chem. Soc., 82 6181 (1960)) was added. The resulting solution was treated at 10C with perfluoroallyl fluoro-sulfate prepared as in Example 2A, and after the addition ~1731g9 was complete, the mixture was stirred at 25C for 3 hours, then it was poured int~ water (500 ml). The l~wer layer was washed with water (100 ml), dried and distilled to give l-[l-pentafluoro-2-propenyloxy)]hexafluoropropane-2-sulfonyl fluoride (25.7 y, 0.068 mol, 68~) bp 50C (60 mm Hg), pure by gas liquid partition chromatography (glpc). The product structure was confirmed by:
~max 5.55 (CF=CF2), 6.78 (SO2F) and 7.5-10 um (CF,C-O,SO2);

19F NMR, 54.9 (d J = 20.7 Hz, each member q of J = 10.4 Hz, d J = 3.6 HZ) lF, SO2F, -71.8 (d J = 25.0 Hz, each member t J = 13.8 Hz, d J = 13.8 Hz, d J = 7.4 Hz) 2F, OCF2C=C, -72.1 (m) 3F, CF3, -75.5 (m) 2F, CFCF2O, -91.0 (d J = 50.7 Hz, each member d J = 39.4 Hz, t J = 7.4 Hz) lF, cis-CF2CF=CE', -104.6 (d J = 117.6 Hz, each member d J = 50.7 Hz, t J =
25.0 Hz) lF, trans-CF2CF=C~F, -166.4 (d J = 14.6 Hz, each member q J z 7.2 Hz, d J = 3.6 Hz) lF, CF, and -191.1 ppm (d J = 117.6 Hz, each member d J = 39.4 Hz, t J = 13.8 Hz, t J
= 1.7 Wz) lE' CF2CF=C.

~nal. Calcd for C6F12O3S: C, 18.96; F, 59.98; S, 8.44 Found: C, 18.70; F, 60.09; S, 8.08 Perfluoro(4-oxa-6-heptenenitrile) A. 3-Methoxytetra1uoro-propionamide CH30cF2cF2c02cH3 ~ CH30CF2CF2cON~2 A solution of 140 g (0.74 mol) of methyl 3-methoxy-tetrafluoropropionate in 100 ml of ether was treated at 0 with 15.3 g (0.90 mol) of NH3. The resulting viscous mixture was stirred at 25 overnight and evaporated to dryness at 25 (10 mm). The crude residue was then recrystallized from ~' ~173199 ether/hexane to give 123.6 g (95~) of 3-methoxytetrafluoro-propionamide, mp 78-80. An analytical sample was recrys-tallized from ether/hexane, mp 83-85~. IR (KBr): 2.95, 3.02 and 3.10 (NH2), 3.37 and 3.49 (sat'd CH), 5.92 (C=O), 6.19 (NH2), 7.5-10 ~ (CF, C-O). NMR ((CD3)2CO): lH 6.67 (broad, 2H, NH2) and 3.66 ppm (s, 3H, OCH3); 19F - 120.6 (t, JFF 4.7 ~Z~ 2F, CF2) and -121.8 ppm (t, JFF 4.7 Hz, of d, JHF 2-1 Hz, 2F, CF2).
Anal. Calcd. for C4HsF4NO2: C, 27.44; H, 2.88; N, 8.00 Found: C, 27.74: H, 2.93; N, 7.99 B. 3-Methox~tetrafluoropropionitrile CH30CF2CF2CO~H2 ~ CH30CF2CF2CN
A solution of 52.5 g (0.30 mol) of the amide from Part A in 200 ml of diglyme was stirred at -10 while 47.5 g (0.60 mol) of pyridine and 63.0 g (0.30 mol) of trifluoro-acetic anhydride were added. The cooling bath was removed, and the mixture was stirred at ca 25 for 2 hr. Evaporation of volatiles to 40 (4.5 mm) gave 42.7 g of crude product, which was distilled to afford 36.5 g (77%) of 3-methoxy-20 tetrafluoropropionitrile, bp 53. IR (neat): 3.36 and 3.48 (sat'd CH), 4.42 (CN), 8-10 u (CF, C-O). NMR: lH 3.78 ppm (8, OCH3); 19F -93.2 (t, JFF 6.3 Hz, 2F, CF2) and -108.8 ppm (t, JFF 6-3 Hz, 2F, CF2).
Anal. Calcd. for C4H3F4NO: C, 30.59; H, 1.92; N, 8.92 Found: C, 30.83; H, 1.94; N, 8.77 C Cyanodifluoroacetyl fluoride CH30CF2CF2CN > FCCF2CN
When 55.5 g (0.69 mol) of SO3 was added to 109 g (0.69 mol) of nitrile prepared as in Part B, a mild exother-mic reaction ensued. The mixture was stirred 2 hr, then ~i 117~199 heated at reflux (50) for 4 hr, during which time the pot temperature rose from 73 to 91 and some volatiles were collected in the -80 trap. Distillation gave 19.1 g (18%
assuming pure) of recovered nitrile and 67.3 g (86%) of methyl fluorosulfate. T~e bath temperature was taken ultimately to 170. Considerable tarry residue and 22 ml at -80 of volatile products were also formed. Distillation of the volatiles gave 17 g (20~ conversion) of cyanodifluoro-acetyl fluoride, bp 8. IR (gas phase): 4.42 (CN), 5.27 (COF), 8-10 u (CF) with small amounts of SO2 and an unknown impurity present. NMR: l9F + 16.7 (t, JFF 11.0 Hz, lF, COF) and -98.0 ppm (d, JFF 11.0 ~z, 2F, CF2). Mass spec: m/c 122.9926 (M+; calcd. for C F NO, 122.9932), 103.9939 (M+-F;

calcd. for C F ~O, 103.9949), 75.9961 (CF CN+; calcd. for C
F ~, 75.9999)-V. Perfluoro(4-Oxa-6-heptenenitrile) FCCF2CN + KF + CF2=CFCF2OSO2F ~ CF2=CFCF2OCF2CF2CN

To a suspension of 9.0 g (0.156 mol) of flame-dried KF in 200 ml of dry diglyme at -10 was added 16 g (0.13 mol) of cyanodifluoroacetyl fluoride from Part C. The mixture was stirred at 0 for 30 min, after which it was homogeneous. Then 33.9 g (0.15 mol) of CF2=CFCF2OSO2F was added at 0, and the mixture was stirred at 0-5 for 4 hr, then at 25 for 1 hr. Volatile~ were removed at 40 (5 mm) and fractionated to give 22.4 g (63%) of perfluoro-~4-oxa-6-heptenenitrile), bp 66-67. IR (CCl4): 4.31 (CN), 5.61 (CF=CF2), 8-10 u (CF, C-O). NMR: 19F - 71.9 (d of d of t of d, JFF 25.0, 13.6, 12.7, 7.3 Hz, 2F, OCF2C=), -88.1 (t of t of m, JFF 12.7, 5.0 Hz, 2F, OCF2CF2), -90.9 (d of d of t, 1~731g~

JFF 50-3, 39.1, 7.3 Hz, aF, cis-CF2CF=CFF), -104.5 (d of d of t, JFF 116.6, 50.3, 25.0, lF, trans-CF2CF=CFF), -109.3 (t, JFF 5-0 Hz, 2F, CF2CN), and -19O.9 ppm (d of d of t of m, J 116.6, 39.1, 13.6 Hz, lF, CF CF=).
Anal. Calcd. for C6Fg~O: C, 26.39; N, 5.13 Found: C, 26.37; N, 5.31 Methyl Perfluoro(5-methyl-4,7-dioxa-9-decenoate) o CIF3 CH3OCCF2CF2OCFCOF + KF + CF =CFCF2OSO2F >

CH3OCCF2CF2OCFCF2OCF2CF=CF2 Condensation of 5-carbomethoxyperfluoro(2-methyl-3-oxavaleroyl) fluoride with KF/CF2=CFCF2OSO2F was demon-strated by adding 16.1 g (0.50 mol) of it to a suspension of 32.0 g (0.55 mol) of flame dried KF in 500 ml of dry diglyme stirred at 0. The mixture was stirred at 0-10 for 10 min, after which most of the KF had dissolved. Then 126.5 g (0.55 mol) of CF2=CFCF2OSO2F was added rapidly, and the mixture was stirred at 5-10 for 3 hours, then 1 hr at 25.
The reaction mixture was poured into 2 1. of water, and the lower layer was washed with water, extracted with 25 ml of conc. H2SO4, clarified with CaSO4, filtered and distilled to give 63.7 g (27%) of methyl perfluoro(5-methyl-4,7-dioxa-9-decenoate), bp 61-62 (10 mm). IR (neat): 3.31, 3.37, and 3.48 (sat'd CH), 5.58 (broad; C=O, CF=CF2), 7-10 ~ (CF, C-O). NMR: lH 3.93 ppm (s, OCH3); 19F -72.0 (m, 2F, CF
C=), -80.6 (m, 3F, CF3), -83.4 (m, 2F, CF2O), -83.9 (m, 2F, CF2O), -91.9 (d of d of t, JFF 52.7, 39.5, 7.4 Hz, lF, c -CF2CF=CFF), -105.2 (d of d of t, JFF 117.3, 52.7, 25.0 ~ .

11~3199 Hz, lF, trans-CF2CF=CFF), -122.0 (t, JFF3.1 Hz, 2F, CF2C=O), -145.9 (t, JFF20.5 Hz, of m, lF, CF) and -191.1 ppm (d of d of t, JFFl17.3, 39.5, 13.9 Hz, lF, CF2CF=CF2).
Anal. Calcd- or C10 3 15 4 Found: C, 25.57; H, 0.66.

A. Perfluoro(3-allyloxyglutaroyl) Fluoride and Perfluoro(3-keto-6-oxa-8-nonenoyl) fluoride O O O
,. - -CF2=CFCF2OSO2F + KF + FCCF2CCF2CF -O O
CF2=CFCF2OCF(CF2COF)2 ~ FCCF2CCF2CF2OCF2CF=CF2 To a suspension of 29.0 g (0.50 mol) of flame-dried KF in 600 ml of diglyme stirred at O was added 111.0 g (0.50 mol) of 3-ketotetrafluoroglutaroylfluoride prepared by the action of SO3 on bis(2-methoxytetrafluoroethyl)-ketone. The mixture was stirred for 30 min at 0-5, when nearly all of the KF had dissolved. Then 115 g (0.50 mol) of perfluoroallyl fluorosulfate was added dropwise, and the mixture was stirred at 0-5 for 4 hr, warmed slowly to 25, and volatiles removed to 40 (5 mm) in the pot. The volatiles, 135.2 g, were distilled to give fractions, bp 45-61 (100 mm), 105.2 g (57% crude), of which 100 g had bp 59-61 (100 mm) and was indicated by gc to contain one major component and minor (0-15%) amounts of a second product.
IR (CC14): 5.31 (COF), 5.57 (CF=CF2, C=O), 7.2-10 u (CF, C-0). For a late fraction, bp 61 (100 mm), of nearly pure perfluoro(3-allyloxyglutaroyl)fluoride, NMR (CC14): lH v.
small amount diglyme impurity; 9F 24.6 (m, 2F, COF), -68.5 (m, 2F, OCF2C=), -91.2(d of d of t, JFF51.4, 39.5, 7.3 Hz ~173199 lF, cls-CF2CF=CFF), -104.8 (d of d of t, JFF117.6, 51.4, 25 . 2 HZ , lF , trans-CF2CF=CFF), -116.1 (m, 4F , CF2C=O), -141.2 (m, lF, CF), and -190.8 ppm (d of d of d of t, JFF
117.6, 39.5, 13.5 Hz, lF, CF2CF-). An earlier fraction contained 2% of a second fluorinated component identified as perfluoro(3-keto-6-oxa-8-nonenoyl)fluoride by 19F NMR.
B. Dimethyl Perfluoro-3-allyloxyglutarate and Methyl Perfluoro(3-keto-6-oxa-8-nonanoate) CF2=CFCF20CF(CF2COF)2 + CH30H~ CF2=CFCF20CF(CF2CO2CH3)2 O o (+ CH30CCF2CCF2CF20CF2CF=CF2) Perfluoro(3-allyloxyglutaroyl)fluoride from Part A was easily converted to its dimethyl ester by treatment at 25-40 with a mixture of methanol and NaF.
Filtration and distillation gave pure dimethyl perfluoro (3-allyloxyglutarate), bp 77 (0.70 mm), identified by comparison of its IR spectrum with that of an authentic sample, in 42% overall yield from 3-ketotetrafluoroglu-taroyl fluoride. Since the coproduct, methyl per-fluoro(3-keto-6-oxa-8-nonanoate), is considerably lower boiling, it was easily separated during the fractionation.

Perfluoro-1,6-bis(2-propenyloxy)hexane o o .. ..
FC(CF2) 4CF + CF2=CFCF20S02F~ (CF2=CFCF20CF2CF2CF2) 2 + CF2=CFCF2O(CF2)5COF

diglyme 2 CFCF2O(CF2)5COF + H O ~CF2=CFCF2O(CF2)5 002H-1/2 diglyme A mixture of potassium fluoride (11.62 g. 0.20 mol), diglyme (200 ml) and octafluoroadipoyl difluoride (PCR 28.2 g, 0.096 mol) was stirred at 5C for 1.5 hours. The mixture was kept at 5-10C while perfluoroallyl fluorosulfate prepared as in Example 2A (46.0 g, 0.20 mol) was added dropwise. When the addition was complete, the mixture was stirred at 5C for 30 min, then it was allowed to warm to 25C and the stirring was continued for a further 3 hours.
After having stood overnight, the mixture was poured into water (1 Q.)i the lower layer was washed with water (150 ml), dried and distilled to give two products.
The lower-boiling fraction was perfluoro-l, 6-bis-(2-propenyloxy)hexane (21.1 g, 0.0355 mole, 37%), bp 84-86C (20 mm Hg) whose structure was confirmed by:
~max 5 59 (CF=CF2) and 7.2-9.5 ,um (C-F, C-O):19F NMR, -72.1 (d J = 25.7 Hz, each member t J = 13.3 Hz, d J = 13.3 Hz, t J = 7.6 Hz) 2F, OCF2C=C, -84.2(m) 2F, CF2O, -92.3 (d J = 52.7 Hz, each member d J =39.5 Hz, t J = 7.6 Hz) lF, cis-CF2CF=CF, -105.5 (d J = 117.8 Hz, each member d J
= 52.7 Hz, t J = 25.7 Hz) lF, trans-CF2CF=CF, -122.9 (m), CF2, -126.2 (m) 2F, CF2, and -191.0 ppm (d J = 117.8 Hz, each member d J = 39.5 Hz, t J = 13.8 Hz) lF, CF2-CF=C.

.

~173199 Anal- Calcd for C12F222 C~ 24-26; F~ 70-35 Found:C, 24.43; F, 70.38 The higher boiling fraction was the 2:1 complex of perfluoro-6-(2-propenyloxy)hexanoic acid with diglyme (7.9 g, 0.155 mol, 16%), bp 109-110C (5 mm Hg), formed by hydrolysis of perfluoro-6-(2-propenyloxy)hexanoyl fluoride in the aqueous diglyme wash solutions. This complex had ~max3~4 (OH,C-H), 5.59 (with shoulder, CF2=CF,CO2H), and 7.2-9 ~m (CF, C-O,CH); lE NMR, ~11.93(s) lH, CO2H, 3.75 10(s) 4X, OCH2, and 3.52 (s) 3H, OCH3; F NMR, -71.9 (d J = 25.1 Hz, each member t J = 13.4 Hz, d J = 13.4 Hz, d J = 7.5 Hz) 2F, OCF2C=C, -84.1 tm) 2F, CF2CF2O, -92.0 (d J = 52.3 Hz, each member d J = 39.3 Hz, t J = 7.4 Hz) lF, cis-CF2CF=CF, -105.2 (d J = 117.7 Hz, each member d J = 52.3 Hz, t J = 25.1 Hz), lF, trans-CF2CF-CF, -119.6 (t J = 12.6 Hz, each member t J = 3.2 Hz) 2F, CF2, -122.¢ (m) 2F, CF2, -123.5 (m) 2F, CF2, -126.1 (m) 2F, CF2, and -190.9 ppm (d J =
117.7 Hz, each member d J = 39.3 Hz, t J = 13.8 Hz, t J
20s5 1.8 Hz lF, CF2CF=C.

Methyl Perfluoro-3,6-dioxanon-8-enoate ,, CH30H
CF2=cFcF2ocF2cF2ocF2cF~ ~ CF2 CFCF2Oc 2C 2 2 2 3 A suspension of 42 g (1.0 mol) of NaF in 100 ml of methanol was stirred at 5C while 114 g (0.317 mol) of acid fluoride was added rapidly. After addition had been completed, the mixture was stirred overnight at 25C, filtered and the solid rinsed with ether. Distillation afforded 102.0 g (86~) of methyl perfluoro-3,6-dioxanon-8-enoate, bp 60-61C (20 mm Hg), containing small amounts ~' ` ~173~99 of impurities. Redistillation gave somewhat more pure ester (1-2% impurities by gc), bp 61-62C (20 mm Hg).
Structure was confirmed by Ir (neat):
3.32, 3.37, 3.49 (CH3), 5.57 (C=0), 8-9.5,u (CF, C-O).
NMR: H 3.95 ppm (s) with small impurities at 3.53 and 3.33 ppm; 9F -72.0 (d of d of t o~ d, JFF24, 13, 13, 7-5 Hz, 2 F, =CFCF2), -78.0 (t, JFF11.6 Hz, 2 F, CF2CO2CH3), -89-0 (t~ JFFll-6 Hz, 2 F~ CF2CF2C2C~3)' -89-5 (t~ JFF
12-6 Hz, 2F, =CFCF2OCF2), -92.3(d of d of t, JFF53.2, 39.2, 7.5 Hz, 1 F, cis-CF2CF=CF), -105.2 (d of d of t, JFF117.3,`53.2, 24.3 Hz, lF, trans-CF2CF-CF), and -190.8 ppm (d of d of t of t, JFF117.3, 39.2, 14.0, 1.6 Hz, 1 F, CF2CF=)-Anal- Calcd- for C8H3F114 C, 25.82; H, 0.81;F, 56-17 Found: C, 26.17; H, 0.66;F, 56.24 Dimethyl Perfluoro-3-alloxyglutarate A. 1,3,3,5-Tetramethoxyoctafluoropentane The synthesis of bis(2-methoxytetrafluoroethyl)-ketone from dimethyl cæbonate tetrafluoroethylene, and sodium methoxide has been described by D. W. Wiley (U.S. 2,988,537(1961)).
An extension of this synthesis has given 1,3,3,5-tetramethoxyocta-fluoropentane in a one-pot reaction.
CCF
CH30Na + 2 CF2-CF2 + CH30COCH3 )CH30CF2CF2l 2CF2 3 CH3ocF2cF2c(OcH3)2cF2cF2ocH3 A mixture of 27.0 g (0.50 mol)of sodium methoxide, 56.0 g (0.62 mol) of dimethyl carbonate, and 100 ml of dry tetrahydrofuran was agitated in a 350 ml tube under 1-3 atm of tetrafluoroethylene.

~173199 Tetrafluoroethylene was pressured in as consumed until 110 g (1.1 mol) had been added. The mildly exothermic reaction kept the temperature near 35C; a~ter the addition, the reaction mixture was heated at 40C for 1 hour. The viscous solution from this reaction was treated directly with 75.6 g (0.60 mol) of dimethyl sulfate at 40C for 15 hours.
Filtration and distillation af~orded 87.6 g (52~) of 1,3,3,-5-tetramethoxyoctafluoropentane, bp 54C (0.3 mm Hg), nD24 1.3605, whose structure was confirmed by Ir 3.29, 3.33, and 3.42 (sat'd CH) 8-9 u (CF, COC). Nmr (CC14) 'H ~ 3.68 (s, 1, CF2OCH3) and 3.57 (P, JHF 1.3 Hz, 1, C (OCH3)2); 19F

-88.2 (m, 1, CR2O) and -116.5 ppm (m, 1, CF2).

Anal. Calcd. for CgH12FgO4: C, 32.16; H, 3.60, F, 45.21 Found: C, 32.57; H, 3.72; F, 44.61 B. Dimethyl Tetrafluoroacetone-1,3-dicarboxylate conc. H2S04 CH3OCF2CF2C(OCH3)2cF2cF2OcH3 O O O
Il 11 Il, To 50 ml of conc. H2SO4 was added dropwise 33.6 g (0.10 mol) of the tetraether. A~ter the mildly exothermic reaction had subsided, the mixture was heated at 70C (50 mm Hg) to remove volatiles and then distilled at ca. 50C (1 mm Hg). The crude distillate was then fractionated to afford 16.9 ~ (69~) of dimethyl tetrafluoroacetone-1,3-dicarboxy-late, bp 58C (2 mm), nD22 1.3713. Structure was confirmed by Ir 3.28, 3.34 and 3.48 (sat'd CH), 5.57 (C=O) 5.64 (sh-C=O), 8-9 ~ (CF, COC). Nmr (CC14) 'H ~ 4.00 (s, OCH3);

19F -113 ppm (s, CF2) 1~319~
Anal. Calcd. for C7H6F40s: C, 34.16; H, 2.46; F, 30.88 mol wt, 246 Found: C, 34.18; H, 2.66; F, 30.95;
mol wt, 246 (mass spec ) The same reaction on a 0.56 mole scale gave the diester in 82% yield.

C. Dimethyl Perfluoro-3-alloxyglutarate O O O
CH3OCCF2CCF2COCH3 + CsF + CF2=CFCF20S

Il ( CH30C--CF2 ) 2cFocE~2cF=cF2 To 27.3 g (0.18 mol~ dry CsF in 100 ml diglyme was added 43.5 g (0.18 mol) 0=C(CF2COOCH3)2 at 5-10C and stirred for 1 hour; 41.4 g (0.18 mol) CF2=CFCF2OSO2F was added at 5-10C and the mixture was stirred further for 3 hourc. The reaction mixture was thrown into 1 litre of H20 and the lower layer separated. This was washed twice with H2O. After treatment with 20 ml H2SO4 at 0C and extraction with Freon~ 113, the extract was distilled in a molecular still to give 4.54 g (7.2% yield) of product, bp = 51-53C

(0.1 mm). Structure was confirmed by 19F nmr (Fll): -68.48 ppm (OCF2CF=); -93.45 ppm cls-(CF=CFF); -105.91 ppm trans-(CF=CF); -117.10 ppm (CF2COOCH3); -142.78 ppm (CF2CF2OCF=)j -190.35 ppm (CF=CF ). 'H nmr (Fll/TMS): 3.96 (singlet, CH3).
Ir (neat): 3.37 u, 3.49 u (sat'd CH); 5.60 2 ( C=O, CF2=CF);

8-10 u (CF, CO).
Anal. Calcd. for CloFloH6Os: C, 30.32; F, 47.96; H, 1.53 Found: C, 30.45; F, 48.10; H, 1.48 ,,~
~.

11731~

Perfluoro-3-(2-propoxy-2-methylethox~)propene CF3CF2CF20CFCOF ~ KF + CF2=CFCF20~02F --~

CF3cF2cF2ocFcF2ocF2cF=cF2 A mixture of potassium fluoride (6.96 g, 0.12 mol), diglyme ~150 ml) and 2-(1-heptafluoropropoxy)tetrafluoro-propionyl fluoride (dimer of hexafluoropropene oxide obtained 10 by treatment with fluoride ion) (29.4 g, 0.089 mol) was stirred at 5C for 1 hour. Perfluoroallyl fluorosulfate prepared as in Example 2A (27.6 g, 0.12 mol) was added drop-wi~e at 5C, then the mixture was stirred at 5C for 3 hours, and at 25C overnight. The reaction mixture was poured into water (1 1), the lower layer was separated and the volatile component~ were removed at 25C (0.5 mm Hg). Distillation of the volatile components from concentrated sulfuric acid gave perfluoro-3-(2-propoxy-2-methylethoxy)propene (25.2 g, 0.052 mol, 59%, bp 62-63C (100 mm Hg) whose structure was confirmed by:
Amax 5-57 (CF=CF2) and 7.5-9 ~m (C-F, C-0); 19F NMR, -72.2 (d J = 25.5 Hz, each member t J = 13.3 Hz, d J = 13.3 Hz, d J =
7.4 Hz) 2F, OCF2C=C, -81.0 (m) 3F, CF3, -82.3 (m) 5F, CF3 +
OCF2, -84.1 (m) 2F, CF20, -92.1 (d J = 52.7 Hz, each member d J = 39.7 Hz, t J = 7.4 Hz) lF, cis-CF2CF=CF, -105.5 (d J =
117.8 Hz, each member d J = 52.7 Hz, t J = 25.5 Hz), lF, trans-CF2CF=C~F, -130.4 (s) 2F, CF2, -145.9 (m) lF, CF, and -191.0 ppm (d J = 117.8 Hz, each member d J = 39.7 Hz, t J =
13.6 Hz) lF, CF2CF=C.
30 Anal. Calcd for CgH1802: C, 22.42; F, 70.94 Found: C, 22.18; F, 70.96 ~:;

J~731~9 Perfluoro-1,3-bis(2-propenyloxy~ropane O O
ll ll FCCF2CF ~ KF + CF2 = CFCF2OSO2F ~ (CF2=cFcF2cF2)2cF
A mixture of potassium fluoride (15.3 g, 0.26 mol), diglyme (200 ml) and difluoromalonyl difluoride prepared as in Example 5A (17.3 g, 0.12 mol) was stirred at 5C for 15 min. Perfluoroallyl fluorosulfate (57.5 g, 0.25 mol) was added at 5-10C over a 45 min period, and the mixture was stirred at 5C for an additional hour, then at 25C for 2 hours. The reaction mixture was poured into water (1 Q.), the lower layer was washed with water (100 ml), dried and distilled to give perfluoro-1,3-bis (2-propenyloxy)propane (12.0 g, 0.027 mol, 23%) bp 88-90C (200 mm Hg) whose structure was confirmed by: ~max 5 59 (CF=CF2) and 7.2-9.5 ~m (C-F, C-O); 19F NMR, -72.2 (m) 2F, OCF2C=C, -84-6 (m) 2F, CF2CF2O, -92.3 (d J = 53.0 Hz, each member d J = 39.5 Hz, t J = 7.2 Hz) lF, cis-CF2CF=CF, -105.6 (d J = 117.8 Hz, each member d J = 53.0 Hz, t J = 25.2 Hz) 20 lF, trans-CF2CF=CF, -130.0 (s) lF, CF2 and -191.0 ppm (d J = 117.8 Hz, each member d J = 39.5 Hz, t J = 13.5 Hz) lF, CF2CF=C.
Anal. Calcd for CgF16O2: C, 24.34; F, 68.45 Found: C, 24.67; F, 68.36 Perfluoro-3-(butoxy)propene CF3CF2CF2COF + KF + CF2=cFcF2oso2F--~CF3CF2CF2CF20CF2CF CF2 A mixture of dry potassium fluoride (7.50 g, 0.13 mol), diglyme (100 ml) and heptafluorobutyroyl fluoride ~r 117319~

(prepared from the acid by treatment with sulfur tetrafluoride) (28~1 g, 0.13 mol) was stirred at 5C for 30 min. Perfluoroallyl fluorosulfate was added dropwise at 5C, the mixture was stirred at this temperature for 1 hour, then at 25C for 3 hours. The volatile components were transferred by distillation at 40C (8 mm Hg), washed with water (100 ml), and distilled from a small amount of concen-trated sulfuric acid to give perfluoro-3-(butoxy)propene (30.3 g, 0.083 mol, 64%) bp 80-84C whose structure was max 5.57 (CF=CF2) and 7.2-9.5 ~m (C F
C-O): 19F NMR -72.1 (d J = 25.2 Hz, each member t J =
13.5 Hz, d J = 13.5 Hz, d J = 7.4 Hz) 2F, OCF2C=C, -82.1 (t J = 8.1 Hz, each member m), 3F, CF3, -84.5 (m) 2F, CF2O, -92.1 (d J = 52.3 Hz, each member d J = ~9.4 Hz, t J = 7.4 Hz) lF, cis-CF2CF=CF, -105.5 (d J = 117.5 Hz, each member d J = 52.3 Hz, t J = 25.2 Hz) lF, trans-CF2CF=C_, -127.3 (m) 4F, CF2, and -191.0 ppm (d J = 117.5 Hz, each member d J = 39.4 Hz, t J = 13.7 Hz, m) lF, CF2CF=C.
Anal. Calcd for C7F14O: C, 22.97; F, 72-66 Found: C, 23.20; F, 72.80 Perfluoro-3-(octyloxy)propene F(CF2)7COF + KF + CF3=CFCF2OSO2F ~ F(cF2)8ocF2cF=cF2 A mixture of potassium fluoride (5.80 g, 0.10 mol), diglyme (150 ml) and pentadecafluorooctanoyl fluoride (prepared by treating commercial perfluorooctanoic acid with sulfur tetrafluoride) (25.0 g, 0.06 mol) was stirred at 5C
for 1 hour. Perfluoroallyl fluorosulfate (23.0 g, 0.10 mol) was added dropwise and the mixture was stirred at 5C for 4 hours, then at 25C for an additional 3 hours. The mixture was poured into water (1 Q.), separated, and the lower layer was distilled from concentrated sulfuric acid to give perfluoro-3-(octyloxy)propene (27.1 g, 0.04~ mol, 80%) bp 69-70C (20 mm Hg) whose structure was confirmed by: ~max S.59 (CF=CF2) and 8-9 ~m (CF, C-O); F NMR -71.8 (d J =
25.1 Hz, each member d J = 13.4 Hz, t J = 13.4 Hz, d J = 7~7 Hz) 2F, OCF2C=C, -81.6 (t J = 10.0 Hz) 3F, CF3, -83.8 (m) 2F, CF2CF20, -92.3 (d J = 53.~ Hz, each member d J = 39.9 Hz, t J = 1.7 Hz) lF/ cis-CF2CF=CF, -105.5 (d J = 117.8 Hz, each member d J = 53.5 Hz, t J = 25.1 ~Iz) lF, trans-CF2CF=CF, -122.2 (m) 6F, CF2, -122.9 (m) 2F, CF2, -125.7 (m) 2F, CF2, -126.5 (m) 2F, CF2, and -190.8 ppm (d J = 117.8 Ez, each member d J = 39.9 Hz, t 13.7 Hz, t 1.7 Hz) lF, CF2CF=C.
Anal. Calcd for CllF22O: C, 23-34; F, 73-84 Found: C, 22.99; F, 73.94 2-Trifluoromethoxypentafluoropropene(Perfluoro(allylmethylether)) CF2 + CsF + CF2=CFCF2S2F - ~ CF3OCF2CF C 2 A mixture of carbonyl fluoride (18.0 g, 0.27 mol), cesium fluoride (38.0 g, 0.25 mol) and dry diglyme (300 ml) was stirred at -20C to 10C for 2 hours, then kept at -10C
or below while perfluoroallyl fluorosulfate (46.0 g, 0.20 mol) was added. The mixture was stirred at -10C for 2 hours, at 0C for 2 hours, then at 25C overnight. The mixture was warmed under a slight vacuum, and the volatile distillate (11 ml of liquid collected at -80C) was redistilled through a low temperature still to give 2-trifluoromethoxypropene (3.2 g, 2.0 ml at -80C, 0.014 mol, 7%) bp 11-12C. The structure was established by its spectra: ~max (gas phase) 5.55 (CF=CF2), 8-9 (CF, C-O) and 5.35 ~m (weak COF impurity band);

` 1173199 19F NMR (CCl4), -56.5 (t J = 9.2 Hz) 3F, CF30, -74.6 (d J =
25.8 Hz, each member d J = 13.6, q J = 9.2 Hz, d J = 7.1 Hz) 2F, OCF2C=C; -92.2 (d J = 53.4 Hz, each member d J = 39.2 Hz, t J = 7.1 ~z) 1F, CiS-CF2CF=CF, -105.5 (d J = 118.0 Hz, each member d J = 53.4 Hz, t J = 25.8 Hz), 1F, tranS-CF2CF=CF~
and -190.9 ppm (d J = 118.0 Hz, each member d J = 39.2 Hz, t J = 13.6 Hz) lF, CF2CF=C.

Perfluoro-6-(2~ropenyloxy)hexanoic Acid and Its ~ethyl Ester FCO(CF2)4COF + KF + CF2 = CFCF2OSO2F
CF2 = CFcF2ocF2cF2cF2)2 + CF2 = CFCF2O(CF2)5COF

CF2 = CFCF2O(CF2)5COF - ~ CF2 = CFCF2O(CF2)5CO2H 1/2 ( 3 2cH2ocH2cH2ocH3) distil~ CF2 = CFcF2o(cF2)5co2H +
CF2 = CFCF20(CF2) 5C02CH3 A mixture of potassium fluoride (11.7 g, 0.20 mol), diglyme (250 ml) and octafluoroadipoyl difluoride (PCR 58.8 g, 0.20 1) was stirred at 0-5C for 30 min. The mixture was kept at 0-5C while perfluoroallyl fluorosulfate (Example 2A, 46.0 g, 0.20 mol) was added dropwise. When the addition was complete, the mixture was stirred at 0-5C for 2 hours, then it was allowed to warm to 25C and the stirring was continued for a further 4 hours. Evacuation of the reaction mixture to 35C (3 mm Hg) removed 45 ml of liquid. The higher boiling residue was poured in water (1 Q.); the lower layer (10 ml) was combined with the volatile fraction from above and treated with a mixture of water (100 ml) and diglyme (20 ml). After the resulting exothermic reaction, the mixture was allowed to cool, and the lower layer was separated and distilledto give perfluoro-~.

11731~
1,6-bis(2-propenyloxy)hexane (Example 13, 13.6 g. 0.023 m~l, 23%) bp 61 (6mm Hg) and the 2:1 complex of perfluoro-6-(2-propenyloxy~
hexanoic acid with diglyme (E~ple 13, 52.8 g, 0.109 mol, 54.5%) bp 82-84C (0.8 mm Hg).
The diglyme ccmplex of the higher boiling fraction was distilled from concentrated sulfuric acid (40 ml) to give perfluoro-6-(2-propenyloxy)hexanoic acid containing 12~ of its methyl ester. The ester arises from the action of sulfuric acid on the diglyme present in the complex.
These products were identified by infrared ~maX2.82 and 3-4(OH,CH3), 5.58 (CF=CF2), 5.61 (C=O) and 7-10 um (CF,C-O,CH) and by lH NMR, 3.92(OCH3) and 11.33 ppm (OH) signals in the ratio of 1:7.2; thel9F NMR spectrum was also in accord with these structures.

Perfluoro-6-(2-propenyloxy)hexanoic Acid A reaction was carried out as described in Example 21. The crude reaction mixture was poured into water (750 ml), and the lower layer was washed with water (100 ml). The same two products were obtained as in Example 21 by distillation of the crude lower layer.
The fraction bp 45-53C (6 mm Hg) was freed of diglyme by water washing to leave crude perfluoro-l, 6-bis(2-propenyl-oxy)hexane (9.5 g, 0.016 mol, 16%).
The higher boiling complex of perfluoro-6-(2-propenyloxy)hexanoic acid with diglyme was dissolved in 1,1,2-trichloro-1,2,2-trifluoroethylene (50 ml) and extracted in turn with 50 ml and 25 ml of concentrated sulfuric acid. The organic layer was treated with calcium sulfate, filtered, and distilled to give pure perfluoro-6-(2- propenyloxy)hexanoic acid (42.2 g, ~'.
.~

0.0988 mol, 49%) bp 75C (1.0 mm Hg). This material was identified by infrared ~max 2.85-4.0 (H-bonded OH), 5.57 (CF=CF2), 5.63 (sh,C=O) and 8-9 ~m (CF, C-O), and by its lH and 19F NMR spectra.
Anal. Calcd. for CgHF15O3: C, 24.45; H, 0.23; F, 64-66 Found: C, 24.48; H, 0.45; F, 65.76 Perfluoro(4,7-dioxa-6,9-dimethyl-9-propoxy)non-1-ene C, 3 ,3 CF3CF2CF2OCFCF2OCFCOF + KF + CF=CFCF2OSO2F >

CF3 CF 1 C,F3 CF CF CF2(ocFcF2)2ocF2cF=cF2 + CF3 2 2 2 2 3 A suspension of 58.1 g (1.0 mol) of flame-driedKF
in 1400 ml of dry diglyme was stirred at 25 while 333 g (0.67 mol) of hexafluoropropene oxide trimer was added rapidly. The two-phase system was stirred at 25 for 2 hr, during which time about half of the fluorocarbon layer slowly dissolved. The mixture was stirred at 5-10 while 230 g ~1.0 mol) of 1 was added. The mixture was stirred at 5-10 for 2.5 hr, then overnight at 25,and poured into 2 1.
of H2O. The aqueous layer was extracted with 100 ml of CFC12CF2Cl, and the combined organic layers washed with 2 1.
of H2O, extracted with 100 ml of conc. H2SO4, clarified with CaSO4, filtered and distilled. Hydrolysis and bubbling were apparent in the water washed. Distillation afforded major fractions of 2 and 3, bp 55-71 (20 mm) and 140 g of crude CF3CF2CF20CF(CF3)CF20CF(CF3)C02H, bp mainly 101-104 (20 mm).
Redistillation of ccmbined fractions of 2 and 3 gave 80 g of impure 3, bp 81-86 (80 mm) and 33.0 g (8~) of 2, bp 94-95 (80 mm).
For 2, IR (neat): 5.59 (CF=CF2), 7.5-9 ,u ~' ~.

(CF~ C-0). NMR: F -72.4 (d of d of t of d, JFp, 25.5, 1~.2, ~13, 7.0 Hz, 2F, OCF2C=), -80.9 (m, 8F, 2CF3CF ~ CFCF20CF)~
-~2-4 (broad s, 5F, CF3CF2CF2), -84.3 ~broad, 2F, CFCF20CF2), -92.0 (d of d of t of d JFF 52.1, 39.3, 7.0, 3.1 Hz, lF, cis-CF~CFF), -105.5 (d of d of t, JFF 117.9, 52.1, 25.5 Hz, lF, trans-CF-CFF)~ -130.6 (s, 2F, CF3C 2)' -14~.1 (m, 2F, CF), and -191.1 ppm (d of d of t, JFF 117.9, 39.3, 13-2 H2, 1~, -CF CF2).
Anal. Calcd. for C12F240~: C~ 22-24; F~ 70-36 Found: C, 22.50, F, 71.78.

Perfluoro-6-Phenoxy-4-oxa-1-Heptene , 3 C6F50CFCOF + KF t CF2-CFCF20S02~ -C6F50CFCF20CF2CF'CF2 A suspension of 17.4 g (0,~0 mol) of flame-drled KF in 500 ml of diglyme was stirred at 5 whi~ 86~1 g (0.26 mol) of perfluoro-2-phenoxypropionyl fluorlde pre-pared by reaction o~ a metal salt of pentafluorophenol with HFPO) was added dropwlse. The mixture was st~rred ~or 30 min at 5, arter which the KF had partially dissolved. Then 69.o g (0.30 mol) of perfluoroallyl fluorosulfate was added drop-~ise, and the mixture was stirred at 5-10 for 3 hr. The cooling bath was remo~ed, a~d the mixture was stirred over-night. The reaction mixture was then drowned in 2 1. of water, and the lower layer was washed with 1 1., then with 500 ml of water, dried over CaS04, filtered and distilled to afford 20.8 g (17~) of per$1uoro-6-phenoxy-4-oxa-1-heptene, bp 68-75 (10 mm). A late fraction was analyzed.
IR (neat): 5.58 (CF~CF2), 6.57 and 6.80 (arom. C~C)~ 7.5-9 1l73l99 IR (neat): 5.58 (CF~CF2), 6.57 and 6.80 (arom. C~C), 7.5-9 (CF, C-O~ with a ,re~k peak at 5.64 (-OCF=CFCF3). NMR
(CC14~: 19F -77.8 (d of d o~ t of d, JFF 25.5, 1~.7, ~13, 7.2 Hz, 2F, OCF2C~ 79.8 (m, 3F, CF3), -83-o (m, 2F~
CF~O), -91.7 (d o~ d of t, JFF ~2.0, 39.2, 7.2 Hz, lF, cis-CF2CF~CFF), -105.1 (d of d o~ t, JFF 118.0, 52.0, 25.~ Hz, lF, trans-CF2CF-CFF), -139.9 (t of m, JFF 18.7 Hz, lF, CF), -150.8 (m, 2F arom. CF), -156.1 (t, JFF 21.0 Hz, IF, arom.
CF), -162.3 ~m, 2F, arom. CF), and -190.6 ppm (d of d of t of t, JFF 118.0, 39.~, 13.7, 1.6 Hz, lF, CF2CF=). Impurity bands ascribable to the isomer C~F50CF(CF3)CF20CF=CFCF3 were also present.
The followln~ examples illustrate the preparat~on o~ userul copolymers ~rom the polyfluoroallyloxy comonomers o~ this invention. The general propert~es of these co-po~ymer~ were discussed above.
UTILITY EXAMPLES
Example A
Solution Polymerization of Tetrafluoroeth~lene wlth 2-rl (Pentafluoro-2-~ro~e~Yloxy)~tetrafluoroethanesulfon~l Fluorlde n x CF~ - CF~ ~ xCF~ ~ CFCF90CF~CF~SO~
_ _ : _ -(CF~-cF~)n -CF27F r CF~OCF~CF~SO~F x An 80-ml stainless steel-llned tube was char~ed wlth cold mlxture (-45-C) of 1,1,2-trlchloro-1,2,2-trifluoro-ethane (Freon~ 113) (10 ml), 8~ 1,1,2-tr~chloro-1,2,2-tri-fluoroethane ~olution of pentaf~uoroproplonyl peroxlde (3P
lnitlator) (1 ml), and 2-[~-(pentafluoro-~-propenyloxy)]-tetra~luoroethanesulfonyl fluoride (Example 7, 17.5 g,O.053 mol).
The tube was closed, cooled to -40C, evacuated, and charged ~o with tetrar~uoroethylene (20 g, 0.20.mol). The tube was warm-ed to 25-C and sha~en at thls temperature for 20 hours. The ll731g9 volatile materials were allowed to evaporate, and the product polymer was evacuated to 0.5 mm Hg. The product was then extracted with 1,1,2-trichloro-1,2,2-trifluoroethane, and dried under vacuum to give the solid white copolymer (16.9 g, 85%): ~max (KBr) 6.79 (SO2F) and 12.3 ~m (broad) in addition to the usual polytetrafluoroethylene infrared band~. Gravi-metric sulfur analysis gave 0.48 and 0.20% S, corresponding to an average of 0.34% S or 3.5 wt. % (1.1 mole %) of poly-fluoroallyloxy comonomer corresponding to an equivalent weight of 9400. Equivalent weight is the molecular weight of the polymer per functional group (here -SO2F). Differential scanning calorimetry (DSC) showed a 12% depression of the endotherm peak (mp) compared to polytetrafluoroethylene.
Example B
Solution_P~merization of Tetrafluoroethylene with 1-[1-(Pentafluor_-2~propenyloxy)]hexafluoropropane-2-sulfonyl Fluoride x CF2=CFCF20CF2CF-S02F + nxCF2=CF2 ~ ~ '(CF2~CF2)n~CF2CF - _ CF3 ¦ ICF3 CF20CFS02F x The procedure of Example A was followed with 1,1,2-trichloro-1,2,2-tri~luoroethane (10 ml), 8% pentafluoropropionyl peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane (2.0 ml), l-[l-(pentafluoro-2-propenyloxy)]hexafluoropropane-2-sulfonyl fluoride (Example 9, 17.4 g, 0.046 mol) and tetrafluoro-ethylene (20 g, 0.20 mol) to give 16.7 g (79%) of copolymer.
Analysis by X-ray fluorescence showed 0.49% S present, corresponding to 5.8 wt-~ (1.6 mole ~) of polyfluoroallyloxy comonomer corresponding to an equivalent weight of 6540.
The sample had a mp depression of 11C compared to polytetrafluoroethylene by DSC.

-~' Example C
Solution Polymerization of Tetrafluoroethylene with 3~
(Pentafluoro-2-propenyloxy)tetrafluoropropionyl Fluoride x CF2=~20CF2CF20CF + nxCF2=OE2 ~ C 2 2 n 21 L~ L CF2a~F2CF2C;~ x NaOH
--F(CF2-CF2 ) n-CF2TF - - - ---- ~

CF2ocF2cF2co2Na~x The procedure of Example A was used with 3-[1-(pentafluoro-2-propenyloxy)]tetrafluoropropionyl fluoride (Example 5, 13.3 g, 0.045 mol) in place of 2-[1-(pentafluoro-2-propenyloxy)]-tetrafluoroethanesulfonyl fluoride to give 17.8 g (86~) of copolymer: ~ max (XBr) 5.62 (CO2H, weak) and 9.7~m bands in addition to the polytetrafluoro-ethylene bands; mp depression (DSC) was 14C compared to polytetrafluoroethylene; gravimetric analysis showed 3.7 wt % of polyfluoroallyloxy comonomer corresponding to an equivalent weight of 7900.
A sample of the polymer was stirred with a solution of sodium hydroxide in 33~ ethanol for 2 days, filtered, and washed with water until the extracts were no longer basic. The resulting polymer, now readily wetted by water, was dried under vacuum. Analysis by atomic absorption spectroscopy showed 0.29% Na, corresponding to 3.7 wt-~ (1.3 mole ~) of the original comonomer.

~173199 Example D

Solution Polymerization of Tetrafluoroethylene with 1-(l,l,L,2,3,3-Hexafluoro-3-chloro-2-propoxy)pentafluoro-2-propene X CF2=~20CFCF2Cl + xnCF2=CF2 ~ (C 2 C 2)n 2 L cF2ocFcF2cl1 X

The procedure of Example A was used with 1-(1,1,1,2,3,3-hexafluoro-3-chloro-2-propoxy)pentafluoro-2-propene (Example 2, 14.3 g, 0.043 mol) in place of 2-[1-(pentafluoro-2-propenyloxy)]-tetrafluoroethanesulfonyl fluoride to give 18.3 g (87%) of copolymer: mp depression (DSC) 14C compared to polytetrafluoroethylene; gravimetric analysis gave 0.61 and 0.61~ Cl, corresponding to 5.7 wt-~
of polyfluoroallyloxy comonomer and an equivalent weight of 5800; more accurate analysis by X-ray fluorescence gave 0.53% Cl corresponding to 5.0 wt-% (1.56 mole ~) of polyfluoroallyloxy comonomer. The mp depression of 14C
compared to polytetrafluoroethylene corresponds to a depression of 1C per 0.1 mol % of poly-fluoroallyloxy comonomer present. In contrast to this result, the smaller branch in hexafluoropropene gives a mp depression corresponding to about 1C per 0.3 mol-% of comonomer in its copolymer with tetrafluoroethylene. This means that the copolymers prepared from the polyfluoroallyloxy comonomers have better molding properties for the same mol-~ incorporation of comonomer than those prepared from hexafluoropropene comonomer.

.,~, ~1731~9 Example E
Solution Polymerization of Tetrafluoroethylene with 2~
Pentafluoro-2-propenyloxy)hexafluoropro~ane-l-sulfonylFluoride x CF2=CFCF2OCFCF2SO2F + xn CF2 = CF2 ~(CF2-CF2~ CF2CF
CF2ocFcF2so2 x The procedure of Example A was used with 2-(1-pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl fluoride (Example 3, 16.1 g, 0.042 mol) in place of 2-[l~(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride to give 18.5 g (88~) of copolymer: mp depression (DSC) 8C compared to polytetrafluoroethylene; analysis by X-ray fluorescence showed 0.43% S, corresponding to 5.1 wt-% (1.4 mole ~) of polyfluoroallyloxy comonomer and an equivalent weight of 7460.
Example F
Solution Polymerization of Vinylidene Fluoride with 2-~1-(Pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl Fluoride 2 2 CF2 = CFCF2OCF2CF2SO2F - ~ Copolymer The procedure of Example A was used with vinylidene fluoride (20 g, 0.32 mol), 2-[1-(pentafluoro-2-propenyloxy)]-tetrafluoroethanesulfonyl fluoride (Example 7, 16.5 g, 0.05 mol), 1,1,2-trichloro-1,2,2-trifluoroethane (10 ml), and 8% 1,1,2-trichloro-1,2,2-trifluoroethane solution of penta-fluoropropionyl peroxide (5 ml). The mixture was shaken overnight, the maximum recorded temperature being 31C.

~r~
,,~

~173~g~

The solid copolymer produced (21.5 g 60%) contained 46 wt %
(14.2 mol ~) of polyfluoroallyloxy comonomer with an equiva-lent weight of 71.9 DSC showed no thermal events between 25C
and 400C.
Anal. Calcd for (CH2=cF2)6.0s (cF2=cFcF2ocF2cF2so2F) C, 28.62, EI, 1.70; S, 4.47 Found: C, 28.49; H, 1.71; S, 4.46 EXAMPLE G
Solution Polymerizat_ion of Vinylidene Fluoride with l-Hepta-fluoro-2-propoxy)-1,1,3,3-tetrafluoro-2-chloro-2-propene CH2=CF2 + CF2 = CclcF2ocF(cF3)2 ~ Copolymer The procedure of Example F was used with l-hepta-fluoro-2-propoxy)-1,1,3,3-tetrafluoro-2-chloro-2~propene (Example 1, 10.5 g, 0.032 mol) in place of 2-[1-pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride to give a solid copolymer (20.6 g, 73~). This material contained 36 wt-% (9.8 mol-%) of poly1uoroallyloxy comonomer with an equivalent weight of 878. DSC confirmed the structure as a copolymer and indicated its stability, because no thermal events were observed in the range 25-400~C.
EXAMPLE H
Solution Polymeri~ation of Tetrafluoroethylene with .
Perfluoro-3-(butoxy)propene CF2=CF2 + CF3(CF2)30CF2CF=CF2 - ~ Copolymer The procedure of Example A, when used with perfluoro-3(butyoxy)propene (Example 18, 19.0 g, 0.052 mol), tetrafluoroethylene (20 g, 0.20 mol), 1,1,2-trichloro-1,2,2-trifluoroethane (10 ml) and 8% pentafluoropropionyl peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane (2 ml) gave 18.9 of solid copolymer. This crude material was chopped in a ' ~731~g blender with more solvent, rinsed, and dried to give 16.5 g of copolymer with a mp of 309C, indicating that it was a true copolymer.
EXAMPLE I
Solution Polymerization of Tetrafluoroethylene with Perfluoro -1,6-bis(2-propenylox~)hexane CF2=CF2 + (CF2=CFcF2OcF2cF2cF2)2 --~Copolymer The procedure of Example H was followed, using perfluoro-1,6-bis(2-propenyloxy)hexane (Example 13, 20 g, 0.20 mol) for the polyfluoroallyloxy comonomer. This gave 16.3 g of dry pulverized polymer with ~max 5-55 ,um (CF=CF );

the remainder of the infrared spectrum resembled that of poly(tetrafluoroethylene). DSC showed a pronounced exotherm Tp 315C followed by an endotherm Tp - 333C and 339C on the first heating; the second heating showed no exotherm and a broad endotherm Tp _ 326C. Infrared spectra indicated that pyrolytic reactions of pendant pentafluoroallyloxy groups had occurred during the first heating; the broad DSC endotherm near the normally sharp mp of poly(tetrafluoroethylene) indicates that crosslinking had occurred.
EXAMPLE J
Solution Polymerization of Vinylidene Fluoride and Perfluoro-1,3-bis(2-propenyloxy)propane CH2 = CF2 + (cF2=cFcF2ocF2)2cF2 ~ Copolymer A mixture of perfluoro-1,3-bis(2-propenyloxy)-propane (Example 17, 5.7 g, 0.013 mol), 1,1,2-trichloro-1,2, 2-trifluoroethane (25 ml), and 8% pentafluoropropionyl peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane (5 ml) was held at -40C in a stainless steel-lined shaker tube while 30 vinylidene fluoride (20 g, 0.32 mol) was condensed into the tube. The mixture was shaken overnight at room temperature, -~ 1731~

and the product was isolated as described above. The crude polymer was dried under vacuum, pulverized in a blender with 95% ethanol, filtered and dried to give 24.0 g of solid copolymer. DSC showed an endotherm Tp 124C, stable to at least 300C, indicating that a true copolymer had been formed since poly(vinylidene fluoride) has mp 171~C. The insolu-bility of this product in acetone and the lack of absorption bands in the infrared for pendant CF=CF2 groups indicates that crosslinXing had occurred.
EXAMPLE K
Copolymer of TFE with Methyl Perfluoro-3,6-dioxanon-8-enoate 45 g of methyl perfluoro-3,6-dioxanon-8-enoate and 0.04 g of perfluoropropionyl peroxide were reacted at 50C
for 4 hours under a 10 psi pressure of tetrafluoroethylene.
Filtration gave a solid which on drying at 50C in a vacuum oven weighed 0.71 g. The amount of TFE added was 4 g.
Equivalent weight by titration gave 1176; therefore the amount of the ester incorporated in the polymer was 2~% and the yield based on TFE was 20%. A transparent film was obtained by heating at 220C in a Carver press.
EXAMPLE L
Dyeable Fluorocarbon Polymers Samples of the polymers of Examples B and E were treated with aqueous alcoholic ammonia solution for one day at 25C, filtered, washed with aqueous ethanol and dried under vacuum.
A sample of the polymer of Example C was similarly treated with aqueous alcoholic sodium hydroxide.
The above partly hydrolyzed polymers were immersed in aqueous ethanol solutions of SevronO Red GL (Sevron~ is a line of cationic dyes especially suited for dyeing Orlon~ and ,,, ~173199 other acrylic fibers, having outstanding fastness and brilliance - Du Pont Products Book, January 1975, p. 34) at 25C for 1-3 hours, then they are extracted until the extracts no longer contained dye. All three samples dyed well to an orange-red color.
EXAMPLE M
Wettable Fluorocarbon Polymer A sample of the polymer of Example C was treated with aqueous alcoholic sodium hydroxide as described in Example L. The resulting fluorocarbon polymer contained carbonyl groups and was wettable with water.
EXAMPLE N
Emulsion Polymerization of Tetrafluoroethylene with 2 .

(Pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl Fluoride CF2=CF2 + CF2=CFCF20CF2CF2SO2F ~ Copolymer A stainless steel shaker tube was charged with water ~140 ml), 1,1,2-trichloro-1,2,2-trifluoroethane (10 ml),2-~1-pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride (Example 7, 6.0 g), potassium perfluorooctanesulfon-ate (0.16 g), ammonium carbonate (O.S0 g) and ammoniumpersulfate (0.50 g). The mixture was brought to an internal pressure of 200 p.s.i.g. with tetrafluoroethylene and heated to 70C. Tetrafluoroethylene pressure was maintained at 200 p.s.i.g. for 45 min at 70C. The polymeric product thus obtained was filtered, washed and dried to give 43.2 g of white solid which contained approximately 1.4 wt ~ (0.43 mol ~) of polyfluoroallyloxy comonomer by infrared analysis.
Differential thermal analysis (DTA) showed a crystalline transition at 10C, a recycle freezing temperature of 293C
and a recycle melting point of 311C from which the . ~

~17319~
polyfluoroall~lox~ comonomer content is estimated as 3.5 wt %

(1.09 mol %).

Emulsion Polymerization of Tetrafluoroethylene with 2-[1-(Pentafluoro-2-propenylox~ tetrafluoroethanesul~onyl Fluoride cF2=cF~ + CF2=CFCF20CF2CF2So2F -~ Copolymer The procedure of Example N was followed using 8.0 g of 2-~1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride, 0.20 g of potassium perfluorooctanesulfonate and tetrafluoroethylene at a pressure of 30 p.s.i.g. at 70C for a reaction period of 8 hours. The amounts of the other reagents were not changed. This gave 45 g of solid polymer whose infrared spectrum showed strong S02F absorption. ~rA
showed a crystalline transition at 5C, a recycle freezing tem~erature of 282C, and a recycle melting point of 300C, corresponding to a polyfluoroallyloxy comonomer content of 5.9 wt ~ (1.86 mol %).
EXAMPLE P

Emulsion Polymerization of Tetrafluoroethylene with 2-[1-iPentafluoro-2-propenyloxy)Jtetrafluoroethanesulfonyl Fluorlde The procedure of Example N was followed using 10.7 g of 2-~1-pentafluoro-2-propenyloxy)]tetrafluorosulfonyl fluoride, 0.20 g of ammonium persulfate, and tetrafluoro-ethylene at a pressure of 50 p.s.i.g. at 70C for a reaction period of 5 hours. The amounts of other reagents were not changed. This gave 28.6 y of white polymer whose infrared spectrum showed the pressence of S02F groups corresponding to 3.5 wt ~ (1.08 mol g) polyfluoroallyloxy comonomer. DTA
showed two melting peaXs at 290C and 317C, with an estimated comonomer content of 5.5 wt g (1.73 mol ~).

~' ~173199 UTILITY EXAMPLE Q

Copolymerization of Tetrafluoroethylene and 2-[1-(~entafluoro-2-propeny_oxy)tetrafluoroethanesulfonyl Fluoride, and Preparation of Electrically Conductive Films from the Co~olymer Product -nxCF2=CF2 + XCF2=cFcF2ocF2cF2so2F . .

~CF2-CF2 ) -CF2CF

x A steel tube charged with 2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride (Example 7, 52.8 g) and 6% 1,1,2-trichloro-1,2,2-trifluoroethane solution of pentafluoropropionyl peroxide initiator (0.19 y). The mixture was heated to 40C and brought to an internal pressure of 10 psiy with tetrafluoroethylene (TFE). TFE
pressure was maintained at 10 psig for 6 hours at 40C. The polymeric product thus obtained was filtered, washed and dried to give a white solid (9.82 g): ~max (KBr) 8.65 (S02F) and 8-10 Tnm (broad) in addition to the usual polytetrafluoroethylene IR bands. The DSC melting point depression was 91C compared with polytetrafluoroethylene.
Sulur analysi~ by x-ray fluorescence gave 2.7% S or 28.0 wt.
% (8.5 mol %) of polyfluoroallyloxy comonomer, corresponding to an equivalent weight of 1180.
The product was pressed into a clear 4-5 mil film at 220-240C. Four inch diameter film samples were reacted for 1 hour at 90C with 13-15% potassium hydroxide solution and dried to give a copolymer of TFE and CF2=CFCF20CF2CF2S03-K+. IR spectra showed essentially complete conversion of -S02F functions to sulfonate salt.

~ 17~

The Eour-inch diameter, 4-5 mil film was inserted as the ion exchange membrane in a chlor-alkali electrolysis cell operated at 2.0 am~s/in 2. Cell voltage and current efficiency were measured as a function of cell operating time and sodium hydroxide concentration. The followiny results were obtained for a 15-day test:

Sodium ~ydroxide Currency Efficiency Cell Voltage Day Product (%) (~) (volts) 1 21.570.7 3.35 10 10 21.571.2 3.45 30.065.2 3.60 UTILITY EXAMPLE R

Copolymerization of Tetrafluoroethylene and Perfluoro-6-oxanon-8-enoic acid, and Preparation of Electrically Conductive Films from the Copolymer Product nXCF2=CF2 ~ xcF2=cFcF2o(cF2)4cOOH >

~ 2 2)n 2 L C 2 (C 2)4C H J

The procedure of Example Q was followed with perfluoro-6-oxanon-8-enoic acid (47.5 g), 8 pentafluoro-propionyl peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane (0.05 g), and TFE at 10 psiy (40C) to give 2.41 g of solid, white copolymer: ~SC
melting point depression was 157C compared with polytetrafluoroethylene. Analysis of carboxyl groups by titration showed 36.8 wt. % (9.3 mol ~) of polyfluoroallyloxy comonomer, corresponding to an equivalent weight of 1070.

~ ~r 1~73199 The copolymer product was pressed into 4-5 mil film and hydrolyzed as described in Example Q. IR spectra showed essentially complete conversion of -COF functions to carboxylate salt, indicating a copolymer of TFE and CF2=CFcF2O(~2)4co2 K -A four-inch diameter sample of the 4-5 mil film was inserted as the ion-exchanye membrane in a chlor-alkali cell operated at 2.0 amps/in2, and the following results were obtained in a 76 day test:

Sodium Hydroxide Current Efficiency Cell voltage Day Product (%) (%) (volts) 1 37.1 93.3 4.02 39.2 90.9 4.60 39.4 87.7 4.25 32.9 92.0 4.11 76 34.6 85.8 4.67 This application is a division of copending Canadian Application Serial No. 350,850, filed April 29, 1980.

~0 X

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A copolymer of a polyfluoroallyloxy compound and at least one ethylenically unsaturated monomer, said polyfluoroallyloxy compound being a compound of the formula CF2=?-CF2ORF
wherein -X is -C1 or -F;

-Y is -F or -CF3;
R1 is a linear or branched perfluoroalkyl group of 11 to 14 carbon atoms, 0 to 1 of which is a keto group, interruptable no more frequently than every second carbon atom by from 1 to 4 oxygen atoms, having 0 to 2 functional groups selected from the class consisting of -SO2F, -COF, -C1, -CF=CF2, -CO2H and -CO2R3 where R3 is -CH3 or -C2H5; or R1 is a linear or branched perfluoroalkyl group of 1 to 14 carbon atoms, 0 to 1 of which is a keto group, interruptable no more frequently than every second carbon atom by from 1 to 4 oxygen atoms, having 1 or 2 functional groups selected from the class consisting of -Br, -I, -CN, and -OC6F5; or R1 is a linear or branched perfluoroalkyl group of 1 to 10 carbon atoms, 1 of which is a keto group, interruptable no more frequently than every second carbon atom by from 1 to 4 oxygen atoms having 0 to 2 functional groups selected from -SO2F, -COF, -C1, -CF=CF2, -CO2H, and -CO2R3 where R3 is -CH3 or -C2H5; and R2 is -CF2CN, -CF2COF, or -CF2CO2H.

2. An electrically conductive membrane formed of a hydrolyzed or ionized copolymer of a polyfluoroallyloxy compound and at least one ethylenically unsaturated monomer, said polyfluoroallyloxy compound being of the formula wherein -X is -F;

RF is or -CF(R2)2;

Y is -F or -CF3;
R1 is a linear or branched perfluoroalkyl of 1 to 14 carbon atoms, none of which is a keto group, interruptable no more frequently than every second carbon atom by from 1 to 4 oxygen atoms, having 0 to 2 functional groups selected from the class consisting of -SO2F, -OC6F5, -COF, -CN, -CO2H and -CO2R3 where R3 is -CH3 or -C2H5; and R2 is -CF2COF or -CF2CO2H.

3. The membrane of Claim 2 wherein the ethylenically unsaturated monomer is tetrafluoroethylene, chlorotrifluoro-ethylene, vinylidene fluoride or trifluoromethyl trifluorovinyl ether.

4. A process of producing an alkali metal hydroxide in a chlor-alkali cell using the membrane of Claim 2.