CA1155801A - Conductive membrane of polyfluoro-allyloxy copolymers - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

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

Description

1 15~8~ 1 BACKGROUND OF T~E INVE~TION

Field of the Invention r 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 prepara-tion of perfluoroallyloxy-l,1-dihydroperfluoroalkanes from 3-chloropentafluoropropene and a l,l-dihydro-perfluoroalkanol in alkaline medium, e.g.
CF2=CFCF2Cl + HOCH2CF3~- KOH ) 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=CFCF20CH3

3. M. E. Redwood and C. J. Willis, Canad. J _ hem., 45, 389 (1967) describe the reaction of allyl bromide with cesium heptafluoro-2-propoxide to form 2-allyloxyheptafluoro-propane:
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 anlons 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 reactlons Or perfluoroallcoxlde anlons.
U.S. Patent 3,450,684 to R. A. Darby dlscloses the '~

l 15S80 1 preparation of fluorocarbon polyethers and their polymers by reaction of perfluoroalkanoyl fluorides with potassium or quaternary ammonium fluoride and hexa~luoropropene epoxlde.

i.e. RfCOF ~ CF3-CF~-~ CF2 -t 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 ~. L. Wasley, dlscloses 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 dis-closes the preparation of (perfluoroalkoxy)vinyl compounds by reactlon of a perfluoroketone with an alkali metal fluoride and a 1,2-dihaloethane, followed by dehydro-halogenation of the intermediate 2-perfluoroalkoxyhalo-ethane.
e.g. (CF3)2CO + KF + BrCH2CH2Br (CF3)2CFOCH2CH2Br HBr ~ (cF3)2cFocH=cH2 10. U. S. Patent 3,321,532 to C. E. Lorenz dlscloses the rearrangement of per~luoro-2-alkoxYalkanoyl fluorides 1155~01 to perfluoroalkoxyolerins by passage over a metal oxide at 100-400C, ~.g.

ZnO + CF3CF_coF 30o-325oc~ CF30CF=CF2 + ZnF2 + C02 SUMMARY OF THE INVEN'~ION
According to the present invention there is provided a polyfluoroallyloxy compound having the formula W D
CF=C-CF-O-CG
. .
Z X E
wherein X is -Cl or -F;
W and Z, when taken independently, are -F
and, when taken together, are -CF2-;
D, taken independently, is -F, F
CF3-~ \ ~ CF3 CF3 f~o/

CF2=CFCF20 or -RF where -RF is a linear or branched perfluoroalkyl of l to lO carbon atoms, interruptable no more frequently than every second carbon atom by from 1 to 4 oxygen atoms, having O to 2 functlonal groups selected from -S02F, -COF, -C02H, -Co2R3, -Cl -OCF2CF=CF2 and -oCF2Co2R3 where R3 is -CH3 or -C2H5 E, taken independently, is -F, -CF3, -CF2Cl, ~F2Co2R3, or -RFOCF(G)2 where ~ has the meaning defined above, and D and E, when taken together, form a 5-or 6-membered ring whose members are -RF-~where RF is a perfluoroalkylene chain of 4 or 5 members, interruptable by one or two oxygen atoms, and having 0 to 2 sub-stituent -CF3 groups, or CF3y xcF3 CF3 ~ O

O--G is -F or -CF3.
There is also provided a process for preparing a polyfluoroallyloxy compound which comprises:
(1) mixing and reacting a carbonyl compound having the formula:

A- C- B

wherein A, taken independently, is -F, -COCF3 or-Rl where RF is a linear or branched perfluoroalkyl of 1 to 10 carbon atoms, 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, -SO2OCF2CH3, -COF, -Cl, -OCF2CF=CF2, and -Co2R3 where R3is -CH3 or -C2H5, B, taken independently is 1~55~0 1 -F~ -CF3, ~CF2Cl, CF2Co2R3 where R3 has the meaning defined above, or -CF2ORF, where RF is as defined above; and A and B, taken together, form a 5- or 6-membered ring whose members are -RF- where RF is a perfluoroalkylene chain of 4 or 5 members, interruptable by one or two oxygen atoms, and having 0 to 2 substituent trifluoromethyl groups wlth a metal fluoride of the formula MF where M is K-, Rb-, C8-, or R4N- where each -R, alike or dlfferent, ls alkyl of 1 to 6 carbon atoms; and ~2) mixing the mixture from (1) with a perfluoro-allyl compound of the formula:

.z CF=C-CF
W X Y
wherein X is -Cl or -F;
W and Z, when taken independently, are -.F and, when taken together, are -CF2-, and Y is -Cl or -OSO2F.
Also provided is a copolymer of the aforesaid polyfluoroallyloxy compound with at least one ethylenically unsaturated monomer.
DETAILS OF THE INVEMTION
This invenkion relates to compounds of formula 4 prepared ~rom startin~ materials 1, ~ and 3 according to the 3 following equation:

z ~ W D
W ~ 11 Z
~C-C-C-F ~ MF ~ A-C-B ~ C~C-C-O-C-G ~ MY
/ I ~ ;/ ~ ' ' X Y F X F E
1 2 3 ~ 5 In the above equat~on, starting materlals 1, 2, and ~ react to give product 4 and a metal salt ~. The letters A, B, D, E, G, M, W, X, Y and Z are as given in the Summary. Products represented by general structure 4 can be conver~ed into useful copolymers especially with tetrafluoroethylene, trifluoroethylene, vinyl~dene fluoride, and chlorotrifluoroethylene.
Preferred polyfluoroallyloxy compounds of rormula ~ have D and E taken independently with D preferably being -F or RF and E preferably being -F, -CF3, -CF2Cl or CF2Co2R3 where R3 is CH3 or -C2H5. The preferred compounds also have W and Z taken independently and X as -F. RF is preferably a linear or branched perfluoroalkyl of 1 to 8 carbon atoms, inter-ruptable with no more than 1 oxygen atom, having O to 1 functional groups selected from -502F, -COF, -Cl, -C02H, -Co2R3, -OCF2CF=CF2 and -oCF2Co2R3 where R3 is -CH3 or -C2H5.
Especially preferred polyfluoroallyloxy compounds of the lnvention have the formula:
D

CF =C-CF -O-CF
2 , 2 X E
wherein X is -Cl or -F (preferably -F);
E i~ -F, -CF3, -CF2C02R3where ~ is CH3 2 5' 2 ~ 1 5 .~
(preferably -F, -CF3 or -CE2C02R ) and D is -CF2R4 or CFR4 where R4 is -F, -SO2F, -COF, -CO2H, -CO2R , -OCF2CO2R where R is -CH3 or -C2H5, or tCF2)xR where x is 1 to 6 and R
iS CF3~ -COF, -C02H, -CO2R , -SO2F or -OCF2CF=CF2. R is preferably -SO2F, -COF, -CO2H or -OCE2CO2R where R is -CH or -C H .

The polyfluoroallyl group of the product 4 is derived from the corresponding polyfluoroallyl chloride or fluorosulfate (1) by nucleophilic displacement of the chloride or fluorosulfate group with a preformed poly-fluoroalkoxide anion derived from the metal fluoride (2) and the carbonyl compound (3). The synthesis is thus a one-vessel sequential addition of reagents 3 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 be prepared conveniently by treatment of polyfluoroalkenes with sulfur trioxide, as described in B. E. Smart, J. Org. Chem., 41, 2353 (1976). Such reactions are typically carried out in sealed Carius 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 fluorosulfate) is given in Example 2.

3~

~r~

1 ~55~0 1 Stable metal polyfluoroalkoxides are formed by the reac~ion of certain metal fluorides with polyfluorinated ketones and acid fluorides (J. A. Young, loc. cit.), thus:

(CF3)2CO ~ K~ ~ CF3-~-O K

F
CF3COF + KF ~ _ CF3-C-O K
F

The usefulness Or such intermediate Polyrluoroalkoxides is determlned by their stabil~ty, as meaSured by their ease of thermal decomPOSitiOn. Because their rOrmation is reversible~ the equilibrium concentrat~ons of various species in a given reaction mixture are important quan-tlties which determine whether or not the subsequent dis-placement will occur to form product 4. Solutions in whlch the equilibrium lies towards the right (high con-centration of anion) will be more effective than those in which it lies towards the left (high concentration of carbonyl compound).
Poly~luoroalkoxide anion formation and chemistry i8 dependent upon the followlng ~our conditions, discussed ln further detail by J. A. Youn~, 1 , cit., F. W. Evans, M. H. Litt, A. M. Weidler-~ubane~ and F. P. Avonda, ~0

5~, Chem., 3~, 18~7, 18~9 (1968), and M. A. RRdwood and C, J. Willi~, Canad. J. Chem., 45, 389 (1967).
~1) Stable polyfluoroalkoxlde an~on8 are formed when the carbonyl compound i~ highly fluorlnated becau~e the 3 electron-withdrawln~ effect of the fluorine atom~ dis-_g_ tributes the negatl~e charge o~er the entlre anlon.
Substitutlon o~ some of the fluorine by chlorlne, other fluoroalkyl groups or hydrogen destablizes the anlon because the~e ~roups are less electron-withdrawing and the negatlve ch&rge is not as readily accommodated. (2) Large catlons such as K+, Rb~, Cs~ and R~N~ favor the formation o~ stable polyfluoroalkoxides more than 8 cations such as Li+ and Na~ because the lattice energy of metallic fluorides 18 inver6ely proportional to cation slze. In other words, large cation size and 8mall lattice energy favors dl8ruption o~ the ~etallic fluorido cry6tal etructure to form the anion. (~) Solvents which ha~e a high heat of 601ution for the polyfluoroalkoxide ~avor lts formatlon~ Aprotic polar solvents such as N,N-d~methylformamide (DMF), acetonitrile, and 1,2-dimethoxyethane (glyme) are very e~fectlve ~or thls purpoee. (4) When there are fluorine atoms alpha to the oxygen atom ln the anlon, 1088 of rluoride lon may co~pete with the desired reactions, e.g., ~0 CF~ CF3 o c b o haB no o-fluorlne to lose and 1' 1 , CFo CF9 ~orme mAny etable derivatives.

CFo CF3 - I - regulres a reactive compound F such as allyl bromide for nucleo-phillc substltution.
CFS0 u~ually ellminates ~~; nucleophilic eubstitution is known with per-3 ~luoroa~lyl fluorosulfate.

1 l~S~O 1 In the practice of this lnvention, the polyfluoro-alkoxide anion is preferably pre~ormed by the addition of the carbonyl compound to a stirred mixture of the metal fluorid~
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 reaction progresses, Thestoichiometry of polyfluoroallcoxide anion formation requires one molar equivalent of metal ~luoride for each carbonyl group whlch is con~erted to its anion, e,g.:

(CF3)2CO ~ ~F ~_ ~ CF3`- ~ - O E+

P~(CF2)~CF + 2KF ~ K 0 - C(CF~)~b - 0 ~

me presence o~ up to a twice-molar excess of metal M uoride is generally not detrimental. Two side e~fects of excess met~l fluoride are: (1) to hlnder the observation Or 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 hexafluoro-propene.
Because of the limited thermal stability of polyfluoroalkoxides, their formatlon is usually accom-pli~hed between -20C and +60C, preferably with external cooling to maintain the temperature between 0C and 10C.
3o The time required to complete poly~luoroalkoxide 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-dlmethyl~cetamide (DMAC),-~-butyrolactone, 1,2-dimethoxyethane ~glyme), l-(2-methox~ethoxy)-2-methoxy-ethane (diglyme), 2,5,8,11-tetraoxadodecane (triglyme), 1~ dioxane, sulfolane, nitroben~ene and benzonltrlle Qre sultable, illustrative aprotic polar solvents for the preparation of polyfluoroalkoxides and their subsequent reaction with the polyfluoroallyl chloride 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:

tRF)2CFO + H20 - ~ (RF)2C(OH2) + F

RFCF2o + H20 > 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 ((C2Hs)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 o~ handling.

.a~s~ol Polyfluorinated carbonyl compounds which are useful in this invention are ketones and carboxylic acid fluorides and a perfluorinated lactone 3,6-bis(trifluoro-methyl)3,5,5,6-tetrafluoro-1,4-dioxan-2-one. Ketones and the lactone give branched fluorocarbon products, whereas acid fluorides give primary fluorocarbon products in which the new ether linkage is at the primary or secondary center:

(R )2CO -----------~> (RF)2C-O CF2CF CF2 (ketone) ~ ~ F
RF C=O ~~~~~~~~~~~ ~ RF ,C ~ C 2 2 (lactone) 0 ~0 RFCOF ----_______~ RFCF2OCF2CF=CF2 (acid fluoride) Polyfluorinated ketones which are useful include hexafluoroacetone, chloropentafluoroacetone, 1,3-dichloro-tetrafluorGacetone, l,l-difluoroethyl 2-oxopentafluoro-propanesulfonate, dimethyltetrafluoroacetone-1,3-dicarboxylate, l,3-bis(2-heptafluoropropoxy)tetrafluoro-propanone, octafluorobutanone, decafluoro-2-pentanone, dodecalfluoro-2-hexanone, tetradecafluoro-2-heptanone, hexadecafluoro-2-octanone, octadecafluoro-2-nonanone, eicosafluoro-2-decanone, and hexafluoro-2,3-butanedione.
Hexafluoro-2,3-butanedione is a special case (Example 12) in that the initially formed perfluoroalkoxide reacts both with perfluoroallyl fluorosulfate and with ,,~, another molar equivalent of hexafluoro-2,3-butanedione to form a mixture of two hetero-cyclic compounds.

Polyfluorinated acid fluorldes which are useful include carbonyl fluorlde, tri~luoroacetyl fluoride, pentarluoropropionyl fluoride, heptafluorobutyroyl fluoride, nonafluoropentanoyl fluoride, tetrafluorodiglycolyl O O
FCCF20CF2CF, undecafluorohexanoYl flu3ride, trldecafluoroheptanoyl rluoride~ pentadecafluorooctanoyl fluoride~ heptadecafluorononanoyl fluorlde, nonadecafluoro-decanoyl fluoride, difluoromalonyl dirluoride, tetra-fluorosuccinyl difluoride, hexafluoropropane-1,3-dioyl difluoride (hexafluoroglutaryl difluoride), octafluorobutane-1,4-dioyl difluoride (octa-rluoroadipoyl difluoride~, decafluoropentane-1,5-dioyl difluorlde (decafluoropimelyl difluoride), dodecafluoro-hexane-1,6-dioyl difluoride (dodecafluorosuberyl difluoride), ~luoroBuifonyldifluoroacetyl ~luoride, 2-(fluoro~ulfonyl)-t~trafluoropropionyl fluorlde, 2- (1-hepta~luoropropo~r)-tetra~luoropropion;yl rluorlde, 2- r2- (l-heptafluoropropo~r ) h~xa~luoropropo~y~tetrafluoropropionyl ~luorlde, and 2 ~2-t2-(1-hept~fluoropropoxy)hexa~luoropropoxy~hexa-~luoropropoxy}tetrafluoropropionyl fluoride, carbomethoxy-difluoroacetyl fluoride.
The ketone l,l-difluoroethyl 2-oxopentafluoro-propanesulfonate (Example 3) is a special case as a starting material because it is an _ situ source of 2-oxopenta-fluoropropanesulfonyl fluorlde since the latter has not been lsolated.
; 3 115~8 F
ClT3COCF2SO20CF;~CH3 ~ [CF3COCF~SOzF] - >

FSO2CFzCFOCF2CF=CFz Many of the above starting material~ are commerclally available, e.g, PCR, Gainesvllle, Florida iB a supplier o~ fluorinated ketones and carboxylic acids.
~ampl~s 2, 3, 4~ 5, 7, 9, lo, 11, 12, 13~ 16 and 19 give sources and methods of preparation of some compounds which 1~ are not commercially avall~ble. Generally, perflu~roketones can be prepared from the esters of perfluoro-a~Xanecarboxyllc aclds and from the reaction of carbonyl fluoride wlth perfluoroalkenes (W. A. Sheppard and G. M.
Sharts, "Organic Fluorine Chemistry", p. ~65-368, W. A.
~enJamin, New York, 1969, H. P, Braendlin and E. T. McBeeJ
Ad~ances ln Fluorlne Chemlst~ , 1 (1963)), Perf~oro-alkanecarboxyllc acid fluorides and per~luoroalXane-a,~_~icarboxylic acld di~luorides are prep~red by treat-ment of the corresponding acids with sulrur tetrafluorlde, by the addition o~ carbonyl fluorlde to perfluoroalkenes (~ S. Fawcett, C. W. Tullock and D. D. Co~fman, J. Amer.
Chem. ~ 4 4275, 4285 (1962)) and by electrolysis o~
alX~ecarboxylic acids ln hydrogen fluoride (M. Hudlicky, "Cheml~try of Fluorine Compounds", ~. 86, MacMillan Co., New York, 1962). Perfluoroalkanedicarboxylic ac~ds are prepared by oxidation of fluorinated a,~-dlalX~nes or fluorlnated cycloalkenes (Hudlic ~, loc. cit., p. 150-15~). Perfluoroalkyl polyethers with a terminal ac~d fl~oride group can be m~de from hexafluoropropene oxlde 3o and lts fluoride lon induced oligomer~, as described by R. A. Darby, U.S. Patent 3,450,684 (1969) ~nd by P.
.Tarran~, C. G. Allison, K. P. Barthold and E. C. Stump, Jr., luorine Chem. Rev., 5, 88 (19713.
The stoichiometry o~ the di6placement wlth polyfluoroallyl chloride or fluoro~ulfate requires one molar equivalent of thi~ reagent for each reacti~e center : in the polyfluoroalkoxide ~nion. Wlth a difunctlonal poly-fluoroalkoxide, however, the stoichlometry can be adJusted to glve elther the mono- or the di~Rubstltution product, thus:

O O O
F~CF2~F + KF + CF2,CFCF20S02F ~ F~CF2CF20CF2CF~CF~

~Example 5) O O
F~CF2~F ~ 2KF ~ 2CF2=CFCF20S02F - -, tC~2~CFCFaOCFa)~CFa (Exam~le 17) FCO(CF2)4COF + KF + CF2 = CFCF20S02F ~ CF2 = CFcF2otcF2)5coF
21~ (Examples 21, 22 ) FCO(CF2)4COF + 2KF + 2CF2 = CFCF20S02 F ~ (CF2=CFC~'20CF2CF2CF2)2 (Example 13 ) The formation of the poly~luoroalkoxide and lts ~ubse~uent reaction with the polyfluoroallyl chloride or ~luorosulfate can be carrled out sequentlally without isolati4n of intermediates in glass apparatus at atmos-pherlc pressure using the normal precautions to exclude ~oi~ture, m e use o~ cooling baths and low temperature cond0nsers (e.g. those packed wlth dry ice and acetone 1~55~01 mixtures) serves to moderate the reactions ~nd facilita~e the retention of volatile rer~gents and products, Ihe progress of the displacement reactlon is convenlently followed by the appearance of a precipitat~ of the salt MY (~), by gas liquid partition chromatography (glpc) and by fluorine nuclear magnetic resonance spectroscopy 9F Nli~R ) .
The displacement reaction can be carried out between -20C and +80C, ~nd ls preferably between OVC
and 30C. TypicallyJ the reaction mixture ~s cooled e~ternally to O C to 15C dur1ng the additlon of th~
polyfluoroal-yl chloride or fluorosul~ate, and 1~ then allowed to warm up to 25C to 30C for the remainder of the reaction time.
~he time required 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 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 uaed (diglyme bp 162C, DMF bp 153C) and can be distilled into a trap cooled to -80C by warming the reaction vessel 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. The 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, trlfluoroethylene, hexafluoropropylene, vinylidene fluoride, vinylidene chloride, trifluoromethyl trifluorovinyl ether and chlorotrifluoroethylene, and acrylic acid or methacrylic acid esters. Halogenated olefins are preferred, especially tetra-fluoroethylene,chlorotrifluoroethylene, trifluoromethyl trifluorovinyl ether, hexafluoropropylene and vinylidene fluorlde. Such copolymers have either more desirable or entlrely new properties not possessed by e.g., poly(tetrafluoro-ethylene), poly(trlfluoroethylene), poly(vinylidene fluoride),poly(chlorotrifluoroethylene) or polyethylene. Copolymerization may be deflned as any process whereby two or more monomers are incorporated as lntegral parts of a high polymer. A copolymer ls the product resulting from such a process. It is not necessary that the relative numbers of the different types of unit be the same ln dlfferent molecules of the copolymer or even in different portions of a single molecule.
Copolymers which contain from about 5-55 welght per-cent (about 1-25 mole percent) of polyfluoroallyloxy comonomer have lower melting points than the corresponding polyfluoro-5~
olefins, 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. This cannot be done with polyfluoroolefins which do not have incorporated comonomer of this type. Copoiymers which contain from about 5 to 35 weight percent (about 1.0 to 10 mole percent) of a polyfluoroallyloxy comonomer with pendant SO2F or COF groups can also be partially or essen-tially completely hydrolyzed to a copolymer bearing hydrophilic SO2OH and CO2H groups. Such a copolymer has an affinity for water and is water-wettable. Polyfluoro-olefins 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, publi~hed 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 portions of the cell from which chlorine and sodium hydroxide are respectively pro-duced from brine flowing within the anode portion of the cell.

The properties of each copolymer depend uponthe distribution of monomer units along the polymer chain since a copolymer is not a physical mixture of two o~ more polymers each derived from the respective mono-mers but a new material incorporating each monomer. It is well known thatthe composltion 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 relative 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 agltation. This type of reaction is well known to those skilled in the art.
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 (c2Fscoo)2~ dinitrogen difluoride (N2F2), azobisisobutyronltrile, ultraviolet irradlation and ammonium or potassium persulfate; mlxtures of lron (II) sulfate with hydrogen peroxide, ammonlum or potassium persulfate, cumene hydroperoxide, t-butyl hydroperoxide; mixtures of sllver nltrate and ammonium or potassium persulfate;
mlxtures of trlfluoroacetic acld, pentafluoroproplonic acid, heptafluorobutyric acid or pentadecafluorooctanoic acid with ammonium or potassium persulfate. The peroxide systems may contain additionally sodium sulfite, sodium metablsulfite, or sodium thiosulfate.
When aqueous emulsion systems are used for copolymerization they contaln emulsi~ying agents in the form of the sodiumor potassium salts of saturated aliphatic acids of between about 14 and 20 carbon atoms or of perfluoroalkanoic aclds and perfluoroal~anesulfonic 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 reactlon mixture and preferably constitute between 0.5 and 5 parts by weight percent.
Aqueous emulsion systems are customarily bu~fered to pH 7 or above by the addition of reagents such as dlsodium hydrogen phosphate, sodium metaborate, or ammonium metaborate to the amount of about 1 to 4 welght percent of the reaction mixture.
The following three types of copolymerization systems are preferre~ in preparing the preferred copolymers of this invention:
1) Solutlons of two or more comonomers in 1,1,2-tricnloro-3 1,2,2-~rifluoroe~hane (~reon~ 113) solvent con~;lLIlin~

pentafluoroproplonyl peroxide are shaken ln 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 ollgomers by washing with more solvent.
2) An aqueous emulsion of two or more comonomers containlng an emulsifier such as potassium perfluorooctanesulfonate and an initiator such as ammonlum persulfate is shaken ln 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 filtratlon or centrlfugatlon.
3) The polyfluoroallyloxy comonomer may be used as the solvent in place of 1,1,2-trichloro-1,2,2-trifluoro-ethane ln method (1) when it is 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 carrylng out the invention. All parts and ' 20 percentages are by weight unless otherwise stated. For ~tru¢ture confirmatlon analyses, fluorine nuclear magnetic resonance chemical shifts are in parts per million from lnternal ~luorotrichloromethane, and proton nuclear magnetic resonance chemlcal shifts are in parts per million -- from internal tetramethylsilane. Infrared and nuclear magnetic resonance spectra were recorded on undiluted liquid samples unless otherwise stated.
EX~MPLE 1 l-(H~pt.lrl~lo o-2-~ropoxy)~ 3,3-tetrarluoro-2-chloro-2-propene 3 (C~ CO I KF ~ CF2~CClCFrCl- ~ (cF3)~cFocFrccl~cF2 Hexafluoroacetone (16 6 g, 0.10 mol) was di~-tilled lnto a stirred mlxture of pota~sium fluorlde (5.80 g, 0.10 mol) and 1-(2~methoxyethoxy)-2-methoxyethane (here-lnafter referred to as diglyme) (100 ml) to g~ve a homo-geneou~ solution, This mlxture was mainta~ned at 25-~O-C
and treated with 1,2-dlchloro-1,1,~,3-tetrafluoropropéne (18.3 g, 0.10 mol, prepared according to J E, Bis~ey, H. Goldwhite and D G. Row~ell, J. Org. Chem" 32, 1542 (lg67)~. The mixture was stlrred overnight and then it was poured into water (500 ml). The lower layer was washed with water (250 ml), dried, and distilled to give l-(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); 9F NMR, -64.~ (m) 2F, -OCF2CC; -76.o (2nd order m) 2F, C~CF2; -81.2 (t ~ - 5,7 Hz, each member d J - 2.2 Hz) 6F, CF~; and -146.7 ppm (t J 5 22.9 Hz each member septet J = 2.2 Hz) 1~, CFO.
Anal. Calcd for C6ClFl10: C, 21.67; Cl, 10.66 Found: C, 21.43; Cl, 10.89 1-(1,1,1,2,3,3-Hexa~luoro-3-chloro-2-propoxy)-pentafluoro-2-~ro~ene A. Pentafluoro-2-propenyl fluorosulfate (Perfluoroallyl ~luorosulfate) CF3CF ~- CFz ~ S03 ~ CF2 - CF-CFa C,F2~CF-C~90502F

A mixture Or commerclal liquld ~ulfur trioxide (10 ml) and hexafluoropropene (45 g, 0.~0 mol) was ~ealed in a C~rius tube at llquid nitr~gen temperature, mlxed well at 25-C, allowed to stand for 4 days at 25-C, and finally heated in a steam bath for 6 hours ~rom two such tube~, there was obtained by dlstillatlon, 3-(trifluoro-methyl)-3,4,4-trifluoro-1-oxa-2-thlacyclobutane 2,2-dloxide (2-hydroxy-1-trifluoromethyl-1,2,2-tr~luoroethan~
~ulfonic acid sultone, D. C. Engl~nd, M. A. Dietr~ch and R. V. Llndsey, Jr,, J. Amer. Chem. Soc.. 82, 6181 (1960)) (25 e, 22%) bp 44C, and pentafluoro-2-propenyl fluoro-sul~ate (hereinafter re~erred to as perfluoroallyl fluoro-sulfate) ~73 g, 6~%), bp 58-60-C.
Perfluoroallyl ~luorosulfate i5 characterlzed by: ~max 5.55 (C-C) ~nd 6.75 ~m (S0z); 9F NM~, 46.1 (t J - 8.5 Hz, each member d J = 1.8 Hz) 7F, S02F, -74,0 (d J = 28.2 Hz, each member d J a 1~9 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 ~ a 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 s 1~.9 Hz, d J = 1.8 Hz) lF.
B. 1-(1,1,1,2,3,3-Hexafluoro-3-chloro-2-propoxy)-penta~luoro-2~-propene .

CF3COCF2Cl ~ ~ ~ CF2=CFCFzOSO~F
CF2Cl CF3CFOCFzCF=CF2 A ~uspenslon of pot~sslum fluoride (5.80 g, 0,10 mol) and dlglyme (100 ml) wa~ ~tirred at 20-C in a 3~

cooling b~th while chloropent~fluoroacetone (18.3 g, 0.10 mol) was dlstllled in. A~ter the pota~sium fluoride had dis~olved, perfluoroallyl fluorosul~ate (23,0 g, 0.10 mol) was added rapldly with cooling of the reaction mlxture. ~he resultlng exothermic reactlon was accompanied by the preclpltatlon of 601id. The mixture was stirred at 25-C for one hour, and then the volatlle component3 were transferred to a trap cooled to -80-C by heating the reactlon mlxture at 42-C (5 mm Hg). The v~latil~ product 10 was distilled from phosphorus pentoxide to give 1-(1,1,1,2,3,3-hexa~luoro-3-chloro-2-propoxy)-pentafluoro-2-propene, (19.6 g, 0.059 mol, 59%) bp 85-86C which was character~Zed by: ~max 5-55 (CF = CF2) and 7-10 ~m (CF, C-0); 9F NMR, -68.6 (m) 2F, CF2Cl, -69.1 (m) 2F, CF20, -78.8 (m) 3F, CF9, -93.2 (d J - 54.7 Hz, each member d J = 39.8 Hz, t J 3 7.5 Hz), lF, cis-CF2-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 ~or C6ClFl10: C, 21.67; Cl, 10.66 Found: C, 21.34; Cl, 10.21 3o EXAM~LE ~
2~ Pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl fluoride (2-Perfluoroallylox~propane~l-sul~onyl fluorlde) A 2-OYopentafluoro~ropa~esulfonic ~cld .

OC~Hs CF3C-CF2 + S03 -- ~` CF3~CF~SO20C~H5 ~ CF3~CFa~SO20H

O O
Il 11 CF3CCF~SO~OC2Hs ~ CF3C02H - -~ CF9~CFzSO20H

CF3CO~C2H5 (1) Dropwl~e add~tion of ~ulfur trioxlde (12.8 K, 0.16 mol) to 2-ethoxy-?,1,3,3,~-penta~luoropropene (D, W. Wiley and H. E, Slmmon~J J, Or~. Chem., 29, 1876 ~1964)) (29.0 g, 0.165 mol) produced an exo-thermic reactl~n, The black reactlon mlxture was dlstilled to give reco~ered 2-ethoxy-1,1,3,3,3-pentafluoropropene (6.3 g, 0.0~6 mol, 22~, identi~ied by lr) and ethyl 2-oxopenta~luoropropane~ulfonate (20.2 g, o.o78 mol, 49% con~ers~on and 6~% yield) bp 47-48C (12 mm Hg): ~max 3.34 and 3.41 (s~turated CH), 5.60 (C ~ O), 7.09 (SO20), and 7.6-~.5 ~m (C~F, SO2); H NMR, ~ 4,59 (q J c 7.2 Hz) 2H, OCH2 ~nd 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.
(~1) me above reaction was repeated at 0-5'C with sulfur trloxlde (88 g, 1.1 mol) and 2-ethoxy-1,1,3,3,3-penta~luoropropene (176 g, 1.0 mol). me colorless 11~5801 reactlon mixtureJ whlch darkened on standing o~er-night, wa~ di~t~lled to glve recovered 2-ethoxy-1,1, ~,3,3-pentafluoropropene (28.6 ~, 0.16 mol, 16%) bp 46-48-C, ethyl 2-oxopentafluoropr~p~nesulfonate (145.1 g, O.57 mol, 57% conver3ion and 68~ yield) bp 48-52C (12 mm Hg), and a higher boillng fraction composed mainly of 2-oxopentafluoropropanesulfonic acld. The crude acid was redistilled at 81-82C
(6.2 mm Hg), yield 35.6 g (0.16 mol, 16% conversion and 19% yleld) of pure acid: ~Bx (~Cl~, CaF2 plates) 3.~ and 4.2 (broad) (SOH), 5.58 (C~O), 7.13 (SOzO) and 7.5 - 9 ~m (CF, S0z); H NMR ~ 10,2 ppm (B) SO20H; 9F NMR, -76.2 (t J 8 7.5 Hz) 3F, C~3, and -108 ppm (q J - 7,5 Hz) 2F, CFz.
Anal. Calcd for C3HFsO~S: C, 1~,80; H, O.44: F, 41.65;
S, 1 .o6 Found: C, 15.95; H, O.55; F, 41.55;
S, 13.89 (lii) Ethyl 2-oxopentafluoropropane~ulfonate (25.6 g, O.lO mol) was stlrred at 25-C and treated with trlfluoroacetlc acid (17.1 g, 0.15 mol). me mixture was allowed to stand overnight, and then it was heated to reflux (60C) in a spinning band ~till. Fractional dlstlllation 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. 1J l-Dl~luoroethYl 2-oxo~entafluor ~ro~nesul~onate O O
CFsCCFzS020H ~ CF2~CHz ~ CF3CCFzS020C~zCH3 3o 1 15~80 1 A metal tube contalnlng 2-oxopentafluoropropane-~lfonic acld (2~.8 ~, 0.10 mol) was cooled below -40C and ~inylidene fluoride (l,l-difluoroethene) (1~ g, O.20 mol) was added. The mlxture was shaken and warmed to 25C where it was kept for 4 hours. Distil-lation of the liquid product gave 20.4 g (0.07 mol, 70%) of l,l-difluoroethyl 2~oxopentafluoropropanesulfonate, bp 62-63~C (50 mm Hg): ~max (CC14) 5.54 (C=O), 6.96 (SO20) and 7.5 - 9 ~m (CF~ SO2); H NMR, ~ 2.06 ppm (t J - 14.3 Hzj CH3; 19F NMR, - 58.3 (q J =

14.~ Hz, each member t J = 7,1 Hz) 2F, OCF2, -75,0 (t J = 8.o Hz) 3F, CF3 and -106,1 ppm (q J = 8.0 Hz, each member t J - 7.1 Hz) 2F, .CFzS02.

Anal. Calcd for CsH3F70~S: C, 20.56; H, 1.0~; F, 45.52 Found: C, 20.7~; H, 1.0~; F, 45.72 A similar experiment on a 0.8-mol ~cale gave an 86% yield of product bp,60-C (50 mm Hg). Th~s material was ~tored in polytetrafluoroethylene bottleR to a~oid degradation, C. 2~ Pentafluoro-2-propenyloxy)hexafluoropropane-1-~ul~onYl fluorlde O .
CF3JCFzSO20CFzCH3 t KF t CF2-CFCFzOSO2F
1,' CF3-CFOCFzCF=CFz + CH3COF ~ KOSO~F

CFzSO2F
A suspenslon of dry potassium fluoride (5.80 g;
0.10 mol) ln 2, 5, 8, ll-tetraoxadodecane (triglyme) 3o ~00 ml~ wa~ stirred and cooled at 0C while l,l-difluoroethyl 2-oxopentafluoropropanesulfonate prepared as ln Example 3B (29.2 g, 0.10 mol) was added. When the potassium fluoride had nearly all dissolved, per-rluoroallyl fluorosulfate prepared as in Example 2A
(23.0 g, 0.10 mol) ~Jas add~ at 0C, and the resulting mixture was s~irred at 20-26C for 3 hour~ latlle co~-ponents were rcmoved by distillation at a flask tempera-ture o~ 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)hexa-fluoropropane-l-sulfonyl fluor1de (13.0 g, 0.034 mol, 34%), bp 47-48C (60 mm Hg) whose structure was confirmed by: ~m~x 5.59 (CF~CFz), 6.80 (S0zF) and 7.5 - 10 ~m (C-F, C-0, S02); 9F ~R, + 45.4 (m) lF~ SO~F, -70.0 (m) 2F, OCF2, -78.o (qulntet J = 10.7 Hz) 3F, CF3, -91.5 (d J = 51,5 Hz, each member d J = ~9,5 Hz, t J = 7,5 Hz) lF~ ci8-CF2CF - CF, -104,8 ~d J - 117!0 Hz, each member d J a 51.5 Hz, t J = 25.5 Hz) lF, trans-CF2CF - CF~ -107.0 and-108.4 (AB J - 255 Hz, each member ~ J = 10.7 Hz, m) 2~, CF2S02F, -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 ~ 1~.0 Hz) lF, CF2CF=C.

Anal. Calcd for C~Fl203S: C, l~.g6i F, 59.98; S, 8.43 Found: C, 19.24; 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 sm~ll ~mounts of hexafluoropropene and sulfuryl fluoride, 3o ' 1- ~1,3-bis(2-Hepta~luoropropoxv)-2-PentafluoroProPoxY~-pentafluoro-2-propene A. 1,3-bis(2-HePtafluoroPropox~L~etrafluoroproPanone O o 2(CF3)2CO + KF + C1~2CCCF2Cl ~ (CF3)2C~;OCF2CCF~OCF(CF3)2 A mixture o~ dry potassium fluoride (21.0g, 0.36 mol), dry N,N-dimethylform~mide (DMF) (150 ml), hexafluoro-acetone (59.8 g, o.36 mol) and 1,3-dichlorotetrafluoro-acetone (35.~ g, 0.18 mol) was heate`d at -reflux (40-60C) for 3 days. Distlllatlon lnto a trap cooled to -80C gave recovered hexafluoroacetone (16.5 ml, 46~o) and ~ 63 g of liquid bp 30-145C. The higher-bolling material was redis-tilled rrom sulfuric acid to give 1,3-bls(2-heptafluoro-propoxy)tetrafluoropropanone (18.7 g, 0.037 mol, 21~ con-version, 39~o yield based on hexafluoroacetone~, bp 117-118C;
AmaX (CCl4) 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~CFa) , ?35 [ ( CF3)aCFOCFa] , 169 ( C3F7) , 147 (CF3COCFa) , 97 (CF3CO) and 69 (CF3) ; l9F NMR, -75.0 (d J = 21.5 Hz, each member septet J = 5.5 Hz) 2F, OCFa~ -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 CsFl~03: C, 21.70; F, 68~66 Found: C, 21.60; F, 68.5g B. 1-{1~3-bls(2-HePtafluoropropox~)-2-pentafluoropropox~y}
~entafluoro-2-ProPene (CF3)aCFOCFaCCFaOCF(CF3) 2 + KF + CFa - CFCFaOSOaF
~I
CF~ = CFCFaOCF[CF~OCF(CFo)~ ~2 3o A mlxture of 1,3-bls(2-hepta~luoropropoxy)tetra-fluoropropanone (20.0 g, 0.04 mol), dlglyme (100 ml) and potassium fluoride (2.32 g, 0.04 mol) was stirred and warmed to 55C. The two liquid phases and solid originally present became homogeneous and stayed so upon cooling. Perfluoro-allyl fluorosulfate prepared as in Example 2A (10.0 g, 0.043 mol) was added rapidly at 10C and the mixture was allowed to warm. The slight exothermic reaction was accompanied by precipitation Or solid and the appearance of a second liquid phase. The mixture was stirred for 2.hours 21.
then poured lnto water (350 ml). The lower layer was washed with water (75 ml), dried ovcr phosphorus pentoxide and dlstilled to give l-~1,3-bis(2-heptafluoropropoxy)-2-penta-rluoropropoxy~-pentafluoro-2-propene (16.1 g, 0.024 mol, 62Z) bp 64-67C (25 mm H~) whose ~tr~tuP~ was confirmed by:
Amax 5.57 (CF~ - CF) and 7.5-9 ~m (CF, C-O);

~F NMR, -69.4 (m) 2F, OCF~C=C; -80.3 ~broad) 4F, CFOCFa -81,5 (8) 12F, CF~, -93.7 (d J = 54.0 Hz, each member d J = 39.6 Hz, t J = 7.8 Hz) lF, cls~CFa ~ CF = CF , -106.3 (d J = 117.4 Hz, each member d J = 54.0 Hz, t J = 23.7 Hz) lF~ trans-cFacF - CF , -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~ CF~C~ - C.
Anal, Calcd for C~2F~03: C, 22.24; F, 70.35 Found: C, 22.66; F, 70.27 3o 1 lSS~O 1 EXAMPLE ~
3~ Pentafluoro-2-Propen~loxy)tetrafluoroproplonyl fluoride A. D~fluoro_alonyl difluoride CH~OCF2CF~COF ---> ~ CF~CF

3-Methoxytetrafluoropropionyl fluoride (F. S. Fawcett, C.W. Tullock and D. D. Coffman, J. Amer. Chem.
Soc., 84, 4275 (1962)3 (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 continuously removed by distillation through a low temperature still, yield 58 g (0.40 mol, 90~). The product structure was confirmed by:
Am~X 1~6O cm ~COF), l9F NMR (no solvent), ~17.1 ppm ( t J ~ 10 Xz ) 2F, COF and -114 . 2 ppm (t J = lO Hz ) 2F, CFa .
B. 3~ Pent~luoro-2-Propenvlox~y~tetrafluoro~ropionyl fluoride O O ' O
~1 11 . "
FCCF~ CP' ~ KF ~ CF~ =CFCF~ OSO~ F FCCFa CF~ OCF:~ CE'=CF~

A mixture of dry potassium ~luoride (7.5 g, 0.13 msl) and dielyme (lOO ml) was stirred at 10C and difluoromalonyl dl~luorlde from part A (18.5 g, 0.13 mol) was distilled into it. A~ker 20 min. the potassium fluoride was nearly all dlssolYed, and perfluoroallyl fluorosulfate prepared as in Example 2A (29.9 g, 0.13 mol) was added dropwlse at 10-15C.
The mixture was stirred for 3 hours, then the volatile compc.n~nts were removed at a pot temperature o~ 32C and 4.8 mm Hg pressure. Fractionation of the distillate gave 3-(1-pentafluoro-2-propenyloxy)tetrarluoropropionyl fluoride (14.9 g, 0.051 mol, 39%) bp 70-71Cand a small 1155~01 amount Or higher bp material. The product structure was ~ ~max 5.33 (COF), 5.60 (CF = CF~) and 7.5-lO ~m (CF~C-O); l9F NMR 23.7 (apparent qulntet, J ~ 7.5 Hz) lF, COF -71.9 (d J 2 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, CF20, -91.6 (d J = 51.8 Hz, each member d J - 39.4 Hz, t J - 7.4 Hz) lF, cls-CF~CF = CF, -105.1 (d J = 117.1 Hz, each member d J=51.8 Hz, t J ~ 24.6 Hz) lF, trans-cFa-cF=cF~ -122.0 (d J = 8.2 Hz, each member t J = 3.1 Hz) 2F, FCOCF~, and -l91.O ppm (d, J = 117.1 Hz, each member d, J = 39,4 Hz, t J = 13.9 Hz, t J = 1.6 Hz) lF, CFa~CF=C.
Anal. Calcd ~or C~FloOa: C, 24.51 Found: C, 24.56 P~rrluoro-3.~-dioxanon-8-enoyl Iluori.de 1\. '1'~1;ra:rluoro(1Lrr..Ylco]..~,rl C~llorldc Cl Cl F2QF8 KMnO" Hzso HO2CCFzOCF2CO~II

O o SOCl2 ClCCF20CFzCCl A mlxture of 307.6 g (1.46 mol) o~ dichlorotetra-~luorodlhydrofuran, 157.8 g (3.9 mol) of NaOH, 312 g (1.97 mol) of potassium permanganate and 1500 ml o~ water was refluxed ~or 17 hours. A brlef (steam) distillatlon gave 10.6 g (3%) o~ recovered dihydrofuran. The reaction mixture was ~iltered and the ~ilter ca~e triturated wlth 2 x 400 ml o~ water. The 115$801 combined aqueous solutlons were evaporated to 1500 ml, treated cold with 300 ml of conc. H2S04 and extracted continuously with ether for a day. The extracts were evaporated until ether was no longer evol~ed at 25C (0.5 mm Hg). To the crude solid diacid, 279 g (up to 93% yleld), was added 5 g (o.06 mol of pyridine and 416.5 g (3.5 mol) of thionyl chloride. Little 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, untll 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, -CF20-).
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), 170~ (19~9).
B. Tetrafluorodi~Ylcol.Yl Fluoride O O O O
ClCCF20CF2CCl ' > FCCFzOCF2CF

Conversion of the diacid chloride to the correspond-lng fluoride, bp 32-33C, was accomplished by a scale-up of the procedure o~ 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 tetrafluorodlglycolyl dichloride, 140.5 g (3.35 mol) of NaF, and 1200 ml of anhydrous acetonitrile was 3o stirred overnight, then distllled to give a fraction collected at 35-79C. The distillate was treated with 20 g of NaF
and distilled to give 105 g o~ tetra~luorodiglycolyl difluoride, bp 32-33C. Addition of another 100 g (2.38 mol) of NaF to the reaction mixture and slow distillatioll afforded another fraction, bp 35-81C. Treatment with 10 g of NaF and fraction-ation gave another 37.0 g of difluoride product, bp 32-33C, for a total of 142 g (76%).
C. ~erlJuoro-3~-d:lo~nnon-8-(!no~ uor.ld~

FCCli'20CF2CF t KF -t CF2=CFCF20SOzF
R

CF2=CFCF20CF2CF20CF2CF

A mixture of 38.9 g (o.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 mole) of perfluoroallyl fluorosulfate was added rapidly at 5~C and the mixture was stirred at 0-5C for 3 hours, at 25C for 2 hours, and allowed to stand overnight.
Volatlles were evaporated to diglyme reflux at 38C (3 mm Hg).
Di8tillation of volatilcs from 20 g of NaF gave 28.2 g (20~) of recovercd diacid fluoride, bp 32-33C, a.nd 125.0 g (52~) of mono~cid f:luoride, ~lmost a.ll of lt bp 93-94C. Structure was conrirmed by:
ir (CCl4): 5.30 (COF), 5.59 (C=C), 8-9 ~
(CF, C-O). NMR: F 13.3 (m, 1 F, COF), -72.0 (d of d of t of d, JFF 25, 13, 13, 7.7 ~Iz, 2F, =CFCF2), -77.5 (t of d, JFF 11.5, 2.~ ~Iz, 2 F, CI~'2C02E'), -88.8 (t, J~F ].1.5 I~z, 2 F, CF20CF2COF), 3o ~155~1 -89.4 (t, JFF 12.7 Hz, 2 ~, aCFCF20CF2), -91.9 (d o~ d of t, JFF 52.7, 39.3, 7.7 Hz, lF, cis-CF2CF=CF), -105 3 (d of d o~ 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, 39.3, 13.7, 1.6 Hz, 1 F, CF2CF= ~ .

2~ Pentafluoro-2-pr~en~loxy)tetrafluoroethanesulfon fluoride o FSOa CFa CF + KF ~ CF~ =CFCFa OSOa F--> ESO~ CFa CF~ OCF~ CF~CFa A suspe~lsiol~ o~ ~ot;as~ ll rlu~-ri(lo (5.~ ~,, 0.10 mo~) ln diglyme (100 ml) was stirred and cooled while fluoro-sulfonyldifluoroacetyl fluorlde (18.0 g, 0.10 mol) (D.C.

England, M. A. Dietrich and R. V. Lindsey, Jr., J. Amer. Chem.
Soc., 8~ 6181 (1960)) was added rapidly. The mixture wa6 stirred for 15 mln at 20-30C during which time the potassium ~luoride dissolved, and then it was treated wlth perfluoro-allyl fluorosulfate prepared as in Example 2A (25.0 g, 0.11 mol) at 20-25C over 5 min. The mixture was stirred ~or 2 hours, during which time solid precipitated, and the temperature rose to 28C and fell again. The volatile components were trans-ferred to a trap cooled to -aooc by warming the solution to reflux at 38C (5 mm Hg). The distillate was treated with con-centrated sulfuric acid (10 ml) to remove diglyme, then dis-tllled to gi~e 2-(1-pentafluoro-2-propenyloxy)tetrafluoro-ethane~ulfonyl 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 (SO~F) and 7-10 ~m (CF,C-O,S0~ 9F NMR, ~44.9 (t J 3 6 Hz, each member t J = 6 Hz) lF, FS0~, -71.8 (d J - 25.3 Hz, each member t J - 13.8 Hz, d J = 13.8 Hz, 1~55801 d J - 7.3 Hz) 2F, OCF~C=C, -83.o (m) 2F, CF~CFaO, -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) lF, trans-CF2CF=CF, -113.0 (d J = 5.6 Hz, each member t J = 2.9 Hz) 2F, FSOaCFa, and -190.9 ppm (d J = 117.6 Hz, each member d J = 39.5 Hz, t J = 13.8 Hz, t J = 3.2 Hz) lF, CF2CF -C.
Anal. CalcA for C6F~oO~S C, 18.19; F, 57.55; S, 9.71 Found: C, 18.35; F, 57.40; S, 9.69 2-(l-Pentafluoro-2-Pro~en:vlox~v)tetraflu-oroethanesulfon~
fluoride FSO~CFa~F ~ KF ~ CF~ = CFCFaOSOaF ~ FSOaC~aCFaOCFaCF=CF~
The procedure of Example 7 was followed, sub-stltuting acetonitrile for diglyme as the solvent. The acetonitrile wa~ not rigorously purified, and the yields of 2-(1-pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluorlde, pb 54-55C (150 mm Hg) ranged from 40-50%.

1- rl- ~Pentafluoro-2-~roPenylox.Y) lhexafluoroProPane-2-sulfon.vl ~luoride ~ E~ CF3 FSO~CFCOF ~ KF ~ CF~2CFCFaOSOaF ~FSO~CFCFaOCF~CF=CF~
A mlxture of potassium fluoride (5.80 g, 0.10 mol) and diglyme (100 ml) was stirred at 10C while 2-fluorosulfonyl-tetrafluoropropionyl fluoride (23.0 g, 0.10 mol) (D. C. England, M. A. Dletrlch and R. ~. Llndsey, Jr., J. Amer. Chem. Soc., ~ 6181 (1960)) was added. m e resultlng solution was treated at 10C wlth perfluoroallyl fluorosulfate prepared as in ~15~01 Example 2A, and after the addition was complete, the mixture was stirred at 25C for 3 hours, then it was poured into water (500 ml). The lower layer was washed with water (10~ ml), dried and distilled to give l-[l-(pentafluoro-2-propenyloxy)~
hexafluoropropane-2-sulfonyl fluoride (25.7 g, 0.068 mol, 68%) bp 50C (60 mm Hg), pure by gas liquid partition chromatography (glpc). The product structure was confirmed by:
5.55 (CF=CFa), 6.78 (SOaF) and 7.5-lO ~m (CF,C-O,SO~);
~F NM~, 54.9 (d J = 20.7 Hz, each member q o~ J = 10.4 H%, d J - 3.6 Hz) lF, SOaFJ -71.8 (d J - 25.0 Hz, each member t J = 13.8 Hz, d J ~ 13.8 ~z, d J = 7 . 4 Hz ) 2F, OCFa C=C, -72.1 (m) 3F, CF~, -75.5 (m) 2F, CFCFaO~ -91.0 (d J = 5O.7 Hz, each member d J = 39.4 Hz, t J = 7-4 Hz) lF, cis -CFa CF=CF, -104.6 (d J ~ 117.6 Hz, each member d J = 5O.7 Hz, t J = 25.0 HZ) lF, trans-cFacF=cF~ -166.4 (d J = 14.6 Hz, each member q J = 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 ~z, t J = 1.7 Hz) lF
CF2CF =C.
Anal. Calcd for C~Fl~03S: C, 18.96; F, 59.98; s, 8.44 Found: C, 18.70; F~ 6O.O9; S, 8.o8 ?- r~ 2~L4~4-pentafluoro-2-c.yclobutenvloxy)ltetra rluoroethanesulfonyl fluor~de F F
Fal ¦ OSOa F ~OCFa CFa S2 F
F + KF + FCOCFa SO:~ F - ~

-l 15580 1 A suspension of potasslum ~luorlde t5.80 g, 0.10 mol) in diglyme (100 ml) was stirred and held at 15C by external cooling while fluorosulfonyldifluoroacetyl fluoride (18.0 g, 0.10 mol) was added rapidly. This mixture was treat-ed at 10-15C with 1-(1,2,3,4,4-pentafluoro-2-cyclobutenyl)-fluorosul~ate (24.2 g, 0.10 mol) tB.E. Smart, J. Org. Chem., 4~ 2353 (1976) and then stirred at 25C for 3 h~rs an~
poured into water (500 ml). The lower layer was washed with water (100 ml), dried and distilled to give 2-Cl-(1,2,3,4~4-pentafluoro-2-cyclobutenyloxy)]tetrafluoroethane-sulronyl fluoride (24.0 g, 0.07 mol, 70%) bp 62C (1~0 mm H)-The product structure was confirmed by:

~ma 5~53 (C-C), 6.80 (SO~F) and 8-9.5 ~m (C-F, C-O, SOa);
9F NMRJ 44.8 (t J = 6.o Hz, each member t J = 6.0 Hz, m) lF, SOaF, -80.3 and -83.8 (AB J = 146 Hz, each member m) 2F, OCFa, -112.7 (m) 2F CFzSOaF, -117.6 and -119.7 (AB J = 190 Hz, each member m) 2F, ring CFaJ -121.8 (m) lF, CF, -127.1 (m~ lF, CF, and -128.4 ppm (m) lF, CF.
Anal. Calcd for C~F~oOaS: C, 21.07; S, 9.37 Found: C, 21.38; S, 9.44 2-(1-Pentafluoro-?-Propen.vloxv)-3~6-bi~(trifluorometh,Yl)-2.3,5,5,6-~entafluoro-1,4-dioxane F F

~ ~ ~ KF ~ CFa=CFCFaOSOaF > ~ ~
~ CFa CFa=CFCFaO ,- ~ F

A mixture of pOtassium ~luoride (5.8 g, 0.10 mol) and dlglyme (100 ml) was treated at 25C with 3,6-biæ-1155~01 (trifluoromethyl)-3,5,5,6-tetrafluoro-1,4-dloxan-2-on~
(S. Selman, U.S. Paten~ 3,321,517) (31.0 g, 0.10 mol). The mixture was stirred for 1 hour and then treated dropwise with perfluoroally1fluorosulrate prepared as in Example 2A
(23.0 g, 0.10 mol), the exothermic reaction being maintained at 35-40C with an ex~ernal ice bath. The mixture was stirred overnight at 25C, during which time no gas evolu-tion was detected and a yellow-orange color developed.
The mixture was poured into water (500 ml), the lower layer was washed with water (100 ml), dried and distilled at 73-74C (180-140 mm Hg). The distillate was treated with a small amount of phosphorus pentoxide and refractionated to give 2-(1-pentafluoro-2-propenyloxy)-3,6-bis-(trifluoromethyl)-2,3,5,5,6-pentafluoro-1,4-dioxane as a mixture of isomers, bp 55-57C (60 mm Hg). The product structure was confirmed by: Amax 5-57 (CF=CF2) and 7.5-10 ~m (CF,C-O); l9F NMR, -70.7 and -71.8 (AB J = 159 Hz, each member m) 2F, OCFaC=CJ -77.3 and -87.91 (AB J = 153 Xz, each member m) 2F, ring OCF2, -81.4 (m) 4F, CF3 ~ OCFO, -82.4 (m) 3F, CF3, -92.3 ~d J - 52.0 Hz, each member d J = 39.3 Hz, t J ~ 7.2 Hz) lF, cis-CF~CF~CF- -105.3 (d J = 117.1 Hz, each member d J ~ 52.0 Hz, t J = 25.4 Hz) lF, trans-CFaCF=CF,-123.3, -124.7, -126.2, -132.2, -132.9 and -134.1 (m) 2F CF3CF~O, -190.5 (d J = 117.1 Hz, each member d J = 39.3 Hz, t J - 13.7 Hz) lF, CFa~C~ =C. Small underlying signals caused by the presence o~ isomers were obser~ed at -92.1, -105.3, and -190.5 ppm.
Anal. Calcd for CsF-~03: C, 23.50; F, 66.o7 Found: C, 23.71; FJ 66.17 3o 11~S801 ?-rl-(Pentafluoro-2-ProPenyloxy~l-2~5~6-tetrakis(trifluoro-methvl)-5-fluoro-1.4 7-trioxabicyclo~2.2.11hePtane and 2-rl-(Pentaf-luoro-2-propen~lox~)tetrafluoroeth~vll-4-~l-(pentafluor 2-ProPenYloxY)1-2,4,5-tris(trifluoromethYl)-5-fluoro-1,3-dioxolane O O O O K
Il 1~ ll l CF3CCCF3 ~ KF > CF3C - C - CF3 F

¦ CF2=CFCF~OSOa CF,~8CoCF~ r F-OCD2~2 CF3 C OCFacF=cF~ CFa=CFCFa CF~
A suspenslon of anhydrous potasslum fluoride (5,ôO g, 0.10 mol) $n diglyme (100 ml) was stirred at 10C
while hex~fluoro-2,3-butanedione (hexafluorobiacetyl, L. O.
Moore and J. W. Clark, J. Ore. Chem., ~, 2472 (1965)) (19.4 g, 0.10 mol) w~s di6tilled in. me mix~ure was 6tir-red until the potassium fluoride had nearly all d~ssolved, and the~ it,was treated rapidly wlth perfluoroallyl fluoro-~ul~ate prepared as in Example 2A (2~.0 g, 0.10 mol) at 15C The sllghtly exothermic reaction raised the tempera-ture to 30C. The pale yellow mixture was stirred overnight at 25C and then distilled. The two phase distillate collected at bp 49-54~ (10 mm Hg) was shaken with concentrated sul~uric acid (8 ml), treated with anhydrous calcium sulfate and ~ractlonated ln a splnning-band stlll. 2-~1-(Penta~luoro-1 1~580 1 2-propenyloxy)]-2~3,5,6-tetrakis(trifluoromethyl)-5-fIuoro-l, 4,7-trioxabicyclo[2.2.1]heptane (3.0 g, 0.0055 mol, 11%) bp 50-51C (15 mm Hg) contained one ma~or component by glpc. The analytlcal sample of this product was obtained by preparative glpc and its structure confirmed by:
A 5.58 (CF=CF2), and 7.5-10 ~m (C-F,C-O); l9F NMR, -65.6 and -71.0 (AB J - 155 Hz, each member m), 2F, OCF~, -74.7 (m) 3F, CF3~ -78.5 (m) 3F, CF~, -79.3 (s) 3F, CF3, -79.9 (d J = 13 Hz, each member septet J = 4 Hz), 3F, CF3, -92.0 (d J = 52.1 Hz, each member d J - 39.5 Hz, d J = 8.3 Hz, d J = 6.6 Hz) lF, cis~CFaCF=CF~ -105.5 (d J = 117.2 Hz, each member d J = 52.1 Hz, d J = 27.0 Hz, t J = 21.8 Hz, q J = 3.0 Hz) lF, trans-cFacFzc~ -121.7 (q J = 20.5 Hz, each member q J = 13.1 Hz) lF, CF, and -191.2 ppm (d J = 117.2 Hz, each member d J = 39,5 Hz, t J - 13.8 Hz) lF, CFa-CF =C.
Anal: Calcd for CllFl8 04 C, 24.55; F, 63.55 Found: C, 24.57; F, 63.60 m e second fraction was a mixbure o~ isomers of 2-[1-(penta~luoro-2-propenyloxy)tetrafluoroethyl] 4~
(pentafluoro-2-propenyloxy)~-2,4,5-tris(trifluoromethyl)-5-fluoro~1,3-dioxolane (7.2 g, 0.01 mol, 21%), which con-tAlned only minor impurities by glpc. Thi8 product structure was confirmed by:
AmaX 5.56 (CF-CFa) and 7-10 ~m (CF,C-O), 19F NMR -72.8 ppm ~AB) 2F, OCF~, -75.4, -76.8, -78.3, -78.7 and -79.1 (m) 12F, CF3, -93.1 (m) 2F cis-CFaCF-C~/ -105.8 (m) 2F, trans-CF~CF-CF, -121.0, -136.5 and -141.6 (m) 2F, CF, and -190.8 ppm (m) 2F, CFaCF=C.
Anal. Calcd for Cl~Fa~O~: C, 24.44; F, 66.26 Found: C, 24.73; F, 66.48 3o Perfluoro-1,6-bis~2-Prop-enylo~)hexane O O
FC(CFa )4CF + KF + CFa=CFCFaOSOaF - ~ (CFa=CFCFaOCFaCFaCF~ )a CFa-CFCFaO(CFa )~ COF

CFa=CFCFaO(CFa )6 COF + HaO ~ CFa~CFCFaO(CFa )6 COaH-~ diglyme A m~xture of potassium fluoride (11.62 g, 0.20 mol), diglyme (200 ml) and octafluoroadipoyl difluoride (PCR 28.2 g, o.og6 mol) was stlrred at 5C for 1.5 hours. The mixture was kept at 5-10C while perfluoroallyl ~luorosulfate 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 lt was allowed to warm to 25C and the stirring was continued for a further 3 hours. After having stood over-night, the mixture was poured into water (1 Q.); the lower layer was washed with water (150 ml), dried and distilled to glve two products.
The lower-bolllng fractlon was perfluoro-1,6-bis-(2-propenyloxy)hexane (21.1 g, 0.0355 mole, 37%), bp 84-86C
(20 mm Hg)whose structure was confirmed by:
A~ 5.59 ~CF~CF~ ) ~nd 7.2-9.5 ~m (C-F,C-O): 19F NMR, -72.1 (d J z 25.7 Hz, each member t J - 13.3 Hz, d J = 13.3 Hz, t J = 7.6 Hz) 2F, OCFaC=C, -84.2 (m) 2F,C~?O, -92.3 (d J = 52.7 Hz, each member d J = 39.5 Hz, t J = 7.6 Hz) lF, cis-CFaCF=CF~
-105.5 (d J = 117.8 Hz, each member d J = 52.7 Hz, t J =25.7 Hz) lF, tran~-CFaCF--C~, 122.9 (m), CF~, -126.2 (m) 2F, CFaJ and -191.0 ppm (d J - 117,8 Hz, each member d J ~ 39.5 Hz7 t J ~ 13.8 Hz) lF, CF~-CF C.

1~5S801 Anal. Calcd for C~2F~aO~: C, 24,26; F, 7O.35 Found: C, 24.43; F, 70.38 The higher boiling fraction was the 2:1 complex of perfluoro 6-t2-propenyloxy)hexanoic acid with diglyme (7.9 g, 0.0155 mol, 16%), bp 109-110C (5 mm Hg), formed by hydrolysis of perfluoro-6-(2-propenyloxy)hex~noyl fluorlde in the aqueous diglyme wash solutions, m is complex had ~max 3~4 (OH,C-H), 5.59 (with shoulder, GF~~CF,COaH), and 7.2-9 ~m ~CF,C-O,CH);
H NMR, ~ 11.93 (s) lH, CO~HJ 3.75 (s) 4H, OCHa~ and 3.52 (s) 3H, OCHb; l9F 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, OCF~C=C, -~4.1 (m) 2F, CFaCFaO~ -92.0 (d J = 52.3 Hz, each member d J - 39.3 Hz, t J = 7.4 Hz) lF~ cis~CFaCF=CF~ -105.2 (d J - 117.7 ~z, each member d J ~ 52.3 Hz, t J = 25.1 Hz), lF, trans-CF~CF=CF, -119.6 (t ~ = 12.6 Hz, each member t J = 3.2 Hz) 2F, CFaJ -122.6 (m) 2F, CFa~ -123.5 (m) 2F, CFa~ -126.1 (m) 2F, CF~, and -19O.9 ppm (d J = 117.7 Hz, each member d J = 39.3 Hz, t, J = 13.8 Hz, ~ J = 1.8 Hz lF, CF~ CF=C .

Meth.Yl ~'crfluoro-3.~-~ioY.anon-~-enoate R ~1130~3 Cl~'2-l~FCI~20CF2C~'20CF2CE~' ~ CF2=CFC~`20CE~2CFzOCF2COzCH3 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 fluorlde was added rapidly. After addition had been completed, the mixture was stirred overnight at 25C, filtered and the solid rlnsed 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 of impurities. Redistillation gave somewhat more pure ester (1-2% impurities by gc), bp 61-62C
3o (20 mm Hg). Structure was confirmed by Ir (neat):
3.32, 3.~7, 3.49 ~CH3), 5.57 (C=0), 8-9.5~ (CF, C-0).
NMf~: H 3.95 ppm (s) with sma.ll impu-rities at 3.53 and 3.33 ppm;
F 72-0 (d of d of t of d, JFF 24, ].3, 13, 7.5 ~z, 2 F, =CFCF2~, -78.o (t, JFFI ~.1.6 Hz, 2 F, CF2C02CH3), -~ .0 (t, JFF 11.6 Hz, 2 F, CF20CF2C02CH3), -89.5 (t, JFF 12.6 Hz, 2 ,`, =CFCF20CF2), -92.3 (d of d of t, JFF 53.2, 39.2, 7.5 llz, 1 F, cis-CF2CF=CF), -105.2 (d of d of t, JF~ 117.3, 53.2, 2~.3 Hz, lF, trans-CF2CF-CF), and -190.~ ppm (d of d of t of t, J~,~, 117.3, 39.2, 14.0, 1.6 ~lz, 1 F, CF2CF=).
Anal. Calcd. for C8H F1104: C, 25.82; H, 0.81; F, 5G~.17 Found: C, 26.17; H, o.66; F, 56.24.

Dlmeth.Yl Perfluoro-3-allox~lutarate A. Bis(2-methox.Ytetrafluoroeth~l)ketone l'he synthesis of bis(2-methoxytetrafluoroethyl)-ketone from diMethyl c~rbonate tetrafluoroethylene, and sodium mcthoxide h~s becn described by D. W. Wiley (U. S.
2,~,537 (1961)). An extension of this synthesis has given 1,3,3,5-tetramethoxyoctafluoroperltane in a one-pot reaction.
o O~Na+
C~J30Na. + 2 CF2=CF2 ~ CH30COCH3 ~ CH30CF2CF2bCF2CF20CH3 CH30CF2CF2C( OCII9 ) 2CF2CF20C~I3 A mixture of 27.0 g (0.50 moi) of sodium methoxide, 56.o g (0.62 mol) of dimethyl ca.rbonate, and 100 ml of dry tetrahydrofuran was agitated in a 350 ml tube under 1-3 atm Or ~e~rafluoroethylene. Tetrafluoroethylene was pressured in as consumed until 110 g (1.1 mol) had been added. The mildly exothermic reaction kept the temperature near 35C; after 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 afforded 87.6 g (52%) of 1,3,3,5-tetramethoxyoctafluoropentane, bp 54C (0.3 mm Hg3, nD24 1.3605, whose structure was confirmed by Ir 3.29, 3.33, and 3.42 (satd CH)~
8-9 ~ (CF, COC). Nmr (CC14) 'H ~ 3.68 (s, 1, CF20CH~) a.nd 3.57 (P' J~lF 1.3 Hz, 1, C (OCH3)2); 9F -8~.2 (m, 1, CR20) and -116.5 ppm (m, 1, CFz).
Anal. Calcd. for CgH12F~0l~: C, 32.1~; H, 3.60; F, 45.21 Found: C, 32~57; ~, 3.72; ~ 4.61.

. Dimethvl Tetrafluoroacetone~ -dicarbox~late conc. H2S04 C~3ocr~2cF~c ( OC113 ) 2CF2CF20C113 O O O

CT~30CCF2CCF2COCE~3 To 50 ml of conc. H2S04 wa.s added dropwise 33.6 g (0,10 ~nol) of the te~raether. Aft~r the mildly exothcrmic reaction llad subsided, the mixture was hea.ted at 70C
(50 mm Hg) to remove volatiles and then distilled at ca. 50C
(1 mm Hg). The crude distlllate was then fractionated to afford lG.~ g (69~) of dimethyl tetrafluoroacetone-1,3-dicarboxylate, bp 5~C (2 mm), nD 1.3713. Structure was con~irmed by Ir ~.28, 3.34 and 3.48 (satd CII), 5.57 (C=0) 5.64 (sh-C=0), 8-9 ~ (CF, COC
~lmr (CC14) ~ 4.00 (s, OC~13); 9~' -113 ppm (s, CF2).

Anal. Calcd. forC7H6F405: C, 34.16; ~I, 2.4~; F, 30.~8 mol wt, 246 Found: C~ 34.18; II, 2.6G; F, 30.95;
mol wt, 246 (mass spec~.

The same reaction on a 0.56 mole scale gave the diester ln 82% yield.

C. Dim~t~Yl Pcrfluoro~ lloxyF~lutarate .
O O O
Il 11 11 Cli30CCF2(:CF2COCIi3 + (~sF ~ CF2=CFCF20S02F7 O ~
( C~13 0C-CF2 ) 2cFocF2cF~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=CFCF20S02F was added at 5-10C
and the mixture was stirred further for 3 hours. The reaction mlxture was thrown into 1 liter of H20 and the lower layer separated. This was washed twice with H20. After treatment wlth 20 ml H~S04 at 0C and extraction with Freon~ 113, the extract w~ distilled in a molecular still to give 4.54 g (7.2~ yield) 0~ pl'O~UCt, bp = 51-53C (0.1 mm). Structure was confirmed by F nmr (Fll): -68.48 ppm (OCFzCF=); -93.45 ppm cis-(CF=CFF);
-105.91 ppm trans-(CF=CF); -117.10 ppm (CFzCOOC~13); -142.78 ppm (CF2CF20C'F--); -190.35 ppm (CF=CF2). '~I nmr (Fll/TMS):
3.96 (sin~lel;, C1~3). Ir (neat): 3.37 ~, 3.49 ~L (sat CH);
5.~0 2 (,C=O, CFz=CF); 8-10 11 (CF, CO).
Anal- Calcd for CloFloH605 C, 30.32i F, 47.96; II, 1.53 Found: C, 30.45; F, 48.10; I~, 1.4~.

1 1~S80 1 , Perfluoro-3-~2-propoxy-2-methylethoxy~Propen-e CF3CFaCFaOCFCOF + KF + CFa=CFCFaOSOaF ~cF3cFacFaocFcFaocFacF=cFa A mixture of potassium fluoride (6.96 g, 0.12 mol), diglyme (150 ml) and 2-(1-heptafluoropropoxy)tetrafluoro-propionyl fluoride (dlmer of hexa~luoropropene oxide obtaln-ed by treatment with fluoride ion) (29.4 g, o.o8g mol~ was stirred at 5C for 1 hour. Perfluoroallyl fluorosulfateprepared as in Example 2A (27.6 g, 0.12 mol) was added dropwise at 5C, then the mixture was stirred at 5C for 3 hours, and at 25C overnight. The reaction mixture was poured into water (1 Q.), the lower layer was separated and the volatlle components were removed at 25C (0.5 mm Hg)~ Distil-lation 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:
~ma 5~57 (CF=CFa) and 7.5-9 ~m (C-F, C-o);l9F

NMR, -72.2 (d J - 25.5 Hz, each member t J - 13.3 H~, d J = 13.3 Hz, d J = 7.4 Hz) 2F, OCFaC=C, -81.0 (m) 3F, CF~, -82.3 (m) 5F, CF3 + OCFa, -84.1 (m) 2F, CFaO, -92.1 (d J - 52.7 Hz, each member d J = 39.7 Hz, t J = 7.4 Hz) 1~, cis-cFacF=cF~ -105.5 (d J = 117.8 Hz, each member d J ~ 52 . 7 Hz, t J = 25 . 5 Hz), lF, trans-cFacF=cF~ -130.4 (s) 2F, CFa~ -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, CFaCF=C.

Anal. Calcd for CgHl80a: C, 22.42; F, 70.94 Found: C, 22 .18; F, iO . 96 ~15580 Perfluoro-l, 3-bi s ( 2-proPen,Yloxy~ Propane O O
FaCFa~F + KF + CFa = CFCFaOSOaF 3 (CFa-CFCFaOCF~)aCFa A mixture Or 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 0 was stirred at 5C for an addltional hour, then at 25C for 2 hours. The reaction mixture was poured into water (1 Q.), the lower layer was washed wlth water (100 ml), dried and distilled to give perfluoro-1,3-bis (2-propenyloxy)propane (12.0 g, 0.027 mol, 23%) bp 88-gooc (200 mm Hg) whose structure was confirmed by AmaX 5.59 (CF=CF~) and 7.2-9.5 ~m (C-F,C-O);
9F NMR, -72.2 (m) 2F, oCF2C=C,-84.6 (m) 2F, CF2CFaO~ -92.3 (d J ~ 53.O Hz, each member d J = 39.5 Hz, t J = ~.2 Hz) lF, cis-CF2CF-CF~ -105,6 (d J = 117.8 Hz, each member d ~ = 53.O Hz, t J ~ 25.2 Hz) lF, trans-cFacFccFJ -130,0 (s) lF, CFa and ~0 -191,0 ppm (d J - 117.8 Hz, each member d J = 39,5 H2, t J ~ 13.5 Hz) lF, CFaCF=C.
Anal. Calcd for C3F-flO~: C, 24.34; F, 68,45 Found: C, 24.67; F, 68.36 Perfluoro-3- (butox.Y)Propene CF~CFaCFaCOF + KF ~ CFa=CFCF~OSOaF ~ CF3CFaCF~CFaOCFaCF=CFa A mlxture of dry potassium fluoride (7.5O g, 0.13 mol), dl~lyme (lOO ml) and heptafluorobutyroyl fluoride (prepared from the acid by treatment with 8ulfur tetrafluoride) (28.1 g, 3 0.13 mol) was ~tlrred at 5C for 30 min. Perfluoroallyl fluorosulfate was added dropwise at 5C~ the mixture was stlr-red 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 concentrated sulfuric acid to give perfluoro-3-(butoxy~propene (30.3 g, 0.083 mol, 64%) bp 80-84C whose structure was confirmed by:
~max 5.57 (CF=CFa) and 7.2-9.5 llm (C-F,C-O); 1 F 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, OCF~C=C, -82.1 (t J = 8.1 Hz, each member m), 3F, CF3, -84.5 (m) 2F, C~ O, -92.1 (d J = 52.3 Hz, each mem-ber d J a 39,4 Hz, t J = 7.4 Hz) lF, cis~CFaCF=CF~ -105.5 (d J - 117.5 Hz, each member d J = 52.3 Hz, t J 2 25.2 Hz) lF, trans-CF2CF=CF, -127.3 (m) 4F, CFa, and -l91.O ppm (d J - 117.5 Hz, each member d J = 39.4 Hz, t J = 13.7 Hz, m) lF, CFzCF ~C.
Anal. Calcd for C7Fl4O: C, 22.97; F, 72.66 Found: C, 23.20; F, 72.80 EXAMPL~ l~

Perfluoro-3-(octYloxy)propene F(CF~)7COF + KF ~ CF~=CFCF20SOaF ~ F(CF~)80CF~CF~CF~
A mlxture of potassium fluoride t5.ôO g, O.lO mol), dlglyme ~150 ml) and pentadecafluorooctanoyl ~luorlde (pre-pared by treating commerclal perfluorooctanoic acid wlth ~ulfur tetrafluoride) (25.0 g, o.o6 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 addltional 3 hours. The mixture was poured into water (l Q.), separated, and the lower layer was dis-3o tilled from concentrated sulfuric acid to glve perfluoro-3-(octyloxy)propene (27.1 g, o.o48 mol, 80%) bp 69-70C
(20 mm Hg) whose structure was confirmed by:
Ama 5 ~59 (CF=CFa) and 8-9 ~m ~CF C-O); F MMR -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, OCF~C=C, -81.6 (t J = 10.0 Hz) 3F, CF3, -83.8 (m) 2F, CFaCFaOJ -92.3 (~ J - 53.6 Hz, each member d J = 39.9 Hz, t J = 7.7 Hz) lF, Cis~CFaCF=CF~ -105.5 (d J = 117.8 Hz, each member d J = 53.5 Hz, t J = 25.1 Hz) lF, trans-cFacF=cFJ -122.2 (m) 6F, CFa~ -122.9 (m) 2F, CF2, -125.7 (m) 2F, CF2, -126 .5 (m) 2F, CFa> and -190.8 ppm (d J = 117.8 Hz, each member d J - 39.9 Hz, t 13.7 Hz, t 1.7 Hz) lF, CF~CF=C, Anal. Calcd for CllF~aO: C, 23.34; F, 73.84 Found: C~ 22.99; F, 73~94 2-TrifAluoromethoxYpentafluoropro~ene (Perfluoro(allylmethylether)) COF2 + CsF + CFa=CFCFaOSO2F -~ CFsOCF2CF=CFa A mixture of carbonyl ~luoride (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 be-low whlle perfluoroallyl fluorosulfate (46.o g, 0.20 mol) was added. The mlxture was stirred at -10C for 2 hours, at 0C for 2 hours, then at 25C overnight. The mixture was warmed under a 511ght vacuum, and the volatile distillate (11 ml of liquid collected at -80C) was redlstilled through a low temperature ~tlll to give 2-trifluoromethoxypropene (3.2 g, 2.0 ml at -80C, 0.014 mol, 7~) bp 11-12C. ~he structure was established by i~s spectra: ~ (gas pha~e) 5.55 (CF=CFa), 8-9 (CF, C-O) and 5.35 ~m (weak COF impurlty band); ~9F NMR (CCl~), -56.5 (t J ~ 9.2 Hz) 3F, CF30, -74.6 (d J - 25.8 ~z, each member d J = 13.6, q J = 9.2 Hz, d J = 7.1 H~) 2F, OCF~C=C; -92.2 (d J = 53.4 Hz, each member d J a 39.2 Hz, t J ~ 7.1 Hz) lF, cis ~CFaC~-CFJ -105.5 (d J - 118.0 Hz, each member d J = 53. 4 Hz, t J = 25 . 8 Hz ), lF, trans-CFa C~CF, and -190.9 ppm (d J = 118.0 H7,, each member d J = 39.2 ~z, t J = 13.6 Hz ) lF, CFa C~C .

Pcrfluoro-6-(?-~1openyloxy)hex~noic Aci.d and Its ~iethyl Ester FCO ( Cl~'2 )4COF + l'~ CF~ = CFCF~OS02F ~
(C~ = CFCF~OC~cF2cF2)2 ~ C~2 CFCF2 ( 2)5 CF~ - CI; CF~O ( C~, ) 5COF 2 > 2 2 (- 2 ) 5 ~' ~

3 2 2 2 2C1~33 -d ' t 4 > C~2 = CFcF2o(cF2)5co2H ~-C~i 2 = Cl~ CF20 ( CF2 ) 5C02CH3 A mlxture of potassium fluoride (11.7 g, 0. 20 mol), diglyme (250 ml) and octafluoroadipoyl difluoride (PCR 58.8 g, 0.20 mol) was stirred at 0-5C for 30 min. The mixture was kept at 0-5C while perfluoroallyl fluorosulfate (~xample 2A, 46.0 g, 0.20 mol) was added dropwise. When the addition was ¢omplete, the mlxture was stirred at 0-5C for 2 hours, then it wa~ 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.); 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 resultlng exothermic reaction, the mixture was allowed to cool, and the lower layer was separated and distilled to give perfluoro-1,6-bis(2-propenyloxy)hexane (Example 13, 13.6 g, 0.023 mol, 23~) 1 1558~ 1 bp 61 (6 mm Hg) and the 2:1 complex of perfluoro-6-(2-propenyloxy) hexanoic acid wlth diglyme (Example 13, 52.8 g, 0.109 mol, 54.5%) bp 82-84C (O.8 mm Hg).

The diglyme complex 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 identi~ied by infrared ~max 2.82 and 3-4 (OH,CH3), 5.58 (C~=CF2), 5.61 (C-O) and 7-10 ~m (CF,C-O,CH) and by lH NMR, ~ 3.92 (OCH3) and 11.33 ppm (OH) signals in the ratio of 1:7.2; the 19F NMR spectrum was also in accord with these structures.

Perrluoro-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 ln Example 21 by distlllatlon o~ the crude lower layer.
The ~ractlon bp 45-53~C (6 mm H~) was freed o~ di~lyme by water washlng to leave crude perfluoro-l, 6-bis(2-propenyl_ oxy)hexane (9.5 g, 0.016 mol, 16%).
The hlgher boiling complex of perfluoro-6-(2-pro-penyloxy)hexanoic acid with diglyme was dissolved in 1,1,2-trlchloro-1,2,2-trifluoroethylene (50 ml) and extracted in turn with 50 ml and 25 ml of concentrated sul~uric acid. The organic layer was treated with calclum sul~ate, filtered, and distilled to give pure 3o perfluoro-6-(2-propenyloxy)llexanoi.c acid (42.2 g, o.og88 mol~ 49%) bp 75C (1.0 mm Hg). This material was ldentified by infrared ~max 2.85-4.0 (H-bonded 0~), ~.57 (CF=CF2), 5.63 (sh,C=O) and 8-9 ~m (C~,C-O), and by its lH and 19F NMR spectra.
Anal. Calcd. for C HF1503: C, 24.45; H, 0.23; F, 64.66 Found: C, 24 . 48; H, 0.45; F, 65.76 The following examples illustrate the preparation of useful copolymers ~rom the polyfluoroallyloxy comonomers of this invention. m e general properties of these co-polymers were discussed above.

UTILITY EXAMPLES
Example A
Solution P~ erization of Tetrafluoroethylene with 2-El-(Pèntafluoro-2-~ro~en~lox~)]tetrafluoroethanesulfon~l Fluoride n x CFa 8 CFa + xCFa ~ CFCFaOCF2CFaSOaF (C-~ (cFa-cF~)n -CF2CF
L CF~OCFaCF~SO~FJ x An 80-ml stainless steel-lined tube was charged with a cold mixture (-45C) of 1,1,2-trichloro-1,2,2-trifluoro-ethane (Freon~ 113) (10 ml), 8% 1,1,2-trlchloro-1,2,2-tri-fluoroethane solution of pentafluoroproplonyl peroxide (3P
lnitlator) (1 ml), and 2-[1-(pentafluoro-2-propenyloxy)~-tetrafluoroethanesulfonyl fluoride ~Example 7, 17.5 g,O.053 mol).
m e tube was closed, cooled to -40C, evacuated, and charged wlth tetrafluoroethylene (20 g, 0.20 mol). The tube was warm-ed to 25C and shaken at this temperature for 20 hour~.- The volatile materials were allowed to evaporate, and the product 3o polymer was evacuated to 0. 5 mm Hg. The product was then extracted wlth l,1,2-trichloro-1J2,2-trlfluoroe~hane, and dried under vacuum to give the solid white copolymer (16.9 g, 85%):
~max (KBr) 6.79 (SO~F) and 12.3 ~m (broad) ln additlon to the usual polytetrafluoroethylene infrared bands, Gravlmetric sulfur analysi~ gave o.48 and 0.2 ~ ~ 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 -S02F).
Differential scanning calorimetry (DSC) showed a 12% depres-sion of the endotherm peak (mp) compared to polytetrafluoro-ethylene.

, ExamPle B
Solution Pol~erization of Tetrafluoroethylene with 1-[1-LPentafluoro-2-~roPenvlox~)lhexafluoroproPane-2-sulfonyl Fluoride x C~2=CFCF~OCFslF-SOaF ~ nxcFa=cFa -~ ~(CF2-CF2)n~CFaCF -CF3 1 ¦ CF~
L CF~OCFSO~E x The procedure of Example A was followed with 1,1,2-trichloro-1,2,2-trl~luoroethane (10 ml), ~ pentafluoropropionyl peroxide ln l,1,2-trichloro-1,2,2-trifluoroethane (2.0 ml), l-~l-(pentafluoro-2-propenyloxy)~hexafluoropropane-2-sulfonyl fluoride (Example 9, 17.4 g, o.o46 mol) and tetrafluoro-ethylene (20 g, 0.20 mol) to glve 16.7 g (7 ~ ) of copolymer.

Analy~ls by X-ray fluorescence showed 0.49 ~ S present, cor-responding to 5.8 wt-% (1.6 mole %) of poly~luoroallyloxy comonomer corresponding to an equilvalent weight of 6540.
The sample had a mp depression o~ 11C compared to poly~
3 tetrafluoroethylene by DSC.

1 155~0 1 Example c Solution Polymerization of Tetr~fluoroethvlene with ~ l-(Pent~fluoro-2-pro~en~loxy)tetrafluoropropionYl Fluoride x CFa =CFCFa OCFa CFa COF + nxCF~ =CFa ~ ~ CFa -CF:~ )n~ CF:a CF

CF~ OCFa CFa CO Y x NaOH
--F(CFa~CFa )n-CFa I F
L CF~ OCF2 CFa CC)2 N~

The procedure of Example A was used with 3-[-l(penta-fluoro-2-propenyloxy)]tetrafluoropropionyl fluoride (Example 5, 13.3 g, 0.045 mol) in place of 2-[l-(pentafluoro-2-propenyloxy)]-tetrafluoroethane-sulfonyl fluorlde to give 17.8 g (86%) of copolymer:
~max (KBr) 5.62 (C02H, weak) and 9.7 ~m bands in addition to the polytetrafluoroethylene bands; mp depression (DSC) was 14C compared to polytetra-fluoroethylene; 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 solutlon of sodlum 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.

3o Example D

Solution Polymerization of Tetrafluoroeth~lene with 1-~ ~1,2,3,3~Hexafluoro-3-chloro-2-pro~oxy)pentafluoro-2-pro~ene x CF,=CFCF,OCFCF,Cl + xncFa=cF~ CF,-CFa) -CF,CF ~

CF2OIFCF~C x CF~

The procedure of Example A was used with 1-~1,1,1,2,3,3-hexafluoro-3-chloro-2-propoxy)penta-fluoro-2-propene (Example 2, 14.3 g, 0.043 mol) in place of 2-~1-(pentafluoro-2-propenyloxy)]-tetra-fluoroethanesulfonyl fluoride to give 18.3 g (87%) of copolymer: mp depression (DSC)14C compared to polytetrafluoroethylene, gravimetric analysis ga-~e 0.61 and 0.61% Cl, corresponding to 5.7 Wt-% of poly-fluoroallyloxy 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 o~ 1C per 0.1 mol % of poly-fluoroallyloxy comonomer present. In contrast to this result, the smaller branch in hexafluoropropene gives a mp depression correspondlng to about 1C per 0.3 mol-% of comonomer in lts copolymer wlth 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.

ample E
Solution Pol,Ymerization of Tetrafluoroeth,vlene with 2~
Pentafluoro-2-propen,yloxy¦hexafluo~E~ a_e-1-sulfon,yl Fluoride X CF2 =CFCFa OCFCFz SOa F + xn CFa = CF2 - >
--F' CFa -CFa ~ CF2 CF
L CFs~OCFCF~ SO~ F~ x ~Fs The procedure of Example A was used with 2~ penta-fluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl ~luoride (Example 3, 16.1 g, 0.042 mol) in place of 2-~1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride to give 18.5 ~ (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 conomomer and an equivalent weight of 7460.
EXamP1e F
Solutlon Pol,ymerlzation of Vin,ylidene_Fluoride with 2-[1-(Pentafluoro-2-proPen,Ylox~)ltetrafluoroethanesul~onyl Fluoride CHa-CF~ + CFa = CFCF~OCF~CFaSO~F > 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-tri~luoroethane tlO ml), and 8~ 1,1,2-trlchloro-1,2,2-tri~luoroethane solution of penta-fluoropropionyl peroxide (5 ml). The mixture was shaken o~ernight, the maximum recorded temperature being 31C. The solid copolymer produced (21.5 g, 60%) contained 46 wt %
(14.2 mol %) of poly~luoroallyloxy comonomer with an equivalent 1 15~80 1 weight oî 71. 9 DSC showed no thermal events between 25C and 400C .
Anal . Calc d for ~ CF~ )~, . O ~ ( CFa =CFCF2 0CF2 CF:~ SO~ F):
C, 28.62; H, 1~70; S, 4.47 Found: C, 28.49; H, 1.71; S, 4.46 Solution Pol~erization of Vinylldene Fluoride with l-~He~ta-fluoro-2-pro~oxy)-1~1,3,3-tetrafluoro-2-chloro-2-propene CH~-CF~ + CFa = CClCF20CF~CF3 )a ~ Copolymer 1 The procedure o~ 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) ln place of 2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride to give a solld copolymer (20.6 g, 73~). This material contained 36 wt-% (9.8 mol-%) of polyfluoroallyloxy comonomer with an equlvalent weight of 878. DSC confirmed the structure as a copolymer and indlcated its stability, because ~o thermal events were observed in the range 25-400C.
Example H
Solution Pol~merization Or Tetrafluoroethxlene with Per~luoro-~-(butoxy)propene CFa~CFa + CF3 (CFa )30CFaCF=CFg ~ Copolymer m e procedure of Example A, when used with perfluoro-3-(butoxy)propene (Example 1~., 19.0 g, 0.052 mol), tetra-~luoroethylene (20 g, 0.20 mol), 1,1,2-trichloro-lJ2,2-tri-f~uoroethane (10 ml) and 8% penta~luoropropionyl peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane (2 ml) gave 18.9 g of solid copolymer. mis crude material was chopped in a blender with more solvent, rinsed, and dried to give 16,5 g o~ copolymer with a mp of 309C, lndicating that it was a true copolymer.

1~S5~01 Solution Pol~merization of Tetra luoroeth~lene wlth Per~luoro-1,6-bis(2-propenYloxv)hexane _ _ CFa -CF2 + ( CF:~ CFCF~ OCF2 CF~ CF~ ) ~ - ---~ Copol-ymer The procedure of Example H was ~ollowed, using per-fluoro-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 ~m (CF=CFa); the remalnder of the infrared spectrum resembled that o~ poly(tetrafluoro-ethylene). DSC showed a pronounced exotherm Tp 315C follow- -ed by an endotherm Tp ~ 333C and 339C on the flrst heating;
the second heating showed no exotherm and a broad endotherm Tp ~ 326C. Infrared spectra indicated that pyrolytic re-actions of pendant pentafluoroa~lyloxy groups had occurred during the first heating; the broad DSC endotherm near the normally sharp mp of poly(tetrafluoroethylene) indicates that cro~slinking had occurred.
Example J
Solution Polymerizatlon of Vinylidene Fluoride and PerrluorO-1.3-bis(2-~ropenyloxy)propane CH~ ~ CF~ ~ (CFa=CFCF~OCF~)aCF~ ~ Copolymer A mlxture of perfluoro-1,3-bls(2-propenyloxy)-propane (Example 17, 5.7 g, 0.013 mol), 1,1,2-trichloro-1,2,2-trlfluoroethane (25 ml), and 8~ pentafluoropropionyl peroxide in 1,1,2-trlchloro-1,2,2-tri~luoroethane (5 ml) was held at -40C ln a stalnless steel-llned shaker tube whlle vlnylidene fluorlde (20 g, 0.32 mol) was condensed into the tube. m e mlxture was shaken overnight at room temperature, and the product was isolated as descrlbed above. m e crude polymer was drled under vacuum, pulverized ln a blender l 15580 1 wlth 95~ ethanol, filtered and dried to glve 24.0 g of solld copolymer. DSC showed an endotherm Tp 124~C, stable to at least 300C, indicatlng that a true copolymer had been form-ed since poly(vinylidene ~luoridej has mp 171C. The in-solubility of thls product in acetone and the lack of absorp-tion bands in the infrared for pendant CF=CF8 groups in-dicates that crosslinking 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 o~ pcrfluoroproplonyl peroxlde were reacted at 50C ~or 4 hr.
under a 10 psl pressure of tetrafluoroethylene. Filtration gave a solid which on drying at 50C in a vacuum oven weighed 0.71 g. The amount of ~F~ a~ded was 4 g. Equivalent wei~ht by titration gave 1176; therefore the amount of the ester incorporated in the polymer was 28~ and the yield based on TFE was 20~. A transparent film was obtained by heating at 220C in a Carver press.
EXAMPLE L
~eable Fluorocarbon Pol~mers Samples of the polymers of Examples B and E were treated with aqueous alcoholic ~mmonia 301ution for one day at 25C, filtered, washed with aqueous ethanol and dried un-der vacuum.
A ~ample of the polymer Or Example C was simllarly treated with aqueous alcoholic sodlum hydroxide.
m e above partly hydrolyzed polymers were immersed ln aqueous ethanol solutions o~ Se~ron~ Red GL (Se~ron~ is a llne of catlonic dyes especially suited for dyeing Orlon~
and other acrylic fibers, having outstandlng fastness and 3~ brilliance - Du Pont Products Book, January 1975, p. 34) at 25C ~or 1-3 hours, then they are extracted until the ex-1 1~580 1 tracts no longer contalned dye. All three samples dyed well to an orange-red color.
EXAMPLE M
Wettable Fluorocarbon Polymer A sample o~ the polymer of Example C was treated wlth 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 Tetrafluoroeth.~lene with 2~L~
(PerLtal'luoro-2-Propenylox~v)1t;ctr;lrluoroctllatlesuli`ol~yl_Fluor:L(lc Cli~a =Cli`a + Cl;'2 =CFCl~`a OCIi ~ CI-'`2 SOa li' ~, COpOlyl~lCr A stainless steel shaker tube was charged with water (1l~0 ml), 1,1,2-trichloro-1,2,2-trifluoroethane (10 ml), 2-[1-(pentafluoro-2-propenyloxy)ltetrafluoroethanesulfonyl fluoride (Example 7, 6.o g), potassium perfluorooctane-sulfonate (0.16 g), ammonium car~on~e (0.50 g) and ammonium persulfate (0.50 ~). 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.5.i.~. for 45 min at 70C. l~le polymeric product thus obtained was filtered, washed and dried to give 43.2 g of whito solld which contained approxim~t~ly 1.4 wt % (0,43 mol ~) of polyfluoroallyloxy comonomer by lnfrared analysls.
Differentlal thermal analysls (DTA) showed a crystalline transltlon at 10C, a recycle freezing temperature of 293C
and a recycle meltlng point of 311C from which the polyfluoroallyloxy comonomer content is estimated as 3.5 wt % (1.09 mol %).
3o EXAMPLE O
nulsion Poly1ncri%atlon Or 'rc~rafluoroc~Ylenc wi~}l 2~
(~entarluoro-?-~ro~env~oY,y)ltetrafluoroe~llanesulfoll~l Fluor:ide CF2=CF2 ~ CF2=Cl;'CF2OC~2Cl~2S02F ~ Copolymer The procedure of ~xample N was rollowed using ~, O g of 2-[l-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride, 0.20 g of potassium pcrf`luorooctancsulfonate and tetrafluoroethylene at a pressure Or 3O p.s.i.g. at; 7OC ror a reaction period of 8 hours. The amounts of the other reagents were no~ changed. This gave 45 g of solid polymer whose infr~r¢d spectrum showed stron~ ~OaF absorption. D'l'~ showed a crystalline transition at 5C, a recycle rreezin~ tcmpera-ture of 282C, and a recycle meltine point of 300C, cor-responding to a polyfluoroallyloxy comonomer content of 5.9 wt % (1.86 mol %).
EXAMPLE P
Emulslon Polymerization of Tetrafluoroethylene with 2-[1-(Pentafl_oro-2-propenyloxy)]tetrafluoroethanesulfonyl Fluoride The procedure of Example N was followed using 10.7 g of 2-~1-pentafluoro-2-propenyloxy)]tetrafluoro-sulfonyl fluorlde, 0.20 g of ammonium persulfate~ and ketrafluoroethylene at a pressure of 50 p.s.i.g. at 70C for a reactlon perlod of 5 hours. The amounts of other reagents were not changed. This gave 28.6 g of white polymer whose infrared spectrum showed the presence of S02F groups corresponding to 3.5 wt %
(1.08 mol %) polyfluoroallyloxy comonomer. DTA showed two melting peaks at 290C and 317C, with an estimated conomomer content of 5.5 wt % (1.73 mol %).

UTILITY EXAMPLE Q
CoPol.Ymeri.zation of Tetrafluoroeth.Ylene_and 2-[1-(Pentafluoro-2-ProPenYlox.Y~]tetra~fluoroethanesulfon~l Fluoride, and Prer~aration Or ElectrlcallY Conductive Films from the Co~ol.Ymer Product nxCF2=CF2 ~ xCF2=CFCF20CF2CF2s02F

~CF2-CF2 )-CF2CF' CF2OCF2CF2SO~F

x ~ 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 g). The mixture was heated to 40C and brought to aninternal pressure of 10 psig 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 (K~r) 8.65 ~ (SO2F) and 8-10 mm (broad) in addition to the usual polytetrafluoroethylene IR
bands. The DSC melting point depression was 91C compared with polytetrafluoroethylene. Sulfur analysis by x-ray fluor-escence gave 2.7% S or 28.0 wt. ~ (8.5 mol ~) of poly-fluoroallyloxy comonomer, corresponding to an equivalent weight of 1180.
The product was pressed into a clear 4-5 mil film ~t 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.

11~5801 The four-lnch diameter, 4-5 mil film was inserted ~s the lon exchange membr~ne in a chlor-alkali electrolysis cell operated at 2.0 amps/in2. Cell voltage and current efficiency were measured as a function of cell operating time and sodium hydroxide concentration. The following results were obtained for a 15-day test:
Sodium HydroxideCurrent EfficiencyCell Voltage Da~ Product (~ ) (volts~_ _ 1 21.5 70.7 ~-35 21.5 71.2 3.45 ~0.0 65.2 3.60 UTILITY ~XAMPLE R
Co~olYmerization of Tetrafluoroeth~lene and Perfluoro-

6-oxsnon-8-enoic acid. and PreParation of Electrlcall~
Conductive Films from the CoPolYmer Product nxCF2=CF2 + xCFz=CFCF20(CF2)4COOH

~ CF2CF2)n-CF2-CF - '-L CF20( CF2 )4 The procedure of Example Q was followed with perfluoro-6-oxanon-8-enoic acid (47.5 g), 8~ pentafluoro-propionyl peroxide in l,1,2-trichloro-1,2,2-trifluoroethane (0.05 g), and TFE at 10 pslg (40C) to give 2.41 g of solid, white copolymer: DSC 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.

The copolymer product was pressed lnto 4-5 mil film and hydrolyzed as described in Example ~. IR spectra showed essentially complete conversion of -COF functions to carboxylate salt, indicating a copolymer of TFE and CF2=CFCFzO(CF2)4CO2 K~.
A four-inch diameter sample of the 4-5 mil film was inserted as the ion-exchange membrane in a chlor-alkali - cell operated at 2.0 amps/ln2, and the following results were obtained in a 76 day test:

Sodium Hydroxide Current Efficiency Cell Voltage Da.vProduct (~ ) (volts) 1 37.1 93.3 4.02 39.2 90.9 4.60 39.4 ~7.7 4-25 32.9. 92.0 4.11 76 34.6 85.8 4.67 The application is a division of copending Canadian Application Serial No. 292 106, filed 1976 November 30.

3o

Claims (3)

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

1. An electrically conductive membrane formed of a hydrolyzed or ionized copolymer of the polyfluoro-allyloxy compound having the formula wherein X is -Cl or -F;
D is -CF2R or where R4 is -COF, -CO2H, -CO2R3, -SO2F or -OCF2CO2R3 where R3 is -CH3, or -C2H5; or ?CF2)xR5 where x is 1 to 6 and R5 is -CF3 or -OCF2CF=CF2; and E is -CF2CO2R3, and at least one ethylenically unsaturated monomer, said polymer having a mole percentage of polyfluoroallyloxy comonomer of about 1.0 to 10.

2. The membrane of Claim 1 wherein the ethylenically unsaturated monomer is tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride or trifluoromethyl trifluorovinyl ether.

3. The membrane of Claim 2 wherein X is F.