CA1188849A - Perfluorodiglycidyl ethers - Google Patents

Abstract

TITLE
Perfluorodiglycidyl Ethers and Precursors Therefor ABSTRACT OF THE DISCLOSURE
Homopolymers and copolymers of perfluoroglycidyl ethers of the formula

Description

TITLE
Perfluor~diglycidyl Ethers and Precursors Therefor TEC~NICAL FIELD
This invention relates tO perf].uoxodiqlycidyl 5 ethers, ~heir preparation and polymers therefrom.
BACKGROUND ART
P. Tarrant, C. Go AllisonJ ~. P. Barthold and E. C~ stumpS Jr.y "Fluorine Chemistry Reviewsn, Vol. 5, P. Tarrant, Ed.l Dekkerl New York, New York ~1971) p 77 disclose fluorinated epoxides of the g~neral formula CF2-5FRF
O
wherein R~ may be a perfluoroalkyl group ~f up to 10 carbons containing one or more functional Bub5tituent5

2 b~ 2 Oxidations of the type CF2 CFCF2X ~ ~2 or H202/OH -~cF2~cFcF2x are disclosed ~0 ~) where X is -F, ~(CF2)5H ~VOS~ Patent 3,358,003)~
-CF2Cl or -CF2Br (T. I. Ito et al, Abstracts, Div. Fluor3. Chem., Am. Chem. Soc., 1st ~CS/C3S Chem.
Congress, ~lonolulu, ~I, April 1979) Oligomers and polymers o perfluoroepoxides CF2-CF-R~ 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 R~OCF~COF
are also known, and the insertion of one or more rnoles of hexafluoropropene epoxide into said nonfunotional perfluoroethers is disclosed in U.S.
Patent 3,250l808:

RF~CF2cOF ~ n (C~2 5FC~3) RFOCF2C~20 -~F CF20 ~ CFCOF (1) CF3 /n-l CF3 5 ~here n is 1 to at least 6 and RF i~
perfluoroalkyl, perfluoroalkoxy, or perfl~oroalkoxyalkyl.
Glycidyl ethers containing the segment CH2-CHC~20- are widely disclosed. The glycidyl C~2-~CHCH20C6~15 is disclosed in V.S. Patent 4,127,615.
O DISCLOSURE OF INVENTION
Novel perfluoroglycidyl ethers are provided having the general formula 1S CF2~ FCF20Rl?
I
wherein ~ i :
(i) -CFR CFQ
2n y yl wherein R is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -OCF2CF=CF2 or ~OCF2CF-~CF2 Y and Y' are 25 -F or -CF3, provided that only one of Y and Y' can be

3;
(ii) - (CF2CFo)nR3Q
y wherein R3 is a linear or branched perfluoroalkylene 30 group of carbon content such that the moiety -(CF2CFo)nR3 does not exceed 15 carbsn atoms; Y inde-pendently is -F or -CF3; n is 1 to 4; and Q is as defined above. Ethers of formula I where Q is 35 -OCF2CF=CF2 are useful as intermediates in the preparation of the corresponding perfluorodiglycidyl ether.
I

Perfluoroylycidyl ethers of formula I are prepared by contacting and reacting the corresponding perfluorodiallyl 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 perfluorodiglycidyl ethers of formula I.
Polymers prepared from formula I glycidyl ethers provide crosslinking or cure sites and are stable elastomeric ma~erials useful as sealants, caulks, and fabricated objects. Preferred are ethers of formula I where RF is -CFRlCFQ or ~CF2CFOCF2CF2OCFCF2Q; Y and Y' are -F; and Q is -OCF2CF-CF2.
\0/

Perfluorodiallyl e-thers, when reacted with 2' also yield, in addition to the perfluoro-diglycidyl ethers of formula I, coproduct fluoroformyl difluoromethyl ethers containing one less carbon atom which have the general formula II
wherein RF is as defined above.
The novel perfluoroglycidyl ethers of this invention are prepared from the perfluorodiallyl ethers which are disclosed by Krespan in U.S.
30 Patent No. ~,275,225, issued June 23, 1981. These perfluorodiallyl ethers are of the formula CF2=CFCF20R~
wherein RF is:
(i) -CFR CFQ
Y Y' wherein R is a carbon carbon bond or a linear or bxanched per~luoroalkylene group of 1 to 12 carbon atoms; Q is -OCF~CF=C~; Y and Y' are -F or -CF3~ 1 provided that only one of the Y and Y' can be 5 -CF3; or (ii) (CF2C~O) rlR3Ql .

wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety 10 ~(CF2CFo)~R3 does not exceed 15 carbon atoms; Y is y -F or -CF3; n is 1 to 4; and ~ is as defined above.
The perfluoroglycidylethers of this invention are also prepared from perfluorodiallyl ethers of the 15 formula CF2=CFCF20 (CF2CFO) nR ~2 wherein R3, Ql, and n are as defined under (ii) above, and Y, independently, can be -F or CF3.
These perfluorodiallyl ethers are prepared by ~lj mixing and reacting (a) a carbonyl compound having the formula:
o 1 "
A C-Y
wherein A i5 QICFRl Y' where R1 i5 a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbcn atoms; Q'is -OC~2CF=CF2; Y anQ Y' are -~ or -CF3, provided that only one of Y and Y' can be -CF3; or (b) a carbonyl compound having the formula:

~ 8~

o ~
A -C-F
wherein A2 is O~R3(ocFcF2)n-1,cF
where R is a linear or branched per-fluoroalkylene group of carbon content such that the moiety R3(0CFCF2)n lOCF-Y Y
does not e~ceed 14 carbon atoms; Y
independently is -F or -CF3; n is 1 to 4; and Q' is defi.ned as above;
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) mixins the mixture from (1) with a perfluoroallyl compound of the formula CF2=CF-CF2Z
wherein z is -Cl, -Br or -OSO2F.
The perfluoroglycidyl ethers of formula I and the fluoroformyl difluoromethyl ethers of formula II are prepared from the perfluorodiallyl ethers by partial or complete reaction with oxygen at about 20 to about 200C, preferably about 80 to about 160C:

CF2=CFCF2~ (2) (x) C~2/CFCF2ORF + (y) FOC-CF2ORF + ~y) COF2 I II
where x and y are, respectively, the mole fractions of products I and II, and RF and RF are defined as above. Ethers of formula I are normally stable at the reaction temperature. Formation o-E ethers of formula II, together with carbonyl fl~loride, i~
presumed to result from oxidative cleavage of an allylic double bond in ~he s~arting perfluorodiallyl ether. The by product CO~2 is norm~lly inert.
The epoxidation reactio~ may be carried out at pressures of abollt S to about 3000 psi, preferably about 50 to about 1500 psi. Solvents are not essential, but inert diluents such as 1,1,2-trichloro-1,2,2-trifluoroethane (CFC12CF2Cl) or perfluorodimethylcyclobutane may be u~ed.
Reactant proportions ~ay vary from a large molar excess of olefin over 2 (e g / 100:1) to a large ex~ess of 2 over olefin te.g., 100:~), a modest excess of 2~ e.g., about 1.1:1 to about 10:1, is normally preferred to insure complete reactio~ of the olefin. When preparing 2 perfluoroglycidyl ether of formula I wherein Q is -OCF2CF=CF2l the reaction of the starting diolefin with 2 should be run with at least a 2:1 molar excess of diolefin over 2~ and further addition ~ 2 should be avoided.
The epoxidation reaction ~8 ~ost conveniently initiated thermally~ but may be catalyzed by the use of free-radical initiators or by ultra~;olet irradiation in the prese~ce of a 2~ photoactive material such as bromine. The epoxidation may be conducted in a batchwise or continuous manner.
The epoxidation product of form~la I is generally isolated by direct fractlona~ distillationt altho~gh in some cases a preliminary treatrnent with Br2 or C12 may ~e helpful. When epoxidation 1 carried out at lower temperatu~e~ ~ 100~ addition of radical acceptor ~ ch as ~-dichlorobenzene to the mixture just prior to fractionatic)n ~s a desirable 35 precaution against the poss i2~1e presence o peroxides.
Perfluoroglycidyl ethers of formula I
can be homopolymerized or copolymeriæed with ~uitable fluorinated epoxides such as HFPO, tetrafluoroethylene epoxide (TF~:O), other perfluoroglycidyl et:hers of formula I and perfluoroglycldyl ethers disclosed in the copending Canadian Patent Application No. 399,788 of C.G. Krespan et al, filed simultaneously herewith;
HFPO and TFEO are preferred comonomers with H~PO most preferred. (Co~-polymeri~ation proceeds in the presence of a suitable solvent and initiator at temper-atures of about -45~ to about +25~C, preferably about -35 to about 0C. The quantity of solvent may be from about 5 to about 40 mole percent of the total monomer feed. Suitable solvents include commercial ethers such as diethyl ethex, diglyme, triglyme and tetraglyme (di-, tri-, and tetraethyleneglycol dimethyl ether), and fluorinated solvents such as 1,1,2-trichlorotri-fluoroethane, chlorotrifluoroethylene, dichlorodi-fluoromethane, hydro~en-capped HFPO oligomers of the 3 2C~2O[CF(CF3~CF2O]nCHFCF3, where n is 1 to 6, dimers and trimers of hexafluoropropene (HFP)~
and ~FP itself; the latter is a preferred solvent~
Solvents should be thoroughly dried, pre~erably by means of m~lecular sieves, before use~
Catalysts suitable for the (co)polymerization of formula I ethers include anionic initiators which are effective for the polymerization of hexafluoro-propylene oxide (HFPO), such as carbon ~lack or, preferably, combinations CsF-LiBr, KF-LiBr, (C6H5)3PCH3l -LiBr, CsF-FOCCF(CF3)OCF2CE'2OCF(CF3)COF, CsF-CF3CF2CF2O[CF(CF3)CF2O]nCF(CF33COF, 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~Sr 3,322,826~ Catalyst concentration shculd be about 0.05 to about 1 mole percent of th~ total g~

monomer feed when higher molecular weight products are desired.
The pexfluoroylycidyl ethers of formula I and comonomers such as HFPO should be reasonably pure and dry before (co)polymerizatlon. Monomers may be dried with molecular sieves or, preferably, over KOH CaH2.
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 atmo-spheres or more; pressures in the vicinity of one atmosphere are normally preferred.
The copolymerization of ~he perfluoroglycidyl ethers of formula I with HFPO, TFEO and other per-fluoroglycidyl ethers can be a random copolymerization whereby the various monomers are added and reacted with one another simultaneously, or the copolymerization can be sequential, i.e.l the perfluorodiglycidyl ethexs of formula I wherein Q is -OCF2C\ 5F2 copolymerized with material previously polymerized, such as hexafluoropropylene oxide homopolymers as disclosed in copending Canadian Patent Application No.
399,790 of l'.R. Darling filed simultaneously herewith and hexafluoropropylene oxide/perfluoroglycidyl ether copolymers as disclosed in the aforementioned copending Canadian patent application of C.G. Xrespan et al.
Such a sequential copolymerization can serve as a specialized form of chain extension.
In the following examples of specific embodl-ments of the present invention~ parts and percentages are by weight and all temperatures are in degrees C
unless otherwise specified. The most preferred polymer of the pr4sent invention is that of Example 9.

_9_ Perfluoro-1,2-epoxy-13,14-epoxy 4,11-dioxatetradecane ~nd Perfluoro-12,13-^epoxy-~~ 3,10-d;o~atridecanoyl Fluoride __ 5 (cF;~=c~cF2ocF2cF2clF2~2 - ~ (C~CFCF2(~CF2CF~ClF2~'2 CF2CFCF20(CF2~ 6CF2CC)F

o A sample of perfluoro-4?11-dioxatetradeca-1,13-diene (5107 9, O.OB7 mol, purified by distillation from conc. ~2S04) was diluted ~o 75 ml with dry C~Cl~CF~Cl, loaded into a 100-ml stainless ~teel tube and heated at 140 while 2 15 was injected in 50 psi increment~. The maximum pressure was 500 psi, at which point 2 con~umption ceased as judged by lack of pressure drop.
Distillation of the liquid products gave 39.1 9 of fractions with ~p 56 (95 ~m) - 81 (800 mm).
20 Analysis by gc revealed a single major peak for ~11 fracti~ns with a total of 5-15~ of varying impurities present~ ~owever~ IR and NMR showed that this main peak represented bo~h products. An early fraction, 6.4 y, bp 52-64G (9 mm) I was nearly pure 25 perfluoro-12,13-epoxy-3,10~dioxatridecanoyl fluoride~ IR ~CFC12CF2Cl): 5.28 ~COF), 6.59 (epoxide), 7~5~9.5~ (CF, C-O). NMR (CC14/CFC13):

. 19F 13.1 (m, lF, COF), -77.2 (t of d, JF~ 11.6, - 2.5 Ræ, 2F, CF2COF), -83.3 (m, 4F, CF20), 122.5 30 ~m~ 4F, CF2), -1~508 (m, 4F, CF23, and -156.7 ppm (~ J~F 18 ~z, lF, CF) with AB gro~pings for ring CF2 at 103gOl and 10433 ~z (d of t, JFF 18~8, g.6 Hz, lF) and -10617 and -10659 Hz (d, JFF 170 4 ~z, lF'), and for CF2 adjacent to epoxide ring at 35 -7369, -7523~ -7553, and -7706 ~z (m, 2F).

Higher-boiling cuts, 21.8 g, bp mainly 68 70 (8 mm), contained chiefly diepoxide with epoxyacid fluoride as a major imp~rity. ~hese higher cuts were combined and shaken with 200 ml of cold 5 water for 5 min. Heat of reaction, cloudiness and some foaming were apparent~ A portion of the lower layer was dried over anhydrous CaSO~. It was then transferred trap~to-trap twice under vacuum to give

4.26 9 of clear colorless perfluoro-1l2-epoxy-13,14-10 epoxy-4,11-dioxatetradecane, 99% pure by gc~ IR
(neat1: 6.59 lepoxide) and 7O5-9~5~ (CF, C-O) with no bands for OH, C-O, or C-C detected. NMR
(CC14/CFC13) 19F -83.5 (m, 4F, CF2O), -122.7 (m, 4FI CF2), -125.9 ~m, 4F, CF2), and -156.9 ppm 15 (t, JFF 18 Hz, 2F, CF) with AB groupings for ring CF2 at -10391 and -10658 H~ (d, JyF 17.4 Hz, 2F) and for CF2 adjacent to epoxide ring at -7378, -7531, -7561 and -7714 Hz (m, 4F) with only trace impurities present.
Anal. Calcd for C12F224 C, 23-02 Foundo C~ 23~6f30 It is considered probable that the epoxidation reaction proceeded via the allyloxy-epoxide intermediate CF2~CF-CF2OlcF2~6OcF2cF=cF
O

Perfl~oro(1,2-epoxy-1~,16-epoxy-6011 dime~hyl-4,7,10,13-tetraoxahexadecane n 1 3 CF3 ~ A. (FCCFOCF2~2 2 KF 3~ (CF2=CFCF20CF2cFOcF2) 2 (5 2 CF2=CFCF20SO?F

--~ 1 A suspension of 20.3 g ~0.35 mol~ of flame-dried KF in 300 ml of dry diglyme while st~rred at 0-5 while 53.0 g (0~125 mcl) of perfluorol2,7-dimethyl-3,6-di~xasuberoyl) fluoride was added. The mixture was stirred for 30 min, after which 80.5 9 (0.35 mol) of perfl~oroallyl fluorosulfate was added at 0-5. After having stirred for 3 hr at G-5, then at 25 for 2 hr, the mixture was po~red into lQ of cold water. The lower layer was washed ~ith 500 ml of water, dried over CaSO4 and fractionated to afford 47.3 g (52%) of pure perfl~oro(6,11-di~ethyl-4,7,10,13-tetraoxahexadeca-ltlS-diene)~ neat)- 5.58 ~C=C~, 8~ ~CF~ C-O). NMR (CC14~CFCC13)o 19F -72.1 15 td of t of d of d, JFF 24.7, ~13.7, 13.7, 7~3 Hz, 4~, OCF2C=), -80.7 ~m, 6F, CF3), -84.1 (m, 4F, OCF )~ -92.1 (d of d of t, JFF
Hz, 2F, cls-CF2CF=CFF~3, -105.5 (d of d of t, JFF
118.0, 52.6, 24.7 Hz, 2F, trans~CF2CF=CFF), -146.0 20 (t, JFF 21.3 ~z, 2F, CF), and -190.9 ppm ~d of d of t, ~FF 118.0, 39.4, 13.7 Hz, 2F, -CF2C~=CF2), with an AB pa~ern for OCF2 at -7988, -8122~ -8142, and -8258 Hz (m, 4F).
Anal. CalcdD for C14F264 C, 23-15 Found: Cl 23.29.
C~3 CF3 B. (CF2=CFCF2OCF2CFOCF2~2 ~ (CF2CFCF2OCF2CFOCF2~2 O (6) + CF2CFCF20CF2CFOCF2CF20CFCF20CF2CF
o A solution of 45O7 g (0.D63 mol) of th2 above he~adecadiene in 75 ml of CFC12CF2Cl was heated a~ 140 in a 100~ml stainless stee~-lined tube while oxygen was injected por~ionwise un~il reaction was complete. Distillation of ~he liquid product afforded 37.2 ~ of fractions with bp 63 ~10 mm)-55 (4 mm) shown by IR and NMR to be perfluoro(l,2-epo~y-15,16-epoxy-6,11-dimethyl-4,7,10~13-~etraoxahexadecane containing perfluoro(l4,15-epoxy-5,10-dimethyl-3,6~9,12-te~raoxapen~adecanoyl) fluorlde as the major impurity. Several fractions ~22.7 9) ~ere combined and contacted with CaH2 while standing open to atmospheric moisture for a dayO The open mixture was then stirred for 4 hr and filtered. Volatiles were ~ransferxed at 50 (0.05 mm), stirred with CaSO4 for 2 hrs, and then transferred again at 45 ~0.05 ~m) to give 5.5 9 of nearly pure diepoxide. IR
(neat)- 6.47 (epoxide) and 8-9~(CF, C-O) with very weak impurity bands present at 5528 (COF) and 6~64 ~CO2H).
Other fractions were shown by 19F NMX to contain about 8~2 9 of diepoxide as 80% pure material, for a total of 13.7 9 ~294).

Perfluoro(1,2-epoxy-10,11-epoxv-4,8~dioxaundecane) (CF2-CFCF2OCF2~2CF2 ~ (CF2CFCF2OCF2~2~F~ (7) O
A 100-ml metal tube containing 107 9 (0~24 mol) of perfluoro(4,8-dioxa-1,10 undecadiene) was heated a~ 140 while oxygen was injected portionwise until reaction was nearly complete. Fractionation of the liquia prcducts gave 66 0 7 9 ~ bp 42-64 (50 mm), containing mainly diepoxide and epoxyacid fluroide.
This dis~illate was irradiated with excess bromine to remove any olefinic material, resid~al bromine was evaporated, and the residue was ~haken with a m.ixture of 250 ml of ice ~ater and 50 ml of CFC12CF2Cl.
The organic layer was dried over CaS04 and distilled ~o give 27.5 9 o nearly pure diepoxide, bp S0-68 (100 mm). The distillate was treated wi~h CaS04, filtered and redistilled to give 19.6 9 (17%) of pure diepoxide, bp 54-56 (50 mm). IR
(CC14fCFC12CF2Cl~: 6.49 (epGxide) t 8-9~ (CF, C-O). NMR (CC14~CFC13~. F -84~2 (m, 4F, OCF2), -130~1 (s, 2F, CF2), and -15701 ppm (t, JFF 17.5 Hz, 2F~ CF) with AB patterns for CF2 adjacent to epoxide ring a~ ~7399, -7550, -7594, and -7747 Hz ~m, 4F) and for ring CF~ at -10415 and -10457 (d of t, JFF 18.7, 9.7 ~z, 2F) and -10643 and -10684 Hz (d, JFF 16.4 ~z, ~F)u Anal. Calcd. for C9F1604- ~, 22-71: F~ 63-85-Found: C, 22.99; Fl 63~920 Copolymerizat;orl of Perfluoro(1,2-epoxy-15~16~epoxy-6,11-dimethyl-4~7,10,13-tetraoxahexadecane~ with ~ e l~orop~E~ _ ne Oxide _ _ The polymerization catalyst was prepared by reacting 2.09 9 (0.0137 moli CsF, 6.07 9 t0.0273 mol) tetraglyme and 7.97 9 ~0.0120 mol~ HFPO tetramer.
The catalyst was shaken for at least 6 h and centrifuged for 30 min at 0. To a thoroughly dried ~-neck 500-ml flask was injected 4 millimole of the prepared catalyst. The reaction mixture was then cooled ~o ~35C. Hexafluoropropylene ~dried by passing ~hrough molecular sieves) was added at a rate of 1 g/min for a total of 20 9.
4.g7 9 of ~he diepoxide of ~xample 1 and 144 g of HFPO (dried by passing over XOH and CaH2~
were copolymerized over a period of 35.3 hr at -34 to -35~ After this period, the stirring was extremely difficult due to the almost semisolid condition of the polymer. Part of the recovered polymer, 15 9 was reacted with 10% NaOH in ethyl carbitol to a neutral point with phenolphthalein indicator. The sodium salt was decarboxylated by heating to 160 for 30 minO The isolated polymer gave ninh of 0.195 in Freon~ E3 [F~CFCF2O~3CHFCF~]. The calculated molecular weigh~ is 200,000. Based on the 3.34~ by weight of added diepoxide I the ratio of HFPO units to diglycidyl monomer units is approximately 132:1 ~15-Terpolymerization of 2er1uoro(1,2~epoxy 15,16~
epoxy-6,11 dimethyl-4/7,10,13-~etraoxahexadecane) and Perfl~oro-6,7-e~oxy-4-oxaheptanenitrile with _ ~exafluoro~o~ylene Ox_de Two monomers were co~bined as follows: 2 of the diepoxide of Example 1 were mixed with 4 . 67 9 of the epoxynitrile~ Following the procedure for HFPO copolymerization (~xample 4), 6~34 ~ of the 10 mixed monomers and 177 g of H~PO were copolymerized at ~33 to -35" over a period of 42. 3 hr . The moleclJlar weigh~ by inherent viscosity was 41~000.
On starJding at room temperature over a perlod o 3 1/2 months, there was further curing of the polymer 15 resulti2~g in a partially solidified material. From the weight ~ added monomers the ratio of EFPO unit~
to nitxile monomer units to diglycidyl monomer units is approximately 431 8~
EXAMPLE S
Curl~g of Terpolymer of Perfl~oro(1,2-epoxy-15,16-epoxy-6,11-dimethyl-4,7,10-13-tetraoxahexadecane) r Per1uoro 6,7-epoxy-4-oxaheptanenitrile and _ Hexafluoro~ropylene Oxide The following was milled until a homogeneous 25 mix was obtained: 5O46 g of the terpolymer of Example

5, Q.55 9 carbon black, 0,16 q tetraphenyltin and 0,16 g magnesium oxide. The milled material was de~assed by placing in a vacuum oven for 16 hr at 50. This was then placed in a microtensile bar mold 30 and pressed in a Carver* press under 500 psi a~ 210 for 4 hr. At this point a soft rubbery tensile bar was obtained.

3s *denotes trade mark EXAMPL~ 7 Copol~erization of Perfluoro(1,2-eRoxy-10,11-epoxy-4,8-dioxaundecane) with Hexafluoropropylene Ox_ e _ _ Following the procedure for ~FPO
copolymerization (Example 4), 5O78 9 of the diepcxide of Example 3 and 16$ g of HFPO were copolymerized over a period of Slol h at -34 ~o -36. The molecular weight by XR was 16,000. The ratio of HFPO
units to diglycidyl monomer units is approxLmately 82^1 On standin~ a~ room ~emperature for 3 wee~s, there was a visible i~crease in viscosity.
EXA~PLE 3 Copolymerizatio~ of Per1uoro 6,7-~poxy-4-ox~he~tanenitrlle with ~exafluororr~ le e o~
The pol~merization vesse~ consisted of afully glass jacket~d four-neck round bottom reactor which is equipped with a paddle stirrer, Dry Ice reflux conden~er, gas inlet port and a thermocouple well. The entire reactor was dried thoroughly at 200~C in a dry nitrogen a~mosphere and was assembled and kept dry with a blanket of high purity dry nitrogen. Methanol was used as a coolant and was p~mped thxough the coolant jacket ~rom a Neslab ULT80*
low temperature circulator and refrigerator system.
Initiator was prepared by adding, ~nder dry nitrogen, 7.95 grams (7~8 milliliters, 0.0358 mole) of tetra-glyme to 2.54 grams ~0.0167 mole) of cesium fluoride and tAe~ adding 2.91 grams ~1.75 ml, 0.0068 mole) of 2,2'-[(tetrafluoroethylene)dioxy]bis-(tetrafluoro-propionyl fluoride). The mixture was shaken overnight at room temperature and then c~ntr~ugedfor 30 minutes to remove unreacted cesium fluoride. With the reactor at r~om temperature 4 milliliters of initiator 35 was introduced by means of syringe and the xeactor was cooled to an internal temperature of betwePn -30 to -34 DC. Liqui~ied hexafluoropropylene was used * denotes trade mark as a solvent ~o dilute the cold viscous in~tiator solution. The polym~ri~ation was carried out at -34~C
using the following monomers and diluent addition schedule. The approximate additicn rates were 5 0.126 g~hr for perfluoro 6,7~epoxy-4 oxaheptanenitrile and 5.7 g/hr for hexafluoropropylene oxide which was purified in a two-stage (potassium hydroxide/calcium hydride) scrubber and was added as a gas in semi-~atch ~ashionO
10 Addition HFP Curesite HFP0 Time (hrs) Diluent (g) Monomer ~g) (g~
0.23 7 0 2.67 0 15.2 10.3 1029 SB.7 23~0 2.90 131.0 ~.0 30 22.25 _ 2.80 126.8 Total 67 6.99 331.7 EXP*lPLE 9 Subsequent Copolymeri2ation with Perfluoro-1,2 epoxy-13,14-epoxy-4,11-dioxatetradecane 30 grams of hexafluoropropylene (HFP) were 25 added ~o the product of Example 8 to reduce viscosity and improve mixing of the polymer mass. Then a solution of 1.9 g of diepoxide ~perfluoro-1,2-epoxy-13,14 epoxy-4,11-dioxatetradecane) in 30 grams of liquid HFP at 40C was added to the reactor over a period of 2 hours.
30 The reactor was maintained at -34C for 24 hours~ The polymer was isolated by removing the HFP diluent under vacuum at -39C and allowing the pol~mer to warm 510wly to room temperature. The polymer mass was protected by a dry nitrogen atmosphere. The ~erentviscosity of the 35 polymer in Freon~ E-3 at 30C was 0.16 dl/g correspond-ing to a number average molecular weight of 75,000.
Freon~ E-3 is ?H-heptadecafluoro-5t8-bis(trif methyl)-3,6,9-trioxadodecane.

~18-He~t Treatment and Vulcanization of Poly-Hexafl~oropropylene Oxide Containing Nitr~le Cure Site S The polymer pxepared as in Example 9 was he~t treated at 140C/6.7 Pa for one hour, giving a partially gelled pol~ner. The polymer was washed with water on a wash mill for 20 minutes at room te~perature and was then dried under nitrogen at 10 75C /2.67 kPa for 2 days. Then 41 g ~f the pol~mer was milled at room temperature on a roll mill with 1.24 g (3 parts per hundred rubber) of microni~ed tetraphenyl tin and 6.2 g (15 phr) of 5AF carbon black predried under ni rogen 120C/2.67 kPa. ~he lS compound was dried a!~ 92C/2~67 kPa for 3.5 hours, and 5O5 g portions were compression molded in a 63 x 18 x 1.5 mm steel mold at 210~C and 17 MPa for 2 hours. The cured slabs were removed from the mold at xoom temperature and were then post cured 2D under nitrogen according to the following schedule:
70~2046 hrs @204lB hrs 04~2B8~6 hrs ~2B818 hrs 25 @315~48 hrs Stress-strain properties of a typical vulcanizate at room temperature at lO0~ modulus, MPa l.0 Tensile-at-break, MPa 4.6 Elongation-at-break, ~ 250 Permanent Set~ ~4 Hardness, Shore A 30 O-rings prepared by compression molding and post-curing the compound under ~he above 35 conditions but without the final post-curing at 315 had compression set (ASTM D395 78, Methvd B) at rs~m temperature/70 hours approximately zero percent and at 204~/70 hours approximately 40 percent~

-18a~
This application ls a division of copending Canadian Application Serial No. 399,789, filed March 30~ ]982.

18a

Claims (10)

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

1. The homopolymer of a perfluoroglycidyl ether of the formula wherein RF is:
(i) wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -OCF2CF=CF2 or ; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; or (ii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms; Y, independently, is -F or -CF3; n is 1 to 4;
and Q is as defined above.

2. A copolymer of a perfluoroglycidyl ether of the formula wherein RF is:
(i) wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -OCF2CF=CF2 or ; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; or (ii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms; Y, independently, is -F or -CF3; n is 1 to 4;
and Q is as defined above;
and at least one comonomer selected from the group consisting of hexafluoropropylene oxide, tetrafluoro-ethylene oxide, a different perfluoroglycidyl ether of the above formula and a perfluoroglycidyl ether of the formula wherein RF1 is:
(i) wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q1 is -SO2F, -COF, -F, -Cl, -Br, -I, -CN, -CO2H, -OC6F5, or -CO2R4 where R4 is -CH3 or -C2H5; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; or (ii) -CF(R2)2 wherein R2 is -F, -CF2Cl, -CF2CN, -CF2COF, -CF2CO2H, -CF2OCF(CF3)2 or -CF2CO2R4 where R4 is defined as above; or (iii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms; Y, independently, is -F or -CF3; n is 1 to 4;
and Q1 is as defined above; or (iv) -C6F5.

3. A copolymer of Claim 2 in which the comonomer is hexafluoropropylene oxide.

4. A copolymer of a perfluorodiglycidyl ether of the formula wherein RF is:
(i) wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -OCF2CF=CF2 or ; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; or (ii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms; Y, independently, is -F or -CF3; n is 1 to 4;
and Q is as defined above;
and a polymer selected from the group consisting of homopolymers of hexafluoropropylene oxide, homopoly-mers of tetrafluoroethylene oxide, and copolymers of at least two of hexafluoropropylene oxide, tetrafluoroethylene oxide and perfluoroglycidyl ethers of the formula wherein RF1 is:
(i) wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q1 is -SO2F, -COF, -F, -Cl, -Br, -I, -CN, -CO2H, -OC6F5, or -CO2R where R4 is -CH3 or -C2H5; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; or (ii) -CF(R2)2 wherein R2 is -F, -CF2Cl, -CF2CN, -CF2COF, -CF2CO2H, -CF2OCF(CF3)2 or -CF2CO2R4 where R4 is defined as above; or (iii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms; Y, independently, is -F or -CF3; n is 1 to 4;
and Q1 is as defined above; or (iv) -C6F5.

5. A copolymer of a perfluorodiglycidyl ether of the formula wherein RF is:
(i) wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -OCF2CF=CF2 or ; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; or (ii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms; Y, independently, is -F or -CF3; n is 1 to 4;
and Q is as defined above;
and a polymer selected from the group consisting of homopolymers of hexafluoropropylene oxide and copolymers of hexafluoropropylene oxide and perfluoroglycidyl ethers of the formula wherein RF1 is:
(i) wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q1 is -SO2F, -COF, -F, -Cl, -Br, -I, -CN, -CO2H, -OC6F5, or -CO2R4 where R4 is -CH3 or -C2H5; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; or (ii) -CF(R2)2 wherein R2 is -F, -CF2Cl, -CF2CN, -CF2COF, -CF2CO2H, -CF2OCF(CF3)2 or -CF2CO2R4 where R4 is defined as above; or (iii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms; Y, independently, is -F or -CF3; n is 1 to 4;
and Q1 is as defined above; or (iv) -C6F5.

6. A copolymer of a perfluorodiglycidyl ether of the formula wherein RF is:
(i) wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -OCF2CF=CF2 or ; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; or (ii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms; Y, independently, is -F or -CF3; n is 1 to 4;
and Q is as defined above;
and a copolymer of hexafluoropropylene oxide and perfluoro-6,7-epoxy-4-oxaheptanenitrile.

7. The copolymer of Claim 6 in which the perfluorodiylycidyl ether is perfluoro-1,2-epoxy-13, 14-epoxy-4,11-dioxatetradecane.

8. The copolymer of Claim 6 wherein the perfluorodiglycidyl ether is perfluoro-1,2-epoxy-15, 16-epoxy-6,11-dimethyl-4,7,10,13-tetraoxahexadecane.

9. A vulcanized article made from a copolymer of Claim 4.

10. A polymer selected from the group consisting of (A) homopolymers of a perfluoroglycidyl ether of the formula wherein RF is:
(i) wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -OCF2CF=CF2 or ; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; or (ii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms; Y, independently, is -F or -CF3; n is 1 -to 4;
and Q is as defined above; and (B) copolymers of a perfluoroglycidyl ether of the above formula and at least one comonomer selected from the group consisting of hexafluoropropylene oxide, tetrafluoroethylene oxide, a different perfluoroglycidyl ether of the above formula and a perfluoroglycidyl ether of the formula wherein RF1 is:
wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q1 is -SO2F, -COF, -F, -Cl, -Br, -I, -CN, -CO2H, -OC6F5, or -CO2R4 where R4 is -CH3 or -C2H5, Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; or (ii) -CF(R2)2 wherein R2 is -F, -CF2Cl, -CF2CN, -CF2COF, -CF2CO2H, -CF2OCF(CF3)2 or -CF2CO2R4 where R4 is defined as above; or (iii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms, Y, independently, is -F or -CF3; n is 1 to 4;
and Q1 is as defined above; or (iv) -C6F5.