CA1174685A - Polyfluoroallyloxy compounds, their preparation and copolymers therefrom - Google Patents
Polyfluoroallyloxy compounds, their preparation and copolymers therefromInfo
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- CA1174685A CA1174685A CA000292106A CA292106A CA1174685A CA 1174685 A CA1174685 A CA 1174685A CA 000292106 A CA000292106 A CA 000292106A CA 292106 A CA292106 A CA 292106A CA 1174685 A CA1174685 A CA 1174685A
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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 compounds 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.
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 compounds 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
s BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to polyfluoroallyloxy compounds, processes for their preparation and copolymers prepared therefrom.
Rela~ion to the Prior Art 1. U.S. Patent 2,856,435 to E.S. Lo discloses the prepara-tion of perfluoroallyloxy-l,l-dihydroperfluoroalkanes from 3-chloropentafluoropropene and a l,l-dihydro-perfluoroalkanol in alkaline medium, e.g.
CF2=CFCF2Cl + HOCH2CF3~ KOH 1 CF2=cFcF2ocH2cF3
Field of the Invention This invention relates to polyfluoroallyloxy compounds, processes for their preparation and copolymers prepared therefrom.
Rela~ion to the Prior Art 1. U.S. Patent 2,856,435 to E.S. Lo discloses the prepara-tion of perfluoroallyloxy-l,l-dihydroperfluoroalkanes from 3-chloropentafluoropropene and a l,l-dihydro-perfluoroalkanol in alkaline medium, e.g.
CF2=CFCF2Cl + HOCH2CF3~ KOH 1 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) wlth methoxy, cyano, iodo and nitrate groups, e.g.
CF2=CFCF2Cl + NaOCH3 ~ CF2=CFCF20CH3
CF2=CFCF2Cl + NaOCH3 ~ CF2=CFCF20CH3
3. M. E. Redwood and C. J. Willis, Canad. J: Chem., 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=CHCH20CF(CF3)2 + CsBr
CH2=CHCH2Br + (CF3)2CFO Cs+
CH2=CHCH20CF(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.
3 5. U.S. Patent 3,450,684 to R. A. Darby discloses the s preparation of fluorocarbon polyethers and their polymers by reaction of perrluoroalkanoyl fluorides with potassium or quaternary ammonium fluoride and hexaf:Luoropropene epoxide.
i.e. RfCOF + CF3-CF~-~ CF2 ~ RfiCF20CFCOF
6. U.S. Patent 3,674,820 to A. G. Pittman and W. L. Wasley discloses the reaction of fluoroketones with an alkali metal ~luoride and an omega-haloalkanoic acid ester to ~orm an omega-(perfluoroalkoxy) alkanoic acid ester, e.g.
(CF3)2CO + KF + Br(cH2?4co2cH3 (CF3)2CFO(CH2)4C02CH3 7. U.S. Patent 3,795,684 to E. Domba also discloses the reaction of hexaf'luoroacetone with potassium f'luoride 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. 3,79g,992 to A. G. Pittman and W. L. Wasley dis-closes the preparation of' (perfluoroalkoxy)vinyl compounds by reaction of a perfluoroketone with an alkali metal ~luoride and a 1,2-dihaloethane, followed by dehydro-halogenation of the intermediate 2-perrluoroalkoxyhalo-ethane.
e.g. (CF3)2CO + KF + BrCH2CH2Br - - ) (CF3)2CFOCH2CH2Br }l~r ~ (CF3)2CFOCH=CH2 10. U. S. Patent 3~321~532 to C. E. Lorenz discloses the rearran~e~ent of perfluoro-2-alkoxYalkarloyl f'luorides 7'~3S
to perfluoroalkoxyolefins by passage over a metal oxide at 100-400C, e.g.
F 300-3?5C~ CF3OCF=CF2 + ZnF2 + CO2 SUMMARY OF THE INVEN'rION
According to the present invention there is provided a polyfluoroallyloxy compound having the formula W D
CF=C-CF-O-CG
o 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, CF3-l~ \ ~ CF3 f CF2=CFCF20 0 or -RF where -RF is a linear or branched perfluoroalkyl of 1 to 10 carbon atoms, interruptable no more frequently than every second carbon atom by ~rom 1 to 4 oxygen atoms, having 0 to 2 functional groups selected from -SO2F, -COF, -CO2H, -Co2R3, -Cl -OCF2CF=CF2 and -oCF2Co2R3 where R3 is -CH3 or -C2H5 E, taken independently, is o -F, -CF3, -cF2cl~-cF2co2R3~ or ~74~5 -RFOCF(G)2 where ~ has the meaning defined above, and D and E, when taken together, form a 5-or 6-membered rlng 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 O ~ X and;
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 f ormula:
o A- C- B
wherein A, taken independently, is -F, -COCF3 or-RF 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 O to 2 functional groups selected from -SO2F, -SO20CF2CH3, -COF, -Cl, -OCF2CF=CF2, and -Co2R3 where R3is -CH3 or -C2H5, B, taken independently is ~3L74~;135 -F, -CF3, -CF2Cl, CF2Co2R3 where R3 has the meaning defined above, or -CF20Rl, 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 O to 2 substituent trifluoromethyl ;LO groups with a metal fluoride of the formula MF where M is K-, Rb-, C8-, or R4N- where each -R, allke or different, is alkyl of 1 to 6 carbon atoms; and (2) mlxing 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;
O W and Z, when taken independently, are-.F and, when taken together, are CF d ~ 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 INVENTION
~ , This invention relates to compounds of formula ~
~ prepared ~rom starting materials 1, ~ and 3 according to the O ~ollowing equation;
;
x~s W ,Z z W D
~C=C-C-F + ~F + A-C-B ~ ~C=C-C-O-C-G + MY
X Y X F E
In the above equation, starting materials 1, 2, and 3 react to give product 4 and a metal salt 5. 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 converted into useful copolymers especially with tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, and chlorotrifluoroethylene.
Preferred polyfluoroallyloxy compounds of formula 4 have D and E taken independently with D preferably being -F or RF and E preferably being -F, -CF3, -CF2C1 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, interruptable with no more than 1 oxygen atom, having ~ to 1 functional groups selected from -SO2F, -COF, -Cl, -CO2H, -Co2R3, -OCF2CF=CF2 and -oCF2Co2R3 where R3 is -CH or -C2H5.
Especially preferred polyfluoroallyloxy compounds of the invention have the formula:
CF2=C-CF2-O-CF
wherein X is -Cl or -F (preferably -F);
E is -F, -CF3, -CF2CO2R where R
is -CH3 or c2H5, or C 2 ~ ~^
1174S~35 (preferably -F, -CF3 or -CF2Co2R3) and D is -CF2R4 or CFR4 where R4 is -F -SO2F, -COF, -CO2H, CO2 -oCF2Co2R3 where R3 is -CH3 or -C2H5, or ~CF2)XR5 where x is 1 to 6 and R5 is CF3, -COF, -CO2H, -Co2R3~ -SO2F or -OCF2CF=CF2. R4 is preferably -SO2F, -COF, -CO2H or -oCF2Co2R3 where R3 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, ~. Org. Chem., 4~, 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.
,;Y,~ ~ ~
~ ~, " , ~
, Sta~le metal polyfluoroalkoxides are formed by the reaction of certain metal fluorides with polyfluorinated ketones and acid fluorides (J.A. Yo~ng, loc. cit.), thus:
3)2CO + KF _ CF3-C-O-K+
CF3COF + KF ~c~- ~ CF8-C- K
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 dis-placement will occur to form product 4. Solutions in which the equilibrium lies towards the right (high con-centration of anion) will be more effective than those in which it lies towards the lef~ ~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.N. Weidler-Xubanek and F.P. Avonda, J.
Org. Chem., 33, 1837, 1839 (1968), and M.A. Redwood and C.J. Willis, Canad. J. Chem., 4~, 389 (1967).
(1) Stable polyfluoroalkoxide anions are formed when the carbonyl compound is highly fluorinated because the electron-withdrawing effect o the fluorine atoms dis-~7~5 tributes the negatl~e charge over the entlre anion.Sub~tltutlon of aome of the fluorine by chlorine, other ~luoroalkyl group~ or hydrogen destablizes the anion because the~e group~ are less electrQn-withdrawing and the negative charge 18 not as readily accommodated. (2) Large catlons ~uch as K+, Rb+, Cs+ and ~N+ favor the formatlon of stable polyfluoroalkoxide~ more th~n small cations ~uch as Ll~ ~nd Na~ because the lattice energy of metallic fluorides i8 inverBely proportlonal to cation size. In other words, large cation slze and 8m~11 lattlce energy favors di~ruptlon of the metalllc fluorlda crystal structure to form the anion. (~) Solvent~ whlch have a high heat of solution for the polyfluoroalkoxide favor lts ~ormatlon. Aprotic polar solvents euch as N,N-dimethylformamide (DMF), acetonitrlle, and 1,2-dimethoxyethane (gigme) ~re ~ery effectl~e for thls purpose. (4) When there are fluorlne atom6 alpha to the oxygen atom ln the anion, 10BS 0~ ~luoride ion m~y compete with the desired reactions, e.g., o b c o has no a-fluorine to lose ~nd CF~ CF9 forms many stable derivatl~es.
CF3 - C - 0 re~uires a reactlve compound such as allyl bromide for nucleo-phllic substltutlon.
CF90 UBUally ell~inates F ; nucleophllic i ~ubBtltution is Xnown with per-fluoroallyl fluoro~ul~ate.
., .
~10~
1~7~5 i In ~he 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 reaction progresses. The stoichiometry of polyfluoroalk-oxide anion formation requires one molar equivalent of metal fluoride for each carbonyl group which is converted to its anion, e.g.:
(CF3)2CO + KF _ CF - C - O K
O O F F
FC(CF2)4CF + 2KF~; _ Kfo - C(CF2)4C - O K
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 hexafluoro-propene.
-~ 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.
4~rj 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 u6ually determined by how long it takes the reaction mix-ture to become homogeneous.
N,N-Dimethylformamide (DMF), acetonitrile, N,N-dimethylacetamide (DMAC), y-butyrolactone, 1,2-dimethoxyethane (glyme), l-(2-methoxyethoxy)-2-methoxy-ethane (diglyme), 2,5,8,11-tetraoxadodecane (triglyme), dioxane, sulfolane, nitrobenzene and benzonitrile are suitable, illustrative aprotic polar solvents for the preparation of polyfluoroalkoxides and their subsequent reaction with the polyfluoroallyl chloride or fluoro-sulfate. DMF, diglyme, triglyme and acetonitrile are preferred solvent~ 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 I H20 3 (RF) 2C (OH2) + F
RFCF2O + H2 RFC02H + HF2 Metal fluorides which are useful in this invention are potassium fluoride (XF), 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.
~ :~.7~
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:
(RF)2CO (RF)2,C-O-CF2CF CF~ (ketone) C=O R ~ C ~
~ O t ~ CF2cF=cF2 (lactone) RFCOF ~ RFCF2OcF2cF CF2 (acid fluoride) Polyfluorinated ketones which are useful include hexafluoroacetone, chloropentafluoroacetone, 1,3-dichlorotetrafluoroacetone, 1,1-difluoroethyl-2-oxopentafluoropropanesulfonate, dimethyltetrafluoro-acetone-1,3-dicarboxylate, 1,3-bis(2-heptafluoropropoxy) tetrafluoropropanone, 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 perfluoroakoxide reacts both with perfluoroallyl fluorosulfate and with ~7'~8S
another molar equivalent of hexafluoro-2,3-butanedione to form a mixture of two heterocyclic compounds.
Polyfluorinated acid fluorides which are useful include carbonyl fluoride, trifluoroacetyl fluoride, pentafluoropropionyl fluoride, heptafluorobutyroyl fluorîde, nonafluoropentanoyl fluoride, tetrafluorodiglycolyl O O
~ CCF20CF2CF, undecafluorohexanoyl fluoride tridecafluoroheptanoyl fluoride, pentadecafluorooctanoyl fluoride, heptadecafluorononanoyl fluoride, nonadecafluoro-decanoyl fluoride, difluoromalonyl difluoride, tetra-fluorosuccinyl difluoride, hexafluoropropane-1,3-dioyl difluoride (hexafluoroglutaryl difluoride), octafluorobutane-1,4-dioyl difluoride (octafluoroadipoyl difluoride), decafluoropentane-1,5-dioyl difluoride (decafluoropimely~ difluoride), dodecafluorohexane-l, 6-dioyl difluoride (dodecafluorosuberyl difluoride), fluorosulfonyldifluoroacetyl fluoride, 2-(fluorosulfonyl)-tetrafluoropropionyl fluoride, 2- U-hePtafluoroproPoxy)-tetrafluoropropio~yl fluoride, 2-[?-(1-heptafluoropropoxy) hexafluoropropoxy]tetrafluoropropionyl fluoride, and 2- ~2-[2-(1-heptafluoropropoxy)hexafluoropropoxy]hexa-fluoropropoxy~ tetrafluoropropionyl fluoride, carbomethoxy-di.fluoroacetyl fluoride.
The ketone l,l-difluoroethyl 2-oxopentafluoro-propanesulfonate (Example 3) is a special case as a start-in~ material because it is an in situ source of 2-oxopenta-fluoropropanesulfonyl fluoride since the latter has not been isolated.
:~ ~.'7~ 35 CF3cocF2so2ocF2cH3 - ~- [CF3COCF2S02F] ~
FS02CF2CFOCF2CF=CF2 Many of the above starting materials are commercially available, e.g. PCR, Gainesville, Florida is a supplier of fluorinated ketones and carboxylic acids.
Examples 2, 3, 4, 5, 7, 9, lO, ll, 12, 13, 16 and l9 give sources and methods of preparation of some compounds which are not commercially available. Generally, perfluoroketones can be prepared from the esters of perfluoroalkanecarboxylic acids and from the reaction of carbonyl fluoride with perfluoroalkenes (W.A. Sheppard and C.M. Sharts, "Orgar.ic Fluorine Chemistryn, p. 365-368, W.A. Benjamin, New York, 1969, H.P. Braendlin and E.T. McBee, Advances in Fluorine Chemistry, 3, l (1963)). Perfluoroalkane-carboxylic acid fluorides and perfluoroalkane-a,~-di-carboxylic acid difluorides are prepared by treatment 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 alkanecarboxylic acids in hydrogen fluoride (M. Hudlicky, "Chemistry of Fluorine Compounds", p. 86, MacMillan Co., New York, 1962). Perfluoroalkanedicarboxylic acids are prepared by oxidation of fluorinated ~ dialkenes or fluorinated cycloalkenes (Hudlick'y, 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~
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 or fluorosulfate requires one molar equivalent of this reagent for each reactive ce~ter in the polyfluoroalkoxide anion. With a difunctional poly-fluoroalkoxide, however, the stoichiometry can be adjusted to give ei~her the mono- or the di-substitution product, thus:
O O O
n 2CF I KF + CF2=CFCF20S02F ~ FCCF2CF2OCF2CF CF2 ~Example 5) O O
FCCF2CF + 2KF ~ 2cF2=cFcF2oso2F____~ (CF2=CFCF20CF2)2CF2 (Example 17) FCO(CF2)4COF + KF + CF2 = CFCF2OSO2F~ CF2 = CFCF2O(CF~)5COF
(Examples 21, 22) FCO(CF2)4COF + 2KF + 2CF2 = CFCF20S02F~ (CF2=~r~20CP2OE2 2)2 (Example 13) The formation of the Dolyfluoroalkoxide and its subsequent reaction with the polyfluoroallyl chloride or fluorosulfate can be carried out sequentially without isolation of intermediates in glass apparatus at atmos-pheric 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 ~ 7~6~35 mixtures) serves to moderate the reactions and facilitate the retention of volatile reaqents and products. The progress of the displacement reaction is conveniently followed by the appearance of a precipitate of the salt MY (5), by gas liqu~d partition chromatography (.glpc) and by fluorine nuclear magnetic resonance spectroscopy (19F 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 or fluorosulfate, and is then allowed to warm up to 25C to 30C for the remainder of the reaction time.
The time required to com?lete 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 ro~m 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 then 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 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 f`ree of solvent with more water, dried, and fractionally distilled from phosphorus pentoxide or concentrated sulfuric acid.
The polyfluoroallyloxy compounds of this inventlon 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, trifluoroethylene, 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 trlfluorovinyl ether, hexafluoropropylene and vinylidene fluoride. Such copolymers have either more desirable or entirely new properties not possessed by e.g., poly(tetrafluoro-ethylene), 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 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 per-cent (about 1-25 mole percent) of polyfluoroallyloxy comonomer have lower melting points than the corresponding polyfluoro-~4~S
olefins, and consequently are more readily molded and shaped into useful objects. Copolymers which contain from about 0.1-10 weight percent, preferably about l-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 C02H 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. Copolymers which contain from about 5 to 35 weight percent (about 1.0 to 10 mole percent) of a polyfluoroallyloxy conomomer with pendant SO2~' or COF groups can also be partially or essentially completely hydrolyzed to a copolymer bearing hydrophilic SO20H and CO2H
groups. Such a copolymer has an affinity for water and is water~
wettable. Polyfluoroolefins 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 co-monomer bearing -SO2OH or -CO2H groups or ionized forms thereof; e.g. -SO2O Na or C02 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 Or two or more polymers each derived from the respective mono-mers but a new material incorporating each monomer. It is well known thatthe 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 ;0 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 Radlcals 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.
- 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 o~ 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), .
4~
azobisisobutyronitrile, ultraviolet irradiation andammonium or potassium persulfate; mixtures of iron (II) sulfate wlth hydro~en 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 persulfa~e. 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 sodiumor 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 such as disodium hydrogen phosphate, sodium metaborate, or ammonium metaborate to the amount of about 1 to 4 weight percent 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-tric~loro-) 1,2,2-trifluoroe~hane (~reon~ 113) solvent ~o~ nlt -~7~5 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 washlng 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 ls deslred 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. For structure confirmation analyses~ fluorine nuclear magnetic resonance chemical shifts are in parts per million from internal ~luorotrichloromethane, and proton nuclear magnetic resonance chemical shifts are in parts per million ~rom internal tetramethylsilane. Infrared and nuclear magnetic resonance spectra were recorded on undiluted liquid samples unless otherwise stated.
l-(H~pt~f~lloro-2-r)ropoxy)~ 3~3-t~t;rafluoro-2-chloro-2-propene 3 (CF9)~CO + KF + CF2~CClCF2Cl- ~ (CF9~2CFOCF~CCl3CF2 Hexafluoroacetone (16.6 ~, 0.10 mol) was dis-tilled into a stirred mixture of potassium fluoride (5.80 g, 0.10 mol) and 1-(2-methoxyethoxy)-2-methoxyethane (here-inafter referred to as diglyme) (100 ml) to give a homo-geneous solution. This mixture was maintained 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 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); 19F NMR, -64.9 (m) 2F, -OCF2CzC; -76.0 (2nd order m) 2F, C=CF2; -81.2 (t ~ = 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 C ClF O: C, 21.67; Cl, 10.66 6 Fo ~ d: C, 21.43; Cl, 10.89 1-(1,1,1,2,3,3-Hexafluoro-3-chloro-2-propoxy)-pentafluoro-2-~ro~ene A. Pentafluoro-2-propenyl fluorosulfate (Perfluoroallyl fluorosulfate) CF3CF = CF2 + SO3 ~ CF2 - CIF CF3 I CF2=C~-CF2OSO2F
~ ~ 7~ S
A mixture o~ commerci~l llquld sulrur trioxid~
(10 ml) and hexafluoropropene (45 g, 0.30 mol) was sealed ln a Carlus tube at llquld nltrogen temperature, mixed well at 25-C, allowed to stand for 4 days at 25-C, and finally heated in a ~team bath ~or 6 hours. From two such tube6, there was obtained by distillatlon, ~-(trifluoro-methyl)-3,4,4-trifluoro-1-oxa-2-thiacyclobutane 2,2-dloxide (2-hydroxy-1-trifluoromethyl-1,2,2-trifluoroethano sulfonic acid sultone, ~. C. England, M. A. Dietrlch and R. V. Lindsey, Jr., J. Amer. Chem. Soc,. 82, 6181 (1960)) (25 g, 22%) bp 44~C, and pentafluoro-2-propenyl fluoro-sulfate (hereinafter referred to as perfluoroallyl ~luoro-sulfate) (7~ g, 6~%), bp 58-60-C.
Perfluoroallyl fluorosulfate is char~cterlzed by: ~max 5.55 (C.C) and 6,75 ~m (SO~); 9F NMR, 46.1 (t J - ô.5 Hz, each member d J - 1.8 Hz) lF, SO2F, -74.0 (d J = 28.2 ~z, each member d J 3 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 3 119.4 Hz, each member d J = 40.5 Hz, t J -1~.9 Hz, d J = 1.8 Hz) lF.
B. 1-(1,1,1,2,3,3-Hexa~luoro-3-chloro-2-propoxy)-pentafluoro-2-ProPene .
CF3COCFzCl + KF ~ CF~=CFCFzOSO2F
CF2Cl CF3CFOCF2CF=CF2 A ~u~penslon of potn~slum fluorlde (5.80 g, 0.10 mol) and dlglyme (100 ml) was ~tlrred at 20-C ln a 1~7~35 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 pro-duct was distilled from phosphorus pentoxide to give 1-~1,1,1,2,3,3-hexafluoro-3-chloro-2-propoxy)-pentafluoro-2-propene, (19.6 g, 0~059 mol, 59~o)bp 85-86~C which was characterized by: ~max 5. 55 (CF = CF2) and 7-10 ~m (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-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 20 member d J = 39.8 Hz, t J = 13.4 Hz) lF, -CF2CF=C.
Anal. Calcd for C6ClFl O: C, 21.67; Cl, 10.66 Fou~d: C, 21.34; Cl, 10.21 ~. ' .
7L1 ~6~3 5 :
2-(1-Pentafluoro-2-propenyloxy)hexafluoropropane-1-~ul~onyl fluorlde (2-Perfluoroallyloxypropane~ ulfonyl ~luoride) .. . ... . . _ . .
A, 2-Ox.openta~luorop-rop-a-nesul~o-ni--c Acid CF3C-CF2 + SO3 - ----- ~ CF3CCFzSO20C~Hs + CF3BCF,~SO20H
O O
Il 11 CF3CCFrSO~OC2Hs + CF3C02H > CF3CCFaSO~OH +
. 10 - CF3COzC2H5 (i) Dropwise additlon of sulfur trioxide (12.8 g, 0.16 - mol) to 2-ethoxy-1,1,3,3,3-pentafluoropropene (D. W Wiley and H. E. Simmions, J, Ore. Chem.. 29, 1876 (1964)) (29.0 g, 0.165 mol) produced ~n exo-thermic reaction. me black reaction mixture was dlstilled to give recovered 2-eth~xy-1,1,3,3,3-pentafluoropropene (6.3 g, o.o36 mol, 22~, identified by ir) ~nd ethyl 2-oxopentarluoropropaneiulfonate (20.2 g, 0.078 mol, 49% con~er~lon and 63% yield) `~ bp 47-48C (12 mm Hg): ~max 3.~4 and 3.41 (saturated ;
CH~, 5.60 (C - O), 7.09 (SO?O), and 7.6-8.5 ~m (C-F, S02 ); H NMR, ~ 4.59 (q J ~ 7.2 Hz) 2H, OCH2 and 1.51 ppm (t J 2 7.2 Hz) 3H, C~3; 19F
NMR, -75.0 (t J = 8.3 Hz) 3F, CF3, and -107.4 ppm (~ J = 8.3 Hz) 2F, CF2, (ii) The above reaction was repeated at 0-5-C wlth sulfur trioxide (88 g, 1.1 mol) and 2-ethoxy-1,1,3,3,3-pentarluoropropene (176 g, 1.0 mol). The colorle~s ~1746Z 3~
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 fxaction 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 ~.2 (broad) (SOH), 5.58 (C=O), 7.13 (SO2O) and 7.5 - 9 ~m (CF, SO2); lH NMR ~ 10.2 ppm (s) S020H; 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,HF504S: C, 15.80; H, 0.44; 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
ll ll CF3CCF2S020H + CF2 CH2 ~ CF3CCF2S020CF2CH3 t~
~7~35 A metal tube containing 2-oxopentafluoropropane-sulfonic acid (23.8 g, 0.10 mol) was cooled below -40C and vinylidene fluoride (l,l-difluoroethene) (13 g, 0.20 mol) was added. The mixture was shaken and warmed to 25C where it was kept for 4 hours. Dis-tillation of the liquid product gave 20.4 g (0.07 mol, 70~) of l,l-difluoroethyl 2-oxopentafluoropropanesul-fonate, bp 62-63C (50 mm Hg): ~max (CC14) 5.54 (C=O), 6.96 (SO2O) and 7.5 - 9 ~m (CF, SO2); lH 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, CF2 S2 ~
Anal. Calcd for C H F O S: C, 20.56; H, 1.03; F, 45.52
References 5-9 which follow are examples of the nucleophilic reactions of perfluoroalkoxide anions.
3 5. U.S. Patent 3,450,684 to R. A. Darby discloses the s preparation of fluorocarbon polyethers and their polymers by reaction of perrluoroalkanoyl fluorides with potassium or quaternary ammonium fluoride and hexaf:Luoropropene epoxide.
i.e. RfCOF + CF3-CF~-~ CF2 ~ RfiCF20CFCOF
6. U.S. Patent 3,674,820 to A. G. Pittman and W. L. Wasley discloses the reaction of fluoroketones with an alkali metal ~luoride and an omega-haloalkanoic acid ester to ~orm an omega-(perfluoroalkoxy) alkanoic acid ester, e.g.
(CF3)2CO + KF + Br(cH2?4co2cH3 (CF3)2CFO(CH2)4C02CH3 7. U.S. Patent 3,795,684 to E. Domba also discloses the reaction of hexaf'luoroacetone with potassium f'luoride 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. 3,79g,992 to A. G. Pittman and W. L. Wasley dis-closes the preparation of' (perfluoroalkoxy)vinyl compounds by reaction of a perfluoroketone with an alkali metal ~luoride and a 1,2-dihaloethane, followed by dehydro-halogenation of the intermediate 2-perrluoroalkoxyhalo-ethane.
e.g. (CF3)2CO + KF + BrCH2CH2Br - - ) (CF3)2CFOCH2CH2Br }l~r ~ (CF3)2CFOCH=CH2 10. U. S. Patent 3~321~532 to C. E. Lorenz discloses the rearran~e~ent of perfluoro-2-alkoxYalkarloyl f'luorides 7'~3S
to perfluoroalkoxyolefins by passage over a metal oxide at 100-400C, e.g.
F 300-3?5C~ CF3OCF=CF2 + ZnF2 + CO2 SUMMARY OF THE INVEN'rION
According to the present invention there is provided a polyfluoroallyloxy compound having the formula W D
CF=C-CF-O-CG
o 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, CF3-l~ \ ~ CF3 f CF2=CFCF20 0 or -RF where -RF is a linear or branched perfluoroalkyl of 1 to 10 carbon atoms, interruptable no more frequently than every second carbon atom by ~rom 1 to 4 oxygen atoms, having 0 to 2 functional groups selected from -SO2F, -COF, -CO2H, -Co2R3, -Cl -OCF2CF=CF2 and -oCF2Co2R3 where R3 is -CH3 or -C2H5 E, taken independently, is o -F, -CF3, -cF2cl~-cF2co2R3~ or ~74~5 -RFOCF(G)2 where ~ has the meaning defined above, and D and E, when taken together, form a 5-or 6-membered rlng 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 O ~ X and;
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 f ormula:
o A- C- B
wherein A, taken independently, is -F, -COCF3 or-RF 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 O to 2 functional groups selected from -SO2F, -SO20CF2CH3, -COF, -Cl, -OCF2CF=CF2, and -Co2R3 where R3is -CH3 or -C2H5, B, taken independently is ~3L74~;135 -F, -CF3, -CF2Cl, CF2Co2R3 where R3 has the meaning defined above, or -CF20Rl, 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 O to 2 substituent trifluoromethyl ;LO groups with a metal fluoride of the formula MF where M is K-, Rb-, C8-, or R4N- where each -R, allke or different, is alkyl of 1 to 6 carbon atoms; and (2) mlxing 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;
O W and Z, when taken independently, are-.F and, when taken together, are CF d ~ 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 INVENTION
~ , This invention relates to compounds of formula ~
~ prepared ~rom starting materials 1, ~ and 3 according to the O ~ollowing equation;
;
x~s W ,Z z W D
~C=C-C-F + ~F + A-C-B ~ ~C=C-C-O-C-G + MY
X Y X F E
In the above equation, starting materials 1, 2, and 3 react to give product 4 and a metal salt 5. 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 converted into useful copolymers especially with tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, and chlorotrifluoroethylene.
Preferred polyfluoroallyloxy compounds of formula 4 have D and E taken independently with D preferably being -F or RF and E preferably being -F, -CF3, -CF2C1 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, interruptable with no more than 1 oxygen atom, having ~ to 1 functional groups selected from -SO2F, -COF, -Cl, -CO2H, -Co2R3, -OCF2CF=CF2 and -oCF2Co2R3 where R3 is -CH or -C2H5.
Especially preferred polyfluoroallyloxy compounds of the invention have the formula:
CF2=C-CF2-O-CF
wherein X is -Cl or -F (preferably -F);
E is -F, -CF3, -CF2CO2R where R
is -CH3 or c2H5, or C 2 ~ ~^
1174S~35 (preferably -F, -CF3 or -CF2Co2R3) and D is -CF2R4 or CFR4 where R4 is -F -SO2F, -COF, -CO2H, CO2 -oCF2Co2R3 where R3 is -CH3 or -C2H5, or ~CF2)XR5 where x is 1 to 6 and R5 is CF3, -COF, -CO2H, -Co2R3~ -SO2F or -OCF2CF=CF2. R4 is preferably -SO2F, -COF, -CO2H or -oCF2Co2R3 where R3 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, ~. Org. Chem., 4~, 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.
,;Y,~ ~ ~
~ ~, " , ~
, Sta~le metal polyfluoroalkoxides are formed by the reaction of certain metal fluorides with polyfluorinated ketones and acid fluorides (J.A. Yo~ng, loc. cit.), thus:
3)2CO + KF _ CF3-C-O-K+
CF3COF + KF ~c~- ~ CF8-C- K
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 dis-placement will occur to form product 4. Solutions in which the equilibrium lies towards the right (high con-centration of anion) will be more effective than those in which it lies towards the lef~ ~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.N. Weidler-Xubanek and F.P. Avonda, J.
Org. Chem., 33, 1837, 1839 (1968), and M.A. Redwood and C.J. Willis, Canad. J. Chem., 4~, 389 (1967).
(1) Stable polyfluoroalkoxide anions are formed when the carbonyl compound is highly fluorinated because the electron-withdrawing effect o the fluorine atoms dis-~7~5 tributes the negatl~e charge over the entlre anion.Sub~tltutlon of aome of the fluorine by chlorine, other ~luoroalkyl group~ or hydrogen destablizes the anion because the~e group~ are less electrQn-withdrawing and the negative charge 18 not as readily accommodated. (2) Large catlons ~uch as K+, Rb+, Cs+ and ~N+ favor the formatlon of stable polyfluoroalkoxide~ more th~n small cations ~uch as Ll~ ~nd Na~ because the lattice energy of metallic fluorides i8 inverBely proportlonal to cation size. In other words, large cation slze and 8m~11 lattlce energy favors di~ruptlon of the metalllc fluorlda crystal structure to form the anion. (~) Solvent~ whlch have a high heat of solution for the polyfluoroalkoxide favor lts ~ormatlon. Aprotic polar solvents euch as N,N-dimethylformamide (DMF), acetonitrlle, and 1,2-dimethoxyethane (gigme) ~re ~ery effectl~e for thls purpose. (4) When there are fluorlne atom6 alpha to the oxygen atom ln the anion, 10BS 0~ ~luoride ion m~y compete with the desired reactions, e.g., o b c o has no a-fluorine to lose ~nd CF~ CF9 forms many stable derivatl~es.
CF3 - C - 0 re~uires a reactlve compound such as allyl bromide for nucleo-phllic substltutlon.
CF90 UBUally ell~inates F ; nucleophllic i ~ubBtltution is Xnown with per-fluoroallyl fluoro~ul~ate.
., .
~10~
1~7~5 i In ~he 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 reaction progresses. The stoichiometry of polyfluoroalk-oxide anion formation requires one molar equivalent of metal fluoride for each carbonyl group which is converted to its anion, e.g.:
(CF3)2CO + KF _ CF - C - O K
O O F F
FC(CF2)4CF + 2KF~; _ Kfo - C(CF2)4C - O K
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 hexafluoro-propene.
-~ 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.
4~rj 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 u6ually determined by how long it takes the reaction mix-ture to become homogeneous.
N,N-Dimethylformamide (DMF), acetonitrile, N,N-dimethylacetamide (DMAC), y-butyrolactone, 1,2-dimethoxyethane (glyme), l-(2-methoxyethoxy)-2-methoxy-ethane (diglyme), 2,5,8,11-tetraoxadodecane (triglyme), dioxane, sulfolane, nitrobenzene and benzonitrile are suitable, illustrative aprotic polar solvents for the preparation of polyfluoroalkoxides and their subsequent reaction with the polyfluoroallyl chloride or fluoro-sulfate. DMF, diglyme, triglyme and acetonitrile are preferred solvent~ 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 I H20 3 (RF) 2C (OH2) + F
RFCF2O + H2 RFC02H + HF2 Metal fluorides which are useful in this invention are potassium fluoride (XF), 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.
~ :~.7~
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:
(RF)2CO (RF)2,C-O-CF2CF CF~ (ketone) C=O R ~ C ~
~ O t ~ CF2cF=cF2 (lactone) RFCOF ~ RFCF2OcF2cF CF2 (acid fluoride) Polyfluorinated ketones which are useful include hexafluoroacetone, chloropentafluoroacetone, 1,3-dichlorotetrafluoroacetone, 1,1-difluoroethyl-2-oxopentafluoropropanesulfonate, dimethyltetrafluoro-acetone-1,3-dicarboxylate, 1,3-bis(2-heptafluoropropoxy) tetrafluoropropanone, 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 perfluoroakoxide reacts both with perfluoroallyl fluorosulfate and with ~7'~8S
another molar equivalent of hexafluoro-2,3-butanedione to form a mixture of two heterocyclic compounds.
Polyfluorinated acid fluorides which are useful include carbonyl fluoride, trifluoroacetyl fluoride, pentafluoropropionyl fluoride, heptafluorobutyroyl fluorîde, nonafluoropentanoyl fluoride, tetrafluorodiglycolyl O O
~ CCF20CF2CF, undecafluorohexanoyl fluoride tridecafluoroheptanoyl fluoride, pentadecafluorooctanoyl fluoride, heptadecafluorononanoyl fluoride, nonadecafluoro-decanoyl fluoride, difluoromalonyl difluoride, tetra-fluorosuccinyl difluoride, hexafluoropropane-1,3-dioyl difluoride (hexafluoroglutaryl difluoride), octafluorobutane-1,4-dioyl difluoride (octafluoroadipoyl difluoride), decafluoropentane-1,5-dioyl difluoride (decafluoropimely~ difluoride), dodecafluorohexane-l, 6-dioyl difluoride (dodecafluorosuberyl difluoride), fluorosulfonyldifluoroacetyl fluoride, 2-(fluorosulfonyl)-tetrafluoropropionyl fluoride, 2- U-hePtafluoroproPoxy)-tetrafluoropropio~yl fluoride, 2-[?-(1-heptafluoropropoxy) hexafluoropropoxy]tetrafluoropropionyl fluoride, and 2- ~2-[2-(1-heptafluoropropoxy)hexafluoropropoxy]hexa-fluoropropoxy~ tetrafluoropropionyl fluoride, carbomethoxy-di.fluoroacetyl fluoride.
The ketone l,l-difluoroethyl 2-oxopentafluoro-propanesulfonate (Example 3) is a special case as a start-in~ material because it is an in situ source of 2-oxopenta-fluoropropanesulfonyl fluoride since the latter has not been isolated.
:~ ~.'7~ 35 CF3cocF2so2ocF2cH3 - ~- [CF3COCF2S02F] ~
FS02CF2CFOCF2CF=CF2 Many of the above starting materials are commercially available, e.g. PCR, Gainesville, Florida is a supplier of fluorinated ketones and carboxylic acids.
Examples 2, 3, 4, 5, 7, 9, lO, ll, 12, 13, 16 and l9 give sources and methods of preparation of some compounds which are not commercially available. Generally, perfluoroketones can be prepared from the esters of perfluoroalkanecarboxylic acids and from the reaction of carbonyl fluoride with perfluoroalkenes (W.A. Sheppard and C.M. Sharts, "Orgar.ic Fluorine Chemistryn, p. 365-368, W.A. Benjamin, New York, 1969, H.P. Braendlin and E.T. McBee, Advances in Fluorine Chemistry, 3, l (1963)). Perfluoroalkane-carboxylic acid fluorides and perfluoroalkane-a,~-di-carboxylic acid difluorides are prepared by treatment 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 alkanecarboxylic acids in hydrogen fluoride (M. Hudlicky, "Chemistry of Fluorine Compounds", p. 86, MacMillan Co., New York, 1962). Perfluoroalkanedicarboxylic acids are prepared by oxidation of fluorinated ~ dialkenes or fluorinated cycloalkenes (Hudlick'y, 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~
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 or fluorosulfate requires one molar equivalent of this reagent for each reactive ce~ter in the polyfluoroalkoxide anion. With a difunctional poly-fluoroalkoxide, however, the stoichiometry can be adjusted to give ei~her the mono- or the di-substitution product, thus:
O O O
n 2CF I KF + CF2=CFCF20S02F ~ FCCF2CF2OCF2CF CF2 ~Example 5) O O
FCCF2CF + 2KF ~ 2cF2=cFcF2oso2F____~ (CF2=CFCF20CF2)2CF2 (Example 17) FCO(CF2)4COF + KF + CF2 = CFCF2OSO2F~ CF2 = CFCF2O(CF~)5COF
(Examples 21, 22) FCO(CF2)4COF + 2KF + 2CF2 = CFCF20S02F~ (CF2=~r~20CP2OE2 2)2 (Example 13) The formation of the Dolyfluoroalkoxide and its subsequent reaction with the polyfluoroallyl chloride or fluorosulfate can be carried out sequentially without isolation of intermediates in glass apparatus at atmos-pheric 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 ~ 7~6~35 mixtures) serves to moderate the reactions and facilitate the retention of volatile reaqents and products. The progress of the displacement reaction is conveniently followed by the appearance of a precipitate of the salt MY (5), by gas liqu~d partition chromatography (.glpc) and by fluorine nuclear magnetic resonance spectroscopy (19F 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 or fluorosulfate, and is then allowed to warm up to 25C to 30C for the remainder of the reaction time.
The time required to com?lete 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 ro~m 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 then 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 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 f`ree of solvent with more water, dried, and fractionally distilled from phosphorus pentoxide or concentrated sulfuric acid.
The polyfluoroallyloxy compounds of this inventlon 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, trifluoroethylene, 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 trlfluorovinyl ether, hexafluoropropylene and vinylidene fluoride. Such copolymers have either more desirable or entirely new properties not possessed by e.g., poly(tetrafluoro-ethylene), 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 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 per-cent (about 1-25 mole percent) of polyfluoroallyloxy comonomer have lower melting points than the corresponding polyfluoro-~4~S
olefins, and consequently are more readily molded and shaped into useful objects. Copolymers which contain from about 0.1-10 weight percent, preferably about l-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 C02H 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. Copolymers which contain from about 5 to 35 weight percent (about 1.0 to 10 mole percent) of a polyfluoroallyloxy conomomer with pendant SO2~' or COF groups can also be partially or essentially completely hydrolyzed to a copolymer bearing hydrophilic SO20H and CO2H
groups. Such a copolymer has an affinity for water and is water~
wettable. Polyfluoroolefins 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 co-monomer bearing -SO2OH or -CO2H groups or ionized forms thereof; e.g. -SO2O Na or C02 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 Or two or more polymers each derived from the respective mono-mers but a new material incorporating each monomer. It is well known thatthe 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 ;0 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 Radlcals 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.
- 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 o~ 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), .
4~
azobisisobutyronitrile, ultraviolet irradiation andammonium or potassium persulfate; mixtures of iron (II) sulfate wlth hydro~en 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 persulfa~e. 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 sodiumor 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 such as disodium hydrogen phosphate, sodium metaborate, or ammonium metaborate to the amount of about 1 to 4 weight percent 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-tric~loro-) 1,2,2-trifluoroe~hane (~reon~ 113) solvent ~o~ nlt -~7~5 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 washlng 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 ls deslred 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. For structure confirmation analyses~ fluorine nuclear magnetic resonance chemical shifts are in parts per million from internal ~luorotrichloromethane, and proton nuclear magnetic resonance chemical shifts are in parts per million ~rom internal tetramethylsilane. Infrared and nuclear magnetic resonance spectra were recorded on undiluted liquid samples unless otherwise stated.
l-(H~pt~f~lloro-2-r)ropoxy)~ 3~3-t~t;rafluoro-2-chloro-2-propene 3 (CF9)~CO + KF + CF2~CClCF2Cl- ~ (CF9~2CFOCF~CCl3CF2 Hexafluoroacetone (16.6 ~, 0.10 mol) was dis-tilled into a stirred mixture of potassium fluoride (5.80 g, 0.10 mol) and 1-(2-methoxyethoxy)-2-methoxyethane (here-inafter referred to as diglyme) (100 ml) to give a homo-geneous solution. This mixture was maintained 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 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); 19F NMR, -64.9 (m) 2F, -OCF2CzC; -76.0 (2nd order m) 2F, C=CF2; -81.2 (t ~ = 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 C ClF O: C, 21.67; Cl, 10.66 6 Fo ~ d: C, 21.43; Cl, 10.89 1-(1,1,1,2,3,3-Hexafluoro-3-chloro-2-propoxy)-pentafluoro-2-~ro~ene A. Pentafluoro-2-propenyl fluorosulfate (Perfluoroallyl fluorosulfate) CF3CF = CF2 + SO3 ~ CF2 - CIF CF3 I CF2=C~-CF2OSO2F
~ ~ 7~ S
A mixture o~ commerci~l llquld sulrur trioxid~
(10 ml) and hexafluoropropene (45 g, 0.30 mol) was sealed ln a Carlus tube at llquld nltrogen temperature, mixed well at 25-C, allowed to stand for 4 days at 25-C, and finally heated in a ~team bath ~or 6 hours. From two such tube6, there was obtained by distillatlon, ~-(trifluoro-methyl)-3,4,4-trifluoro-1-oxa-2-thiacyclobutane 2,2-dloxide (2-hydroxy-1-trifluoromethyl-1,2,2-trifluoroethano sulfonic acid sultone, ~. C. England, M. A. Dietrlch and R. V. Lindsey, Jr., J. Amer. Chem. Soc,. 82, 6181 (1960)) (25 g, 22%) bp 44~C, and pentafluoro-2-propenyl fluoro-sulfate (hereinafter referred to as perfluoroallyl ~luoro-sulfate) (7~ g, 6~%), bp 58-60-C.
Perfluoroallyl fluorosulfate is char~cterlzed by: ~max 5.55 (C.C) and 6,75 ~m (SO~); 9F NMR, 46.1 (t J - ô.5 Hz, each member d J - 1.8 Hz) lF, SO2F, -74.0 (d J = 28.2 ~z, each member d J 3 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 3 119.4 Hz, each member d J = 40.5 Hz, t J -1~.9 Hz, d J = 1.8 Hz) lF.
B. 1-(1,1,1,2,3,3-Hexa~luoro-3-chloro-2-propoxy)-pentafluoro-2-ProPene .
CF3COCFzCl + KF ~ CF~=CFCFzOSO2F
CF2Cl CF3CFOCF2CF=CF2 A ~u~penslon of potn~slum fluorlde (5.80 g, 0.10 mol) and dlglyme (100 ml) was ~tlrred at 20-C ln a 1~7~35 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 pro-duct was distilled from phosphorus pentoxide to give 1-~1,1,1,2,3,3-hexafluoro-3-chloro-2-propoxy)-pentafluoro-2-propene, (19.6 g, 0~059 mol, 59~o)bp 85-86~C which was characterized by: ~max 5. 55 (CF = CF2) and 7-10 ~m (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-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 20 member d J = 39.8 Hz, t J = 13.4 Hz) lF, -CF2CF=C.
Anal. Calcd for C6ClFl O: C, 21.67; Cl, 10.66 Fou~d: C, 21.34; Cl, 10.21 ~. ' .
7L1 ~6~3 5 :
2-(1-Pentafluoro-2-propenyloxy)hexafluoropropane-1-~ul~onyl fluorlde (2-Perfluoroallyloxypropane~ ulfonyl ~luoride) .. . ... . . _ . .
A, 2-Ox.openta~luorop-rop-a-nesul~o-ni--c Acid CF3C-CF2 + SO3 - ----- ~ CF3CCFzSO20C~Hs + CF3BCF,~SO20H
O O
Il 11 CF3CCFrSO~OC2Hs + CF3C02H > CF3CCFaSO~OH +
. 10 - CF3COzC2H5 (i) Dropwise additlon of sulfur trioxide (12.8 g, 0.16 - mol) to 2-ethoxy-1,1,3,3,3-pentafluoropropene (D. W Wiley and H. E. Simmions, J, Ore. Chem.. 29, 1876 (1964)) (29.0 g, 0.165 mol) produced ~n exo-thermic reaction. me black reaction mixture was dlstilled to give recovered 2-eth~xy-1,1,3,3,3-pentafluoropropene (6.3 g, o.o36 mol, 22~, identified by ir) ~nd ethyl 2-oxopentarluoropropaneiulfonate (20.2 g, 0.078 mol, 49% con~er~lon and 63% yield) `~ bp 47-48C (12 mm Hg): ~max 3.~4 and 3.41 (saturated ;
CH~, 5.60 (C - O), 7.09 (SO?O), and 7.6-8.5 ~m (C-F, S02 ); H NMR, ~ 4.59 (q J ~ 7.2 Hz) 2H, OCH2 and 1.51 ppm (t J 2 7.2 Hz) 3H, C~3; 19F
NMR, -75.0 (t J = 8.3 Hz) 3F, CF3, and -107.4 ppm (~ J = 8.3 Hz) 2F, CF2, (ii) The above reaction was repeated at 0-5-C wlth sulfur trioxide (88 g, 1.1 mol) and 2-ethoxy-1,1,3,3,3-pentarluoropropene (176 g, 1.0 mol). The colorle~s ~1746Z 3~
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 fxaction 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 ~.2 (broad) (SOH), 5.58 (C=O), 7.13 (SO2O) and 7.5 - 9 ~m (CF, SO2); lH NMR ~ 10.2 ppm (s) S020H; 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,HF504S: C, 15.80; H, 0.44; 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
ll ll CF3CCF2S020H + CF2 CH2 ~ CF3CCF2S020CF2CH3 t~
~7~35 A metal tube containing 2-oxopentafluoropropane-sulfonic acid (23.8 g, 0.10 mol) was cooled below -40C and vinylidene fluoride (l,l-difluoroethene) (13 g, 0.20 mol) was added. The mixture was shaken and warmed to 25C where it was kept for 4 hours. Dis-tillation of the liquid product gave 20.4 g (0.07 mol, 70~) of l,l-difluoroethyl 2-oxopentafluoropropanesul-fonate, bp 62-63C (50 mm Hg): ~max (CC14) 5.54 (C=O), 6.96 (SO2O) and 7.5 - 9 ~m (CF, SO2); lH 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, CF2 S2 ~
Anal. Calcd for C H F O S: C, 20.56; H, 1.03; F, 45.52
5 3Fou~d: 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 CF3CCF2SO2OCF2CH3 + KF + CF2=CFCF2OSO2F
CF3-CFOCF2CF=CF2 + CH3COF + KOSO2F
A suspension of dry potassium fluoride (5.80 g;
0.10 mol) in 2, 5, 8, ll-tetraoxadodecane (triglyme) ,;
~:~.7~ 5 ~100 ml) was stirred and cooled at 0C while l,1-difluoro-ethyl 2-oxopentafluoropropanesulfonate prepared as in Example 3B (29.2 g, 0.10 mol) was added. When the potassium fluoride had nearly all dissolved, perfluoroallyl fluoro-sulfate prepared as in Example 2A (-23.0 g, 0.10 mol) was added at 0C, and the resulting mixture was stirred at 20-26C for 3 hours. Volatile components were removed by distillation at a flask temperature of 25C and l-mm Hg pressure. The distillate was washed with cold dilute ammonium hydroxide, dried and distilled to give 2-(1-pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl fluoride (13.0 g, 0.034 mol, 34%), bp 47-48C (60 mm Hg) wh~se structure was confirmed by: ~max 5 59 (CF=CF21,
C. 2-(1-Pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl fluoride o CF3CCF2SO2OCF2CH3 + KF + CF2=CFCF2OSO2F
CF3-CFOCF2CF=CF2 + CH3COF + KOSO2F
A suspension of dry potassium fluoride (5.80 g;
0.10 mol) in 2, 5, 8, ll-tetraoxadodecane (triglyme) ,;
~:~.7~ 5 ~100 ml) was stirred and cooled at 0C while l,1-difluoro-ethyl 2-oxopentafluoropropanesulfonate prepared as in Example 3B (29.2 g, 0.10 mol) was added. When the potassium fluoride had nearly all dissolved, perfluoroallyl fluoro-sulfate prepared as in Example 2A (-23.0 g, 0.10 mol) was added at 0C, and the resulting mixture was stirred at 20-26C for 3 hours. Volatile components were removed by distillation at a flask temperature of 25C and l-mm Hg pressure. The distillate was washed with cold dilute ammonium hydroxide, dried and distilled to give 2-(1-pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl fluoride (13.0 g, 0.034 mol, 34%), bp 47-48C (60 mm Hg) wh~se structure was confirmed by: ~max 5 59 (CF=CF21,
6.80 (SO2F) and 7.5 - 10 ~m (C-F, C-O, SO2); F NMR, + 45.4 (m) lF, S02F, - 70.0 (m) 2F, OCF2, -78.0 (~uintet 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 ~08.4 (AB J = 255 Hz, 20 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, CF2CF=C.
Anal. Calcd for C Fl2O S: C, 18.96, F, 59.98; S, 8.43 6 Fou~d: 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 small amounts of hexafluoropropene and sulfuryl fluoride.
3-bis(2-HePtafluoropropox~y)-2-pentafluoropropoxy}
rPentafluoro-2-propene A, 1,3-bis(2-HePtafluoroProPox.y)tetrafluoro~o~anone ,. O O
2(CF3)2CO + KF + ClF2CCCF2Cl (CF3)2CFoCF2CCF20CF(CF3)2 ~ mixture of dry potassium ~luoride (21.0g, 0.36 mol), dry N,N-dimethylformamide (DMF) (150 ml), hexafluoro-acetone (59.8 g, 0.36 mol) and 1,3-dichlorotetrafluoro~
iLoacetone (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-boillng material wa~ redis-tilled from sulfuric acid to give 1,3-bis(2-heptafluoro-propoxy)tetrafluoropropanone (18.7 g, 0.037 mol, 21~ con-version, 3~o yield ba~ed on hexa~luoroacetone), bp 117-118C;
Ama~ (CCl~) 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) , 235 [(CF3)aCFOCFa] , 169 (C3F7) , 147 (CFaCOCFa) , 97 (CF3CO) and 69 (CF3) ; ~9F NMR, -~5.0 (d J - 21.5 Hz, each member ~20septet 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 CsFl80a: C, 21.70; F, 68.66 Found: C, 21.60; F, 68.59 ~. l-tl,:~-bis(2-HePtafluoropropox~y)-2-pentafluoropropoxy}
,.~pentafluoro-2-proPene CF9)aCFOCFaCCFaOCF(CF3)a ~ KF + CFa = CFCF~OSOaF
;, ~l CFa = CFCFaOCF[CFaOCF(CF~ )8 ~2 .
3o ~,~.7L~ 3S
A mixture of 1,3-bis(2-heptafluoropropoxy)tetra-fluoropropanone (20.0 g, 0.04 mol), diglyme ~100 ml) and potassium fluoride (2.32 g, 0.04 mol) was stirred and warmed to 55"C. 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 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-rl,3-bis(2-heptafluoropropoxy)-2-pentafluoropropoxy}-pentafluoro-2-propene (16.1 g, 0.024 mol, 62%) bp 64-67C (25 mm Hg) whose structure was con-firmed 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, CFOCF2 -81.5 (s) 12F, CF3, -93.7 (d J = 54.0 Hz, each member 20 d J = 39.6 Hz, t J = 7.8 Hz) lF, Cis-CF2 - CF = C~, -106.3 (d J = 117.4 Hz, each member d J = 54.0 Hz, t J = 23.7 Hz) lF, trans-CF2CF = 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, CF2CF - C
Anal- Calcd for C12 F24O3 C, 22-24; F~ 70.35 Found: C, 22.66; F, 70.27 s EXAMPLE _5 3-(1-Pentafluoro-2-~ropenyloxy?tetrafluoropropionyl fluoride A. Difluoromalonvl difluoride .
CH3C~CF2CF2COF > 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 10 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:
~max 1860 cm (COF~, 19F 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
., ,. "
FCCF2CF + KF + CF2=CFCF2OSO2F FCCF2CF2OCF2CF=CF2 A mixture of dry potassium fluoride ~7.5 g, 0.13 20 mol~ and diglyme (100 ml) was stirred at 10C and difluoro-malonyl difluoride from part A (18.5 g, 0.13 mol) was dis-tilled 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 tempera-ture of 32C and 4.8 mm Hg pressure. Fractionation of the distillate gave 3-(1-pentafluoro-2-propenyloxy~ tetra-fluoropropionyl fluoride (14.9 g, 0.051 mol, 39%) bp 70-71C
~, s and a small amount of higher bp material. The product struc-ture was confirmed by ~max 5.33 (COF), 5.60 (CF = CF2) and
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, CF2CF=C.
Anal. Calcd for C Fl2O S: C, 18.96, F, 59.98; S, 8.43 6 Fou~d: 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 small amounts of hexafluoropropene and sulfuryl fluoride.
3-bis(2-HePtafluoropropox~y)-2-pentafluoropropoxy}
rPentafluoro-2-propene A, 1,3-bis(2-HePtafluoroProPox.y)tetrafluoro~o~anone ,. O O
2(CF3)2CO + KF + ClF2CCCF2Cl (CF3)2CFoCF2CCF20CF(CF3)2 ~ mixture of dry potassium ~luoride (21.0g, 0.36 mol), dry N,N-dimethylformamide (DMF) (150 ml), hexafluoro-acetone (59.8 g, 0.36 mol) and 1,3-dichlorotetrafluoro~
iLoacetone (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-boillng material wa~ redis-tilled from sulfuric acid to give 1,3-bis(2-heptafluoro-propoxy)tetrafluoropropanone (18.7 g, 0.037 mol, 21~ con-version, 3~o yield ba~ed on hexa~luoroacetone), bp 117-118C;
Ama~ (CCl~) 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) , 235 [(CF3)aCFOCFa] , 169 (C3F7) , 147 (CFaCOCFa) , 97 (CF3CO) and 69 (CF3) ; ~9F NMR, -~5.0 (d J - 21.5 Hz, each member ~20septet 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 CsFl80a: C, 21.70; F, 68.66 Found: C, 21.60; F, 68.59 ~. l-tl,:~-bis(2-HePtafluoropropox~y)-2-pentafluoropropoxy}
,.~pentafluoro-2-proPene CF9)aCFOCFaCCFaOCF(CF3)a ~ KF + CFa = CFCF~OSOaF
;, ~l CFa = CFCFaOCF[CFaOCF(CF~ )8 ~2 .
3o ~,~.7L~ 3S
A mixture of 1,3-bis(2-heptafluoropropoxy)tetra-fluoropropanone (20.0 g, 0.04 mol), diglyme ~100 ml) and potassium fluoride (2.32 g, 0.04 mol) was stirred and warmed to 55"C. 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 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-rl,3-bis(2-heptafluoropropoxy)-2-pentafluoropropoxy}-pentafluoro-2-propene (16.1 g, 0.024 mol, 62%) bp 64-67C (25 mm Hg) whose structure was con-firmed 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, CFOCF2 -81.5 (s) 12F, CF3, -93.7 (d J = 54.0 Hz, each member 20 d J = 39.6 Hz, t J = 7.8 Hz) lF, Cis-CF2 - CF = C~, -106.3 (d J = 117.4 Hz, each member d J = 54.0 Hz, t J = 23.7 Hz) lF, trans-CF2CF = 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, CF2CF - C
Anal- Calcd for C12 F24O3 C, 22-24; F~ 70.35 Found: C, 22.66; F, 70.27 s EXAMPLE _5 3-(1-Pentafluoro-2-~ropenyloxy?tetrafluoropropionyl fluoride A. Difluoromalonvl difluoride .
CH3C~CF2CF2COF > 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 10 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:
~max 1860 cm (COF~, 19F 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
., ,. "
FCCF2CF + KF + CF2=CFCF2OSO2F FCCF2CF2OCF2CF=CF2 A mixture of dry potassium fluoride ~7.5 g, 0.13 20 mol~ and diglyme (100 ml) was stirred at 10C and difluoro-malonyl difluoride from part A (18.5 g, 0.13 mol) was dis-tilled 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 tempera-ture of 32C and 4.8 mm Hg pressure. Fractionation of the distillate gave 3-(1-pentafluoro-2-propenyloxy~ tetra-fluoropropionyl fluoride (14.9 g, 0.051 mol, 39%) bp 70-71C
~, s and a small amount of higher bp material. The product struc-ture 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) lP, 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 Hz, 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-eno 1 Fluoride Y
A. Tetrafluorodi~ylcolyl Chloride Cl ~ Cl F ~ ~F KMnO4 H2SO
2 2 _ ~ HO2CCF2OCF2CO2H
~SOC12 .. ..
ClCCF20CF2CCl A mixture of 307.6 g (1.46 mol) of dichlorotetra-fluorodihydrofuran, lS7.8 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. ~he .
~7~.~6~35 combined aqueous solutions were evaporated to 1500 ml, treated cold with 300 ml of conc. H2S04 and extracted continuously wlth ether for a day. The extracts were evaporated until ether was no longer evolved at 25~C (0.5 mm Hg). To the crude solid diacid, 279 g (up to 93% yield), was added 5 g (o.o6 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, until the head temperature reached 81C and no gas was being evolved. ~ractionation afforded 215.2 g (61% from dihydrofuran) ( of tetrafluorodigylcolyl chloride, bp 94-97C. Structure was confirmed by NMR: 19F -77.0 ppm (s, -CF20-).
Tetrafluorodigyco].yl chloride, bp 96.5C, has previous]y been prepared by a differ~nt route by R. E. Banks, E. D. Burling, B. A. Dodd, and K. Mullen, J. Chem. Soc. (C), 170C (1969).
B. Tetrafluorodi~lcol~l Fluoride ClCCF20C~'2bCl NaF > FCCF20CF2BF
Conversion of the diacid chloride to the correspond-ing 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 (o.885 mol) of tetrafluorodiglycolyl dichloride, 140.5 g (3.35 mol) of NaF, and 1200 ml of anhydrous acetonitrile was 3o stirred overnigllt, 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 mlxture and slow distillation afforded another fract10n, bp 35-81C. Treatment with 10 g of NaF and fraction-' ation gave another 37.0 g of difluoride product, ~p 32-33C, for ; a total of 142 g (76%).
C. ~er~uoro-3 ~-dLo~non-8-eno~Y] F]uorldc ` 10 0 0 , Il 1 FCCF20CFzCF -~ KF -~ CF2=CFCF20SO2F _~
R
'. CF2=CFCF20CF2CF20CF2CF
A mixture of 38.9 g (0.67 mol) of KF, 141.5 g (0.67 mol) of tetrafluorodlglycolyl difluoride, and 500 ml of dry diglyme was stirred for 30 mlnutes at 5C, during which time nearly all of the KF dissolved. Then 154.1 g (o.67 mole) of perfluoroallyl fluorosulfate was added rapidly at 5~C and the mixture was ~tirred at 0-5C for 3 hours, at 25~C 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` recovercd diacid fluoride, bp 32-33C, and 125.0 g (52~) of mono.lc-id f:luoride, almost all of lt 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, 1 F, COF), -72.0 (d of d of t of d, JFF 2~, 13, 13, 7.7 ~Iz, 2F, =CFCF2), -77.5 (t of d, JFF 11.5, 2.7 llz, 2 1', CF2CO2l;`), -88.o (t, J~F ]1.5 llz, 2 F, CFzOCF2C()F), 3o ~7~6~3S
-89.~ (t, JFF 12.7 Hz, 2 F, = CFCF2OCF2), -91.9 (d of d of t, JFF 52.7, 39.3, 7.7 Hz, lF, cis-CF2CF=CF), -105.3 (d of d of t, J~F 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-(1-Pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluoride FSO2CF2CF + KF + CF2=CFCF20S02F_~ FS02CF2CF20CF2CF=CF2 A suspension of potassium fluoride (5.8 g, 0.10 mol) in diglyme (100 ml) was stirred and cooled while fluoro-sulfonyldifluoroacetyl fluoride (18.0 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 perfluoro-allyl fluorosulfate prepared as in Example 2A (25.0 g, 0.11 20 mol) at 20-25C over 5 min. The mixture was stirred for 2 hours, during which time solid precipitated, and the tempera-ture 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-(1-pentafluoro-2-propeny-loxy)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 (S02F) and 30 7-10 ~m (CF,C-O,SO2); 19F NMR, +44.9 (t J = 6 Hz, each member t J = 6 Hz) lF, FSO2, - 71.8 (d J
= 25.3 Hz, each member t J = 13.8 Hz, d J = 13.8 Hz, .~
7~ S
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 Xz) 1~, trans-CF2CF=CF, -113.0 (d J
= 5.6 Hz, each member t J = 2.9 Hz) 2F, FSO2CF2, 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. Calcd for C5F10O3S: C, 18.19; F, 57.55; S, 9.71 Found: C, 18.35; F, 57.40; S, 9.69 EXP~I~LE 8 2-(1-Pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluoride o FSO2CF2CF + KF + CF2 = CFCF2OSO2F-~-- FSO2CF2CF2OCF2CF= CF2 The procedure of Example 7 was followed, sub-stituting acetonitrile for diglyme as the solvent. ~he 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 ,CF3 ,CF3 FS02CFCOF + KF + CF2=CFCF20S02F----~ FS02CFCF20CF2CF=CF2 A mixture of potassium fluoride (5.80 g, 0.10 mol) and diglyme (100 ml) was stirred at 10C while 2-fluorosulfonyltetrafluoro ropionyl 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. Ihe resulting solution -was treated at 10 with perfluoroallyl fluoro ~ fate prepared as in ! .:
1~7~8~
Example 2A, and after the addition was complete, the mi~ture was stirred at 25C for 3 hours, then it was poured into water (500 ml). The lower layer was washed with water (100 ml), dried and distilled to ~ive 1-[1-(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:
~max 5.55 ~CF=CF2), 6.78 (SO2F) and 7.5-10 um (CF,C-O,SO2);
F NMR, 54.9 (d J = 20.7 Hz, each member q of J = 10.4 Hz, d J = 3.6 Hz) lF, S02F, -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=
C_, -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 = 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 Hz) lF CF2CF=C.
Anal. Calcd for C6F12O3S: C, 18.96; F, 59.98; S, 8.44 Found: C, 18.70; F, 60.09; S, 8.08 2~ 1,2,3,4,4-Pentafluoro-2-cyclobutenyloxy)~tetra-fluoroethanesulfonyl fluoride F F
2 ~ ~SO~F 2r -OCF2CF2SO2F
+ KF ~ FCOCF2SO2F ~
, , _ ~ _ F~ F F __ ~ F
?~l~
A suspension of potassium fluoride (5.80 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)-fluorosulfate (24.2 g, 0.10 mol) (B.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-[1-(1,2,3,4,4-pentafluoro-2-cyclobutenyloxy)]tetrafluoroethane-sulfonyl fluoride (24.0 g, 0.07 mol, 70%) bp 62C (100 mm Hg).
The product structure was confirmed by:
5.53 (C~C), 6.80 (SOaF) and 8-9.5 ~m (C-F, C-O, SOa);
9F ~, 44,8 (t 7 ~ 6.0 Hz, each member t J = 6.o Hz, m) lF, SOaF~ -80,3 and -83.8 (AB J = 146 Hz, each member m) 2F, OCFaJ
-112.7 (m) 2F CF2SO~F, -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 CaF1003S: C, 21.07; S, 9.37 Found: C, 21.38; S, 9,44 .
2-(l-Pentafluoro-?-pro~en.vlox,Y-)-3~6-bis(trifluorometh~yl) 2,3,5,5,6-PentaflUOro-1,4-dioxane F F
CFa~ ~ ~ KF + CFa=CFCFa ~S2 F ~ > ~ ~Fa CFa CFa=CFCF~O ~ ~ ctFF
A mixture of potassium fluoride (5.8 g, 0,10 mol) and diglyme (100 ml) was treated at 25C with 3,6-bis-~1~4~5 (trifluoro~ethyl)-3,5,5,6-tetrafluoro-1,4-dioxan-2-one (S. Selman, U.S. Patent 3,321,517) (31.0 g, 0.10 mol). The mixture was stirred for 1 hour and then treated dropwise with perfluoroallylfluorosulfate prepared as in Example 2A
(23.0 g, 0.10 mol), the exothermic reaction being maintained at 35-40C with an external 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=CF~) and 7.5-10 ~m (CF,C-O); 19F NMR, -70.7 and -71.8 (AB J ~ 159 Hz, I each member m) 2F, OCFaC=CJ -77.3 and -87.91 (AB J = 153 Hz, each member m) 2F, ring OCF2, -81.4 (m) 4F, CF3 + OCFO, -82.4 (m) 3F, CF~, -92.3 (d J = 52.0 Hz, each member d J = 39.3 Hz, t J c 7.2 Hz) lF, cis-CF~CF=CFJ -105.3 (d J = 117.1 Hz, each member d J = 52.0 Hz, t J - 25.4 Hz) lF, trans-CF2CF=CF,-123.3, -124.7~ -126.2, -132.2, -132.9 and -134.1 (m) 2F CFsCFO, -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 of isomers were observed at -92.1, -105.3, and -190.5 ppm.
Anal. Calcd for CsF1~03: C, 23.50; F, 66.07 Found: C, 23.71; F, 66.17 3o 2-rl-~Penta~luoro-2-Propenvloxy)l-2~5~6-tetrakis(trifluor meth,vl~ -fluoro-1,4,7-trioxabicyclo[2.2.1lhep-tane and 2-[1-(pentaf:Luoro-2-Pro;pen~v~lox~v)tetrafluoroeth~vll-4-Ll-(~entafluor .
2-~ropen~lox,y)l-2.4,5-tris(trifluorometh~ fluoro-1,3-dioxolane Il 1~ 1~ 1 CFs CCCF3 + KF --------> CFa C - C - CF3 F
~. \
CF2 -CFCF;~ OSOa F \
O ~ CF3 ~C"CF3 F
/o~cF3 . CFs~
CF3~\0~0CFaCF'=CF~ CF~=CFC~/ F-OC~2C~2 A suspension of anhydrous potasslum fluoride (5.80 ~, 0.10 mol) in digl-yme (-100 ml) was stirred at 10C
while hexafluoro-2,3-butanedione (hex~fluorobiacetyl, L. O.
Moore and J. W. Clark, J. Or~._Chem " ~, 2472 (1965)) (19.4 g, 0.10 mol) was distilled in. The mixture was stir-red untll the potassium fluoride had nearly all dissolved, and the~ it,was treated rapidly wlth perfluoroallyl fluoro-sulfate prepared as in Example 2A (23-.0 g, 0.10 mol) at 15C. The slightly 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 49-54C (10 mm Hg) was shaken with concentrated sulfuric acid (8 ml), treated with anhydrous calcium sulfate and fractionated in a spinning-band still. 2-[1-(Penta~luoro-3o 2-propenyloxy)]-2,3,5,6-tetrakis(trifluoromethyl)-5-fluoro-1,4,7-trioxabicyclo[2.2.1]heptane (3.0 g, 0.0055 mol, 11%) bp 50-51C (15 mm ~g) contained one major component by glpc.
The analytical sample of this product was obtained by pre-parative glpc and its structure confirmed by:
~max 5.58 (CF=CF2), and 7.5~10 um (C-F,C-O); 19F NMR, -65.6 and -71.0 (AB J = 155 Hz, each member m), 2F, OCF2, -74.7 (m) 3F, CF3, -78.5 (m) 3F, CF3, -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-CF2CF=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-CF2CF=CF, -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, CF2-C~F=C.
Anal Calcd f~r CllF184 C, 24-55; F~ 63-55 Found: C, 24.57; F, 63.60 The second fraction was a mixture of isomers of 2-[1-(pentafluoro-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-tained only minor impurities by glpc. This product structure was confirmed by:
~max S.56 (CF=CF2) and 7-10 ~m (CF,C-O), F NMR -72.8 ppm ~AB) 2F, OCF2 -75.4, -76.8, -78.3, -78.7 and -79.1 (m) 12F, CF3, -93.1 (m) 2F cis-CF2CF=CF, -105.8 (m) 2F, trans-CF2CF=CF, -121.0, -136.5 and -141.6 (m) 2F, CF, and -190.8 ppm (m) 2F, CF2CF=C.
Anal. Calcd ~or C14 F24O4: C, 24.44; F, 66.26 Found: C, 24.73; F, 66.48 `~
S
Perfluoro-1,6-bis(2-propenyloxy)hexane O O
.. ..
FC(CF2)4CF + KF + CF2--CFCF20602F~ (CF2=CFCF2OCF2CF2CF2)2 + CF2=CFCF2O(CF2)5CO~
CF2=CFCF2O(CF2)5COF + H2O d ~ly ~ CF2=CFCF2O(CF2)5CO2H.
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 S-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.); the lower layer was washed with water (150 ml), dried and distilled to give two products.
The lower-boiling fraction was perfluoro-1,6-bis-t2-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 ~m (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.
`,~`,'`' Anal- Calcd for C12F222 C~ 24-25;
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, 0.015~ mol, 16%), bp 109-110C (5 mm Hg), formed by hydroly-sis of perfluoro-6-(2-propenyloxy)hexanoyl fluoride in the a~ueous diglyme wash solutions. This complex had ~max 3~4 (OH,C-H), 5.59 (with shoulder, C~2=C~,CO2H), and 7.2-9 ~m (CF,C-O,CH); lH NMR, ~ 11.93 (s) lH, CO2H, 3.75 (s) 4H, 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, OC~2C=C, -84.1 (m) 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, -122.6 (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 = 1.8 Hz) lF, CF2CF=C
Methyl Perfluoro-3,6-dioxanon-8-enoate CF2 C C 2 2 2 2 ~ CF2 CFCF2 C 2C 2 C 2 2C 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 of impurities. Redis-3 tillation gave somewhat more pure ester (1-2% imPurities by gc),bp 61-62C
4~5 (20 mm Hg). Structure was confirmed by Ir (neat~:
3-32, 3.37, 3.49 (CH3), 5.57 (C=O), 8-9.5~ (CF, C-O).
NMf~: H 3.95 ppm (s) with small impurities at 3.53 and ~.33 ppm;
9F -72.0 (d of d of t of d, JFF 24, 1~, 13, 7-5 Hz, 2 F, =CFCF2J, -78.o (t, JF~, ].1.6 Hz, 2 F, CF2CO2CH9), -~ .0 (t, JFF 11.6 Hz, 2 F, CF20CF2CO2CH3), -89.5 (t, JFF 12.6 Hz, 2 I', =CFCF20CE~2), -92.3 (d of d of t, JFF 53.2, 39.2, 7.5 Hz, 1 F~ eis-CF2CF=CF), -105.2 (d of d of t, JFF 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 Hz, 1 F, CF2CF=).
Anal. Calcd. for CgH F1104: C, 25.82; H, 0.81; F, 56.17 Found: C, 26.17; H, o.66; F, 56.24.
D~meth~l Perfluoro-7-allox.Y~luta.rate A. Bis(?-methox.Ytetrafluoroeth.Yl)ketone l'he synthesis of bis(2-methoxytetrafluoroethyl)-ketone from di.methyl carbonate tetrafluoroethylene, a.nd sodi.um mcthoxide has becn described by D. W. Wiley (U. S.
2,~,537 (1961)). An extension of this synthesis has given 1,3,~5-tetramethoxyoctafluoroperltane in a one-pot reaction.
o O~Na Il l CH30Na. + 2 CF2=CF2 + CH30COCH3 ~ CH3ocF2cF27cF2cF2ocH3 CH30CF2CF2C(OCH3)2CF2CE`20CH3 A mixture of 27.0 g (0.50 mol) of sodium methoxlde, 56.o g (0.62 mol) of dimethyl ca.rbonate, and 100 ml of dry tetra.hydrofuran was agitated in a ~50 ml tube under 1-~ atm of tetrafluoroethylene. Tetrafluoroethylene was pressu~ed ~l~7~5 in as consumed until ll0 g (l.l mol) had been added. The mildly exothermic reaction kept the temperature near 35C; after the addition, the reaction mixtu.re was heated at 40C for l hour.
The viscous solution from this reaction was treated directly with 75.6 g (o.60 mol) of dimethyl sulfate at 40C for 15 hours.
Filtration and distillation afforded 87.6 g (52%) of l,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).
= 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 Hz, 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-eno 1 Fluoride Y
A. Tetrafluorodi~ylcolyl Chloride Cl ~ Cl F ~ ~F KMnO4 H2SO
2 2 _ ~ HO2CCF2OCF2CO2H
~SOC12 .. ..
ClCCF20CF2CCl A mixture of 307.6 g (1.46 mol) of dichlorotetra-fluorodihydrofuran, lS7.8 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. ~he .
~7~.~6~35 combined aqueous solutions were evaporated to 1500 ml, treated cold with 300 ml of conc. H2S04 and extracted continuously wlth ether for a day. The extracts were evaporated until ether was no longer evolved at 25~C (0.5 mm Hg). To the crude solid diacid, 279 g (up to 93% yield), was added 5 g (o.o6 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, until the head temperature reached 81C and no gas was being evolved. ~ractionation afforded 215.2 g (61% from dihydrofuran) ( of tetrafluorodigylcolyl chloride, bp 94-97C. Structure was confirmed by NMR: 19F -77.0 ppm (s, -CF20-).
Tetrafluorodigyco].yl chloride, bp 96.5C, has previous]y been prepared by a differ~nt route by R. E. Banks, E. D. Burling, B. A. Dodd, and K. Mullen, J. Chem. Soc. (C), 170C (1969).
B. Tetrafluorodi~lcol~l Fluoride ClCCF20C~'2bCl NaF > FCCF20CF2BF
Conversion of the diacid chloride to the correspond-ing 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 (o.885 mol) of tetrafluorodiglycolyl dichloride, 140.5 g (3.35 mol) of NaF, and 1200 ml of anhydrous acetonitrile was 3o stirred overnigllt, 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 mlxture and slow distillation afforded another fract10n, bp 35-81C. Treatment with 10 g of NaF and fraction-' ation gave another 37.0 g of difluoride product, ~p 32-33C, for ; a total of 142 g (76%).
C. ~er~uoro-3 ~-dLo~non-8-eno~Y] F]uorldc ` 10 0 0 , Il 1 FCCF20CFzCF -~ KF -~ CF2=CFCF20SO2F _~
R
'. CF2=CFCF20CF2CF20CF2CF
A mixture of 38.9 g (0.67 mol) of KF, 141.5 g (0.67 mol) of tetrafluorodlglycolyl difluoride, and 500 ml of dry diglyme was stirred for 30 mlnutes at 5C, during which time nearly all of the KF dissolved. Then 154.1 g (o.67 mole) of perfluoroallyl fluorosulfate was added rapidly at 5~C and the mixture was ~tirred at 0-5C for 3 hours, at 25~C 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` recovercd diacid fluoride, bp 32-33C, and 125.0 g (52~) of mono.lc-id f:luoride, almost all of lt 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, 1 F, COF), -72.0 (d of d of t of d, JFF 2~, 13, 13, 7.7 ~Iz, 2F, =CFCF2), -77.5 (t of d, JFF 11.5, 2.7 llz, 2 1', CF2CO2l;`), -88.o (t, J~F ]1.5 llz, 2 F, CFzOCF2C()F), 3o ~7~6~3S
-89.~ (t, JFF 12.7 Hz, 2 F, = CFCF2OCF2), -91.9 (d of d of t, JFF 52.7, 39.3, 7.7 Hz, lF, cis-CF2CF=CF), -105.3 (d of d of t, J~F 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-(1-Pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluoride FSO2CF2CF + KF + CF2=CFCF20S02F_~ FS02CF2CF20CF2CF=CF2 A suspension of potassium fluoride (5.8 g, 0.10 mol) in diglyme (100 ml) was stirred and cooled while fluoro-sulfonyldifluoroacetyl fluoride (18.0 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 perfluoro-allyl fluorosulfate prepared as in Example 2A (25.0 g, 0.11 20 mol) at 20-25C over 5 min. The mixture was stirred for 2 hours, during which time solid precipitated, and the tempera-ture 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-(1-pentafluoro-2-propeny-loxy)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 (S02F) and 30 7-10 ~m (CF,C-O,SO2); 19F NMR, +44.9 (t J = 6 Hz, each member t J = 6 Hz) lF, FSO2, - 71.8 (d J
= 25.3 Hz, each member t J = 13.8 Hz, d J = 13.8 Hz, .~
7~ S
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 Xz) 1~, trans-CF2CF=CF, -113.0 (d J
= 5.6 Hz, each member t J = 2.9 Hz) 2F, FSO2CF2, 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. Calcd for C5F10O3S: C, 18.19; F, 57.55; S, 9.71 Found: C, 18.35; F, 57.40; S, 9.69 EXP~I~LE 8 2-(1-Pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluoride o FSO2CF2CF + KF + CF2 = CFCF2OSO2F-~-- FSO2CF2CF2OCF2CF= CF2 The procedure of Example 7 was followed, sub-stituting acetonitrile for diglyme as the solvent. ~he 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 ,CF3 ,CF3 FS02CFCOF + KF + CF2=CFCF20S02F----~ FS02CFCF20CF2CF=CF2 A mixture of potassium fluoride (5.80 g, 0.10 mol) and diglyme (100 ml) was stirred at 10C while 2-fluorosulfonyltetrafluoro ropionyl 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. Ihe resulting solution -was treated at 10 with perfluoroallyl fluoro ~ fate prepared as in ! .:
1~7~8~
Example 2A, and after the addition was complete, the mi~ture was stirred at 25C for 3 hours, then it was poured into water (500 ml). The lower layer was washed with water (100 ml), dried and distilled to ~ive 1-[1-(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:
~max 5.55 ~CF=CF2), 6.78 (SO2F) and 7.5-10 um (CF,C-O,SO2);
F NMR, 54.9 (d J = 20.7 Hz, each member q of J = 10.4 Hz, d J = 3.6 Hz) lF, S02F, -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=
C_, -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 = 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 Hz) lF CF2CF=C.
Anal. Calcd for C6F12O3S: C, 18.96; F, 59.98; S, 8.44 Found: C, 18.70; F, 60.09; S, 8.08 2~ 1,2,3,4,4-Pentafluoro-2-cyclobutenyloxy)~tetra-fluoroethanesulfonyl fluoride F F
2 ~ ~SO~F 2r -OCF2CF2SO2F
+ KF ~ FCOCF2SO2F ~
, , _ ~ _ F~ F F __ ~ F
?~l~
A suspension of potassium fluoride (5.80 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)-fluorosulfate (24.2 g, 0.10 mol) (B.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-[1-(1,2,3,4,4-pentafluoro-2-cyclobutenyloxy)]tetrafluoroethane-sulfonyl fluoride (24.0 g, 0.07 mol, 70%) bp 62C (100 mm Hg).
The product structure was confirmed by:
5.53 (C~C), 6.80 (SOaF) and 8-9.5 ~m (C-F, C-O, SOa);
9F ~, 44,8 (t 7 ~ 6.0 Hz, each member t J = 6.o Hz, m) lF, SOaF~ -80,3 and -83.8 (AB J = 146 Hz, each member m) 2F, OCFaJ
-112.7 (m) 2F CF2SO~F, -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 CaF1003S: C, 21.07; S, 9.37 Found: C, 21.38; S, 9,44 .
2-(l-Pentafluoro-?-pro~en.vlox,Y-)-3~6-bis(trifluorometh~yl) 2,3,5,5,6-PentaflUOro-1,4-dioxane F F
CFa~ ~ ~ KF + CFa=CFCFa ~S2 F ~ > ~ ~Fa CFa CFa=CFCF~O ~ ~ ctFF
A mixture of potassium fluoride (5.8 g, 0,10 mol) and diglyme (100 ml) was treated at 25C with 3,6-bis-~1~4~5 (trifluoro~ethyl)-3,5,5,6-tetrafluoro-1,4-dioxan-2-one (S. Selman, U.S. Patent 3,321,517) (31.0 g, 0.10 mol). The mixture was stirred for 1 hour and then treated dropwise with perfluoroallylfluorosulfate prepared as in Example 2A
(23.0 g, 0.10 mol), the exothermic reaction being maintained at 35-40C with an external 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=CF~) and 7.5-10 ~m (CF,C-O); 19F NMR, -70.7 and -71.8 (AB J ~ 159 Hz, I each member m) 2F, OCFaC=CJ -77.3 and -87.91 (AB J = 153 Hz, each member m) 2F, ring OCF2, -81.4 (m) 4F, CF3 + OCFO, -82.4 (m) 3F, CF~, -92.3 (d J = 52.0 Hz, each member d J = 39.3 Hz, t J c 7.2 Hz) lF, cis-CF~CF=CFJ -105.3 (d J = 117.1 Hz, each member d J = 52.0 Hz, t J - 25.4 Hz) lF, trans-CF2CF=CF,-123.3, -124.7~ -126.2, -132.2, -132.9 and -134.1 (m) 2F CFsCFO, -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 of isomers were observed at -92.1, -105.3, and -190.5 ppm.
Anal. Calcd for CsF1~03: C, 23.50; F, 66.07 Found: C, 23.71; F, 66.17 3o 2-rl-~Penta~luoro-2-Propenvloxy)l-2~5~6-tetrakis(trifluor meth,vl~ -fluoro-1,4,7-trioxabicyclo[2.2.1lhep-tane and 2-[1-(pentaf:Luoro-2-Pro;pen~v~lox~v)tetrafluoroeth~vll-4-Ll-(~entafluor .
2-~ropen~lox,y)l-2.4,5-tris(trifluorometh~ fluoro-1,3-dioxolane Il 1~ 1~ 1 CFs CCCF3 + KF --------> CFa C - C - CF3 F
~. \
CF2 -CFCF;~ OSOa F \
O ~ CF3 ~C"CF3 F
/o~cF3 . CFs~
CF3~\0~0CFaCF'=CF~ CF~=CFC~/ F-OC~2C~2 A suspension of anhydrous potasslum fluoride (5.80 ~, 0.10 mol) in digl-yme (-100 ml) was stirred at 10C
while hexafluoro-2,3-butanedione (hex~fluorobiacetyl, L. O.
Moore and J. W. Clark, J. Or~._Chem " ~, 2472 (1965)) (19.4 g, 0.10 mol) was distilled in. The mixture was stir-red untll the potassium fluoride had nearly all dissolved, and the~ it,was treated rapidly wlth perfluoroallyl fluoro-sulfate prepared as in Example 2A (23-.0 g, 0.10 mol) at 15C. The slightly 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 49-54C (10 mm Hg) was shaken with concentrated sulfuric acid (8 ml), treated with anhydrous calcium sulfate and fractionated in a spinning-band still. 2-[1-(Penta~luoro-3o 2-propenyloxy)]-2,3,5,6-tetrakis(trifluoromethyl)-5-fluoro-1,4,7-trioxabicyclo[2.2.1]heptane (3.0 g, 0.0055 mol, 11%) bp 50-51C (15 mm ~g) contained one major component by glpc.
The analytical sample of this product was obtained by pre-parative glpc and its structure confirmed by:
~max 5.58 (CF=CF2), and 7.5~10 um (C-F,C-O); 19F NMR, -65.6 and -71.0 (AB J = 155 Hz, each member m), 2F, OCF2, -74.7 (m) 3F, CF3, -78.5 (m) 3F, CF3, -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-CF2CF=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-CF2CF=CF, -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, CF2-C~F=C.
Anal Calcd f~r CllF184 C, 24-55; F~ 63-55 Found: C, 24.57; F, 63.60 The second fraction was a mixture of isomers of 2-[1-(pentafluoro-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-tained only minor impurities by glpc. This product structure was confirmed by:
~max S.56 (CF=CF2) and 7-10 ~m (CF,C-O), F NMR -72.8 ppm ~AB) 2F, OCF2 -75.4, -76.8, -78.3, -78.7 and -79.1 (m) 12F, CF3, -93.1 (m) 2F cis-CF2CF=CF, -105.8 (m) 2F, trans-CF2CF=CF, -121.0, -136.5 and -141.6 (m) 2F, CF, and -190.8 ppm (m) 2F, CF2CF=C.
Anal. Calcd ~or C14 F24O4: C, 24.44; F, 66.26 Found: C, 24.73; F, 66.48 `~
S
Perfluoro-1,6-bis(2-propenyloxy)hexane O O
.. ..
FC(CF2)4CF + KF + CF2--CFCF20602F~ (CF2=CFCF2OCF2CF2CF2)2 + CF2=CFCF2O(CF2)5CO~
CF2=CFCF2O(CF2)5COF + H2O d ~ly ~ CF2=CFCF2O(CF2)5CO2H.
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 S-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.); the lower layer was washed with water (150 ml), dried and distilled to give two products.
The lower-boiling fraction was perfluoro-1,6-bis-t2-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 ~m (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.
`,~`,'`' Anal- Calcd for C12F222 C~ 24-25;
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, 0.015~ mol, 16%), bp 109-110C (5 mm Hg), formed by hydroly-sis of perfluoro-6-(2-propenyloxy)hexanoyl fluoride in the a~ueous diglyme wash solutions. This complex had ~max 3~4 (OH,C-H), 5.59 (with shoulder, C~2=C~,CO2H), and 7.2-9 ~m (CF,C-O,CH); lH NMR, ~ 11.93 (s) lH, CO2H, 3.75 (s) 4H, 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, OC~2C=C, -84.1 (m) 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, -122.6 (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 = 1.8 Hz) lF, CF2CF=C
Methyl Perfluoro-3,6-dioxanon-8-enoate CF2 C C 2 2 2 2 ~ CF2 CFCF2 C 2C 2 C 2 2C 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 of impurities. Redis-3 tillation gave somewhat more pure ester (1-2% imPurities by gc),bp 61-62C
4~5 (20 mm Hg). Structure was confirmed by Ir (neat~:
3-32, 3.37, 3.49 (CH3), 5.57 (C=O), 8-9.5~ (CF, C-O).
NMf~: H 3.95 ppm (s) with small impurities at 3.53 and ~.33 ppm;
9F -72.0 (d of d of t of d, JFF 24, 1~, 13, 7-5 Hz, 2 F, =CFCF2J, -78.o (t, JF~, ].1.6 Hz, 2 F, CF2CO2CH9), -~ .0 (t, JFF 11.6 Hz, 2 F, CF20CF2CO2CH3), -89.5 (t, JFF 12.6 Hz, 2 I', =CFCF20CE~2), -92.3 (d of d of t, JFF 53.2, 39.2, 7.5 Hz, 1 F~ eis-CF2CF=CF), -105.2 (d of d of t, JFF 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 Hz, 1 F, CF2CF=).
Anal. Calcd. for CgH F1104: C, 25.82; H, 0.81; F, 56.17 Found: C, 26.17; H, o.66; F, 56.24.
D~meth~l Perfluoro-7-allox.Y~luta.rate A. Bis(?-methox.Ytetrafluoroeth.Yl)ketone l'he synthesis of bis(2-methoxytetrafluoroethyl)-ketone from di.methyl carbonate tetrafluoroethylene, a.nd sodi.um mcthoxide has becn described by D. W. Wiley (U. S.
2,~,537 (1961)). An extension of this synthesis has given 1,3,~5-tetramethoxyoctafluoroperltane in a one-pot reaction.
o O~Na Il l CH30Na. + 2 CF2=CF2 + CH30COCH3 ~ CH3ocF2cF27cF2cF2ocH3 CH30CF2CF2C(OCH3)2CF2CE`20CH3 A mixture of 27.0 g (0.50 mol) of sodium methoxlde, 56.o g (0.62 mol) of dimethyl ca.rbonate, and 100 ml of dry tetra.hydrofuran was agitated in a ~50 ml tube under 1-~ atm of tetrafluoroethylene. Tetrafluoroethylene was pressu~ed ~l~7~5 in as consumed until ll0 g (l.l mol) had been added. The mildly exothermic reaction kept the temperature near 35C; after the addition, the reaction mixtu.re was heated at 40C for l hour.
The viscous solution from this reaction was treated directly with 75.6 g (o.60 mol) of dimethyl sulfate at 40C for 15 hours.
Filtration and distillation afforded 87.6 g (52%) of l,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, l, CF2OCH3) a.nd 3.57 (P~ J~F 1.3 Hz, l, C (OCH3)2); 9F -88.2 (m, l, CR2O) and -ll~.5 ppm (m, l, CF2).
Anal. Calcd. ror CgHl2F~O~: C, 32.lG; H, 3.60; F, 45.2l Found: C, 32.57; ~, 3.72; F, 4l~.6~.
B. Dlmcth.vl. Tetrafluoroacetone-l.3-dlcarbox.Ylate conc. H2SO4 C'113OCI'2CF2C( OC113 ) 2CF2cF20cll3 O O O
Il 11 11 Cl~30CCF2CCF2COCH3 2~ To 5O ml of conc. H2SO4 wa.s added dropwise 33.6 g (O.l.O mol) of the tetraether. After the mildly exothcrmic reaction had subsided, the mixture was hea.ted a.t 7O~C
(50 mm Hg) to remove volatiles and then distilled at ca. 50C
(l ~n Hg). The crude distillate was then fractionated to afford lG.~ g (G9'~) of dimethyl tetrafluoroa.cetone-l,3-dica.rboxylat;e, bp ~C (2 mm), nD22 1.37:L3. Structure was conflrmed by Ir 3.2~, 3.34 and 3.4~ (sa.td Cl1), 5.57 (C=O) 5.64 (sh-C=O), 8-9 ~ (CF, COCj.
i'~mr (CC14) ~ 4.00 (s, OCH9); 9~' -113 ppm (s, CF2)-4~5 Anal. Ca.lcd. for C H6F40 : C, 34.16; ~l, 2.46; F, 30.88 7 5 mol wt, 246 Found: C, 34.18; Il, 2.~Gi F, 30.95;
mol wt, 246 (m~ S5 spec ) .
The same reaction on a 0.56 mole scale gave the diester in 82% yield.
C. D:i.met~.vl Perfluoro~ llox~lutarate ' O O O
Cl;30CCF2CCF2COCli3 + CsF + CF2=CE'CF20S0 '10 O ~
(CEI30C-CFz)zCFOCFzCF~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 mixture was thrown into 1 liter of H20 and the lower layer separated. This was washed twice with H20. After treatment with 20 ml H2S04 at 0C and extraction with Freon~ 113, the extract was distilled in a molecular sti.ll to give 4.54 g (7.2'~ yield) of product, bp = 51-53C (0.1 mm). Structure was confirmed by F nmr (Fll): -68.48 ppm (OCF2CF=); -93.45 ppm cis-(CF=CFF);
-105.91 ppm trans-(CF=CF); -117.10 ppm (CF2COOCH3)i -142~78 ppm (CF2CF20CF=); -190.35 ppm (CF=CF2). '~1 nmr (Fll/TMS):
3.96 (sin~let, CII3). Ir (neat): 3.37 ~, 3.49 ~ (sat CH);
5.60 2 (,C=0, CF2=CF); 8-10 ~ (CF, C0).
Anal. Calcd for CloFloH605: C, 30.32; F, 47.96; Il, 1-53 Found: C, 30.45; F, 48.]0; lI, 1.4~.
3o .~ .
: ~.
~7'~ 5 EX~PLE 16 Perfluoro-3-(2-pro~oxy-2-methylethoxy)propene ,CF3 ,CF3 CF~CF2CF2OCFCOF + KF + CF2=CFCF20S02F----~ CF3CF2CF2~F2CCF2C~2 A mixture of potass um fluoride (6.96 g, 0.12 mol), diglyme (150 ml) and 2-(1-heptafluoropropoxy)tetrafluoro-propionyl fluoride (dimer of hexafluoropropene oxide obtain-ed by treatment with fluoride ion) (29.4 g, 0.089 mol) was stirred at 5C for 1 hour. Perfluoroallyl fluorosulfate 10 prepared 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 volatile components 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:
~max 5.57 (CF=CF2) and 7.5-9 ~m (C-F, C-O); F
20 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 (ml 5F, CF3 + OCF2, -84.1 (m) 2F, CF2O, -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=CF, -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.
Anal. Calcd for CgH18O2: C, 22-42; F, 70.94 Found: C, 22.18; F, 70.96 `~
~l~ 7~ 5 Perfluoro-1,3-bis(2-propenyloxy)propane O O
.. .-CF2C~ + KF + CF2 = CFCF2OSO2F ~ (cF2=cFcF2ocF2)2cF2 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 ~5 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-propenyl-oxy)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) lF, trans-CF2CF-C~, -130.0 (s~ lF, CF2 and -191.0 ~pm (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=CFCF20S02F~ CF3CP2CF2CF20CF2C C 2 A mixture of dry potassium fluoride (7.50 g, 0.13 mol), diglyme (100 ml) and heptafluorobutyroyl fluoride (pre-pared from the acid by treatment with sulfur tetrafluoride) (28.1 g, 0.13 mol) was stirred at 5C for 30mLn. ~erfluoroallyl ~7~
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 dis-tillation 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=CF2) and 7.2~9.5 ~m (C-F,C-O); F NMR -72.i (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 = 39.4 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=CF, -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)~COF + KF + CF2=CFCF2OSO2F--i~ F(CF2)80CF2CF CF2 A mixture of potassium fluoride (5.80 g, 0.10 moll, diglyme (150 ml) and pentadecafluorooctanoyl fluoride (prepared by treating commercial perfluorooctanoic acid with sulfur tetrafluoride) (25.0 q, 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 ~.), separated, and the lower layer was dis-S
tilled from concentrated sulfuric acid to give perfluoro-3-(octyloxy)propene ~27.1 g, 0.048 mol, 80~) bp 69-70C
(20 mm Hg) whose structure was confirmed by:
~max 5 59 (CF=CF2) and 8-9 ~m (CF C-O); 19F 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, CF2CF2O, -92.3 (d J = 53.6 Hz, each member d J = 39.9 Hz, t J = 7.7 Hz) lF, cis-CF2CF=CF, -105.5 (d J = 117.8 Hz, each member d J = 53.5 Hz, t J = 25.1 Hz) 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 Hz, 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 E~AMPLE 20 ?-Trifluoromethox~tafluoroPropene (Perfluoro(allylmethylether)) COF2 + CsF + CF2=CFCF2OSO2F - 3 C 2 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 25~C overnight. The mixture was warmed under a slight vacuum, and the volatile distillate (11 m~ of llquid collected at -80C) was redistilled through a low tem~erature 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); 19F NMR (CC14), -56.5 (t J = 9.2 Hz) 3F, CF30, -74.6 (d J = 25.8 Hz, each member ;8S
d J = 13.6, q J = 9.2 Hz, d J = 7.1 ~z) 2F, OCF2C=C; -92.2 (d J = 53.4 Hz, each member d J = 39.2 Hz, t J = 7.1 Hz) lF, cis -CF2CF=CF, -105.5 (d J = 118.0 Hz, each member d J = 53.4 Hz, t J = 25.8 Hz), lF, 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-propenyloxy)hexanoic Acid and Its Methyl Ester FCO(CF2)4COF + KF + CF2 = CFCF2OSO2F--~
2 2OCF2CF2CF2)2 + CF2 = CFCF2O(CF2)5COF
C~2 = CFC~2O(CF2)5COF 2 > CF2 = CFCF2O(CF2)5CO2H.
( 3ocH2cH2ocH2cH2ocH3) distil> CF2 = CFCF2O(CF2)5 C2H I CF2 = C~CF2O(C~2)5CO2C 3 A mixture 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 fluoro-sulfate (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 1.); the lower layer (10 ml) was combined with the vola-tile fraction from above and treated with a mixture of water (100 ml) and diglyme (20 ml). After the resulting exother-mic 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~) S
bp 61 (6 mm Hg) and the 2:1 complex of perfluoro-6-(2-propenyloxy) hexanoic acid with d$glyme (Example 13, 52.8 g, 0.109 mol, 54.5%) bp 82-84C (o.8 mm Hg).
l'he dlglyme complex of the higher boiling fraction was distilled from concentrated sulfuric acid (~0 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 ~max 2.82 and 3-4 (OH,CH3), 5.58 (CF=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.
Perfluoro-6-(2-propenyloxy)hexanoic Acld 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 H~) was freed of dlglyme b~
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-pro-penyloxy)hexanoic acid with diglyme was dissolved in 1l1,2-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 dlstilled to glve pure 3o per~luoro-6-(2-propenyloxy)l~exanoic acid (42.2 p, ~7~6~5 o.og88 mol, 49%) bp 75C (1.0 mm Hg). This material was ldentified by infrared ~max 2.85-4.0 (H-bonded OH), 5.57 (CF=C~2), 5.63 (sh,C=O) and 8-9 ~m (CP,C-O), and by its lH and 19F NMR spectra.
Anal. Calcd. for CgHF1503: C, 24.45; H, 0.23; F, 64.66 Found: C, 24.48; H, 0.45; F, 65.76 m e following examples illustrate the preparation of useful copolymers from the polyfluoroallyloxy comonomers of this invention m e general properties of these co-polymers were discussed above.
UTILITY EXAMPLES
ExamPle A
Solution Polymerization of TetrafluoroethYlene with 2~
(Pentafluoro-2-~ro~en.vloxy)ltetrafluoroethanesulfon~l Fluoride n x CFa ~ CFa ~ xCF~ = CFcFaocFacFaso~F (C F CO)-O
~ (cF~-cFa)n -cFzcF +
L CFaOCFaCFaSOaF x An 80-ml stainless steel-lined tube was ch~rged 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
initiator) (1 ml), and 2-[1-(pentafluoro-2-propenyloxy)~-tetrafluoroethanesulfonyl fluoride (Example 7j 17.5 g,O.053 mol).
me tube was closed, cooled to -40C, evacuated, and charged with tetrafluoroethylene (20 g, 0.20 mol). me tube was warm-ed to 25C and shaken at this temperature for 20 hours.- The volatile materials were allowed to evaporate, and the product 3o :~7~
polymer was evacuzted tc 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 bands. Gravimetric 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 polyfluoroallyloxy comonomer corresponding to an equivalent weight of 9400. Equivalent weight is the mole-cular weight of the polymer per functional group (here -SO2F). Differential scanning calorimetry (DSC) showed a 12~ depression of the endotherm peak (mp) compared to poly-tetrafluoroethylene.
;, EX~PLE B
''i Solution Polymerization of Tetrafluoroethylene with 1-[1-(Pentafluoro-2-propenyloxy)]hexafluoropropane-2-sulfonyl Fluoride ., x CF2=CFCF20CF2CF-S02F + nxCF2=CF2~ ---(CF2~CF2)n~CF2CF--_ CF3 ¦ ,CF3 CF2CCFSO2F x The procedure of Example A was followed with 1,1,2-trichloro-1,2,2-trifluoroethane (10 ml), 8% pentafluoropropionyl ` peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane (2.0 ml), , l-[l-~pentafluoro-2-propenyloxy)]hexafluoropropane-2-sul-fonyl fluoride (Example 9, 17.4 g, 0.046 mol) and tetra-fluoroethylene (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 poly-fluoroallyloxy comonomer corresponding to an equilvalent weight of 6540. The sample had a mp depression of 11C
compared to polytetrafluoroethylene by DSC.
'~
1~7g~$85 Example C
Solution Polymerization of Tetrafluoroethylene with 3-[1-(Pentafluoro-2-propenyloxy)tetrafluoropropionyl Fluoride x CF2=cFcF2oOEl2cF2coF ~ nxCF2=CF2~ -F(CF2~'CF2)n~CF2CIF~
L CF20CF2CF2CF ¦
NaOH
~ ( CF2 -CF2 ) n~CF2 CF
L CF20CF2CF2C02Na~
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.
~7~ 5 Example D
Solution olymerization of~Tetrafluor-o t _le_e wi~th 1-(1,1,1,2,3,3-Hexafluoro-3-chloro-2-propoxy)pentafluoro-2-propene CF3 _ _ x CF2~F20CrCF2~ + ~nCF2=C 2 --( 2 2)n CF21C _ - CF3 _ x The procedure of Example A was used with 1-(1,1,1,2j3,3-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.
Example E
Solution Polymerization of Tetrafluoroethylene with 2-(1-Pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonylFluoride x CF2=CFCF2CFCF2S2F + xn CF2 = CF2 --F(CF2-CF2~ CF2f L CF20CFCF2S02F~
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-[1-(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 CH2=CF2 + CF2 = CFCF2OCF2CF2SO2F ~ Copolymer The procedure of Example A was used with vinylidene fluoride (20 g, 0.32 mol), 2-[1-(pent~fluoro-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.
The solid copolymer produced (21.5 g, 60%) contained 46 wt % (14.2 mol %) of polyfluoroallyloxy comonomer with an ~ -~ 7~ S
equivalent weight of 71.9 DSC showed no thermal events between 25C and 400C.
Anal Calcd for (CH2=cF2)6 05 (CF2 CFCF2 2 2 2 C, 28.62; H, 1.70; S, 4.47 Found: C, 28.49; H, 1.71; S, 4.46 _ mple G
Solution Polymerization of Vinxlidene_Fluoride with l-(Hepta-fluoro-2-propoxy)-1 ! 1!3,3-tetrafluoro-2-chloro-2-propene 2 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 polyfluoroallyloxy 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 25-400C.
Example H
Solution Polymerization of Tetrafluoroethylene with Perfluoro-3-(butoxy)propene 2 CF2 + CF8(CF2)3OCF2CF=CF2 ~ Copolymer The procedure of Example A, when used with perfluoro-3-(butoxy)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 g of solid copolymer. This crude material was chopped in a 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-bls(2-propenyloxy)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 ~m (CF=CF2);
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(tetrafluoro-ethylene) 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 vinylidene fluoride (20 g, 0.32 mol) was condensed into the tube. The mixture was shaken overnight at room temperature, 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 form-ed since poly(vinylidene fluoride) has mp 171C. The in-solubility of this product in acetone and the lack of absorp-tion bands in the infrared for pendant CF=CF2 groups in-dicates that crosslinking had occurred.
EXAUPLE K
Copolymer of TFE with Methyl Perfluoro-3,6-dioxanon-8-enoate 45 g of methyl perfluoro-3,6-dioxanon-8-enoate and .04 g of perfluoropropionyl peroxide were reacted at 50C
for 4 hr. 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 28% 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 o.f Example C was similarly treated with aqueous alcoholic sodium hydroxide.
The above partly hydrolyzed polymers were immersed in aqueous ethanol solutions of Sevron~ Red GL (Sevron~ is a line of cationic dyes especially suited for dyeing Orlon~
and 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 ex-:
1 ll7~85 tracts no longer contained dye. All three samples dyed well to an orange-red color.
EXAMPLE ~1 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-[1-(Pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl Fluoride CF2=CF2 ~ CF2=CFcF2OcF2cF2so2F > 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 perfluorooctane-sulfonate (0.16 g), ammonium carbonate (0.50 g) and ammonium persulfate (0.50 g). The mixture was brought to an internal pressure of 200 p.s.i.g. with tetrafluoroethylene and heated at 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 tem-perature of 293C and a recycle melting point of 311C from which the polyfluoroallyloxy comonomer content is estimated as 3.5 wt % (1.09 mol~).
~l~'7'~
EXAMPLE O
Emulsion Polymerization of Tetrafluoroethylene with 2-[1-(Pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonylFluoride CP2=CF2 + CF2=CFCF2OCF2CF2SO2P - > Copolymer The procedure of Example N was followed using 8.0 g of 2-[1-pentafluoro-2-propenyloxy)]tetrafluoroethane-sulfonyl fluoride, 0.20 g of potassium perfluorooctane-sulfonate 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 SO2F
absorption. DTA showed a crystalline transition at 5C, a recycle freezing temperature of 282C, and a recycle melting point of 300C, corresponding to a polyfluoro-allyloxy comonomer content of 5.9 wt ~ (1.86 mol %).
EXAMPLE P
Emulsion Polymerization of Tetrafluoroethylene with 2-[1-(Pentafluoro-2-propenylox~)]tetrafluoroethanesulfonyl Fluoride The procedure of Example N was followed using 10.7 g of 2-[1-pentafluoro-2-propenyloxy)]tetrafluoro-sulfonyl fluoride, 0.20 g of ammonium persulfate, and tetrafluoroethylene 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 g of white polymer whose infrared spectrum showed the presence of SO2F groups corresponding to 3.5 wt %
(1.08 mol~) polyfluoroallyloxy comonomer. DTA showed two melting peaks at 290C and 317C, with an estimated comnno~er content of 5.5 wt % (1.73 mol ~).
UTILIT~ EXAMPLE Q
_ .
CoPolymerization of Tetra.fluoroeth~lene and 2-[1-(~entafluoro-2-~roPen~ oxy)ltetra~fluoroethanesulfon~l Fluorlde. and PrePnra-tion Or Electricall.Y-Conductive Films f`rom the CoPol~mer Product nxCF2=CF2 ~ xCF2=CFCF2OCF2CF2SO2F - - >
_ tCF2-CF2 )-CF2CF-' CF2OCF2CF2SO2F
lQ
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 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 ~ (S02F) and 8-10 mm (broad) in addition to the usual polytetrafluoroethylene IR
bands. The DSC melting point depression was 91C compa.red 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 weig~t of 1180.
The product was pressed lnto 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.
i The four-inch diameter, 4-5 mil film wa~ inserted as the ion exchange membrane in a chlor-alkall electrolysis cell operated at 2.0 amps/in2. Cell voltage and current e~ficlency were measured as a function of cell operating time and sodium hydroxide concentration. The following results were obtained for a 15-day test:
Sodium Hydroxide Current Efficiency Cell Volt~ge DaY Product (~) f~) (volts) 1 21.5 70.7 3-35 21.5 71.2 3.45 30.0 65.2 3.60 UTILITY EXAMPLE R
Co~olYmerization of Tetrafluoroeth~lene and Perfluoro-6-oxanon-8-enoic acid. and PreParation of Electric~llY
Conductive Films from the CoPolYmer Product nxCF2=CF2 + xCF2-CFCF20(CF2)4COOH
_ _ _ (CF2CF2)n-CF2-CF _ CF20(CF2)4COOH
_ _ x The procedure of Example Q was followed with per~luoro-6-oxanon-8-enoic acid (47.5 g), 8~ pentafluoro-propionyl peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane (O.O5 g), and TFE at lO psig (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 into 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)4C02 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/in2, and the following results were obtained in a 76 day test:
Sodium ~ydroxideCurrent Efficiency Cell Volta.ge Da.YProduct (~ ) (volts~
37.1 93.3 4.02 39.2 go.g 4.60 39.4 87.7 4.25 32 .9 92 . o 4 .
76 34.6 85.8 4.67 3o
Anal. Calcd. ror CgHl2F~O~: C, 32.lG; H, 3.60; F, 45.2l Found: C, 32.57; ~, 3.72; F, 4l~.6~.
B. Dlmcth.vl. Tetrafluoroacetone-l.3-dlcarbox.Ylate conc. H2SO4 C'113OCI'2CF2C( OC113 ) 2CF2cF20cll3 O O O
Il 11 11 Cl~30CCF2CCF2COCH3 2~ To 5O ml of conc. H2SO4 wa.s added dropwise 33.6 g (O.l.O mol) of the tetraether. After the mildly exothcrmic reaction had subsided, the mixture was hea.ted a.t 7O~C
(50 mm Hg) to remove volatiles and then distilled at ca. 50C
(l ~n Hg). The crude distillate was then fractionated to afford lG.~ g (G9'~) of dimethyl tetrafluoroa.cetone-l,3-dica.rboxylat;e, bp ~C (2 mm), nD22 1.37:L3. Structure was conflrmed by Ir 3.2~, 3.34 and 3.4~ (sa.td Cl1), 5.57 (C=O) 5.64 (sh-C=O), 8-9 ~ (CF, COCj.
i'~mr (CC14) ~ 4.00 (s, OCH9); 9~' -113 ppm (s, CF2)-4~5 Anal. Ca.lcd. for C H6F40 : C, 34.16; ~l, 2.46; F, 30.88 7 5 mol wt, 246 Found: C, 34.18; Il, 2.~Gi F, 30.95;
mol wt, 246 (m~ S5 spec ) .
The same reaction on a 0.56 mole scale gave the diester in 82% yield.
C. D:i.met~.vl Perfluoro~ llox~lutarate ' O O O
Cl;30CCF2CCF2COCli3 + CsF + CF2=CE'CF20S0 '10 O ~
(CEI30C-CFz)zCFOCFzCF~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 mixture was thrown into 1 liter of H20 and the lower layer separated. This was washed twice with H20. After treatment with 20 ml H2S04 at 0C and extraction with Freon~ 113, the extract was distilled in a molecular sti.ll to give 4.54 g (7.2'~ yield) of product, bp = 51-53C (0.1 mm). Structure was confirmed by F nmr (Fll): -68.48 ppm (OCF2CF=); -93.45 ppm cis-(CF=CFF);
-105.91 ppm trans-(CF=CF); -117.10 ppm (CF2COOCH3)i -142~78 ppm (CF2CF20CF=); -190.35 ppm (CF=CF2). '~1 nmr (Fll/TMS):
3.96 (sin~let, CII3). Ir (neat): 3.37 ~, 3.49 ~ (sat CH);
5.60 2 (,C=0, CF2=CF); 8-10 ~ (CF, C0).
Anal. Calcd for CloFloH605: C, 30.32; F, 47.96; Il, 1-53 Found: C, 30.45; F, 48.]0; lI, 1.4~.
3o .~ .
: ~.
~7'~ 5 EX~PLE 16 Perfluoro-3-(2-pro~oxy-2-methylethoxy)propene ,CF3 ,CF3 CF~CF2CF2OCFCOF + KF + CF2=CFCF20S02F----~ CF3CF2CF2~F2CCF2C~2 A mixture of potass um fluoride (6.96 g, 0.12 mol), diglyme (150 ml) and 2-(1-heptafluoropropoxy)tetrafluoro-propionyl fluoride (dimer of hexafluoropropene oxide obtain-ed by treatment with fluoride ion) (29.4 g, 0.089 mol) was stirred at 5C for 1 hour. Perfluoroallyl fluorosulfate 10 prepared 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 volatile components 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:
~max 5.57 (CF=CF2) and 7.5-9 ~m (C-F, C-O); F
20 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 (ml 5F, CF3 + OCF2, -84.1 (m) 2F, CF2O, -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=CF, -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.
Anal. Calcd for CgH18O2: C, 22-42; F, 70.94 Found: C, 22.18; F, 70.96 `~
~l~ 7~ 5 Perfluoro-1,3-bis(2-propenyloxy)propane O O
.. .-CF2C~ + KF + CF2 = CFCF2OSO2F ~ (cF2=cFcF2ocF2)2cF2 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 ~5 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-propenyl-oxy)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) lF, trans-CF2CF-C~, -130.0 (s~ lF, CF2 and -191.0 ~pm (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=CFCF20S02F~ CF3CP2CF2CF20CF2C C 2 A mixture of dry potassium fluoride (7.50 g, 0.13 mol), diglyme (100 ml) and heptafluorobutyroyl fluoride (pre-pared from the acid by treatment with sulfur tetrafluoride) (28.1 g, 0.13 mol) was stirred at 5C for 30mLn. ~erfluoroallyl ~7~
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 dis-tillation 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=CF2) and 7.2~9.5 ~m (C-F,C-O); F NMR -72.i (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 = 39.4 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=CF, -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)~COF + KF + CF2=CFCF2OSO2F--i~ F(CF2)80CF2CF CF2 A mixture of potassium fluoride (5.80 g, 0.10 moll, diglyme (150 ml) and pentadecafluorooctanoyl fluoride (prepared by treating commercial perfluorooctanoic acid with sulfur tetrafluoride) (25.0 q, 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 ~.), separated, and the lower layer was dis-S
tilled from concentrated sulfuric acid to give perfluoro-3-(octyloxy)propene ~27.1 g, 0.048 mol, 80~) bp 69-70C
(20 mm Hg) whose structure was confirmed by:
~max 5 59 (CF=CF2) and 8-9 ~m (CF C-O); 19F 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, CF2CF2O, -92.3 (d J = 53.6 Hz, each member d J = 39.9 Hz, t J = 7.7 Hz) lF, cis-CF2CF=CF, -105.5 (d J = 117.8 Hz, each member d J = 53.5 Hz, t J = 25.1 Hz) 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 Hz, 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 E~AMPLE 20 ?-Trifluoromethox~tafluoroPropene (Perfluoro(allylmethylether)) COF2 + CsF + CF2=CFCF2OSO2F - 3 C 2 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 25~C overnight. The mixture was warmed under a slight vacuum, and the volatile distillate (11 m~ of llquid collected at -80C) was redistilled through a low tem~erature 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); 19F NMR (CC14), -56.5 (t J = 9.2 Hz) 3F, CF30, -74.6 (d J = 25.8 Hz, each member ;8S
d J = 13.6, q J = 9.2 Hz, d J = 7.1 ~z) 2F, OCF2C=C; -92.2 (d J = 53.4 Hz, each member d J = 39.2 Hz, t J = 7.1 Hz) lF, cis -CF2CF=CF, -105.5 (d J = 118.0 Hz, each member d J = 53.4 Hz, t J = 25.8 Hz), lF, 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-propenyloxy)hexanoic Acid and Its Methyl Ester FCO(CF2)4COF + KF + CF2 = CFCF2OSO2F--~
2 2OCF2CF2CF2)2 + CF2 = CFCF2O(CF2)5COF
C~2 = CFC~2O(CF2)5COF 2 > CF2 = CFCF2O(CF2)5CO2H.
( 3ocH2cH2ocH2cH2ocH3) distil> CF2 = CFCF2O(CF2)5 C2H I CF2 = C~CF2O(C~2)5CO2C 3 A mixture 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 fluoro-sulfate (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 1.); the lower layer (10 ml) was combined with the vola-tile fraction from above and treated with a mixture of water (100 ml) and diglyme (20 ml). After the resulting exother-mic 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~) S
bp 61 (6 mm Hg) and the 2:1 complex of perfluoro-6-(2-propenyloxy) hexanoic acid with d$glyme (Example 13, 52.8 g, 0.109 mol, 54.5%) bp 82-84C (o.8 mm Hg).
l'he dlglyme complex of the higher boiling fraction was distilled from concentrated sulfuric acid (~0 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 ~max 2.82 and 3-4 (OH,CH3), 5.58 (CF=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.
Perfluoro-6-(2-propenyloxy)hexanoic Acld 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 H~) was freed of dlglyme b~
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-pro-penyloxy)hexanoic acid with diglyme was dissolved in 1l1,2-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 dlstilled to glve pure 3o per~luoro-6-(2-propenyloxy)l~exanoic acid (42.2 p, ~7~6~5 o.og88 mol, 49%) bp 75C (1.0 mm Hg). This material was ldentified by infrared ~max 2.85-4.0 (H-bonded OH), 5.57 (CF=C~2), 5.63 (sh,C=O) and 8-9 ~m (CP,C-O), and by its lH and 19F NMR spectra.
Anal. Calcd. for CgHF1503: C, 24.45; H, 0.23; F, 64.66 Found: C, 24.48; H, 0.45; F, 65.76 m e following examples illustrate the preparation of useful copolymers from the polyfluoroallyloxy comonomers of this invention m e general properties of these co-polymers were discussed above.
UTILITY EXAMPLES
ExamPle A
Solution Polymerization of TetrafluoroethYlene with 2~
(Pentafluoro-2-~ro~en.vloxy)ltetrafluoroethanesulfon~l Fluoride n x CFa ~ CFa ~ xCF~ = CFcFaocFacFaso~F (C F CO)-O
~ (cF~-cFa)n -cFzcF +
L CFaOCFaCFaSOaF x An 80-ml stainless steel-lined tube was ch~rged 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
initiator) (1 ml), and 2-[1-(pentafluoro-2-propenyloxy)~-tetrafluoroethanesulfonyl fluoride (Example 7j 17.5 g,O.053 mol).
me tube was closed, cooled to -40C, evacuated, and charged with tetrafluoroethylene (20 g, 0.20 mol). me tube was warm-ed to 25C and shaken at this temperature for 20 hours.- The volatile materials were allowed to evaporate, and the product 3o :~7~
polymer was evacuzted tc 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 bands. Gravimetric 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 polyfluoroallyloxy comonomer corresponding to an equivalent weight of 9400. Equivalent weight is the mole-cular weight of the polymer per functional group (here -SO2F). Differential scanning calorimetry (DSC) showed a 12~ depression of the endotherm peak (mp) compared to poly-tetrafluoroethylene.
;, EX~PLE B
''i Solution Polymerization of Tetrafluoroethylene with 1-[1-(Pentafluoro-2-propenyloxy)]hexafluoropropane-2-sulfonyl Fluoride ., x CF2=CFCF20CF2CF-S02F + nxCF2=CF2~ ---(CF2~CF2)n~CF2CF--_ CF3 ¦ ,CF3 CF2CCFSO2F x The procedure of Example A was followed with 1,1,2-trichloro-1,2,2-trifluoroethane (10 ml), 8% pentafluoropropionyl ` peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane (2.0 ml), , l-[l-~pentafluoro-2-propenyloxy)]hexafluoropropane-2-sul-fonyl fluoride (Example 9, 17.4 g, 0.046 mol) and tetra-fluoroethylene (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 poly-fluoroallyloxy comonomer corresponding to an equilvalent weight of 6540. The sample had a mp depression of 11C
compared to polytetrafluoroethylene by DSC.
'~
1~7g~$85 Example C
Solution Polymerization of Tetrafluoroethylene with 3-[1-(Pentafluoro-2-propenyloxy)tetrafluoropropionyl Fluoride x CF2=cFcF2oOEl2cF2coF ~ nxCF2=CF2~ -F(CF2~'CF2)n~CF2CIF~
L CF20CF2CF2CF ¦
NaOH
~ ( CF2 -CF2 ) n~CF2 CF
L CF20CF2CF2C02Na~
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.
~7~ 5 Example D
Solution olymerization of~Tetrafluor-o t _le_e wi~th 1-(1,1,1,2,3,3-Hexafluoro-3-chloro-2-propoxy)pentafluoro-2-propene CF3 _ _ x CF2~F20CrCF2~ + ~nCF2=C 2 --( 2 2)n CF21C _ - CF3 _ x The procedure of Example A was used with 1-(1,1,1,2j3,3-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.
Example E
Solution Polymerization of Tetrafluoroethylene with 2-(1-Pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonylFluoride x CF2=CFCF2CFCF2S2F + xn CF2 = CF2 --F(CF2-CF2~ CF2f L CF20CFCF2S02F~
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-[1-(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 CH2=CF2 + CF2 = CFCF2OCF2CF2SO2F ~ Copolymer The procedure of Example A was used with vinylidene fluoride (20 g, 0.32 mol), 2-[1-(pent~fluoro-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.
The solid copolymer produced (21.5 g, 60%) contained 46 wt % (14.2 mol %) of polyfluoroallyloxy comonomer with an ~ -~ 7~ S
equivalent weight of 71.9 DSC showed no thermal events between 25C and 400C.
Anal Calcd for (CH2=cF2)6 05 (CF2 CFCF2 2 2 2 C, 28.62; H, 1.70; S, 4.47 Found: C, 28.49; H, 1.71; S, 4.46 _ mple G
Solution Polymerization of Vinxlidene_Fluoride with l-(Hepta-fluoro-2-propoxy)-1 ! 1!3,3-tetrafluoro-2-chloro-2-propene 2 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 polyfluoroallyloxy 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 25-400C.
Example H
Solution Polymerization of Tetrafluoroethylene with Perfluoro-3-(butoxy)propene 2 CF2 + CF8(CF2)3OCF2CF=CF2 ~ Copolymer The procedure of Example A, when used with perfluoro-3-(butoxy)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 g of solid copolymer. This crude material was chopped in a 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-bls(2-propenyloxy)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 ~m (CF=CF2);
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(tetrafluoro-ethylene) 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 vinylidene fluoride (20 g, 0.32 mol) was condensed into the tube. The mixture was shaken overnight at room temperature, 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 form-ed since poly(vinylidene fluoride) has mp 171C. The in-solubility of this product in acetone and the lack of absorp-tion bands in the infrared for pendant CF=CF2 groups in-dicates that crosslinking had occurred.
EXAUPLE K
Copolymer of TFE with Methyl Perfluoro-3,6-dioxanon-8-enoate 45 g of methyl perfluoro-3,6-dioxanon-8-enoate and .04 g of perfluoropropionyl peroxide were reacted at 50C
for 4 hr. 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 28% 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 o.f Example C was similarly treated with aqueous alcoholic sodium hydroxide.
The above partly hydrolyzed polymers were immersed in aqueous ethanol solutions of Sevron~ Red GL (Sevron~ is a line of cationic dyes especially suited for dyeing Orlon~
and 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 ex-:
1 ll7~85 tracts no longer contained dye. All three samples dyed well to an orange-red color.
EXAMPLE ~1 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-[1-(Pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl Fluoride CF2=CF2 ~ CF2=CFcF2OcF2cF2so2F > 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 perfluorooctane-sulfonate (0.16 g), ammonium carbonate (0.50 g) and ammonium persulfate (0.50 g). The mixture was brought to an internal pressure of 200 p.s.i.g. with tetrafluoroethylene and heated at 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 tem-perature of 293C and a recycle melting point of 311C from which the polyfluoroallyloxy comonomer content is estimated as 3.5 wt % (1.09 mol~).
~l~'7'~
EXAMPLE O
Emulsion Polymerization of Tetrafluoroethylene with 2-[1-(Pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonylFluoride CP2=CF2 + CF2=CFCF2OCF2CF2SO2P - > Copolymer The procedure of Example N was followed using 8.0 g of 2-[1-pentafluoro-2-propenyloxy)]tetrafluoroethane-sulfonyl fluoride, 0.20 g of potassium perfluorooctane-sulfonate 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 SO2F
absorption. DTA showed a crystalline transition at 5C, a recycle freezing temperature of 282C, and a recycle melting point of 300C, corresponding to a polyfluoro-allyloxy comonomer content of 5.9 wt ~ (1.86 mol %).
EXAMPLE P
Emulsion Polymerization of Tetrafluoroethylene with 2-[1-(Pentafluoro-2-propenylox~)]tetrafluoroethanesulfonyl Fluoride The procedure of Example N was followed using 10.7 g of 2-[1-pentafluoro-2-propenyloxy)]tetrafluoro-sulfonyl fluoride, 0.20 g of ammonium persulfate, and tetrafluoroethylene 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 g of white polymer whose infrared spectrum showed the presence of SO2F groups corresponding to 3.5 wt %
(1.08 mol~) polyfluoroallyloxy comonomer. DTA showed two melting peaks at 290C and 317C, with an estimated comnno~er content of 5.5 wt % (1.73 mol ~).
UTILIT~ EXAMPLE Q
_ .
CoPolymerization of Tetra.fluoroeth~lene and 2-[1-(~entafluoro-2-~roPen~ oxy)ltetra~fluoroethanesulfon~l Fluorlde. and PrePnra-tion Or Electricall.Y-Conductive Films f`rom the CoPol~mer Product nxCF2=CF2 ~ xCF2=CFCF2OCF2CF2SO2F - - >
_ tCF2-CF2 )-CF2CF-' CF2OCF2CF2SO2F
lQ
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 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 ~ (S02F) and 8-10 mm (broad) in addition to the usual polytetrafluoroethylene IR
bands. The DSC melting point depression was 91C compa.red 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 weig~t of 1180.
The product was pressed lnto 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.
i The four-inch diameter, 4-5 mil film wa~ inserted as the ion exchange membrane in a chlor-alkall electrolysis cell operated at 2.0 amps/in2. Cell voltage and current e~ficlency were measured as a function of cell operating time and sodium hydroxide concentration. The following results were obtained for a 15-day test:
Sodium Hydroxide Current Efficiency Cell Volt~ge DaY Product (~) f~) (volts) 1 21.5 70.7 3-35 21.5 71.2 3.45 30.0 65.2 3.60 UTILITY EXAMPLE R
Co~olYmerization of Tetrafluoroeth~lene and Perfluoro-6-oxanon-8-enoic acid. and PreParation of Electric~llY
Conductive Films from the CoPolYmer Product nxCF2=CF2 + xCF2-CFCF20(CF2)4COOH
_ _ _ (CF2CF2)n-CF2-CF _ CF20(CF2)4COOH
_ _ x The procedure of Example Q was followed with per~luoro-6-oxanon-8-enoic acid (47.5 g), 8~ pentafluoro-propionyl peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane (O.O5 g), and TFE at lO psig (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 into 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)4C02 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/in2, and the following results were obtained in a 76 day test:
Sodium ~ydroxideCurrent Efficiency Cell Volta.ge Da.YProduct (~ ) (volts~
37.1 93.3 4.02 39.2 go.g 4.60 39.4 87.7 4.25 32 .9 92 . o 4 .
76 34.6 85.8 4.67 3o
Claims (25)
1. A polyfluoroallyloxy compound having the formula 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, or -R? where -R? 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, -COF, -CO2H, -CO2R3, -Cl, -OCF2CF=CF2 and -OCF2CO2R3, where R3 is -CH3 or -C2H5.
E, taken independently, is -F, -CF3, -CF2Cl, CF2CO2R3, where R3 has the meaning defined above or -R?OCF (G)2;
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 substituent -CF3 groups, or and;
G is -F or -CF3.
W and Z, when taken independently, are -F
and, when taken together, are -CF2-;
D, taken independently, is -F, or -R? where -R? 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, -COF, -CO2H, -CO2R3, -Cl, -OCF2CF=CF2 and -OCF2CO2R3, where R3 is -CH3 or -C2H5.
E, taken independently, is -F, -CF3, -CF2Cl, CF2CO2R3, where R3 has the meaning defined above or -R?OCF (G)2;
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 substituent -CF3 groups, or and;
G is -F or -CF3.
2. The compound of Claim 1 wherein D and E are taken independently and D is -F or R? as defined in Claim 1 and E is -F, -CF3, -CF2Cl or CF2CO2R3.
3. The compound of Claim 2 wherein W and Z are taken independently.
4. The compound of Claim 3 wherein X is -F.
5. The compound of Claim 4 wherein RF is a linear or branched perfluoroalkyl of 1 to 8 carbon atoms, interruptable with no more than 1 oxygen atom, having 0 to 1 functional groups selected from the class consisting of -SO2F, -COF, -Cl, -CO2H, -CO2R3, -OCF2CF=CF2 and -OCF2CO2R3 where R3 is -CH3 or -C2H5.
6. The compound of claim 1 wherein X is -Cl or -F, D is -CF2R4 or where R4 is -F, -SO2F, -COF, -CO2H, or ?CF2)xR5 where x is 1 to 6 and R5 is -CF3,-OCF2CF=CF2, COF, -CO2CH3 or-SO2F
E is -F, -CF3 or -CF2Cl, G is F and W and Z are taken independently and are -F.
E is -F, -CF3 or -CF2Cl, G is F and W and Z are taken independently and are -F.
7. The compound of claim 6 wherein R5 is -CF3 or -OCF2CF=CF2.
8. The compound of claim 7 wherein X is -F, D is -CF2R4, E is -F and R4 is -SO2F.
9. A polyfluoroallyloxy compound having ths formula:
wherein X is -Cl or -F;
D is -CF2R4 or where R4 is -F;
-SO2F; -COF; -CO2H; -CO2R3; -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 -F, -CF3, -CF2CO2R3.
wherein X is -Cl or -F;
D is -CF2R4 or where R4 is -F;
-SO2F; -COF; -CO2H; -CO2R3; -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 -F, -CF3, -CF2CO2R3.
10. The compound of claim 9 wherein X is -F.
11. The compound of claim 10 wherein E is -CF3.
12. The compound of claim 10 wherein R4 is -SO2F, -COF, -CO2R3, -OCF2CO2R3 where R3 is -CH3 or -C2H5, or -CO2H.
13. The compound of claim 10 wherein E is -F.
14. The compound of claim 13 wherein D is -CF2OCF2CO2CH3.
15. The compound of claim 10 wherein E is -CF2CO2CH3.
16. The compound of claim 13 wherein D is -CF2CO2CH3.
17. A polyfluoroallyloxy compound having the formula:
wherein X is -Cl or -F;
D is -F or -RF
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, -COF, -CO2H, -CO2R3, -OCF2CO2R3 where R3 is -CH3 or -C2H5, -CO2CH3, -Cl, and -OCF2CF=CF2;
E is -F, -CF3, or -CF2CO2R3 where R3 has the meaning defined above, -CF2Cl, or -R?OCF(G)2; and G is -F or CF3.
wherein X is -Cl or -F;
D is -F or -RF
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, -COF, -CO2H, -CO2R3, -OCF2CO2R3 where R3 is -CH3 or -C2H5, -CO2CH3, -Cl, and -OCF2CF=CF2;
E is -F, -CF3, or -CF2CO2R3 where R3 has the meaning defined above, -CF2Cl, or -R?OCF(G)2; and G is -F or CF3.
18. A process for preparing a polyfluoroallyloxy compound comprising: (1) mixing and reacting a carbonyl compound having the formula:
wherein A, taken independently, is -F, -COCF3 or -R? where R? 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 R3 is -CH3 or -C2H5;
B, taken independently, is -F, -CF3, -CF2Cl, -CF2CO2R3, where R3 has the meaning defined above, or -CF2OR? where R? 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;
with a metal fluoride of the formula MF where M is K-, Rb-, Cs-, or R4N- where each -R, alike or different, is alkyl of 1 to 6 carbon atoms; and (2) mixing the mixture from (1) with a perfluoroallyl compound of the formula:
wherein X is -C1 or -F;
W and Z, when taken independently, are -F and, when taken together are -CF2-;
and Y is -Cl or -OSO2F.
wherein A, taken independently, is -F, -COCF3 or -R? where R? 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 R3 is -CH3 or -C2H5;
B, taken independently, is -F, -CF3, -CF2Cl, -CF2CO2R3, where R3 has the meaning defined above, or -CF2OR? where R? 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;
with a metal fluoride of the formula MF where M is K-, Rb-, Cs-, or R4N- where each -R, alike or different, is alkyl of 1 to 6 carbon atoms; and (2) mixing the mixture from (1) with a perfluoroallyl compound of the formula:
wherein X is -C1 or -F;
W and Z, when taken independently, are -F and, when taken together are -CF2-;
and Y is -Cl or -OSO2F.
19. The process of claim 18 wherein W and Z are taken independently, X is -F and Y is -OSO2F.
20. The process of claim 19 wherein M is K-.
21. The process of claim 20 wherein A and B are taken independently.
22. The process of claim 18 wherein steps (1) and (2) are conducted in an anhydrous aprotic polar solvent.
23. The process of claim 22 wherein step (1) is carried out at a temperature in the range of about -20 to +60°C and step (2) is carried out at a temperature in the range of about -20 to +80°C.
24. The process of claim 21 wherein steps (1) and (2) are conducted in an anhydrous aprotic polar solvent, step (1) is carried out at a temperature in the range of about 0-10°C, and step (2) is carried out at a temperature in the range of about 0-30°C.
25. The process of claim 24 wherein the solvent is N,N-dimethylformamide, diglyme, triglyme or acetonitrile.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US74702976A | 1976-12-02 | 1976-12-02 | |
| US747,029 | 1976-12-02 | ||
| US85072977A | 1977-11-11 | 1977-11-11 | |
| US850,729 | 1977-11-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1174685A true CA1174685A (en) | 1984-09-18 |
Family
ID=27114682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000292106A Expired CA1174685A (en) | 1976-12-02 | 1977-11-30 | Polyfluoroallyloxy compounds, their preparation and copolymers therefrom |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1174685A (en) |
-
1977
- 1977-11-30 CA CA000292106A patent/CA1174685A/en not_active Expired
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