PERFLUOROGLYCIDYL ETHERS

' !189524 CR-7880 -ITITLE Per fluoroglycidyl Ethers TECHNICAL FIELD This invention relates to perfluoroglycidyl ethers, their preparation and polymers therefrom.

BACKGROUND ART P. Tarrant, C. G. Allison, K. P. Barthold and E. C. Stump, Jr., "Fluorine Chemistry Reviews", Vol. 5, P. Tarrant, Ed., Decker, New York, New York i0 (1971) p 77 disclose fluorinated epoxides of the general formula CF2 -CFRF \o/ whereìn RF may be a perfluoroalkyl group of up to I0 carbons containing one or more functional substituents -CF=CF2, -CFCF,, -Cl or -}I V'- Oxidations of the type CF2=CFCF2X + 02 or H2 02 /OH--- CF2 -CFCF2 X are disclosed õ/ where X is -F, -(CF2 )5H (O.S. Patent 3,358,003), -CF2CI or -CF2 Br (T. Io Ito et al, Abstracts, Div. Fluoro. Chem., Am. Chem. Soc., Ist ACS/CJS Chem.

Congress, Honolulu, HI, April 1979) Olìgomers and polymers of perfluoroepoxldes CF2-CF-RF are described in U.S. Patent 3,419,610 and \o/ by P. Tarrant et al. in Fluorine Chem. Reviews, 5, pp 96-102 (1971). Nonfunctional fluoroethers of difluoroacetyl fluoride of the formula RFOCF2 COF are also known, and the insertion of one or more moles of hexafluoropropene epoxide into said nonfunctional perfluoroethers is disclosed in U.S.

Patent 3,250,808:

118952 + n (CF2 -CFCF ) RFOCF2COF \O/ / CF3 /n-1 CF3 where n is 1 to at least 6 and RF is perfluoroalkyl, perfluoroalkoxy, or per f luor oa ikoxyal kyl.

Glycidyl ethers containing the segment CH2-CHCH20are widely disclosed. The glycidyl ether i0 No/ CH2-CHCH20C6H5/ is disclosed in U.S. Patent 4,127,615.

%%DESCRIPTION%%z DISCLOSURE OF INVENTION Novel perfluoroglycidy! ethers are provided having the general formula CF2 -CFCF2 Oì %%DESCRIPTION%%/ « I wherein PT is:

(i) -CFRICFQ l ! Y y, wherein RI is a carbon«carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -S02 F, -COF, -F, -CI, -Br, -I, -CN, -CO2 H, -OC6F5, or -CO2R4 where R4 is -CH3 or -C2 H5 ; Y and ¥' are -F or -CF3 , provided that only one of Y and Y' can be -CF3 ; or (ii) -CF(R2)2 wherein R2 is -F, -CF2 C1, -CF2 CN, -CF2 COF, -CF2 C02H, -CF2OCF(CF3)2 or -CF2 C02R4 where R4 is defined as above; or (iii) -(CF2 CFO)nR3Q Y wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety -(CF2 CFO)nR3 does not exceed 15 carbon atoms; Y indeY pendently is -F or -CF3 ; n is 1 to 4; and Q is as i0 defined above; or (iv) -C6 F5.

Perfluoroglycidyl ethers of formula I are prepared by contacting and reacting the corresponding polyfluoroallyl ethers with oxygen.

The ethers of formula I may be homopolymerized, or copolymerized with suitable fluorinated epoxides which include hexafluoropropene oxide, tetrafluoroethylene oxide, and other perfluoroglycidyl ethers of formula fo Homoand copolymers prepared from formula I ethers wherein RF is nonfunctional are useful as stable oils and greases. Polymers prepared from formula I ethers wherein RF contains functional moieties which may provide crosslinking or cure sites are stable elastomeric materials useful as sealants, caulks, and fabricated objects. Preferred ethers of formula I are those which contain functional moieties within RFO Especially preferred are ethers of formula I where RF is-C6 F5, -CFR'CFQ0r-CF(R2)2, I y y' Y and Y' are -F; Q is -SO2 F, -C02R4 -CN -OC6 F5 , R2 -CF2 C02R4 -Br -I and -COF; is , -CF2 COF, -CF2 CN; and R4 is -CH3 or -C2 H5.

Perfluoroallyl ethers, when reacted with 02, also yield, in addition to the perfluoroglycidyl ethers of formula I, coproduct fluoroformyl difluoromethyl ethers containing one less carbon atom which have the general formula FOC-CF20RF II wherein RF is as defined above.

The novel perfluoroglycidyl ethers of this invention are prepared from the perfluoroa!lyl ethers which are disclosed by Krespan in U.S.

Patent NOo 4,275,225, issued 1981 June 23° These perfluoroallyl ethers are of the formula CF22 0RF wherein RF is:

(i) -CFRICFQ y y' wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -S02 F, -COF, -F, -C1, -Br, -I, -CN, -C02H, -OC6 F5 r or -CO2 R4 where R4 is -CH3 or -C2 H5 ; Y and Y' are -F or -CF3 , provided that only one of Y and Y' can be -CF3 ; or l0 (ii) -CF(R2)2 wherein R2 is -F, -CF2 CII -CF2 CN, -CF2 COF, -CF2 CO2 H, -CF2OCF(CF3)2 or -CF2 CO2 R4 where R4 is defined as above; or (iii) -(CF2 CFO)nR3Q Y wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety R3 does not exceed 15 carbon atoms; Y is -(CF2CFO)n Y -F or -CF3 ; n is 1 to 4; and Q is as defined above; or (iv) -C6 F5, The perfluoroglycidyl ethers of this invention are also prepared from perfluoroallyl ethers of the formula CF2 =CFCF2 0(CF2 CFO)nR3Q Y wherein R3, Q and n are as defined under (iii) above, and Y, independently, can be -F or -CF3.

These perfluoroallyl ethers are prepared by (i) mixing and reacting (a) a carbonyl compound having the formula:

AI-c-y wherein A1 is Q,CFRlJ y' where R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q' is -S02F« -SO2 OCF2 CH3 t -COF, -Fs -CI -Br, -fs -CN, -OC6 F5 or -C02R4 where R4 is -CH3 or -C2 H5 ; Y and Y are -F or -CF3 , provided that only one of Y and Y' can be -CF3 ; or (b) a carbonyl compound having the formula:

i0 A2 F wherein A2 is Q, R3 (OíFCF2 ) n_IOCFY Y where R3 is a linear or branched perfluoroalklylene group of carbon content such that the moiety R3(OCFCF2 )n_IOCF-.

Y Y does not exceed 14 carbon atoms; Y independently is -F or -CF3 ; n is 1 to 4; and Q' is defined as above; or (c) an alkali metal salt of pentafluorophenol, with a metal fluoride of the formula MF where M is K-, Rba, Cs-, or R4 Nwhere each -R, alike or different, is alkyl of 1 to 6 carbon atoms; and (2) mixing the mixture from (i) with a perfluoroallyl compound of the formula CF2=CF-CF2Z wherein Z is -CI, -Br or -OS02 F.

The perfluoroglycidyl ethers of formula I and the fluoroformyl difluoromethyl ethers of formula II are prepared from the perfluoroallyl ethers by reaction with oxygen at about 20° to about 200°C, preferably about 80° to about 160°C:

iI 9oZ4 -6 o2 CF2=CFCF2ORF (2) (xl 2îcFc 2o + (yl Foc-c 2 o ÷ (yl c0F2 o I II where x and y are, respectively, the mole fractions of products I and II. Ethers of formula I are normally stable at the reaction temperature.

Formation of ethers of formula II, together with I0 carbonyl fluoride, is presumed to result from oxidative cleavage of the allylic double bond in the starting polyfluoroallyloxy compound.

The by-product COF2 is normally inert, except where RF contains a functional group such as _C02 H with which it can react; e.g.

CF-CF CF O (CFo)5C02H + COF2 -- (3) CF2-CFCF20(CF2)5COF + HF + CO2 \O/ The epoxidation reaction may be carried out at pressures of about 5 to about 3000 psi, preferably about 50 to about 1500 psi. Solvents are not essential, but inert diluents such as 1 1,2-tr ích lor ooi, 2,2-tf i f luor oe th ane (CFCI2CF2 CI ) or perfluorodimethylcyclobutane may be used.

Reactant proportions may vary from a large molar excess of olefin over 02 (e.g., I00:i) to a large excess of 02 over olefin (e.g., 100:1); a modest excess of 02 , e.g., about 1.1:l to about 10:l, is normally preferred to insure complete reaction of the olefin.

The epoxidation reaction is most conveniently initiated thermally, but may be catalyzed by the use of free-radical initiators or by ultraviolet irradiation in the presence of a photoactive material such as bromine° The epoxidation may be conducted in a batchwise or £189S£14 continuous manner° The epoxidation product of formula I is generally isolated by direct fractional distillation, although in some cases a preliminary treatment with Br2 or CI2 may be helpful. When epoxidation is carried out at lower temperatures (I00°), addition of radical acceptors such as o-dichlorobenzene to the mixture just prior to fractionation is a desirable precaution against the possible presence of peroxides° I0 The art teaches the preparation of certain fluoroepoxides, such as hexafluoropropy!ene oxide (HFPO), by reacting the corresponding vinyl compound with alkaline hydrogen peroxide. Said reagent cannot be used for preparing the perfluoroglycidyl ethers of formula I when RF contains a functional group such as -CO2 H, -CO2 R4, -COCI, or -COF which is hydrolytìcally unstable in the presence of alkaline H2 020 Where RF is nonfunctional or contains functional groups which are inert or relatively unreactive to alkaline H2 02 , such as -Br, said reagent can be used as an alternative to molecular oxygen for preparing formula I compounds.

Perfluoroglycidyl ethers of formula I can be homopolymerized or copolymerized with suitable fluorinated epoxides such as HFPO, tetrafluo oethylene epoxide (TFEO) and other perfluoroglycidyl ethers of formula I; HFPO and TFEO are preferred comonomers, with HFPO most preferred, For example :

SrxcF3 çcF2 ÷ R OEF2 CF-CF2 anionic 0 %O/ catalyst -30°C I (4) III wherein x is moles of HFPO per racle of formula I ether, which monomer units may be randomly distributed within the copolymero (Co)-polymerization proceeds in the presence of a suitable solvent and initiator at temperatures of about -45° to about +25°C, preferably about -35« to about 0°Co The quantity of solvent may be from about 5 to about racle percent of the total monomer feed. Suitable solvents include commercial ethers such as diethyl ether, diglyme, triglyme and tetraglyme (di-t tri-, and tetraethyleneglycol dimethyl ether), and fluorinated solvents such as l,l,2-trichlorotrifluoroethane, chlorotrifluoroethylene« dichlorodifluoromethane, hydrogen-capped HFPO oligomers of the formula CF3 CF2 CF2 0[CF( "3 )CF2 0]nCHFCF3 , where n is 1 to 6, divers and ,rimers of hexafluoropropene (HFP), and HFP itself; the latter is a preferred solvent.

Solvents should be thoroughly dried, preferably by means of molecular sieves, before use.

Catalysts suitable for the (co)polymerization of formula I ethers include anionic initiators which are effective for the polymerizatín of hexafluoropropylene oxide (HFPO), such as carbon black or, preferably, combinations CsF-LiBr, KF-LiBr, (C6 H5 )3 PCH3 , -LìBr, CsF-FOCCF(CF3)OCF2CF2OCF(CF3)COF' CsF-CF3CF2CF20[CF{CF3)CF20]nCF(CF3)COF where n is 2 to 6; the latter catalyst wherein n is 4 to 6 is preferred. Preparation of fluoropolyethers such as that used in the last mentioned catalyst is described in U.S. 3,322,826. Catalyst concentration should be about 0.05 to about 1 mole percent of the total monomer feed when higher molecular weight products are desired.

The perfluoroglycidyl ethers of formula I and comonomers such as HFPO should be reasonably pure and dry before (co)polymerization. Monomers may be dried with molecular sieves or, preferably, over KOH-CaH2.

i0 Dryness and high purity are necessary for the prepara- • tion of high molecular weight (co)polymers from formula I ethers.

Polymerization pressures may be in the range of from less than one atmosphere to about 20 atmospheres or more; pressures in "the vicinity of one atmosphere are normally preferred.

Copolymers of the present invention containing the functional groups -COCI, -CONH2, -S02 OH, -S02 0M', -CO2M', or -CN, where M' is alkali metal, ammonium or quaternary ammonium, can be prepared by post-polymerization conversion of functional groups, i.e., by reacting copolymers of the present invention containing the functional groups -COF, -COOH or -S02 F with appropriate reagents. For example, copolymers of the present invention containing -COCI groups can be prepared from the corresponding copolymer containing -COOH groups by refluxing with thionyl chloride (S0C12 ) in the presence of a catalytic amount of dimethylformamide. Copolymers containing -CONH2 groups can be prepared from the corresponding copolymer containing -COOH, -COF, -COCI or -C02R4 groups by esterification and/or ammonolysis.

Copolymers containing -802 OH or -802 0M' group can be prepared hydrolyticaily from the corresponding copolymers containing -SO2 F groups as disclosed in U.S. Patent No. 3,282r875. Copolymers containing -C02 M' groups can be prepared hydroìytically f om the corresponding copoly= mers containing -COF groups as disclosed in U.So Patent No. 4r131,740. Copolymers containing -CN groups can be prepared from the corresponding copolymers containing -CONH2 groups by reaction with a reagent of the formula (CCI3) £ (R5)m l0 where is -CH3 or -C2 H5 , £ is 1 or 2 and m is 0, i or 2, to yield copolymer containing -CN moieties; benzotrichloride is a preferred reagent. Nitrile functions are well suited for providing cure sites in the copolymers of this invention, leading to stable elastomeric materials as described above.

Thus, this invention provides copolymers containing recurring units of the formula wCF=CF20-- CF2 OR'F where R' has the same meaning as RF, defined above, F except that the functional group selection also includes COC1r CONH2 « -S02 OK« -S02 0M « and-CO2 M . The functional groups C02 M , -S02 0M', and -S02 0H impart hydrophilicity and catìon exchange properties to the polymers of the present invention. The acid chloride functional group is a precursor to other useful carboxylated groups, e°g=, -CO0}{, -C02 R4, and -C02 M' The amide functional group is a precursor to the -CN group, which provides useful cure sites in fluoroelastomers ° In the following examples of specific embodiments of the present invention, parts and percentages are by weight and all temperatures are in degrees C unless otherwise specified= Example 2B represents the best mode contemplated for carrying out the invention.

l0 EXAMPLE 1 Per fluor oI 1,2-epoxy-5-me th11,4-oxah exane IJ (CF3)2CFOCF2CF=CF2 > (CF3)2 CFOCF2 COF + COF2 + (CF )oCFOCF CFCF« Ao A 100-ml stainless steel tube was charged with 63.2 g (0.20 mol; 39 ml) of (CF3)2CFOCF2CF=CF2 and 50 ml of CFCI2 CFCI2 i0 and pressured with 02 to 200 psi. When heated slowly, the system showed an obvious loss in pressure near 75°. Temperature was held at ca. 80° and 02 was pressured in as needed to maintain 250 psi over a total of 17 h. Distillation of the liquid products gave 12.0 g (21%) of byproduct acid fluoride, bp 40-43°, and 17o3 g (26%) of perfluoro-2-methyl5,6-epoxy-3-oxahexane, by 57-59°.

Redistillation of the epoxide gave a nearly pure sample, bp 58.5-59°. IR(CCI4) : 6.47 (epoxide), 7o5-9/ (CF, C-O) with a trace COF impurity at 5.31/4.

NMR: 19F -81.6 (t of d, JFF 5, 2°0 Hz 6F, CF3), -146o0 (t of septets, JFF21.6, 2Hz 1Fo (CF3)2CF) and «156.0 ppm (d of d of t, JFF 19.2, 16o9, 2.8 Hz, 1F, ring CF) with broad AB multiplet for OCF2 centered at -7335 Hz and satellites at -7175 Hz and -7496 Hz; and AB pattern for ring CF2 at -104416 and -10458 Hz (d of t JFF 19.2, 9.7 Hz, IF) and -10628 and -10669 Hz (d, JFF 16.9 Hz, IF). Trace impurities were present, as was also indicated by gc analysis.

Anal. Calcd for C6 F12 02 : C, 21o70; F, 68.66 Found: C, 21.00; F, 68.23.

B. Oxidation at a higher temperature than that employed in Paçt A was carried out in an attempt to maximize epoxide formation. A 100-ml tube charged with 56.9 g (0.18 mol 35 ml) of (CF3 )2 CFOCF2 CF=CF2 and 50 ml of CFCI2 CFCI2 was preheated to 140° and Il (5) Ii0 psi before addition of 02 ° As 02 was added in slugs, rapid exothermic reaction occurred.

Temperature control was maintained better with slow continuous feed of 02 between 220-260 psi; after 8 h the pressure remained constant at 260 psi.

Fractionation of the liquid products gave 7.9 g (16%) of crude acid fluoride, bp 38-45°« and 34.6 g (58%) of epoxide, bp 58-61°o Gc and ir indicated 6-7% impurities to be present, including ca. 5% of l0 CFCI2 CFCI2 solvent« EXAMPLE 2 Perfluor_o-5,6-epoxv-3-oxahexanesulfonyl Fluoride o2 FSO2CF2CF2OCF2CF=CF2- ) FSO2 CF2 CF2 OCF2COF + COF2 + FSO2 CF2 CF2 OCF2 CFCF2 (6) \o A° A 100-mi stainless steel tube charged with 68.1 g (0.206 mol, 40 ml) of FSO2CF2CF2OCF2CF=CF2, 50 ml of CF2 C!CFCI2 , and 200 psi of 02 was heated to 80o and 300 psi. The tube was repressured periodically with 02 until pressure was constant at 300 psì (13 h). Forty ml of o-dichlorobenzene was added to the liquid prc uct, and the mixture was fractionated to give 11.4 g (19%) of acid fluoride, bp 48-52° (200 mm), and crude epoxide, bp 58-70° (200 mm).

Redistillation of the crude perfluoro-5,6epoxy-3-oxahexanesulfonyl fluoride gave 13.1 g (18%), bp 59-61" (200 mm) o IR (neat): 6.51 (epoxide), 6.82 (SO2 F), 7.5-9 (CF, C-O)° NMR: 19F 45.2 (t of t, JFF 6.1, 6.1 Hz, IF, SO2 F), -82.5 (m, 2F, CF2CF20), -I13.1 (d of t, JFF 5.6, 2.8 Hz, 2F, SO2CF2), and -156.8 ppm (d of d of mi JFF 18.8 Hz, IF, ring CF) with AB multiplet for OCF2 at 35-7351, -7503, -7539 and -7689 Hz (m, 2F) and an AB multiplet for ring CF2 at -10365 and -10405 Hz (d of t, JFF 18.8, 9.8 Hz, IF) and -10593 and -10633 -13 HZ (d, JFF 16o8 HZ, IF).

Anal. Calcd for C5 FI0 04 S: C, 17.35; S, 9.27 Found: C, 17.19; S, 9.95.

B. A purer sample of epoxide than that in Part A was obtained in higher yield by oxidation of neat olefínic precursor A 100-ml metal tube containing 134.9 g (0.41 mol, 80 ml) of FSO2CF2CF2OCF2CF=CF2 was held at 140-150« while oxygen was added s!owly and continuously for 2 ho Pressure i0 rose from 75 psi to 250 psi and leveled. The pressure was raised to 450 psi with 02 ; no further pressure change occurred in 5 h. The additional oxygen and higher pressure were used to insure complete reaction. Ten ml of o-dichlorobenzene was added to the liquid product, and the mixture was fractionated to give 32°0 (26%) of crude acid fluorìdef bp mainly 80 and 80.5 g (57%) of epoxide, bp 57o65° (200 mm)o Redistillation gave 69.5 g (49%)« bp 93-94o, of pure epoxìde.

Anal. Calcd for C5 FI0 04 S: C, 17o35; S, 9.27 Found: C, 17.60; S, 9.52.

EXAMPLE 3 Perfluoro-9,10-epoxy-7-oxadecanoic Acid and Perfluo!o-9,10-e2_qxy-7-oxadecanoxyl Fluoride HO 2C (CF2)5 OCF2 CF=CF2 ---- FCO (CF2) =OCF,CFCF %%DESCRIPTION%% (7) + HO2 C (CF2) OCFoCFCF --0 Ao A 100-ml tube charged with 117 g (0.26 mol, ml) of HO2 C(CF2 )5 OCF2 CF=CF2 was heated at c__aao 140« while oxygen was added slowly until no exothermic reaction was apparent. Further heating at 140° gave a pressure rise from 332 to 418 psi over 1-2 h. Ten ml of o-dich[orobenzene was added to the liquid product and the mixture was distilled.

Fractions collected at 68-98° (100 mm) had a small second layer of o-dichlorobenzene which was removed, and the crude perf!uoro-9,10-epoxy-7-oxadecanoyl fluoride was refractionated to give 23o2 g (19%) of epoxy acid fluoride, bp 73-75° (100 mm). IR (neat):

5.30 (COF), 6.47 (epoxide), 7.8-9/M (CF, C-O) NMR 19F 23.9 (t of t of t, JFF 8, 6, 1.5 Hz, IF, COF), -83.6 (m, 2F, CF2 CF2 0), -119.0 (t of d of m, JFF 12, 8Hz, 2F, CF2 COF), -122.6 (m 2F, CF2), -123.4 (m, 2F, CF2), -126.2 (me 2F, CF2), i0 and -157.0 ppm (t of m, JFF 18 Hz, IF, ring CF), with AB multiplets for OCF2 at -7389, -7541, -7571, and -7723 Hz (m, 2F) and for ring CF2 at -10396 and -10437 Hz (d of t, JFF 19.0 9.9 Hz, IF) and -10616 and -10657 Hz (da JFF 16.9 Hz, IF).

Anal. Calcd for C9 F16 03 : C, 23.49 Found: C, 23.77.

B. Further fractionation of the reaction mixture gave, after removal of o-dichlorobenzene at m 45-55° (5 mm), 34 .4 g (29%) of perfluoro-9«10-epoxy-7oxadecanoìc acid, bp 63-65° (0.6 mm)° IR (neat):

2.8-4°0 (H-bonded OH), 5.63 (C=O), 6.48 (epoxíde), and 7.3-9/4 (CF, C-O). NMR: IH 12.0 ppm (s, CO2H) ; 19F -83.6 (m, 2F, CF2 CF2 0) -119.8 (t of t, JFF 13, 3.0 Hz, 2F, CF2 CO2 H), -122.6 (m, 2F, CF2 ),-123.3 (m, 2F, CF2 ), -126.2 (in, 2F, CF2), and -156.9 ppm (t of m, JFF' 18 Hz, IF, ring CF) with AB multiplets for OCF2 at -7389, -7572, and -7723 Hz (m, 2F) and for ring CF2 at -10392 and-10434 Hz (d of t, JFF 19.0, 10.0 Hz, IF) and -10613 and 10655 Hz (d, JFF 16.9 Hz, IF).

Anal. Calcd for C9 HF15 04 : C, 23.60; H, 0.22 Found: C, 23.99; Ha 0.39.

EXAMPLE 4 Pe r f luoroT 6 epoxy 4,oxah e£pta hen i tf i le o2 CF2=CFCF2OeF2OF 2íFCF2OEF2OF2 eN (8) A 100-mi stainless steel-lined tube charged with 38.5 g (0.14 mol) of perfluoro-4-oxa-6-heptenenitrìle was heated at 140° while oxygen was added incrementally (over 5.5 h) until reaction was i0 complete. Fractionation of the liquid products gave perfluoro-6,7-epoxy-4-oxaheptanenitrile, bp 65-67°, 15.7 g (39%). IR (CC14 ); 4.40 (CN), 6.47 (epoxide) and 8-9}/ (CF, C-O). NMR (CC14 ): -87.5 (m, 2F, OCF2) -109.2 (t, JFF 4.7 Hz, 2F, CF2 CN), and -156.7 ppm (d of d of m, JFF 18.7, 16.7 Hz, IF, CF) with AB groupings for ring CF2 at -10347 and -10389 Hz (d of t, JFF 18.7, 9.5 Hz, IF) and -10570 and -i0«i0 Hz (d, JFF 16.7 z, IF) and for CF2 adjacent to epoxide ring at -7376, -7529,-7556, and -7707 Hz (me 2F).

Anal. Calcd for C6 F9 NO2 : C, 24.93; N, 4.85 Found: C, 25.19; N, 5°02° EXAMPLE Perfluoro(phenyl glycidyl)ether A. CsOC6 F5 + CF2 =CFCF2 OSO2 F C6 FsOCF2 CF=CF2 (9) Pentafluorophenyl perfluoroallyl ether was obtained by adding perfluoroallyl fluorosulfate rapidly to an equivalent of cesium pentafluorophenoxide in dìglyme at -25°. The temperature carried to +10°, and the product was isolated by drowning the reaction mixture in water, washing the lower layer with water, and drying and distilling, bp 63" (30 mm). Ge showed the olefin to be 96% pure« B. C6 F5 OCF2 CF=CF2 02 C6F5OCF2 F2 A 100-m! metal tubeæharged with 64.0 g (0°204 mol) of pentafluorophenyl perfluoroallyl ether was heated at 140 while oxygen was pressured in 16-- until uptake ceased° Distillation gave O4o0 g of a mixture of pentafluorophenyl pentafluoro-2,3-epoxypropyl ether and starting material, bp 60-658 (30 mm). This distillate was stirred with 40 ml of CFC12 CF2 CI and 16 g (0.i0 mol) of bromine while the mixture was irradiated with a sunlamp at 40-559 for 18 rein. Distillation gave nearly pure epoxide, bp 61-648 (30 mm), 25.5 g. the several fractions were contacted with calcium hydride while open to the i0 air until the acid fluoride impurity peak in the infrared spectrum disappeared, then subjected to vacuum tranfer, contact with CaSO4 , and filtration to give 14.8 g (22%) of purífied epoxide. IR (neat) : 3.29, 3.70, 4.01 (weak bands associated with arom. ring), 6.07, 6.30, 6.57 (atom. C=C), 6.47 (epoxide ring) and 8-9/4 (CF, C-O). NMR (CCI4) :

IH none; 19F-151 .8 (m, 2F, aroma CF), -155.1 (t, JFF 21.1 Hz, IF, aromo aF), -155o7 (t JFF 18 Hz, IF, epoxide ring CF), and -161o6 ppm (m, 2F, atom.

CF), with AB patterns for CF2 adjacent to epoxide ring at -7457, -7598 -7629, and -7771 Hz (m, 2F) nd for ring CF2 at -10365 and -10406 (d of t, JFF 18.6, 9.1 Hz, IF) and -10610 and 10650 Hz (d, JFF 17.5 Hz, IF).

Anal. Calcd. for C9 FI0 02 : C, 32.75; Fs 57.56 Found: C,, 32.89; F, 57.65 EXAMPLE 6 Per fluor o-8 9 6-oxanonanoyl Fluor ide CF2=CFCF20(CF2)4COF + 02 CF2 CFCF2 0(CF2)4COF \o/ 90.5 g (0.23 mol) of CF2 =CFCF2 0(CF2 )4 COF was reacted with small amounts of 02 until 200 psi pressure was obtained at 140«. Pressure was increased with 02 up to 500 psi and maintained for 4 h at 140«. Distillation of the crude mixture gave 35.3 g (37%) of perfluoro-8,9-epoxy-6-oxanonanoyl fluoride, bp 66-67 (150 mm). IR (CC14 ):

(I0) 5o3 (COF), 6.5 ( ) ; 8o9/A (CF, CO) o A weak band at 5.55/ indicated the presence of a small amount of uncreated olefino NMR: 19F (CFCI3 )..

24.!0 (COF), -79.59 ( O ), -82.96 OE (OCF2(CF2)3COF), -ll0.31 and 112.90 (CF CF), -i18.31, \õ ŒEE -122.74,-125.05 (CF»CF»CFgCOF), -156o38 ppm (CF,CF).

i0 OE ŒEE % « \õ/ The 19F NMR also showed small amounts of unreacted starting material.

EXAMPLE 7 P e r f lu or o (me thy i -8,9-epoxyç 6-ox a no na no_a te ) CF2 =CFCF2 0(CF2)4COOCH3 + 02 CF2 -CFCF2 0(CF2) COOCH3 (!i) \oI 4 33 g (.085 mol) of perfluoro(methyl-6«oxa-8nonenoate) was reacted with oxygen at 140° in the usual manner. Distillation of the crude product gave 3.46 g (10%) of perfluoro (methyl-8,9-epoxy-6-oxanonanoa te) , bp=51-52« (1.2 mm) o IR (CC14 ): 3.28, 3.35, 3.45 (-CH3), 5.57 /O (C=O), 6o5 (CF2 F-), 7 5 to 9.5 (CF, CO).

NMR (CFCI ) : 19F7/CF20 3 -77.56 ( ), 83.20 OE (OCF2(CF2)3C00CH3)s -ii0.31 -112.77 (CF2 CF), -119.08, \o/ -128 o18, -125.48 (CF,CF CF COOCH3), -156.27 ppm ,%. ,% oE oE í (CF2 CF) ; IH 1.9 ppm (CH3).

\õ EXAMPLE 8 Per f luor o 9[Î -5çme thyl-4d 7,d ioxadec anen i tf i leI 0 íF3 NH3> Il Br A. CH3 OCCF2 CF2 OCFCF2 OCF2 CF=CF2 (_CF3 CO) 2°, ÍF3 (12) NCCF2CF2OCFCF2OCF2CFBrCF2 Br A mixture of 52°4 g (0.111 mol) of methyl l0 perfluoro(5-methyl-4,7-dioxa-9-decenoate), 17.7 g (0olii mol) of bromine, and 50 ml of CCI4 was stirred and irradiated with a sunlamp intermittently until the exotherm subsided. Another 3.1 g (0.02 mol) of bromine was added and the mixture was irradiated for 30 rein. Volatiles were removed at 1 mm pressure, 150 ml of ether was added to the residue, and anhydrous ammonia was bubbled into the stirred mixture until an excess was present. Volatiles were removed to 0.5 mm of pressure, the residue was dissolved in a little tetrahydrofuran and filtered. A mixture of the filtrate and 250 ml of tetrahydrofuran was stirred at -.20° while there was added successively 19.3 g (0.244 mol) of pyridine and 24.2 g (0.122 mol) of trifluoroacetic anhydride. The resulting mixture was stirred at -20° for 30 rein and then allowed to come to 25°. Dilution with 1 liter of water gave an organic layer which was washed with 500 ml of water, dried over CaSO4 and distilled. There was thus obtained 36.5 g (55%) of perfluoro(9,10-dibromo-5-methyl-4,7dioxadecanenitrile), bp 62« (10 mm). IR (neat): 4.38 19F -80 3 (CN), 8-9 (CF, C-O). NMR (CCI4) :

(m, 3F, CF3 ), -83.9 (m, 2F, CF2 0), -85.0 (m, 2F, CF2 0), -108.9 (t, JFF 5.4 Hz, 2F, CF2CN), -132.6 (t of t, JFF 14.5, 10.5 Hz, IF, CFBr), and -145.5 ppm (t of m, JFF 20.9 Hz, 1F, CF) with AB patterns for CF2 Br at -5200 and -5375 (d of t, JFF 14.5, 9 Hz, IF) and -5474 and -5649 Hz (d of -19 t, JFF 14.5, 14.5 HZ, IF), and for OCF2 at -7001 -7150, -7176, and -7325 Hz (m, 2F).

Anal. Calcd» for C9 Br2 FIsN02 : C, 18o05; N, 2.34 Found: C« 18o34; N, 2.29.

CF3 NCCF2CF2 0CFCF2 OCF2CFBr CF2Br Zn OF3 NCCF2CF2OCF CF20CF2 CF=CF2 (13) i0 A suspension of 7.58 g (0.i16 mol) of zinc dust in 150 ml of diglyme was stirred at 45-52° (5 mm) while 34.7 g (0.058 mol) of the dibromidi was added dropwise. Stirring and heating were continued £or one h. The crude product which collected in a -80i trap was washed with 200 ml of water, dried over CaSO4 and distilled to give 16.7 g (66%) of perfluoro(5-methyl-4,7-dioxa-9-decenenitrile), bp 64° (100 mm). IR (neat): 4.39 (CN), 5.58 (C=C), and 8-9/< (CF, C-O). NMR (CCCI4 ): 19F -72.2 (d of d of t of d, JFF 24.9, 13.9« 13.9, 7.9 Hz« 2F, OCF2 C=), -80.8 (m, 3F, CF3 ), -84.2 (m, 2F, OCF2 ), -85.4 (m, 2F, OCF2 ), -91.5 (d of d of t, JFF 51.6, 39.5, 7.9 [4z, IF, cìs-CF2 CF=CFF), -105.2 (d of d of t, JFF 118.2, 51.6, 24.9 Hz, IF, trans-CF2CF=C[F), -109.3 (t, JFF 5.3 Hzs 2F, CF2CN), -145.8 (t of m), JFF 16.3 Hz, IF, CF), and -191.2 ppm (d of d of t, JFF 118o2, 39.5, 13.9 Hz IF, -CF2 CF=).

Anal. Calcd. for C9 FI5 NO2 : C, 24.62; N, 3.19 Found: C, 24.56; N, 2.99 F3 NCCF2CF2OCFCF2OCF=CF2 F3 (14) NCCF2CF2OCFCF2OCF2 CF2 O Co A 100-ml metal tube charged with 89.1 g (0.203 mol) of the cyanoolefin was heated at 140° while oxygen was pressured in until reaction was complete as judged by lack of pressure drop.

Fractionation of the liquid product afforded a mixture of cyanoepoxide and cyanoacid fluoride, bp 62° (200 mm) -67° (i00 mm). Treatment with Call2 did not remove the acid fluoride component, so the crude product was shaken with a mixture of 50 ml i0 CFCI2 CF2 CI and 300 ml ice and some water. The organic layer was dried over CaSO4 , filtered and distilled to give 33°0 g (36%) of pure perfluoro (9 ,10epoxy-5-methyl-4,7-dioxadecanenitrile bp 64-64.5° (100 mm). IR (neat): 4.37 (CN) 6°47 (peroxide), 8-9 (CF, C-O). NMR (CC14 ) : 19F-80 .3 (m, 2F, CF20), -80.7 (m, 3F, CF3 ), -83.5 (m, 2F, CF2 0), -85.3 (m, 2F, CF2 0) s -109.2 (t, JFF 5.0 Hz, 2F, CF2CN), -145.4 (t, JFF 21.1 Hz, IF, CF), and -157.0 ppm (t, JFF 18.0 Hz, IF, CF) with an AB pattern for ring CF2 at -10400 and -10441 Hz (d of t, JFF 18.5, 9.6 }{z, IF) and -10626 and -10667 Hz (d, JFF 16.8 Hz, IF).

Ana!. Calcd. for C9 FIsNO3 : C, 23.75; N, 3.08 Found: C 23.99; N, 3.27.

EXAMPLE 9 Pe r f lu o][ o (i, 2 -epoxy7-ph eno xy - 4-ox aheptane) Ao o il KF C6F5OCF2CF2CF CF2 =CFCF2 0SO2F C 6 F5 OCF 2CF 2CF 2OCF 2CF=CF 2 (15) A suspension of 14.5 g (0.25 mol) of flame-dried KF in 200 ml of diglyme was stirred at 0-5° while 66.0 g (0.2í] mol) of 3-pentafluorophenoxytetrafluoropropíonyl fluoride was added. The mixture was stirred an additional 15 miñ, after which time 50.6 g (0.23 mol) of perfluoroaliyl fiuorosulfate was added at 0-5°. The resulting mixture was stirred at 0-5° for 2 h and then poured into 1 liter of water° The lower layer was washed with 250 ml of water, dried over CaSO4, and fractionated to give 53.2 g (55%) of perfluoro(7-phenoxy-4-oxa-l-heptene), bp 56-57° (2 mm). IR (neat): 3°32, 3.71, 4.01 (weak, associated with aromatic ring), 5.60 (C=C), 6.07 and 6°59 (arom. C=C) 8-9/4 (CF, C-O). NMR I0 (CC14 ) : 19F -72.0 (d of d of t of d, JFF 25.1, 13.5, 12, 7.2 Hz, 2F, OCF2 C+) -84°6 (m, 4F, CF20), -91.9 (d of d of t, JFF 52.3, 39.2, 7.2 Hz, IF, c is-CF2 CF=CFF ), -105.2 (d of d of t, JFF 117.4, 52.3, 25.1 Hz, IF, trans-CF2 CF=CFF), -129.0 (m, 2F, CF2 ), -151.7 (m, 2F atom. CF), -155o2 (t, JFF 21o0 Hz, IF, arom. CF) -161.7 (m, 2F, atom.

CF), and -190o 5 ppm (d of d of t of m, JFF 117.4, 39.2, 13.5 Hz, IF, CF2 CF=CF2 )0 Anal. Calcd. for C12 F16 02 : C, 30.03; F« 63.32 Found: C, 30.12; F, 63.25 C6F50 (CF æ3 OCF2CF=CF 2 O2 c6 F5 0 (CF2 ) 3OCF2ï-íF2 (161 o A 100-ml metal tube lined with stainless steel and charged with 105.3 g (0°22 mol) of perfluoro(7-phenoxy-4-oxa-l-heptene) was heated at 140° while oxygen was pressured in intermittently until no pressure drop was observed° The liquid product mixture was fractionated to afford 78.5 g of distillate, bp 37-70° (3 min). The distillate was shaken with 1 liter of ice water, and then 25 m! of CFCI2CF2CI and some calcium sulfate were added to hasten separation The lower layer was dried over calcium sulfate and fractionated to give 33.3 g (31%) of per fluoro ( 7-phenoxy-i, 2-epoxy-4-oxaheptane ) bp 55° (1o9 mm). IR (CC14 ): 6.47 (epoxide ring), 6.58 (aromatic C=C) 8-9/< (CF, C-O) o NMR (CCI4) :

19F-84.1 (la, 2F, OCF2 )» -84 6 (m, 2F, OCF2 ), -129.0 (s, 2F, CF2 ), -151°8 (m, 2F, arom. CF), -155.1 (t, JFF 21.0 Hz, !F, arom. CF), -156o6 (t, JFF 17.9 Hz, IF, ring CF), and -161.7 ppm (m, 2F, atom. CF), with AB groupings at -7382, -7534, -7566, and -7719 Hz (m, 2F) for CF2 adjacent to epoxide ring and at-10381 and -10424 Hz (d of t, JFF 18.8, 9.8 Hz, IF) and -10600 and -10642 Hz (d, JFF 17.3 l0 Hz, IF) for epoxide CF2.

Analo Calcd for C12 F16 0: C, 29.05 Found: C, 29.40 EXAMPLE i0 Pe r f lu or o ( 1 -b r omo6,7-__epo x y4-o x ah ep tça nej CCl3 A. BrCF2 CF2 CO2H - BrCF2CF2COCI 3-Bromotetrafluoropropionic acid was obtained by hydrolysis of the ethy! ester; the latter was prepared as described by Y. K. Kìm, J. Org.

Chem., 32, 3673 (1967).

A mixture of 375.9 g (1.67 mol) of 3-bromotetrafluoropropionic acid i0 g of ferric chloride, and 488.7 g (2.50 mol) of benzotrichloride was refluxed for 1.5 h, then crude product was removed, bp about 60°. Redistillation gave 287.9 g (71%) of 3-bromotetrafluoropropionyl chloride, bp 67-68°° IR (CCl4) : 5.53 (C=O).

KF B. BrCF2 CF2 COCI BrCF2 CF2 COF A suspension of 52.3 g (0.90 mol) of flame-dried KF in 450 ml of diglyme was treated with 140 g (0.844 to!!) of hexafluoroacetone to give a solution of potassium heptafluoroisopropoxide.

Dropwise addition of 200 g (0.823 mol) of BrCF2 CF2 COCI from part A at ca. 20° was accomplished by gas evolution through a -20° condenser. The mixture was stirred for 1 h, then (17) (18) warmed to 58° to drive off additional HFA through the condenser. Volatile product was transferred to a -80° trap by heating the pot contents to 90° (50 mm) o Distillation of the crude product fluoride gave 140 g (75%) of 3-bromotetrafluoropropionylfluoride, bp mainly 28°. IR (gas phase) : 5.23y (COF) o C. BrCF2 CF2 COF + KF + CF2 =CFCF2 OSO2 F (19) Bref2CF2 CF20CF2 CF=CF 2 A suspension of 35 9 g (0.617 mol) of i0 flame-dried KF in 750 ml of diglyme was stirred at 0° while 140.0 g (0.617 mol) of 3-bromotetrafluoropropìonyl fluoride from part B was added. The mixture was stirred at 0-5° for another 30 rein and then was treated with 141.9 g (0o617 mol) of perfluoroallyl fluorosulfateo The reaction mixture was stirred for 4 h at 0-5° and then poured into 3 liters of water. The resulting loser layer was washed with 500 ml of water, dried over CaSO4, and distilled to give 132.5 g (57%) of perfluoro(7-bromo4-oxa-l-heptene), bp 96-99°, trace impurity only by GCo A sample from a similar synthesis was analyzed. IR (CCI4) : 5.59/ (CF=CF2). NMR (CCI4) : 19F -64.4 (t of m JFF 9.9 Hz, 2F, CFBr), -71.9 (d of d of t of d, JFF 24.9, 13.8,»-!3, 7.3 Hz, 2F, OCF2 C=), -82.8 (t of t of m, JFFÆ13, 9.9 Hz, 2F CF2 0), -92.0 (d of d of t of t, JFF 52.0, 39.3, 7.3 Hz, IF, cis-CF2CF=CFF), -105.3 (d of d of t, JFF 117.7, 52.0 24 9 Hz, IF, trans-CF2 CF=CFF), -121.9 (m, 2F, CF2 ), and -190.6 ppm (d of d of t of t, JFF 117.7, 39.3 13.8, 1.6 HZ, IF, CF2 CF =)0 Anal. Calcd. for C6 BrFIIO: C, 19.12; Br, 21.í0 Found: C, 19.38; Br, 21.49 D. BrcF2 eF2CF2 OCF2CF=CF2 + 02 ---- (20) BreF2CF2 CF2OCF2 CkFCF 2 O A 100-ml metal tube containing 20.0 g (0.053 mol) of perfluoro(7-bromo-4-oxa-l-heptene) from Part C and 60 ml of CF2 CICFCI2 was heated at 140° while 02 was injected incrementally over a 4 h period until absorption ceased. The mixture was cooled, gases vented, and the liquid product fractionated to give 6.9 g (33%) of perfluoro(l-bromo6,7-epoxy-4-oxaheptane), bp 94-95°. IR(CCI4) :

6.50 (epoxide), 8-9 (CF, C-O) with weak band i0 indicating COF impurity near 5.3/ o NMR (CC14 ) :

19F -65.6 (t of m, JFF 9.8 Hz, 2Ff CF2 Br), -80.2 (AB multiplets 2Fo CF2 0) -80.4 (AB multiple,s, 2F, CF2 0), -121o9 (m, 2F, CF2 ), and -156.6 ppm (t of m, JFF 17.6 Hz, IF, CF), with AB multiplets for ring CF at -10368 and -10409 Hz (d of d of m, JFF 18.5, 9.8 Hz, IF) and -10596 and -10637 Hz (d, JFF 17.3 Hz, IF).

Analo Calcd. for C6 BrFIIO2 : C, 18.34 Found: C, 18.51 EXAMPLE Ii Copolymerízation of Perfluoro-5,6-epoxy-3oxahexanesulfonyl Fluoride with Hexafluoropropylene Oxide (HFPO) CF2 -CFCF2 OCF2 CF2 SO2 F %%DESCRIPTION%%/ ï + x CF«CFCF ) (OCF2CF) n The polymerization catalyst was prepared by reacting 2.09 g (0.0137 mol) CsF, 6.07 g (0.0273 mol) tetraglyme and 7°97 g (0.0120 mol) HFPO te,ramer.

The catalyst was shaken for at least 6 h and centrifuged for 30 rein at 0°. To a thoroughly dried 4-neck 500-mi flask was injected 4 millimole of the prepared catalyst. The reaction mixture was then (21) cooled to -35 C. Hexafluoropropylene (dried by passing through molecular sieves) was added at a rate of 1 g/rein for a total of 20 g. }]exafluoropropylene oxide (dried by passing over KOH and Call2 ) was added at a çate of 0,07 g/rein and the epoxysulfonyl fluoride at the rate of 0.13 g/b. After 52.5 h of reaction at -32 to -35°C, the uncreated gases were removed by applying vacuum. The polymer mixture was then brought slowly to i00° under vacuum to remove i0 any unreacted monomers. Weight of the recovered copolymer was 220 g. Part of the highly viscous polymer 20 g, was reacted with excess ethanol to obtain the corresponding ester end-capped polymer.

The molecular weight by IR based on the ester absorption was 42,200. Amount of incorporated epoxysulfonyl fluoride was 4°2% based on S analysis by X-ray fluorescence, x in the formula is approximately 48.

EXAMPLE 12 Cross-linking of the Copolymer g of the copolymer of Example ii , 2 g hexamethylenediamine carbamatep and 2 g MgO were mixed in a 2-roll mill at 50° until a homogeneous blend was obtained° The blend was pressed at 180° in a Carver press and cured for 2 h. The resulting crosslinked solid was rubbery and was virtually unaffected by the Freon* E3 solvent. On standing, the solid flowed slightly.

EXAMPLE 13 Copolymerization of Perfluoro-5,6-epoxy-3oxahexanesulfonyl Fluoride with Hexafluoropropylene Oxide Using the procedure described in Example II, 132 g of HFPO and 67.15 g of the epoxysulfonyl fluoride were copolymerized at -31.5 to -33° The viscous polymer gave a molecular weight by IR of * denotes trade mark 9600. Amount of incorporated comonomer was 18.5% based on S analysis by X-ray fluorescence, and x is about 9 EXAMPLE 14 Homopolymerization of Perfluoro-5,6e -3-oxahexanesulfonyl Fluoride Following the general procedure for HFPO copolymerization, 8.5 g (0.024 mol) of epoxysulfonyl fluoride was polymerized using 0.00072 mol CsF catalyst in the presence of 1.2 g hexafluoropropeneo After 4 h reaction at -35°, the polymer was worked up by raising the temperature to i00° at 1 mm to remove unreacted monomer° Weight of the dry polymer was 7.74 g. After conversionto the ester end groups, molecular weight was 2800 (degree of polymerization of 8) by ebullioscopy in CFCI2 CF2 CI.

EXAMPLE Copolymerization of Perfluoro-8,9-epoxy-6oxanonanoyl Fluoride with Hexaf luor op r opyl en e_Ox ide CF ÇFCF 0 \ / (CF2 ) 4 ocF2cF CF20 (CF2)4 COF COF + x C 2 CFCF3 \o/ (OCF2CF) X n (22) Following the general procedure for HFPO copolymerization, 183o2 HFPO and 4.59 g of the epoxyacid fluoride were polymerized with 3°6 millimoles catalyst over a period of 43.6 h at -32 to -34«. Weight of the recovered polymer was 182 g. By IR in CFCI2 CF2 CI and allowing for chain transfer, the approximate molecular weight was 40,000. x is approximately i00o i0 EXAMPLE 16 Copolymerization of Perfluoro-6,7-epoxy-4oxaheptane-nitrile with __ Hexafluoro_op p ne Oxide CF.CFCF«0CF«CF2CN + CF2 CFCF3 \ \ oI o OCF 2 îF (OCF2CF) x CF2OCF2CF2CN (23) Following the general procedure for HFPO copolymerizatíon (Example 12), 4.68 g of the epoxynitrile of Example 4 and 179 g of HFPO were copolymerized at -33 to -35° over a period of 47°6 hr. The molecular weight by IR was 43,100. The amount of incorporated epoxynitrìle was 2.5% by nitrogen analysis. X in the formula is approximately 68.

EXAMPLE 17 Crosslinking of the Copolymer of Hexafluoropropylene Oxide and Perfluoro-6,7epoxy4-ox ah ep tan en i t r i i e The following was milled: 30 g of the copolymer of Example 16, 3 g carbon black and 0.9 g tetraphenyltin. The mixture was degassed at 50°/0.1 mm and heated to 200° under N2 for 60 hr; 260° for 1 day and 300° for 2 days. The result was an elastic solid with some flow on standing.

A better curing was obtained when 0.39 g MgO was added to the above formulation° A rubbery solid was obtained with improved toughness.

EXAMPLE 18 Copolymerization of Perfluoro(phenylglycidyl) Ether with Hexafluoropropylene Oxide C6 F OCF.CFCF + D z \/ z CF2 CFCF3 - \o/ o (24) OCF 2çF <OCF2 CFn CF20C6 F5 i0 Following the procedure for HFPO eopolymerization (Example 12), 7.36 g of the perfluoro(phenylglycidyl)ether prepared as in Example 5 and 138 g of HFPO were copolymerized at -32 to -35° over a period of 48 hr. The molecular weight by IR was 25,000° X in the formula is approximately 49 based on the 5% phenoxy monomer added during the polymer i zat ion EXAMPLE 19 Crosslinking of the Copolymer of Perfluoro(phenylglycidyl) Ether and Hexa f luoroprop L!ene Oxide The following was milled until a homogeneous mixture was obtained: 5.2 g of the copolymer of Example 18, 0°20 g dicyclohexyl-18-crown-6, 0.16 g of the dipotassium salt of bisphenol A, 0.20 g MgO and 0.52 g SAF carbon black. The milled material was degassed at 50° in a vacuum oven and cured at 200° under N2 for three days. Post curing was done at 300° for one day under nitrogen. This gave a solid with a very slight amount of flow on standing at room temperature. Differential scanning calorimetry showed a Tg of -58°.

EXAMPLE Copolymerization of Perfluoro(9,10-epoxy-5methyl-4,7-dioxadecanenitrile) with Hexafluor oRr opylene Oxide 1OE 524 F3 CF CFCF OCF CFOCF CF CN \õ/ .< OCF2CF CF3 + CF2 CFCF3 \o/ (OCP2¢F) (25) Following the procedure for HFP0 l0 copolymerization (Example ll) 7 g of per fluor o ( 9,10-epoxy5-me thyl-4,7-diox adec anen itr i le ) prepared as ìn Example 8 and 312 g of HFPO were copolymerìzed at -33 to -35° over a period of 76.4 hr. IR showed a molecular weight of 28,000 and a nítrile comonomer content of 2.7% by weight« X in formula is approximately 99.

EXAMPLE 21 Copolymerization of Perfluoro(1,2-epoxy7-ph enoxy4-ox ah eptane) with Hexa f luor op_ropy fen e Oxide CF2CFCF2OCF2CF2CF2OC6F5 + CF2 CFCF3 \o! %%DESCRIPTION%% OCF2 :F (OCF2 CF) L ç'F2 OCF2 CF2 CF2 OC6 F5 26) Following the procedure for HFPO copolymerization (Example 12), 5.84 g of the phenoxy monomer prepared as in Example 10 and 192.59 g of HFPO were copolymerized over a period of 51 h at -33 to -35°. The molecular weight by IR was 15 000. x in the the formula is-approximately 99.

nli89o EXAMPLE 22 Post-Polymerization Conversion of Acid Fluoride to Amide s (1) L GF3 CF2 0 (ÇF2 )4 COF (27) L c o( )4oo Ll A mixture of 10.0 g of the copolymer prepäred in Example 15, 20 ml of CFCI2 CF2 CI (!,l,2-trichlorotrifluoroethane)« 20 ml of methanol and 5.0 g of sodium fluoride was stirred at 25° for 2 days. The resulting mixture contained copolymers wherein -COF groups were replaced with -C02 CH3 groups. The mixture was stirred further at 25° while ammonia was bubbled in slowly to saturation, and the mixture was stirred for 2 days with occasional addition of more ammonia. Volatiles were then removed under vacuum, the residue was stirred with ml of CFCI2 CF2 Cl, and the mixture was filtered« Evaporation of the filtrate afforded 10.2 g of amidated polymer. IR (neat): 2.84 (NH) and 5.74 (C=O).

The above interconversions may equally well be carried out using starting copolymers of this invention which contain -COCI, -C02 H or -C02 R4 groups in place of -COF. When a -CO2R4 functional polymer is employed, the methanolysis step is unnecessary; methanolysis is optional with polymers containing acyl halide functions.

i0 EXAMPLE 23 Post-Polymerization Conversion of Sulfonyl Fluoride to Sulfonate L CF3 CF2 0CF2 CF2 S02 F CF2 0CF2 CF2 S02 0K Hçl H20 (28) g CF20CF2 CF28020H 50.0 g (0.0255 equivalents) of the copolymer prepared in Example ii was stirred with a solution of g (0.6 mol) of 85% KOH pellets in 160 ml of water for 2 h at 90e. The taffy-like potassium salt of the sulfonated polymer solidified on standing overnight. Analysis by IR showed the sulfonyl fluoride groups to be completely reacted. The solid was broken up and filtered off. The filter cake was stirred with 200 ml of 10 N HCL at 25°, then with 200 ml and 400 ml of i0 N HCL at 95°, during which time it was converted to a soft semisolid. The resulting sulfonated polymer was exceptionally hydrophilic and weighed i00 g after drying under vacuum.

i0 The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

i. Perfluoroglycidyl ethers of the formula CF2-CFCF20RF \o/ wherein RF is:

(i) -CFRIcFQ wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -S02 F, -COF, -F, -Cl, -Br, -I, -CN, -C02 H, -OC6F5, or -C02 R4 where R4 is -CH3 or -C2 H5 ; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CE3 ; or (ii) -CE (R2) 2 wherein R2 is -CF2 CI, -CF2 CN, -CF2 COF, -CF2 CO2 H, -CF2OCF(CF3)2 or -CF2 CO2 R4 where R4 is defined as above; or (iii) -(CF2 CFO) nR3Q Y wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety R3 does not exceed 15 carbon atoms; Y inde- - (CF2 CFO) n Y pendently is -F or -CF3 ; n is 1 to 4; and Q is as defined above; or (iv) -C6 F5.

2. Tihe perfluoroglycidyl ethers of Claim 1 in which RF is -CF2 RIcF2 Q wherein Q is selected from the group consisting of -S02 F, -C02 R4, -CN, -OC6 F5, -Br, -I, and -COF.

3. The perfluoroglycidyl ethers of Claim 1 in which RF is -CF(R2)2 where R2 is -CF2 CO2 R4, -CF2 COF or -CF2 CN; and R4 is -CH3.

4. The perfluoroglycidyl ether of Claim 1 wherein RF is -C6 F5.