MEMBRANE CONDUCTRICE FAITE DE COPOLYMERES POLYFLUORO-ALLYLOXY

CONDUCTIVE MEMBRANE OF POLYFLUORO-ALLYLOXY COPOLYMERS

Abrégé anglais

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

Revendications

The embodiments of the invention in which an
exclusive property or privilege is claimed are defined as
follows:
1. An electrically conductive membrane formed
of a hydrolyzed or ionized copolymer of the polyfluoro-
allyloxy compound having the formula
<IMG>
wherein
X is -Cl or -F;
D is -CF2R or <IMG>
where R4 is -COF, -CO2H, -CO2R3,
-SO2F or -OCF2CO2R3 where R3 is
-CH3, or -C2H5; or ?CF2)xR5 where
x is 1 to 6 and R5 is -CF3 or
-OCF2CF=CF2; and
E is -CF2CO2R3,
and at least one ethylenically unsaturated monomer, said
polymer having a mole percentage of polyfluoroallyloxy
comonomer of about 1.0 to 10.
2. The membrane of Claim 1 wherein the
ethylenically unsaturated monomer is tetrafluoroethylene,
chlorotrifluoroethylene, vinylidene fluoride or
trifluoromethyl trifluorovinyl ether.
3. The membrane of Claim 2 wherein X is F.

Description

1 15~8~ 1
BACKGROUND OF T~E INVE~TION
Field of the Invention
r
This invention relates to polyfluoroallyloxy
compounds, processes for their preparation and copolymers
prepared therefrom.
Relation to the Prior Art
1. U.S. Patent 2,856,435 to E.S. Lo discloses the prepara-
tion of perfluoroallyloxy-l,1-dihydroperfluoroalkanes
from 3-chloropentafluoropropene and a l,l-dihydro-
perfluoroalkanol in alkaline medium, e.g.
CF2=CFCF2Cl + HOCH2CF3~- KOH ) CF2=cFcF2ocH2cF3
2. U,S. Patent 2,671,799 to W. T. Miller discloses a
process for replacing the chlorine in perfluoroallyl
chloride (3-chloropentafluoropropene) with methoxy,
cyano, iodo and nitrate groups, e.g.
CF2=CFCF2Cl + NaOCH3 ~ CF2=CFCF20CH3
3. M. E. Redwood and C. J. Willis, Canad. J _ hem., 45, 389
(1967) describe the reaction of allyl bromide with cesium
heptafluoro-2-propoxide to form 2-allyloxyheptafluoro-
propane:
CH2-CHCH2Br + (CF3)2CFO Cs~ )
CH2=CHCH2OCF(CF3)2 + CsBr
4. J. A. Young, Fluorine Chemistry Reviews, 1, 389-393
(1967) surveys the formation of perfluoroalkoxide anlons
by the action of alkali metal fluorides on perfluoro-
ketones, perfluoroalkyloxiranes, perfluorocarboxylic
acid fluorides and perfluoroalkyl fluorosulfates.
References 5-9 which follow are examples of the
nucleophilic reactlons Or perfluoroallcoxlde anlons.
U.S. Patent 3,450,684 to R. A. Darby dlscloses the
'~
-2-

l 15S80 1
preparation of fluorocarbon polyethers and their
polymers by reaction of perfluoroalkanoyl fluorides
with potassium or quaternary ammonium fluoride and
hexa~luoropropene epoxlde.
i.e. RfCOF ~ CF3-CF~-~ CF2 -t RfCF2OCFCOF
CF3
6. U.S. Patent 3,674,820 to A. G. Pittman and W. L. Wasley
discloses the reaction of fluoroketones with an alkali
metal fluoride and an omega-haloalkanoic acid ester to
form an omega-(perfluoroalkoxy) alkanoic acid ester,
e.g.
(CF3)2CO + KF + Br(CH2?4CO2CH3
(cF3)2cFo(cH2)4co2cH3
7. U.S. Patent 3,795,684 to E. Domba also discloses the
reaction of hexafluoroacetone with potassium fluoride
and an omega-haloalkanoic acid ester.
8. U.S. 3,527,742 to A. G. Pittman and ~. L. Wasley,
dlscloses the reduction of the compounds of Reference 6
to the corresponding alcohols and their esterification
to polymerizable acrylates.
9. U.S. 3,799,992 to A. G. Pittman and W. L. Wasley dis-
closes the preparation of (perfluoroalkoxy)vinyl
compounds by reactlon of a perfluoroketone with an alkali
metal fluoride and a 1,2-dihaloethane, followed by dehydro-
halogenation of the intermediate 2-perfluoroalkoxyhalo-
ethane.
e.g. (CF3)2CO + KF + BrCH2CH2Br
(CF3)2CFOCH2CH2Br HBr ~ (cF3)2cFocH=cH2
10. U. S. Patent 3,321,532 to C. E. Lorenz dlscloses the
rearrangement of per~luoro-2-alkoxYalkanoyl fluorides

1155~01
to perfluoroalkoxyolerins by passage over a metal oxide
at 100-400C, ~.g.
OCF3
ZnO + CF3CF_coF 30o-325oc~ CF30CF=CF2 + ZnF2 + C02
SUMMARY OF THE INVEN'~ION
According to the present invention there is
provided a polyfluoroallyloxy compound having the formula
W D
CF=C-CF-O-CG
. .
Z X E
wherein X is -Cl or -F;
W and Z, when taken independently, are -F
and, when taken together, are -CF2-;
D, taken independently, is -F,
F
CF3-~ \ ~ CF3
CF3 f~o/
CF2=CFCF20
or -RF where -RF is a linear or branched
perfluoroalkyl of l to lO carbon atoms,
interruptable no more frequently than
every second carbon atom by from
1 to 4 oxygen atoms, having O to 2
functlonal groups selected from -S02F,
-COF, -C02H, -Co2R3, -Cl
-OCF2CF=CF2 and -oCF2Co2R3 where R3 is
-CH3 or -C2H5
E, taken independently, is
-F, -CF3, -CF2Cl, ~F2Co2R3, or
--4--

1155801
-RFOCF(G)2 where ~ has the meaning defined
above, and
D and E, when taken together, form a 5-or 6-
membered ring whose members are -RF-
~where RF is a perfluoroalkylene chain of
4 or 5 members, interruptable by one or
two oxygen atoms, and having 0 to 2 sub-
stituent -CF3 groups, or
CF3y xcF3
CF3 ~ O
O--
G is -F or -CF3.
There is also provided a process for preparing
a polyfluoroallyloxy compound which comprises:
(1) mixing and reacting a carbonyl compound
having the formula:
A- C- B
wherein A, taken independently, is
-F, -COCF3 or-Rl where RF is a linear or
branched perfluoroalkyl of 1 to 10
carbon atoms, interruptable no more
frequently than,every second carbon
atom by from 1 to 4 oxygen atoms,
having 0 to 2 functional groups
selected from -SO2F, -SO2OCF2CH3,
-COF, -Cl, -OCF2CF=CF2, and -Co2R3
where R3is -CH3 or -C2H5,
B, taken independently is

1~55~0 1
-F~ -CF3, ~CF2Cl, CF2Co2R3 where R3 has
the meaning defined above, or -CF2ORF,
where RF is as defined above; and
A and B, taken together, form a 5- or
6-membered ring whose members are
-RF- where RF is a perfluoroalkylene
chain of 4 or 5 members, interruptable
by one or two oxygen atoms, and having
0 to 2 substituent trifluoromethyl
groups
wlth a metal fluoride of the formula MF where M is K-, Rb-,
C8-, or R4N- where each -R, alike or dlfferent, ls alkyl of
1 to 6 carbon atoms; and
~2) mixing the mixture from (1) with a perfluoro-
allyl compound of the formula:
.z
CF=C-CF
W X Y
wherein X is -Cl or -F;
W and Z, when taken independently,
are -.F and, when taken together, are
-CF2-, and
Y is -Cl or -OSO2F.
Also provided is a copolymer of the aforesaid
polyfluoroallyloxy compound with at least one ethylenically
unsaturated monomer.
DETAILS OF THE INVEMTION
This invenkion relates to compounds of formula 4
prepared ~rom startin~ materials 1, ~ and 3 according to the
3 following equation:
--6--

115S801
z ~ W D
W ~ 11 Z
~C-C-C-F ~ MF ~ A-C-B ~ C~C-C-O-C-G ~ MY
/ I ~ ;/ ~ ' '
X Y F X F E
1 2 3 ~ 5
In the above equat~on, starting materlals 1,
2, and ~ react to give product 4 and a metal salt ~. The
letters A, B, D, E, G, M, W, X, Y and Z are as given in the
Summary. Products represented by general structure 4 can
be conver~ed into useful copolymers especially with
tetrafluoroethylene, trifluoroethylene, vinyl~dene fluoride,
and chlorotrifluoroethylene.
Preferred polyfluoroallyloxy compounds of
rormula ~ have D and E taken independently with D preferably
being -F or RF and E preferably being -F, -CF3, -CF2Cl or
CF2Co2R3 where R3 is CH3 or -C2H5. The preferred compounds also
have W and Z taken independently and X as -F. RF is preferably a
linear or branched perfluoroalkyl of 1 to 8 carbon atoms, inter-
ruptable with no more than 1 oxygen atom, having O to 1 functional
groups selected from -502F, -COF, -Cl, -C02H, -Co2R3, -OCF2CF=CF2
and -oCF2Co2R3 where R3 is -CH3 or -C2H5.
Especially preferred polyfluoroallyloxy compounds
of the lnvention have the formula:
D
CF =C-CF -O-CF
2 , 2
X E
wherein X is -Cl or -F (preferably -F);
E i~ -F, -CF3, -CF2C02R3where ~ is
CH3 2 5' 2
--7--

~ 1 5 .~
(preferably -F, -CF3 or -CE2C02R ) and
D is -CF2R4 or CFR4 where R4 is
CF3
-F, -SO2F, -COF, -CO2H, -CO2R ,
-OCF2CO2R where R is -CH3 or -C2H5,
or tCF2)xR where x is 1 to 6 and R
iS CF3~ -COF, -C02H, -CO2R , -SO2F or
-OCF2CF=CF2. R is preferably -SO2F,
-COF, -CO2H or -OCE2CO2R where R is
-CH or -C H .
The polyfluoroallyl group of the product 4 is
derived from the corresponding polyfluoroallyl chloride
or fluorosulfate (1) by nucleophilic displacement of the
chloride or fluorosulfate group with a preformed poly-
fluoroalkoxide anion derived from the metal fluoride (2)
and the carbonyl compound (3). The synthesis is thus a
one-vessel sequential addition of reagents 3 and 1 to a
suspension or solution of 2 in a suitable solvent.
Polyfluoroallyl fluorosulfates are the preferred
reagents for this displacement, and they can be prepared
conveniently by treatment of polyfluoroalkenes with sulfur
trioxide, as described in B. E. Smart, J. Org. Chem., 41,
2353 (1976). Such reactions are typically carried out in
sealed Carius tubes at temperatures of 25-95C for periods
of 16 hours to 4 days, and the product fluorosulfates are
purified by fractional distillation. A preparation of
the preferred perfluoroallyl fluorosulfate (pentafluoro-
2-propenyl fluorosulfate) is given in Example 2.
3~
~r~

1 ~55~0 1
Stable metal polyfluoroalkoxides are formed by
the reac~ion of certain metal fluorides with polyfluorinated
ketones and acid fluorides (J. A. Young, loc. cit.), thus:
CF9
(CF3)2CO ~ K~ ~ CF3-~-O K
F
CF3COF + KF ~ _ CF3-C-O K
F
The usefulness Or such intermediate Polyrluoroalkoxides is
determlned by their stabil~ty, as meaSured by their ease
of thermal decomPOSitiOn. Because their rOrmation is
reversible~ the equilibrium concentrat~ons of various
species in a given reaction mixture are important quan-
tlties which determine whether or not the subsequent dis-
placement will occur to form product 4. Solutions in
whlch the equilibrium lies towards the right (high con-
centration of anion) will be more effective than those in
which it lies towards the left (high concentration of
carbonyl compound).
Poly~luoroalkoxide anion formation and chemistry
i8 dependent upon the followlng ~our conditions, discussed
ln further detail by J. A. Youn~, 1 , cit., F. W. Evans,
M. H. Litt, A. M. Weidler-~ubane~ and F. P. Avonda, ~0
5~, Chem., 3~, 18~7, 18~9 (1968), and M. A. RRdwood and
C, J. Willi~, Canad. J. Chem., 45, 389 (1967).
~1) Stable polyfluoroalkoxlde an~on8 are formed when the
carbonyl compound i~ highly fluorlnated becau~e the
3 electron-withdrawln~ effect of the fluorine atom~ dis-
_g_

0 1
tributes the negatl~e charge o~er the entlre anlon.
Substitutlon o~ some of the fluorine by chlorlne, other
fluoroalkyl groups or hydrogen destablizes the anlon
because the~e ~roups are less electron-withdrawing and
the negatlve ch&rge is not as readily accommodated. (2)
Large catlons such as K+, Rb~, Cs~ and R~N~ favor the
formation o~ stable polyfluoroalkoxides more than 8
cations such as Li+ and Na~ because the lattice energy
of metallic fluorides 18 inver6ely proportional to
cation slze. In other words, large cation size and 8mall
lattice energy favors dl8ruption o~ the ~etallic fluorido
cry6tal etructure to form the anion. (~) Solvents which
ha~e a high heat of 601ution for the polyfluoroalkoxide
~avor lts formatlon~ Aprotic polar solvents such as
N,N-d~methylformamide (DMF), acetonitrile, and 1,2-
dimethoxyethane (glyme) are very e~fectlve ~or thls
purpoee. (4) When there are fluorine atoms alpha to the
oxygen atom ln the anlon, 1088 of rluoride lon may co~pete
with the desired reactions, e.g.,
~0
CF~ CF3
o c b o haB no o-fluorlne to lose and
1' 1 ,
CFo CF9 ~orme mAny etable derivatives.
CFo
CF3 - I - regulres a reactive compound
F such as allyl bromide for nucleo-
phillc substltution.
CFS0 u~ually ellminates ~~; nucleophilic
eubstitution is known with per-
3 ~luoroa~lyl fluorosulfate.
-10-

1 l~S~O 1
In the practice of this lnvention, the polyfluoro-
alkoxide anion is preferably pre~ormed by the addition of the
carbonyl compound to a stirred mixture of the metal fluorid~
in a suitable aprotic solvent. The completeness of forma-
tion of the anion is generally signalled by the extent to
- which the metal fluoride dissolves in the solvent as the
reaction progresses, Thestoichiometry of polyfluoroallcoxide
anion formation requires one molar equivalent of metal
~luoride for each carbonyl group whlch is con~erted to
its anion, e,g.:
CF3
(CF3)2CO ~ ~F ~_ ~ CF3`- ~ - O E+
0 0 F
P~(CF2)~CF + 2KF ~ K 0 - C(CF~)~b - 0 ~
me presence o~ up to a twice-molar excess of
metal M uoride is generally not detrimental. Two side
e~fects of excess met~l fluoride are: (1) to hlnder
the observation Or the reaction endpoint because of the
presence of undissolved solid in the reaction mixture, and
(2) excess fluoride ion in solution may react directly
with perfluoroallyl fluorosulfate to form hexafluoro-
propene.
Because of the limited thermal stability of
polyfluoroalkoxides, their formatlon is usually accom-
pli~hed between -20C and +60C, preferably with external
cooling to maintain the temperature between 0C and 10C.
3o

1 15580 1
The time required to complete poly~luoroalkoxide
formation varies with the carbonyl component, but it is
preferably from 0.5 to 2 hours, each individual case being
usually determined by how long it takes the reaction mixture
to become homogeneous.
N,N-Dimethylformamide (DMF), acetonitrile,
N,N-dlmethyl~cetamide (DMAC),-~-butyrolactone, 1,2-
dimethoxyethane ~glyme), l-(2-methox~ethoxy)-2-methoxy-
ethane (diglyme), 2,5,8,11-tetraoxadodecane (triglyme),
1~ dioxane, sulfolane, nitroben~ene and benzonltrlle Qre
sultable, illustrative aprotic polar solvents for the
preparation of polyfluoroalkoxides and their subsequent
reaction with the polyfluoroallyl chloride or fluorosulfate.
DMF, diglyme, triglyme and acetonitrile are preferred
solvents for these reactions.
The apparatus, reactants and solvents should
be adequately dried for use in the process of the invention
because the presence of water hydrolyzes polyfluoroalkoxides:
tRF)2CFO + H20 - ~ (RF)2C(OH2) + F
RFCF2o + H20 > RFC02H + HF2
Metal fluorides which are useful in this
invention are potassium fluoride (KF), rubidium fluoride
(RbF), cesium fluoride (CsF) and tetraalkylammonium
fluorides (R4NF) such as tetraethylammonium fluoride
((C2Hs)4NF) and tetrabutylammonium fluoride (~C4Hg)4NF).
R, alike or different, is alkyl of 1 to 6 carbon atoms,
preferably 1 to 4 carbon atoms. Potassium fluoride is
preferred because of its availability, economic advantage,
and ease o~ handling.

.a~s~ol
Polyfluorinated carbonyl compounds which are
useful in this invention are ketones and carboxylic acid
fluorides and a perfluorinated lactone 3,6-bis(trifluoro-
methyl)3,5,5,6-tetrafluoro-1,4-dioxan-2-one. Ketones and
the lactone give branched fluorocarbon products, whereas
acid fluorides give primary fluorocarbon products in which
the new ether linkage is at the primary or secondary
center:
(R )2CO -----------~> (RF)2C-O CF2CF CF2 (ketone)
~ ~ F
RF C=O ~~~~~~~~~~~ ~ RF ,C ~ C 2 2 (lactone)
0 ~0
RFCOF ----_______~ RFCF2OCF2CF=CF2 (acid fluoride)
Polyfluorinated ketones which are useful include
hexafluoroacetone, chloropentafluoroacetone, 1,3-dichloro-
tetrafluorGacetone, l,l-difluoroethyl 2-oxopentafluoro-
propanesulfonate, dimethyltetrafluoroacetone-1,3-
dicarboxylate, l,3-bis(2-heptafluoropropoxy)tetrafluoro-
propanone, octafluorobutanone, decafluoro-2-pentanone,
dodecalfluoro-2-hexanone, tetradecafluoro-2-heptanone,
hexadecafluoro-2-octanone, octadecafluoro-2-nonanone,
eicosafluoro-2-decanone, and hexafluoro-2,3-butanedione.
Hexafluoro-2,3-butanedione is a special case
(Example 12) in that the initially formed perfluoroalkoxide
reacts both with perfluoroallyl fluorosulfate and with
,,~,

1155801
another molar equivalent of hexafluoro-
2,3-butanedione to form a mixture of two hetero-
cyclic compounds.
Polyfluorinated acid fluorldes which are useful
include carbonyl fluorlde, tri~luoroacetyl fluoride,
pentarluoropropionyl fluoride, heptafluorobutyroyl fluoride,
nonafluoropentanoyl fluoride, tetrafluorodiglycolyl
O O
FCCF20CF2CF, undecafluorohexanoYl flu3ride,
trldecafluoroheptanoyl rluoride~ pentadecafluorooctanoyl
fluoride~ heptadecafluorononanoyl fluorlde, nonadecafluoro-
decanoyl fluoride, difluoromalonyl dirluoride, tetra-
fluorosuccinyl difluoride, hexafluoropropane-1,3-dioyl
difluoride (hexafluoroglutaryl difluoride),
octafluorobutane-1,4-dioyl difluoride (octa-
rluoroadipoyl difluoride~, decafluoropentane-1,5-dioyl
difluorlde (decafluoropimelyl difluoride), dodecafluoro-
hexane-1,6-dioyl difluoride (dodecafluorosuberyl difluoride),
~luoroBuifonyldifluoroacetyl ~luoride, 2-(fluoro~ulfonyl)-
t~trafluoropropionyl fluorlde, 2- (1-hepta~luoropropo~r)-
tetra~luoropropion;yl rluorlde, 2- r2- (l-heptafluoropropo~r )
h~xa~luoropropo~y~tetrafluoropropionyl ~luorlde, and
2 ~2-t2-(1-hept~fluoropropoxy)hexa~luoropropoxy~hexa-
~luoropropoxy}tetrafluoropropionyl fluoride, carbomethoxy-
difluoroacetyl fluoride.
The ketone l,l-difluoroethyl 2-oxopentafluoro-
propanesulfonate (Example 3) is a special case as a starting
material because it is an _ situ source of 2-oxopenta-
fluoropropanesulfonyl fluorlde since the latter has not been
lsolated.
; 3
-14-

115~8
F
ClT3COCF2SO20CF;~CH3 ~ [CF3COCF~SOzF] - >
7F3
FSO2CFzCFOCF2CF=CFz
Many of the above starting material~ are
commerclally available, e.g, PCR, Gainesvllle, Florida
iB a supplier o~ fluorinated ketones and carboxylic acids.
~ampl~s 2, 3, 4~ 5, 7, 9, lo, 11, 12, 13~ 16 and 19 give
sources and methods of preparation of some compounds which
1~ are not commercially avall~ble. Generally, perflu~roketones
can be prepared from the esters of perfluoro-
a~Xanecarboxyllc aclds and from the reaction of carbonyl
fluoride wlth perfluoroalkenes (W. A. Sheppard and G. M.
Sharts, "Organic Fluorine Chemistry", p. ~65-368, W. A.
~enJamin, New York, 1969, H. P, Braendlin and E. T. McBeeJ
Ad~ances ln Fluorlne Chemlst~ , 1 (1963)), Perf~oro-
alkanecarboxyllc acid fluorides and per~luoroalXane-
a,~_~icarboxylic acld di~luorides are prep~red by treat-
ment of the corresponding acids with sulrur tetrafluorlde,
by the addition o~ carbonyl fluorlde to perfluoroalkenes
(~ S. Fawcett, C. W. Tullock and D. D. Co~fman, J. Amer.
Chem. ~ 4 4275, 4285 (1962)) and by electrolysis o~
alX~ecarboxylic acids ln hydrogen fluoride (M. Hudlicky,
"Cheml~try of Fluorine Compounds", ~. 86, MacMillan Co.,
New York, 1962). Perfluoroalkanedicarboxylic ac~ds are
prepared by oxidation of fluorinated a,~-dlalX~nes or
fluorlnated cycloalkenes (Hudlic ~, loc. cit., p. 150-
15~). Perfluoroalkyl polyethers with a terminal ac~d
fl~oride group can be m~de from hexafluoropropene oxlde
3o and lts fluoride lon induced oligomer~, as described by
-15-

1 15S80 1
R. A. Darby, U.S. Patent 3,450,684 (1969) ~nd by P.
.Tarran~, C. G. Allison, K. P. Barthold and E. C. Stump,
Jr., luorine Chem. Rev., 5, 88 (19713.
The stoichiometry o~ the di6placement wlth
polyfluoroallyl chloride or fluoro~ulfate requires one
molar equivalent of thi~ reagent for each reacti~e center
: in the polyfluoroalkoxide ~nion. Wlth a difunctlonal poly-
fluoroalkoxide, however, the stoichlometry can be adJusted
to glve elther the mono- or the di~Rubstltution product,
thus:
O O O
F~CF2~F + KF + CF2,CFCF20S02F ~ F~CF2CF20CF2CF~CF~
~Example 5)
O O
F~CF2~F ~ 2KF ~ 2CF2=CFCF20S02F - -, tC~2~CFCFaOCFa)~CFa
(Exam~le 17)
FCO(CF2)4COF + KF + CF2 = CFCF20S02F ~ CF2 = CFcF2otcF2)5coF
21~ (Examples 21, 22 )
FCO(CF2)4COF + 2KF + 2CF2 = CFCF20S02 F ~ (CF2=CFC~'20CF2CF2CF2)2
(Example 13 )
The formation of the poly~luoroalkoxide and lts
~ubse~uent reaction with the polyfluoroallyl chloride or
~luorosulfate can be carrled out sequentlally without
isolati4n of intermediates in glass apparatus at atmos-
pherlc pressure using the normal precautions to exclude
~oi~ture, m e use o~ cooling baths and low temperature
cond0nsers (e.g. those packed wlth dry ice and acetone
3
-16-

1~55~01
mixtures) serves to moderate the reactions ~nd facilita~e
the retention of volatile rer~gents and products, Ihe
progress of the displacement reactlon is convenlently
followed by the appearance of a precipitat~ of the salt
MY (~), by gas liquid partition chromatography (glpc) and
by fluorine nuclear magnetic resonance spectroscopy
9F Nli~R ) .
The displacement reaction can be carried out
between -20C and +80C, ~nd ls preferably between OVC
and 30C. TypicallyJ the reaction mixture ~s cooled
e~ternally to O C to 15C dur1ng the additlon of th~
polyfluoroal-yl chloride or fluorosul~ate, and 1~ then
allowed to warm up to 25C to 30C for the remainder of
the reaction time.
~he time required to complete the displacement
reaction varies from one to 24 hours, and is preferably from
2 to 4 hours. Typically, the reaction mixture is externally
cooled for 5 to 45 min while the polyfluoroallyl chloride
or fluorosulfate is being added, and is then stirred at
room temperature for 2 to 3 hours.
The products of the reaction are isolated by
standard procedures. In some cases, the reaction product
is appreciably more volatile than the high-boiling solvent
uaed (diglyme bp 162C, DMF bp 153C) and can be
distilled into a trap cooled to -80C by warming the
reaction vessel to 30C to 50C under a reduced pressure
of 1 to 200 mm of Hg. Alternatively, the reaction mixture
can be poured into five to ten times its volume of water; the
insoluble lower layer of fluorinated product is separated,
-17-

1 15580 1
washed free of solvent with more water, dried, and fractionally
distilled from phosphorus pentoxide or concentrated sulfuric acid.
The polyfluoroallyloxy compounds of this invention are
unsaturated monomers which can be converted to new and useful
polymers. Polyfluoroallyloxy monomers can be homopolymerized
under high pressure to oligomeric compositions of matter. The
economic factors of a costly monomer and the necessity for high
pressure operation, however, make it preferable to incorporate
these monomers into copolymers formed with less expensive
ethylenically unsaturated monomers, e.g., olefins such as ethylene
or propylene; halogenated olefins such as tetrafluoroethylene,
trlfluoroethylene, hexafluoropropylene, vinylidene fluoride,
vinylidene chloride, trifluoromethyl trifluorovinyl ether and
chlorotrifluoroethylene, and acrylic acid or methacrylic acid
esters. Halogenated olefins are preferred, especially tetra-
fluoroethylene,chlorotrifluoroethylene, trifluoromethyl
trifluorovinyl ether, hexafluoropropylene and vinylidene
fluorlde. Such copolymers have either more desirable or
entlrely new properties not possessed by e.g., poly(tetrafluoro-
ethylene), poly(trlfluoroethylene), poly(vinylidene fluoride),poly(chlorotrifluoroethylene) or polyethylene. Copolymerization
may be deflned as any process whereby two or more monomers are
incorporated as lntegral parts of a high polymer. A copolymer
ls the product resulting from such a process. It is not necessary
that the relative numbers of the different types of unit be the
same ln dlfferent molecules of the copolymer or even in different
portions of a single molecule.
Copolymers which contain from about 5-55 welght per-
cent (about 1-25 mole percent) of polyfluoroallyloxy comonomer
have lower melting points than the corresponding polyfluoro-
-18-

5~
olefins, and consequently are more readily molded and shaped
into useful objects. Copolymers which contain from about
0.1-10 weight percent, preferably about 1-10 percent (about
0.3-5 mole percent) of a polyfluoroallyloxy comonomer with
pendant SO2F or COF groups can be partially hydrolyzed to
a copolymer bearing SO2OH or CO2H groups which have an
affinity for cationic dye molecules. Thus, it is possible
to dye fluorocarbon polymers in a variety of colors. This
cannot be done with polyfluoroolefins which do not have
incorporated comonomer of this type. Copoiymers which
contain from about 5 to 35 weight percent (about 1.0 to
10 mole percent) of a polyfluoroallyloxy comonomer with
pendant SO2F or COF groups can also be partially or essen-
tially completely hydrolyzed to a copolymer bearing
hydrophilic SO2OH and CO2H groups. Such a copolymer has
an affinity for water and is water-wettable. Polyfluoro-
olefins which do not have incorporated a comonomer of this
type are not wetted and are impermeable to water. A second
important feature of copolymers which contain about 1.0 to
10 mole percent of a polyfluoroallyloxy comonomer bearing
-SO2OH or -CO2H groups or ionized forms thereof; e.g.
-SO2O Na or CO2 Na , is their capacity for ion exchange.
A specific use for such polymers is in a chloroalkali cell,
such as disclosed in German patent application 2,251,660,
publi~hed April 26, 1973, and Netherlands patent application
72.17598, published June 29, 1973, wherein an ion-exchange
polymer in the form of a film membrane or diaphragm is used
to separate the anode and cathode portions of the cell from
which chlorine and sodium hydroxide are respectively pro-
duced from brine flowing within the anode portion of the cell.
--19--

115580 1
The properties of each copolymer depend uponthe distribution of monomer units along the polymer
chain since a copolymer is not a physical mixture of
two o~ more polymers each derived from the respective mono-
mers but a new material incorporating each monomer. It is
well known thatthe composltion of such a copolymer may
also be quite different from that of the monomer mixture
(feed) from which it is formed. Furthermore, "the
relative tendencies of monomers to be incorporated
into polymer chains do not correspond at all to their
relative rates of polymerization alone..... the reactive
properties of a growing polymer chain depend primarily
upon the monomer unit at the growing end, and not upon
the length and composition of the chain as a whole.",
C. Walling, "Free Radicals In Solution", pages 99-100,
John Wiley & Sons, Inc., New York ~1957).
The copolymerization reaction to prepare the
present copolymers can be carried out either in a nonaqueous
or an aqueous medium with the reactants and initiator in
; solution, suspension, or emulsion form in a closed vessel
with agltation. This type of reaction is well known to
those skilled in the art.
The copolymerization is initiated by a free
radical type initiator which is generally present at a
concentration of from 0.001 to 5 percent by weight of the
reaction mixture, and is preferably from 0.01 to 1.0
percent by weight. Such free radical initiator systems
are preferably operable at or below 25C, and are
exemplified by, but not restricted to pentafluoropropionyl
peroxide (c2Fscoo)2~ dinitrogen difluoride (N2F2),
-20-

1 15S80 1
azobisisobutyronltrile, ultraviolet irradlation and ammonium
or potassium persulfate; mlxtures of lron (II) sulfate
with hydrogen peroxide, ammonlum or potassium persulfate,
cumene hydroperoxide, t-butyl hydroperoxide; mixtures of
sllver nltrate and ammonium or potassium persulfate;
mlxtures of trlfluoroacetic acld, pentafluoroproplonic
acid, heptafluorobutyric acid or pentadecafluorooctanoic
acid with ammonium or potassium persulfate. The peroxide
systems may contain additionally sodium sulfite, sodium
metablsulfite, or sodium thiosulfate.
When aqueous emulsion systems are used for
copolymerization they contaln emulsi~ying agents in the
form of the sodiumor potassium salts of saturated
aliphatic acids of between about 14 and 20 carbon atoms
or of perfluoroalkanoic aclds and perfluoroal~anesulfonic
acids of between 6 and 20 carbon atoms, e.g., potassium
stearate or potassium pentadecafluorooctanoate. These
emulsifiers may constitute between 0.1 and 10.0 weight
percent of the reactlon mixture and preferably constitute
between 0.5 and 5 parts by weight percent.
Aqueous emulsion systems are customarily
bu~fered to pH 7 or above by the addition of reagents
such as dlsodium hydrogen phosphate, sodium metaborate,
or ammonium metaborate to the amount of about 1 to 4
welght percent of the reaction mixture.
The following three types of copolymerization
systems are preferre~ in preparing the preferred copolymers
of this invention:
1) Solutlons of two or more comonomers in 1,1,2-tricnloro-
3 1,2,2-~rifluoroe~hane (~reon~ 113) solvent con~;lLIlin~
-21-

1155801
pentafluoroproplonyl peroxide are shaken ln an
autoclave at about 25C for about 20 hours. The crude
polymer is isolated by evaporation of the solvent
and freed from monomers and lower ollgomers by
washing with more solvent.
2) An aqueous emulsion of two or more comonomers containlng
an emulsifier such as potassium perfluorooctanesulfonate
and an initiator such as ammonlum persulfate is shaken
ln an autoclave at about 70C and internal pressures of
.30-200 p.s.i.g. for 0.75 to 8 hours. The polymer is
isolated by filtratlon or centrlfugatlon.
3) The polyfluoroallyloxy comonomer may be used as the
solvent in place of 1,1,2-trichloro-1,2,2-trifluoro-
ethane ln method (1) when it is desired to incorporate
~ a large proportion (up to 25 mole percent) of the
;, polyfluoroallyloxy component in the polymer.
SPECIFIC EMBODIMENTS OF THE INVENTION
The following illustrative examples demonstrate
ways of carrylng out the invention. All parts and
' 20 percentages are by weight unless otherwise stated. For
~tru¢ture confirmatlon analyses, fluorine nuclear magnetic
resonance chemical shifts are in parts per million from
lnternal ~luorotrichloromethane, and proton nuclear
magnetic resonance chemlcal shifts are in parts per million
-- from internal tetramethylsilane. Infrared and nuclear
magnetic resonance spectra were recorded on undiluted
liquid samples unless otherwise stated.
EX~MPLE 1
l-(H~pt.lrl~lo o-2-~ropoxy)~ 3,3-tetrarluoro-2-chloro-2-propene
3 (C~ CO I KF ~ CF2~CClCFrCl- ~ (cF3)~cFocFrccl~cF2
-22-

1 15580 1
Hexafluoroacetone (16 6 g, 0.10 mol) was di~-
tilled lnto a stirred mlxture of pota~sium fluorlde (5.80 g,
0.10 mol) and 1-(2~methoxyethoxy)-2-methoxyethane (here-
lnafter referred to as diglyme) (100 ml) to g~ve a homo-
geneou~ solution, This mlxture was mainta~ned at 25-~O-C
and treated with 1,2-dlchloro-1,1,~,3-tetrafluoropropéne
(18.3 g, 0.10 mol, prepared according to J E, Bis~ey,
H. Goldwhite and D G. Row~ell, J. Org. Chem" 32, 1542
(lg67)~. The mixture was stlrred overnight and then it
was poured into water (500 ml). The lower layer was washed
with water (250 ml), dried, and distilled to give
l-(heptafluoro-2-propoxy)-1,1,3,3-tetrafluoro-2-chloro-
propene (13 0 g, 0.039 mol, 39%), bp 82-83C whose
structure was confirmed by the following: ~max 5.72
(CCl~CF2) and 7.5-10 ~m (CF, C-O); 9F NMR, -64.~ (m)
2F, -OCF2CC; -76.o (2nd order m) 2F, C~CF2; -81.2
(t ~ - 5,7 Hz, each member d J - 2.2 Hz) 6F, CF~; and
-146.7 ppm (t J 5 22.9 Hz each member septet J = 2.2 Hz)
1~, CFO.
Anal. Calcd for C6ClFl10: C, 21.67; Cl, 10.66
Found: C, 21.43; Cl, 10.89
EXAMPLE 2
1-(1,1,1,2,3,3-Hexa~luoro-3-chloro-2-propoxy)-pentafluoro-
2-~ro~ene
A. Pentafluoro-2-propenyl fluorosulfate (Perfluoroallyl
~luorosulfate)
CF3CF ~- CFz ~ S03 ~ CF2 - CF-CFa
O--2
C,F2~CF-C~90502F
-23-

1155801
A mixture Or commerclal liquld ~ulfur trioxide
(10 ml) and hexafluoropropene (45 g, 0.~0 mol) was ~ealed
in a C~rius tube at llquid nitr~gen temperature, mlxed
well at 25-C, allowed to stand for 4 days at 25-C, and
finally heated in a steam bath for 6 hours ~rom two such
tube~, there was obtained by dlstillatlon, 3-(trifluoro-
methyl)-3,4,4-trifluoro-1-oxa-2-thlacyclobutane 2,2-
dloxide (2-hydroxy-1-trifluoromethyl-1,2,2-tr~luoroethan~
~ulfonic acid sultone, D. C. Engl~nd, M. A. Dietr~ch and
R. V. Llndsey, Jr,, J. Amer. Chem. Soc.. 82, 6181 (1960))
(25 e, 22%) bp 44C, and pentafluoro-2-propenyl fluoro-
sul~ate (hereinafter re~erred to as perfluoroallyl fluoro-
sulfate) ~73 g, 6~%), bp 58-60-C.
Perfluoroallyl ~luorosulfate i5 characterlzed
by: ~max 5.55 (C-C) ~nd 6.75 ~m (S0z); 9F NM~, 46.1
(t J - 8.5 Hz, each member d J = 1.8 Hz) 7F, S02F,
-74,0 (d J = 28.2 Hz, each member d J a 1~9 Hz, d J =
8.5 Hz, d J = 7.8 Hz) 2F, -91.2 (d J = 50 Hz, each member
d J - 40.5 Hz, t J - 7.8 Hz) lF, -104.7 (d ~ a 119.4 Hz,
each member d J = 50 Hz, d J = 28.2 Hz) lF, and -192.4
ppm (d J ~ 119,4 Hz, each member d J - 40.5 Hz, t J s
1~.9 Hz, d J = 1.8 Hz) lF.
B. 1-(1,1,1,2,3,3-Hexafluoro-3-chloro-2-propoxy)-penta~luoro-
2~-propene
.
CF3COCF2Cl ~ ~ ~ CF2=CFCFzOSO~F
CF2Cl
CF3CFOCFzCF=CF2
A ~uspenslon of pot~sslum fluoride (5.80 g,
0,10 mol) and dlglyme (100 ml) wa~ ~tirred at 20-C in a
3~
-24-

1155801
cooling b~th while chloropent~fluoroacetone (18.3 g,
0.10 mol) was dlstllled in. A~ter the pota~sium fluoride
had dis~olved, perfluoroallyl fluorosul~ate (23,0 g,
0.10 mol) was added rapldly with cooling of the reaction
mlxture. ~he resultlng exothermic reactlon was accompanied
by the preclpltatlon of 601id. The mixture was stirred
at 25-C for one hour, and then the volatlle component3
were transferred to a trap cooled to -80-C by heating
the reactlon mlxture at 42-C (5 mm Hg). The v~latil~ product
10 was distilled from phosphorus pentoxide to give 1-(1,1,1,2,3,3-
hexa~luoro-3-chloro-2-propoxy)-pentafluoro-2-propene,
(19.6 g, 0.059 mol, 59%) bp 85-86C which was
character~Zed by: ~max 5-55 (CF = CF2) and
7-10 ~m (CF, C-0); 9F NMR, -68.6 (m) 2F, CF2Cl, -69.1
(m) 2F, CF20, -78.8 (m) 3F, CF9, -93.2 (d J - 54.7 Hz,
each member d J = 39.8 Hz, t J 3 7.5 Hz), lF, cis-CF2-CF-CF,
- -105.9 ~d J - 116.7 Hz, each member, d J - 54.7 Hz, t J =
24.0 Hz) lF, trans-CF2-CF-CF, -141.2 (t J ~ 22.8 Hz, each
member m) lF, CF, and -190.4 ppm (d J ~ 116.7 Hz, each
member d J - 39.8 Hz, t J = 13.4 Hz) lF, -CF2CF=C.
Anal, Calcd ~or C6ClFl10: C, 21.67; Cl, 10.66
Found: C, 21.34; Cl, 10.21
3o
-25-

11S5801
EXAM~LE ~
2~ Pentafluoro-2-propenyloxy)hexafluoropropane-1-
sulfonyl fluoride (2-Perfluoroallylox~propane~l-sul~onyl
fluorlde)
A 2-OYopentafluoro~ropa~esulfonic ~cld
.
OC~Hs
CF3C-CF2 + S03 -- ~` CF3~CF~SO20C~H5 ~ CF3~CFa~SO20H
O O
Il 11
CF3CCF~SO~OC2Hs ~ CF3C02H - -~ CF9~CFzSO20H
CF3CO~C2H5
(1) Dropwl~e add~tion of ~ulfur trioxlde (12.8 K, 0.16
mol) to 2-ethoxy-?,1,3,3,~-penta~luoropropene
(D, W. Wiley and H. E, Slmmon~J J, Or~. Chem., 29,
1876 ~1964)) (29.0 g, 0.165 mol) produced an exo-
thermic reactl~n, The black reactlon mlxture was
dlstilled to give reco~ered 2-ethoxy-1,1,3,3,3-
pentafluoropropene (6.3 g, 0.0~6 mol, 22~, identi~ied
by lr) and ethyl 2-oxopenta~luoropropane~ulfonate
(20.2 g, o.o78 mol, 49% con~ers~on and 6~% yield)
bp 47-48C (12 mm Hg): ~max 3.34 and 3.41 (s~turated
CH), 5.60 (C ~ O), 7.09 (SO20), and 7.6-~.5 ~m
(C~F, SO2); H NMR, ~ 4,59 (q J c 7.2 Hz) 2H,
OCH2 ~nd 1.51 ppm (t J = 7.2 Hz) 3H, CH3, 19F
NMR, -75.0 (t J = 8.3 Hz) 3F, CF3, and -107.4 ppm
(q J ~ 8.3 Hz~ 2F, CF2.
(~1) me above reaction was repeated at 0-5'C with sulfur
trloxlde (88 g, 1.1 mol) and 2-ethoxy-1,1,3,3,3-
penta~luoropropene (176 g, 1.0 mol). me colorless
-26-

11~5801
reactlon mixtureJ whlch darkened on standing o~er-
night, wa~ di~t~lled to glve recovered 2-ethoxy-1,1,
~,3,3-pentafluoropropene (28.6 ~, 0.16 mol, 16%)
bp 46-48-C, ethyl 2-oxopentafluoropr~p~nesulfonate
(145.1 g, O.57 mol, 57% conver3ion and 68~ yield)
bp 48-52C (12 mm Hg), and a higher boillng fraction
composed mainly of 2-oxopentafluoropropanesulfonic
acld. The crude acid was redistilled at 81-82C
(6.2 mm Hg), yield 35.6 g (0.16 mol, 16% conversion and
19% yleld) of pure acid: ~Bx (~Cl~, CaF2 plates)
3.~ and 4.2 (broad) (SOH), 5.58 (C~O), 7.13 (SOzO)
and 7.5 - 9 ~m (CF, S0z); H NMR ~ 10,2 ppm (B)
SO20H; 9F NMR, -76.2 (t J 8 7.5 Hz) 3F, C~3, and
-108 ppm (q J - 7,5 Hz) 2F, CFz.
Anal. Calcd for C3HFsO~S: C, 1~,80; H, O.44: F, 41.65;
S, 1 .o6
Found: C, 15.95; H, O.55; F, 41.55;
S, 13.89
(lii) Ethyl 2-oxopentafluoropropane~ulfonate (25.6 g,
O.lO mol) was stlrred at 25-C and treated with
trlfluoroacetlc acid (17.1 g, 0.15 mol). me
mixture was allowed to stand overnight, and then
it was heated to reflux (60C) in a spinning band
~till. Fractional dlstlllation of the mixture at
a pot temperature below 100C gave 2-oxopenta-
fluoropropanesulfonic acid (18.4 g, 0.081 mol, 81%)
bp 73C (2.6 mm Hg).
B. 1J l-Dl~luoroethYl 2-oxo~entafluor ~ro~nesul~onate
O O
CFsCCFzS020H ~ CF2~CHz ~ CF3CCFzS020C~zCH3
3o

1 15~80 1
A metal tube contalnlng 2-oxopentafluoropropane-
~lfonic acld (2~.8 ~, 0.10 mol) was cooled below
-40C and ~inylidene fluoride (l,l-difluoroethene)
(1~ g, O.20 mol) was added. The mlxture was shaken
and warmed to 25C where it was kept for 4 hours. Distil-
lation of the liquid product gave 20.4 g (0.07 mol, 70%)
of l,l-difluoroethyl 2~oxopentafluoropropanesulfonate,
bp 62-63~C (50 mm Hg): ~max (CC14) 5.54 (C=O), 6.96
(SO20) and 7.5 - 9 ~m (CF~ SO2); H NMR, ~ 2.06
ppm (t J - 14.3 Hzj CH3; 19F NMR, - 58.3 (q J =
14.~ Hz, each member t J = 7,1 Hz) 2F, OCF2,
-75,0 (t J = 8.o Hz) 3F, CF3 and -106,1 ppm
(q J = 8.0 Hz, each member t J - 7.1 Hz) 2F,
.CFzS02.
Anal. Calcd for CsH3F70~S: C, 20.56; H, 1.0~; F, 45.52
Found: C, 20.7~; H, 1.0~; F, 45.72
A similar experiment on a 0.8-mol ~cale gave
an 86% yield of product bp,60-C (50 mm Hg). Th~s material
was ~tored in polytetrafluoroethylene bottleR to a~oid
degradation,
C. 2~ Pentafluoro-2-propenyloxy)hexafluoropropane-1-
~ul~onYl fluorlde
O .
CF3JCFzSO20CFzCH3 t KF t CF2-CFCFzOSO2F
1,'
CF3-CFOCFzCF=CFz + CH3COF ~ KOSO~F
CFzSO2F
A suspenslon of dry potassium fluoride (5.80 g;
0.10 mol) ln 2, 5, 8, ll-tetraoxadodecane (triglyme)
3o

1 15580 1
~00 ml~ wa~ stirred and cooled at 0C while l,l-
difluoroethyl 2-oxopentafluoropropanesulfonate prepared
as ln Example 3B (29.2 g, 0.10 mol) was added. When
the potassium fluoride had nearly all dissolved, per-
rluoroallyl fluorosulfate prepared as in Example 2A
(23.0 g, 0.10 mol) ~Jas add~ at 0C, and the resulting
mixture was s~irred at 20-26C for 3 hour~ latlle co~-
ponents were rcmoved by distillation at a flask tempera-
ture o~ 25C and 1 mm Hg pressure. The distillate was
washed with cold dilute ammonium hydroxide, dried and
distilled to give 2-(1-pentafluoro-2-propenyloxy)hexa-
fluoropropane-l-sulfonyl fluor1de (13.0 g, 0.034 mol,
34%), bp 47-48C (60 mm Hg) whose structure was confirmed
by: ~m~x 5.59 (CF~CFz), 6.80 (S0zF) and 7.5 - 10
~m (C-F, C-0, S02); 9F ~R, + 45.4 (m) lF~ SO~F, -70.0
(m) 2F, OCF2, -78.o (qulntet J = 10.7 Hz) 3F, CF3, -91.5
(d J = 51,5 Hz, each member d J = ~9,5 Hz, t J = 7,5 Hz)
lF~ ci8-CF2CF - CF, -104,8 ~d J - 117!0 Hz, each member
d J a 51.5 Hz, t J = 25.5 Hz) lF, trans-CF2CF - CF~ -107.0
and-108.4 (AB J - 255 Hz, each member ~ J = 10.7 Hz, m)
2~, CF2S02F, -138,7 (t J - 20.2 Hz, each member m) lF,
CF, and -190.8 ppm (d J = 117.0 Hz, each member d J ~ 39.5
Hz, t J ~ 1~.0 Hz) lF, CF2CF=C.
Anal. Calcd for C~Fl203S: C, l~.g6i F, 59.98; S, 8.43
Found: C, 19.24; F, 60.06; S, 8.26
In a similar reaction to Example 3C, it was
shown by ir that the gases generated were composed mainly
of acetyl fluoride and sm~ll ~mounts of hexafluoropropene
and sulfuryl fluoride,
3o
-29-

1 15580 1
'
1- ~1,3-bis(2-Hepta~luoropropoxv)-2-PentafluoroProPoxY~-
pentafluoro-2-propene
A. 1,3-bis(2-HePtafluoroPropox~L~etrafluoroproPanone
O o
2(CF3)2CO + KF + C1~2CCCF2Cl ~ (CF3)2C~;OCF2CCF~OCF(CF3)2
A mixture o~ dry potassium fluoride (21.0g, 0.36
mol), dry N,N-dimethylform~mide (DMF) (150 ml), hexafluoro-
acetone (59.8 g, o.36 mol) and 1,3-dichlorotetrafluoro-
acetone (35.~ g, 0.18 mol) was heate`d at -reflux (40-60C)
for 3 days. Distlllatlon lnto a trap cooled to -80C gave
recovered hexafluoroacetone (16.5 ml, 46~o) and ~ 63 g of
liquid bp 30-145C. The higher-bolling material was redis-
tilled rrom sulfuric acid to give 1,3-bls(2-heptafluoro-
propoxy)tetrafluoropropanone (18.7 g, 0.037 mol, 21~ con-
version, 39~o yield based on hexafluoroacetone~, bp 117-118C;
AmaX (CCl4) 5.51 (C=O) and 7.5-9 ~m (CF,C-O-C); MS m/e 479
(M-F) , 313 (M-F-CF3COCF3) , 263 (M~F~CF3COCF3~CFa) ,
?35 [ ( CF3)aCFOCFa] , 169 ( C3F7) , 147 (CF3COCFa) , 97 (CF3CO)
and 69 (CF3) ; l9F NMR, -75.0 (d J = 21.5 Hz, each member
septet J = 5.5 Hz) 2F, OCFa~ -81~4 (m) 6F~ CF3, and -145.3
ppm (t J = 21.5 Hz, each member septet J = 2.1 Hz)lF, CF.
Anal. Calcd for CsFl~03: C, 21.70; F, 68~66
Found: C, 21.60; F, 68.5g
B. 1-{1~3-bls(2-HePtafluoropropox~)-2-pentafluoropropox~y}
~entafluoro-2-ProPene
(CF3)aCFOCFaCCFaOCF(CF3) 2 + KF + CFa - CFCFaOSOaF
~I
CF~ = CFCFaOCF[CF~OCF(CFo)~ ~2
3o
-30-

1155801
A mlxture of 1,3-bls(2-hepta~luoropropoxy)tetra-
fluoropropanone (20.0 g, 0.04 mol), dlglyme (100 ml) and
potassium fluoride (2.32 g, 0.04 mol) was stirred and warmed
to 55C. The two liquid phases and solid originally present
became homogeneous and stayed so upon cooling. Perfluoro-
allyl fluorosulfate prepared as in Example 2A (10.0 g,
0.043 mol) was added rapidly at 10C and the mixture was
allowed to warm. The slight exothermic reaction was
accompanied by precipitation Or solid and the appearance of
a second liquid phase. The mixture was stirred for 2.hours 21.
then poured lnto water (350 ml). The lower layer was washed
with water (75 ml), dried ovcr phosphorus pentoxide and
dlstilled to give l-~1,3-bis(2-heptafluoropropoxy)-2-penta-
rluoropropoxy~-pentafluoro-2-propene (16.1 g, 0.024 mol,
62Z) bp 64-67C (25 mm H~) whose ~tr~tuP~ was confirmed by:
Amax 5.57 (CF~ - CF) and 7.5-9 ~m (CF, C-O);
~F NMR, -69.4 (m) 2F, OCF~C=C; -80.3 ~broad) 4F, CFOCFa
-81,5 (8) 12F, CF~, -93.7 (d J = 54.0 Hz, each member
d J = 39.6 Hz, t J = 7.8 Hz) lF, cls~CFa ~ CF = CF , -106.3
(d J = 117.4 Hz, each member d J = 54.0 Hz, t J = 23.7 Hz)
lF~ trans-cFacF - CF , -145.8 (m) 3F, OCF, and -190.9 ppm
(d J - 117.4 Hz, each member d J = 39.6 Hz, t J = 16.6 Hz)
lF~ CF~C~ - C.
Anal, Calcd for C~2F~03: C, 22.24; F, 70.35
Found: C, 22.66; F, 70.27
3o
-31-

1 lSS~O 1
EXAMPLE ~
3~ Pentafluoro-2-Propen~loxy)tetrafluoroproplonyl fluoride
A. D~fluoro_alonyl difluoride
CH~OCF2CF~COF ---> ~ CF~CF
3-Methoxytetrafluoropropionyl fluoride
(F. S. Fawcett, C.W. Tullock and D. D. Coffman, J. Amer. Chem.
Soc., 84, 4275 (1962)3 (81 g, 0.45 mol) was slowly added to
sulfur trioxide ~80 g, 1.0 mol) at 40C, and the product
difluoromalonyl difluoride, bp -9C, was continuously removed
by distillation through a low temperature still, yield 58 g
(0.40 mol, 90~). The product structure was confirmed by:
Am~X 1~6O cm ~COF), l9F NMR (no solvent), ~17.1 ppm
( t J ~ 10 Xz ) 2F, COF and -114 . 2 ppm (t J = lO Hz ) 2F, CFa .
B. 3~ Pent~luoro-2-Propenvlox~y~tetrafluoro~ropionyl fluoride
O O ' O
~1 11 . "
FCCF~ CP' ~ KF ~ CF~ =CFCF~ OSO~ F FCCFa CF~ OCF:~ CE'=CF~
A mixture of dry potassium ~luoride (7.5 g, 0.13 msl)
and dielyme (lOO ml) was stirred at 10C and difluoromalonyl
dl~luorlde from part A (18.5 g, 0.13 mol) was distilled into
it. A~ker 20 min. the potassium fluoride was nearly all
dlssolYed, and perfluoroallyl fluorosulfate prepared as in
Example 2A (29.9 g, 0.13 mol) was added dropwlse at 10-15C.
The mixture was stirred for 3 hours, then the volatile compc.n~nts
were removed at a pot temperature o~ 32C and 4.8 mm Hg
pressure. Fractionation of the distillate gave
3-(1-pentafluoro-2-propenyloxy)tetrarluoropropionyl
fluoride (14.9 g, 0.051 mol, 39%) bp 70-71Cand a small
-32-

1155~01
amount Or higher bp material. The product structure was
~ ~max 5.33 (COF), 5.60 (CF = CF~) and 7.5-lO ~m
(CF~C-O); l9F NMR 23.7 (apparent qulntet, J ~ 7.5 Hz) lF,
COF -71.9 (d J 2 24.6 Hz, each member t J = 13.9 Hz,
d J = 13.9 Hz, d J = 7.4 Hz) 2F, OCF2C=C, 86.7 (m) 2F, CF20, -91.6
(d J = 51.8 Hz, each member d J - 39.4 Hz, t J - 7.4 Hz) lF,
cls-CF~CF = CF, -105.1 (d J = 117.1 Hz, each member d J=51.8 Hz,
t J ~ 24.6 Hz) lF, trans-cFa-cF=cF~ -122.0 (d J = 8.2 Hz,
each member t J = 3.1 Hz) 2F, FCOCF~, and -l91.O ppm
(d, J = 117.1 Hz, each member d, J = 39,4 Hz, t J = 13.9 Hz,
t J = 1.6 Hz) lF, CFa~CF=C.
Anal. Calcd ~or C~FloOa: C, 24.51
Found: C, 24.56
EXAMPLE 6
P~rrluoro-3.~-dioxanon-8-enoyl Iluori.de
1\. '1'~1;ra:rluoro(1Lrr..Ylco]..~,rl C~llorldc
Cl Cl
F2QF8 KMnO" Hzso HO2CCFzOCF2CO~II
O o SOCl2
ClCCF20CFzCCl
A mlxture of 307.6 g (1.46 mol) o~ dichlorotetra-
~luorodlhydrofuran, 157.8 g (3.9 mol) of NaOH, 312 g (1.97 mol)
of potassium permanganate and 1500 ml o~ water was refluxed
~or 17 hours. A brlef (steam) distillatlon gave 10.6 g (3%)
o~ recovered dihydrofuran. The reaction mixture was ~iltered
and the ~ilter ca~e triturated wlth 2 x 400 ml o~ water. The
-33-

115$801
combined aqueous solutlons were evaporated to 1500 ml, treated
cold with 300 ml of conc. H2S04 and extracted continuously
with ether for a day. The extracts were evaporated until ether
was no longer evol~ed at 25C (0.5 mm Hg). To the crude
solid diacid, 279 g (up to 93% yleld), was added 5 g (o.06 mol
of pyridine and 416.5 g (3.5 mol) of thionyl chloride. Little
gas evolution occurred at this stage, but considerable gas
evolved as the mixture was stirred and warmed past 40C.
Evolved gases were passed through a 0 trap; after 4 hours
at ca. 40C, gassing slowed and trap contents (10 ml) were
returned to the pot. The mixture was then refluxed, with
occasional return of cold trap contents to the reaction,
untll the head temperature reached 81C and no gas was being
evolved. Fractionation afforded 215.2 g (61% from dihydrofuran)
! of tetrafluorodigylcolyl chloride, bp 94-97C. Structure
was confirmed by NMR: 19F -77.0 ppm (s, -CF20-).
Tetrafluorodigycolyl chloride, bp 96.5C, has
previously been prepared by a different route by R. E. Banks,
E. D. Burling, B. A. Dodd, and K. Mullen, J. Chem. Soc. (C),
170~ (19~9).
B. Tetrafluorodi~Ylcol.Yl Fluoride
O O O O
ClCCF20CF2CCl ' > FCCFzOCF2CF
Conversion of the diacid chloride to the correspond-
lng fluoride, bp 32-33C, was accomplished by a scale-up of
the procedure o~ R. E. Banks, E. D. Burling, B. A. Dodd, and
K. Mullen, J. Chem. Soc. (c), 1706 (1969). A mixture of 215 g
(0.885 mol) of tetrafluorodlglycolyl dichloride, 140.5 g
(3.35 mol) of NaF, and 1200 ml of anhydrous acetonitrile was
3o
-34-

1155801
stirred overnight, then distllled to give a fraction collected
at 35-79C. The distillate was treated with 20 g of NaF
and distilled to give 105 g o~ tetra~luorodiglycolyl difluoride,
bp 32-33C. Addition of another 100 g (2.38 mol) of NaF to
the reaction mixture and slow distillatioll afforded another
fraction, bp 35-81C. Treatment with 10 g of NaF and fraction-
ation gave another 37.0 g of difluoride product, bp 32-33C, for
a total of 142 g (76%).
C. ~erlJuoro-3~-d:lo~nnon-8-(!no~ uor.ld~
0 0
FCCli'20CF2CF t KF -t CF2=CFCF20SOzF
R
CF2=CFCF20CF2CF20CF2CF
A mixture of 38.9 g (o.67 mol) of KF, 141.5 g
(0.67 mol) of tetrafluorodiglycolyl difluoride, and 500 ml
of dry diglyme was stirred for 30 minutes at 5C, during
which time nearly all of the KF dissolved. Then 154.1 g
(0.67 mole) of perfluoroallyl fluorosulfate was added
rapidly at 5~C and the mixture was stirred at 0-5C for
3 hours, at 25C for 2 hours, and allowed to stand overnight.
Volatlles were evaporated to diglyme reflux at 38C (3 mm Hg).
Di8tillation of volatilcs from 20 g of NaF gave 28.2 g (20~)
of recovercd diacid fluoride, bp 32-33C, a.nd 125.0 g (52~) of
mono~cid f:luoride, ~lmost a.ll of lt bp 93-94C. Structure
was conrirmed by:
ir (CCl4): 5.30 (COF), 5.59 (C=C), 8-9 ~
(CF, C-O). NMR: F 13.3 (m, 1 F, COF), -72.0 (d of d of t of d,
JFF 25, 13, 13, 7.7 ~Iz, 2F, =CFCF2), -77.5 (t of d, JFF 11.5,
2.~ ~Iz, 2 F, CI~'2C02E'), -88.8 (t, J~F ].1.5 I~z, 2 F, CF20CF2COF),
3o
-35-

~155~1
-89.4 (t, JFF 12.7 Hz, 2 ~, aCFCF20CF2), -91.9 (d o~ d of t,
JFF 52.7, 39.3, 7.7 Hz, lF, cis-CF2CF=CF), -105 3 (d of d o~ t,
JFF 117.6, 52.7, 24.6 Hz, 1 F, trans-CF2CF=CF), and -190.8 ppm
(d of d of t of t, JFF 117.6, 39.3, 13.7, 1.6 Hz, 1 F,
CF2CF= ~ .
EXAMPLE 7
2~ Pentafluoro-2-pr~en~loxy)tetrafluoroethanesulfon
fluoride
o
FSOa CFa CF + KF ~ CF~ =CFCFa OSOa F--> ESO~ CFa CF~ OCF~ CF~CFa
A suspe~lsiol~ o~ ~ot;as~ ll rlu~-ri(lo (5.~ ~,, 0.10 mo~)
ln diglyme (100 ml) was stirred and cooled while fluoro-
sulfonyldifluoroacetyl fluorlde (18.0 g, 0.10 mol) (D.C.
England, M. A. Dietrich and R. V. Lindsey, Jr., J. Amer. Chem.
Soc., 8~ 6181 (1960)) was added rapidly. The mixture wa6
stirred for 15 mln at 20-30C during which time the potassium
~luoride dissolved, and then it was treated wlth perfluoro-
allyl fluorosulfate prepared as in Example 2A (25.0 g, 0.11
mol) at 20-25C over 5 min. The mixture was stirred ~or 2 hours,
during which time solid precipitated, and the temperature rose
to 28C and fell again. The volatile components were trans-
ferred to a trap cooled to -aooc by warming the solution to
reflux at 38C (5 mm Hg). The distillate was treated with con-
centrated sulfuric acid (10 ml) to remove diglyme, then dis-
tllled to gi~e 2-(1-pentafluoro-2-propenyloxy)tetrafluoro-
ethane~ulfonyl fluoride (19.9 g, 0.06 mol, 60%) bp 55-56C
(150 mm Hg). The product structure was confirmed by: ~max 5 53
(CF2-CF), 6.79 (SO~F) and 7-10 ~m (CF,C-O,S0~ 9F NMR,
~44.9 (t J 3 6 Hz, each member t J = 6 Hz) lF, FS0~, -71.8
(d J - 25.3 Hz, each member t J - 13.8 Hz, d J = 13.8 Hz,
-36-

1~55801
d J - 7.3 Hz) 2F, OCF~C=C, -83.o (m) 2F, CF~CFaO, -90.9
(d J = 50.6 Hz~ each member d J = 39.5 Hz, t J = 7.3 Hz) lF,
cis-CF2CF=CF, -104.5 (d J = 117.6 Hz, each member d J = 50.6 Hz,
t J = 25.3 Hz) lF, trans-CF2CF=CF, -113.0 (d J = 5.6 Hz, each
member t J = 2.9 Hz) 2F, FSOaCFa, and -190.9 ppm (d J = 117.6 Hz,
each member d J = 39.5 Hz, t J = 13.8 Hz, t J = 3.2 Hz) lF,
CF2CF -C.
Anal. CalcA for C6F~oO~S C, 18.19; F, 57.55; S, 9.71
Found: C, 18.35; F, 57.40; S, 9.69
EXAMPLE 8
2-(l-Pentafluoro-2-Pro~en:vlox~v)tetraflu-oroethanesulfon~
fluoride
FSO~CFa~F ~ KF ~ CF~ = CFCFaOSOaF ~ FSOaC~aCFaOCFaCF=CF~
The procedure of Example 7 was followed, sub-
stltuting acetonitrile for diglyme as the solvent. The
acetonitrile wa~ not rigorously purified, and the yields of
2-(1-pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl
fluorlde, pb 54-55C (150 mm Hg) ranged from 40-50%.
EXAMPLE 9
1- rl- ~Pentafluoro-2-~roPenylox.Y) lhexafluoroProPane-2-sulfon.vl
~luoride
~ E~ CF3
FSO~CFCOF ~ KF ~ CF~2CFCFaOSOaF ~FSO~CFCFaOCF~CF=CF~
A mlxture of potassium fluoride (5.80 g, 0.10 mol)
and diglyme (100 ml) was stirred at 10C while 2-fluorosulfonyl-
tetrafluoropropionyl fluoride (23.0 g, 0.10 mol) (D. C. England,
M. A. Dletrlch and R. ~. Llndsey, Jr., J. Amer. Chem. Soc.,
~ 6181 (1960)) was added. m e resultlng solution was treated
at 10C wlth perfluoroallyl fluorosulfate prepared as in
-37-

~15~01
Example 2A, and after the addition was complete, the mixture
was stirred at 25C for 3 hours, then it was poured into water
(500 ml). The lower layer was washed with water (10~ ml),
dried and distilled to give l-[l-(pentafluoro-2-propenyloxy)~
hexafluoropropane-2-sulfonyl fluoride (25.7 g, 0.068 mol, 68%)
bp 50C (60 mm Hg), pure by gas liquid partition chromatography
(glpc). The product structure was confirmed by:
5.55 (CF=CFa), 6.78 (SOaF) and 7.5-lO ~m (CF,C-O,SO~);
~F NM~, 54.9 (d J = 20.7 Hz, each member q o~ J = 10.4 H%,
d J - 3.6 Hz) lF, SOaFJ -71.8 (d J - 25.0 Hz, each member
t J = 13.8 Hz, d J ~ 13.8 ~z, d J = 7 . 4 Hz ) 2F, OCFa C=C,
-72.1 (m) 3F, CF~, -75.5 (m) 2F, CFCFaO~ -91.0 (d J = 5O.7 Hz,
each member d J = 39.4 Hz, t J = 7-4 Hz) lF, cis -CFa CF=CF,
-104.6 (d J ~ 117.6 Hz, each member d J = 5O.7 Hz, t J = 25.0 HZ)
lF, trans-cFacF=cF~ -166.4 (d J = 14.6 Hz, each member q
J = 7.2 Hz, d J = 3.6 Hz) lF, CF, and -191.1 ppm (d J = 117.6 Hz,
each member d J - 39.4 Hz, t J = 13.8 ~z, t J = 1.7 Hz) lF
CF2CF =C.
Anal. Calcd for C~Fl~03S: C, 18.96; F, 59.98; s, 8.44
Found: C, 18.70; F~ 6O.O9; S, 8.o8
EXAMPLE 10
?- r~ 2~L4~4-pentafluoro-2-c.yclobutenvloxy)ltetra
rluoroethanesulfonyl fluor~de
F F
Fal ¦ OSOa F ~OCFa CFa S2 F
F + KF + FCOCFa SO:~ F - ~
--38--

-
l 15580 1
A suspension of potasslum ~luorlde t5.80 g, 0.10 mol)
in diglyme (100 ml) was stirred and held at 15C by external
cooling while fluorosulfonyldifluoroacetyl fluoride
(18.0 g, 0.10 mol) was added rapidly. This mixture was treat-
ed at 10-15C with 1-(1,2,3,4,4-pentafluoro-2-cyclobutenyl)-
fluorosul~ate (24.2 g, 0.10 mol) tB.E. Smart, J. Org. Chem.,
4~ 2353 (1976) and then stirred at 25C for 3 h~rs an~
poured into water (500 ml). The lower layer was washed
with water (100 ml), dried and distilled to give 2-Cl-
(1,2,3,4~4-pentafluoro-2-cyclobutenyloxy)]tetrafluoroethane-
sulronyl fluoride (24.0 g, 0.07 mol, 70%) bp 62C (1~0 mm H)-
The product structure was confirmed by:
~ma 5~53 (C-C), 6.80 (SO~F) and 8-9.5 ~m (C-F, C-O, SOa);
9F NMRJ 44.8 (t J = 6.o Hz, each member t J = 6.0 Hz, m) lF,
SOaF, -80.3 and -83.8 (AB J = 146 Hz, each member m) 2F, OCFa,
-112.7 (m) 2F CFzSOaF, -117.6 and -119.7 (AB J = 190 Hz, each
member m) 2F, ring CFaJ -121.8 (m) lF, CF, -127.1 (m~ lF, CF,
and -128.4 ppm (m) lF, CF.
Anal. Calcd for C~F~oOaS: C, 21.07; S, 9.37
Found: C, 21.38; S, 9.44
EXAMPLE 11
2-(1-Pentafluoro-?-Propen.vloxv)-3~6-bi~(trifluorometh,Yl)-
2.3,5,5,6-~entafluoro-1,4-dioxane
F F
~ ~ ~ KF ~ CFa=CFCFaOSOaF > ~ ~
~ CFa CFa=CFCFaO ,- ~ F
A mixture of pOtassium ~luoride (5.8 g, 0.10 mol)
and dlglyme (100 ml) was treated at 25C with 3,6-biæ-
-39-

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

11~S801
EXAMPLE 12
?-rl-(Pentafluoro-2-ProPenyloxy~l-2~5~6-tetrakis(trifluoro-
methvl)-5-fluoro-1.4 7-trioxabicyclo~2.2.11hePtane and 2-rl-
(Pentaf-luoro-2-propen~lox~)tetrafluoroeth~vll-4-~l-(pentafluor
2-ProPenYloxY)1-2,4,5-tris(trifluoromethYl)-5-fluoro-1,3-
dioxolane
O O O O K
Il 1~ ll l
CF3CCCF3 ~ KF > CF3C - C - CF3
F
¦ CF2=CFCF~OSOa
CF,~8CoCF~ r F-OCD2~2
CF3 C OCFacF=cF~ CFa=CFCFa CF~
A suspenslon of anhydrous potasslum fluoride
(5,ôO g, 0.10 mol) $n diglyme (100 ml) was stirred at 10C
while hex~fluoro-2,3-butanedione (hexafluorobiacetyl, L. O.
Moore and J. W. Clark, J. Ore. Chem., ~, 2472 (1965))
(19.4 g, 0.10 mol) w~s di6tilled in. me mix~ure was 6tir-
red until the potassium fluoride had nearly all d~ssolved,
and the~ it,was treated rapidly wlth perfluoroallyl fluoro-
~ul~ate prepared as in Example 2A (2~.0 g, 0.10 mol) at
15C The sllghtly exothermic reaction raised the tempera-
ture to 30C. The pale yellow mixture was stirred overnight
at 25C and then distilled. The two phase distillate
collected at bp 49-54~ (10 mm Hg) was shaken with concentrated
sul~uric acid (8 ml), treated with anhydrous calcium sulfate
and ~ractlonated ln a splnning-band stlll. 2-~1-(Penta~luoro-
-41-

1 1~580 1
2-propenyloxy)]-2~3,5,6-tetrakis(trifluoromethyl)-5-fIuoro-l,
4,7-trioxabicyclo[2.2.1]heptane (3.0 g, 0.0055 mol, 11%) bp
50-51C (15 mm Hg) contained one ma~or component by glpc. The
analytlcal sample of this product was obtained by
preparative glpc and its structure confirmed by:
A 5.58 (CF=CF2), and 7.5-10 ~m (C-F,C-O); l9F NMR, -65.6
and -71.0 (AB J - 155 Hz, each member m), 2F, OCF~, -74.7 (m)
3F, CF3~ -78.5 (m) 3F, CF~, -79.3 (s) 3F, CF3, -79.9 (d
J = 13 Hz, each member septet J = 4 Hz), 3F, CF3, -92.0
(d J = 52.1 Hz, each member d J - 39.5 Hz, d J = 8.3 Hz,
d J = 6.6 Hz) lF, cis~CFaCF=CF~ -105.5 (d J = 117.2 Hz, each
member d J = 52.1 Hz, d J = 27.0 Hz, t J = 21.8 Hz, q J = 3.0 Hz)
lF, trans-cFacFzc~ -121.7 (q J = 20.5 Hz, each member
q J = 13.1 Hz) lF, CF, and -191.2 ppm (d J = 117.2 Hz, each
member d J = 39,5 Hz, t J - 13.8 Hz) lF, CFa-CF =C.
Anal: Calcd for CllFl8 04 C, 24.55; F, 63.55
Found: C, 24.57; F, 63.60
m e second fraction was a mixbure o~ isomers of
2-[1-(penta~luoro-2-propenyloxy)tetrafluoroethyl] 4~
(pentafluoro-2-propenyloxy)~-2,4,5-tris(trifluoromethyl)-
5-fluoro~1,3-dioxolane (7.2 g, 0.01 mol, 21%), which con-
tAlned only minor impurities by glpc. Thi8 product
structure was confirmed by:
AmaX 5.56 (CF-CFa) and 7-10 ~m (CF,C-O), 19F NMR -72.8
ppm ~AB) 2F, OCF~, -75.4, -76.8, -78.3, -78.7 and -79.1
(m) 12F, CF3, -93.1 (m) 2F cis-CFaCF-C~/ -105.8 (m) 2F,
trans-CF~CF-CF, -121.0, -136.5 and -141.6 (m) 2F, CF, and
-190.8 ppm (m) 2F, CFaCF=C.
Anal. Calcd for Cl~Fa~O~: C, 24.44; F, 66.26
Found: C, 24.73; F, 66.48
3o
-42-

1 15580 1
EXAMPLE 1 3
Perfluoro-1,6-bis~2-Prop-enylo~)hexane
O O
FC(CFa )4CF + KF + CFa=CFCFaOSOaF - ~ (CFa=CFCFaOCFaCFaCF~ )a
CFa-CFCFaO(CFa )~ COF
CFa=CFCFaO(CFa )6 COF + HaO ~ CFa~CFCFaO(CFa )6 COaH-~ diglyme
A m~xture of potassium fluoride (11.62 g, 0.20 mol),
diglyme (200 ml) and octafluoroadipoyl difluoride (PCR 28.2 g,
o.og6 mol) was stlrred at 5C for 1.5 hours. The mixture was kept
at 5-10C while perfluoroallyl ~luorosulfate prepared as in
Example 2A (46.0 g, 0.20 mol) was added dropwise. When the
addition was complete, the mixture was stirred at 5C for 30
min, then lt was allowed to warm to 25C and the stirring was
continued for a further 3 hours. After having stood over-
night, the mixture was poured into water (1 Q.); the lower
layer was washed with water (150 ml), dried and distilled
to glve two products.
The lower-bolllng fractlon was perfluoro-1,6-bis-
(2-propenyloxy)hexane (21.1 g, 0.0355 mole, 37%), bp 84-86C
(20 mm Hg)whose structure was confirmed by:
A~ 5.59 ~CF~CF~ ) ~nd 7.2-9.5 ~m (C-F,C-O): 19F NMR,
-72.1 (d J z 25.7 Hz, each member t J - 13.3 Hz, d J = 13.3 Hz,
t J = 7.6 Hz) 2F, OCFaC=C, -84.2 (m) 2F,C~?O, -92.3 (d J = 52.7
Hz, each member d J = 39.5 Hz, t J = 7.6 Hz) lF, cis-CFaCF=CF~
-105.5 (d J = 117.8 Hz, each member d J = 52.7 Hz, t J =25.7 Hz)
lF, tran~-CFaCF--C~, 122.9 (m), CF~, -126.2 (m) 2F, CFaJ and
-191.0 ppm (d J - 117,8 Hz, each member d J ~ 39.5 Hz7
t J ~ 13.8 Hz) lF, CF~-CF C.
-43-

1~5S801
Anal. Calcd for C~2F~aO~: C, 24,26; F, 7O.35
Found: C, 24.43; F, 70.38
The higher boiling fraction was the 2:1 complex of
perfluoro 6-t2-propenyloxy)hexanoic acid with diglyme (7.9 g,
0.0155 mol, 16%), bp 109-110C (5 mm Hg), formed by hydrolysis
of perfluoro-6-(2-propenyloxy)hex~noyl fluorlde in the aqueous
diglyme wash solutions, m is complex had ~max 3~4 (OH,C-H),
5.59 (with shoulder, GF~~CF,COaH), and 7.2-9 ~m ~CF,C-O,CH);
H NMR, ~ 11.93 (s) lH, CO~HJ 3.75 (s) 4H, OCHa~ and 3.52 (s)
3H, OCHb; l9F NMR, -71.9 (d J = 25.1 Hz, each member
t J = 13.4 Hz, d J = 13.4 Hz, d J ~ 7.5 Hz) 2F, OCF~C=C,
-~4.1 (m) 2F, CFaCFaO~ -92.0 (d J = 52.3 Hz, each member
d J - 39.3 Hz, t J = 7.4 Hz) lF~ cis~CFaCF=CF~ -105.2
(d J - 117.7 ~z, each member d J ~ 52.3 Hz, t J = 25.1 Hz),
lF, trans-CF~CF=CF, -119.6 (t ~ = 12.6 Hz, each member
t J = 3.2 Hz) 2F, CFaJ -122.6 (m) 2F, CFa~ -123.5 (m) 2F,
CFa~ -126.1 (m) 2F, CF~, and -19O.9 ppm (d J = 117.7 Hz,
each member d J = 39.3 Hz, t, J = 13.8 Hz, ~ J = 1.8 Hz lF,
CF~ CF=C .
FXAMPLE 14
Meth.Yl ~'crfluoro-3.~-~ioY.anon-~-enoate
R ~1130~3
Cl~'2-l~FCI~20CF2C~'20CF2CE~' ~ CF2=CFC~`20CE~2CFzOCF2COzCH3
A suspension of 42 g (1.0 mol) of NaF in 100 ml
of methanol was stirred at 5C while 114 g (0.317 mol) of acid
fluorlde was added rapidly. After addition had been completed,
the mixture was stirred overnight at 25C, filtered and the
solid rlnsed with ether. Distillation afforded 102.0 g (86%)
of methyl perfluoro-3~6-dioxanon-8-enoate, bp 60-61C (20 mm Hg)~
containing small amounts of impurities. Redistillation gave
somewhat more pure ester (1-2% impurities by gc), bp 61-62C
3o
-44-

1155801
(20 mm Hg). Structure was confirmed by Ir (neat):
3.32, 3.~7, 3.49 ~CH3), 5.57 (C=0), 8-9.5~ (CF, C-0).
NMf~: H 3.95 ppm (s) with sma.ll impu-rities at 3.53 and 3.33 ppm;
F 72-0 (d of d of t of d, JFF 24, ].3, 13, 7.5 ~z,
2 F, =CFCF2~, -78.o (t, JFFI ~.1.6 Hz, 2 F, CF2C02CH3), -~ .0
(t, JFF 11.6 Hz, 2 F, CF20CF2C02CH3), -89.5 (t, JFF 12.6 Hz,
2 ,`, =CFCF20CF2), -92.3 (d of d of t, JFF 53.2, 39.2, 7.5 llz,
1 F, cis-CF2CF=CF), -105.2 (d of d of t, JF~ 117.3, 53.2, 2~.3 Hz,
lF, trans-CF2CF-CF), and -190.~ ppm (d of d of t of t, J~,~, 117.3,
39.2, 14.0, 1.6 ~lz, 1 F, CF2CF=).
Anal. Calcd. for C8H F1104: C, 25.82; H, 0.81; F, 5G~.17
Found: C, 26.17; H, o.66; F, 56.24.
EXAMPLE 15
Dlmeth.Yl Perfluoro-3-allox~lutarate
A. Bis(2-methox.Ytetrafluoroeth~l)ketone
l'he synthesis of bis(2-methoxytetrafluoroethyl)-
ketone from diMethyl c~rbonate tetrafluoroethylene, and
sodium mcthoxide h~s becn described by D. W. Wiley (U. S.
2,~,537 (1961)). An extension of this synthesis
has given 1,3,3,5-tetramethoxyoctafluoroperltane in a one-pot
reaction.
o O~Na+
C~J30Na. + 2 CF2=CF2 ~ CH30COCH3 ~ CH30CF2CF2bCF2CF20CH3
1CH9
CH30SO20CH9
CH30CF2CF2C( OCII9 ) 2CF2CF20C~I3
A mixture of 27.0 g (0.50 moi) of sodium methoxide,
56.o g (0.62 mol) of dimethyl ca.rbonate, and 100 ml of dry
tetrahydrofuran was agitated in a 350 ml tube under 1-3 atm
Or ~e~rafluoroethylene. Tetrafluoroethylene was pressured
-45-

1 15580 1
in as consumed until 110 g (1.1 mol) had been added. The mildly
exothermic reaction kept the temperature near 35C; after the
addition, the reaction mixture was heated at 40C for 1 hour.
The viscous solution from this reaction was treated directly
with 75.6 g (0.60 mol) of dimethyl sulfate at 40C for 15 hours.
Filtration and distillation afforded 87.6 g (52%) of 1,3,3,5-
tetramethoxyoctafluoropentane, bp 54C (0.3 mm Hg3, nD24 1.3605,
whose structure was confirmed by Ir 3.29, 3.33, and 3.42 (satd CH)~
8-9 ~ (CF, COC). Nmr (CC14) 'H ~ 3.68 (s, 1, CF20CH~) a.nd 3.57
(P' J~lF 1.3 Hz, 1, C (OCH3)2); 9F -8~.2 (m, 1, CR20) and
-116.5 ppm (m, 1, CFz).
Anal. Calcd. for CgH12F~0l~: C, 32.1~; H, 3.60; F, 45.21
Found: C, 32~57; ~, 3.72; ~ 4.61.
. Dimethvl Tetrafluoroacetone~ -dicarbox~late
conc. H2S04
C~3ocr~2cF~c ( OC113 ) 2CF2CF20C113
O O O
11 11 11
CT~30CCF2CCF2COCE~3
To 50 ml of conc. H2S04 wa.s added dropwise 33.6 g
(0,10 ~nol) of the te~raether. Aft~r the mildly exothcrmic
reaction llad subsided, the mixture was hea.ted at 70C
(50 mm Hg) to remove volatiles and then distilled at ca. 50C
(1 mm Hg). The crude distlllate was then fractionated to afford
lG.~ g (69~) of dimethyl tetrafluoroacetone-1,3-dicarboxylate,
bp 5~C (2 mm), nD 1.3713. Structure was con~irmed by Ir ~.28,
3.34 and 3.48 (satd CII), 5.57 (C=0) 5.64 (sh-C=0), 8-9 ~ (CF, COC
~lmr (CC14) ~ 4.00 (s, OC~13); 9~' -113 ppm (s, CF2).
-46-

1155801
Anal. Calcd. forC7H6F405: C, 34.16; ~I, 2.4~; F, 30.~8
mol wt, 246
Found: C~ 34.18; II, 2.6G; F, 30.95;
mol wt, 246
(mass spec~.
The same reaction on a 0.56 mole scale gave the
diester ln 82% yield.
C. Dim~t~Yl Pcrfluoro~ lloxyF~lutarate
.
O O O
Il 11 11
Cli30CCF2(:CF2COCIi3 + (~sF ~ CF2=CFCF20S02F7
O ~
( C~13 0C-CF2 ) 2cFocF2cF~cF2
To 27.3 g (0.18 mol) dry CsF in 100 ml diglyme was
added 43.5 g (0.18 mol) 0=C(CF2COOCH3)2 at 5-10C and stirred
for 1 hour; 41.4 g (0.18 mol) CF2=CFCF20S02F was added at 5-10C
and the mixture was stirred further for 3 hours. The reaction
mlxture was thrown into 1 liter of H20 and the lower layer
separated. This was washed twice with H20. After treatment
wlth 20 ml H~S04 at 0C and extraction with Freon~ 113, the extract
w~ distilled in a molecular still to give 4.54 g (7.2~ yield)
0~ pl'O~UCt, bp = 51-53C (0.1 mm). Structure was confirmed by
F nmr (Fll): -68.48 ppm (OCFzCF=); -93.45 ppm cis-(CF=CFF);
-105.91 ppm trans-(CF=CF); -117.10 ppm (CFzCOOC~13); -142.78 ppm
(CF2CF20C'F--); -190.35 ppm (CF=CF2). '~I nmr (Fll/TMS):
3.96 (sin~lel;, C1~3). Ir (neat): 3.37 ~, 3.49 ~L (sat CH);
5.~0 2 (,C=O, CFz=CF); 8-10 11 (CF, CO).
Anal- Calcd for CloFloH605 C, 30.32i F, 47.96; II, 1.53
Found: C, 30.45; F, 48.10; I~, 1.4~.
--47--

1 1~S80 1
EXAMPLE 16
,
Perfluoro-3-~2-propoxy-2-methylethoxy~Propen-e
CF3 CF3
CF3CFaCFaOCFCOF + KF + CFa=CFCFaOSOaF ~cF3cFacFaocFcFaocFacF=cFa
A mixture of potassium fluoride (6.96 g, 0.12 mol),
diglyme (150 ml) and 2-(1-heptafluoropropoxy)tetrafluoro-
propionyl fluoride (dlmer of hexa~luoropropene oxide obtaln-
ed by treatment with fluoride ion) (29.4 g, o.o8g mol~ was
stirred at 5C for 1 hour. Perfluoroallyl fluorosulfateprepared as in Example 2A (27.6 g, 0.12 mol) was added
dropwise at 5C, then the mixture was stirred at 5C for
3 hours, and at 25C overnight. The reaction mixture was poured
into water (1 Q.), the lower layer was separated and the
volatlle components were removed at 25C (0.5 mm Hg)~ Distil-
lation of the volatile components from concentrated sulfuric
acid gave perfluoro-3-(2-propoxy-2-methylethoxy)propene
(25.2 g, 0.052 mol, 59%), bp 62-63C (100 mm Hg) whose
structure was confirmed by:
~ma 5~57 (CF=CFa) and 7.5-9 ~m (C-F, C-o);l9F
NMR, -72.2 (d J - 25.5 Hz, each member t J - 13.3 H~,
d J = 13.3 Hz, d J = 7.4 Hz) 2F, OCFaC=C, -81.0 (m) 3F, CF~,
-82.3 (m) 5F, CF3 + OCFa, -84.1 (m) 2F, CFaO, -92.1
(d J - 52.7 Hz, each member d J = 39.7 Hz, t J = 7.4 Hz)
1~, cis-cFacF=cF~ -105.5 (d J = 117.8 Hz, each member
d J ~ 52 . 7 Hz, t J = 25 . 5 Hz), lF, trans-cFacF=cF~ -130.4
(s) 2F, CFa~ -145.9 (m) lF, CF, and -191.0 ppm (d J ~ 117.8 Hz,
each member d J = 39.7 Hz, t J = 13.6 Hz) lF, CFaCF=C.
Anal. Calcd for CgHl80a: C, 22.42; F, 70.94
Found: C, 22 .18; F, iO . 96
-48-

~15580
EXAMPLE 1 7
Perfluoro-l, 3-bi s ( 2-proPen,Yloxy~ Propane
O O
FaCFa~F + KF + CFa = CFCFaOSOaF 3 (CFa-CFCFaOCF~)aCFa
A mixture Or potassium fluoride (15.3 g, 0.26 mol),
diglyme (200 ml) and difluoromalonyl difluoride prepared as
in Example 5A (17.3 g, 0.12 mol) was stirred at 5C for
15 min. Perfluoroallyl fluorosulfate (57.5 g, 0.25 mol)
was added at 5-10C over a 45 min period, and the mixture
0 was stirred at 5C for an addltional hour, then at 25C for
2 hours. The reaction mixture was poured into water (1 Q.),
the lower layer was washed wlth water (100 ml), dried
and distilled to give perfluoro-1,3-bis (2-propenyloxy)propane
(12.0 g, 0.027 mol, 23%) bp 88-gooc (200 mm Hg) whose structure
was confirmed by AmaX 5.59 (CF=CF~) and 7.2-9.5 ~m (C-F,C-O);
9F NMR, -72.2 (m) 2F, oCF2C=C,-84.6 (m) 2F, CF2CFaO~ -92.3
(d J ~ 53.O Hz, each member d J = 39.5 Hz, t J = ~.2 Hz) lF,
cis-CF2CF-CF~ -105,6 (d J = 117.8 Hz, each member d ~ = 53.O Hz,
t J ~ 25.2 Hz) lF, trans-cFacFccFJ -130,0 (s) lF, CFa and
~0 -191,0 ppm (d J - 117.8 Hz, each member d J = 39,5 H2,
t J ~ 13.5 Hz) lF, CFaCF=C.
Anal. Calcd for C3F-flO~: C, 24.34; F, 68,45
Found: C, 24.67; F, 68.36
EXAMPLE 18
Perfluoro-3- (butox.Y)Propene
CF~CFaCFaCOF + KF ~ CFa=CFCF~OSOaF ~ CF3CFaCF~CFaOCFaCF=CFa
A mlxture of dry potassium fluoride (7.5O g, 0.13 mol),
dl~lyme (lOO ml) and heptafluorobutyroyl fluoride (prepared
from the acid by treatment with 8ulfur tetrafluoride) (28.1 g,
3 0.13 mol) was ~tlrred at 5C for 30 min. Perfluoroallyl
-49-

1155801
fluorosulfate was added dropwise at 5C~ the mixture was stlr-
red at this temperature for 1 hour, then at 25C for 3 hours.
The volatile components were transferred by distillation at 40C
(8 mm Hg), washed with water (100 ml), and distilled from a
small amount of concentrated sulfuric acid to give perfluoro-
3-(butoxy~propene (30.3 g, 0.083 mol, 64%) bp 80-84C whose
structure was confirmed by:
~max 5.57 (CF=CFa) and 7.2-9.5 llm (C-F,C-O); 1 F NMR -72.1 (d
J = 25.2 Hz, each member t J = 13.5 Hz, d J = 13.5 Hz,
d J = 7.4 Hz) 2F, OCF~C=C, -82.1 (t J = 8.1 Hz, each member m),
3F, CF3, -84.5 (m) 2F, C~ O, -92.1 (d J = 52.3 Hz, each mem-
ber d J a 39,4 Hz, t J = 7.4 Hz) lF, cis~CFaCF=CF~ -105.5
(d J - 117.5 Hz, each member d J = 52.3 Hz, t J 2 25.2 Hz)
lF, trans-CF2CF=CF, -127.3 (m) 4F, CFa, and -l91.O ppm
(d J - 117.5 Hz, each member d J = 39.4 Hz, t J = 13.7 Hz, m)
lF, CFzCF ~C.
Anal. Calcd for C7Fl4O: C, 22.97; F, 72.66
Found: C, 23.20; F, 72.80
EXAMPL~ l~
Perfluoro-3-(octYloxy)propene
F(CF~)7COF + KF ~ CF~=CFCF20SOaF ~ F(CF~)80CF~CF~CF~
A mlxture of potassium fluoride t5.ôO g, O.lO mol),
dlglyme ~150 ml) and pentadecafluorooctanoyl ~luorlde (pre-
pared by treating commerclal perfluorooctanoic acid wlth
~ulfur tetrafluoride) (25.0 g, o.o6 mol) was stirred at 5C
for 1 hour, Perfluoroallyl fluorosulfate (23,0 g, 0.10 mol)
was added dropwise and the mixture was stirred at 5C for 4 hours,
then at 25C for an addltional 3 hours. The mixture was poured
into water (l Q.), separated, and the lower layer was dis-
3o
-50-

1155801
tilled from concentrated sulfuric acid to glve perfluoro-3-
(octyloxy)propene (27.1 g, o.o48 mol, 80%) bp 69-70C
(20 mm Hg) whose structure was confirmed by:
Ama 5 ~59 (CF=CFa) and 8-9 ~m ~CF C-O); F MMR -71.8
(d J = 25.1 Hz, each member d J = 13.4 Hz, t J = 13.4 Hz,
d J = 7.7 Hz) 2F, OCF~C=C, -81.6 (t J = 10.0 Hz) 3F, CF3,
-83.8 (m) 2F, CFaCFaOJ -92.3 (~ J - 53.6 Hz, each member
d J = 39.9 Hz, t J = 7.7 Hz) lF, Cis~CFaCF=CF~ -105.5
(d J = 117.8 Hz, each member d J = 53.5 Hz, t J = 25.1 Hz)
lF, trans-cFacF=cFJ -122.2 (m) 6F, CFa~ -122.9 (m) 2F, CF2,
-125.7 (m) 2F, CF2, -126 .5 (m) 2F, CFa> and -190.8 ppm
(d J = 117.8 Hz, each member d J - 39.9 Hz, t 13.7 Hz, t 1.7 Hz)
lF, CF~CF=C,
Anal. Calcd for CllF~aO: C, 23.34; F, 73.84
Found: C~ 22.99; F, 73~94
EXAMPLE 20
2-TrifAluoromethoxYpentafluoropro~ene (Perfluoro(allylmethylether))
COF2 + CsF + CFa=CFCFaOSO2F -~ CFsOCF2CF=CFa
A mixture of carbonyl ~luoride (18.0 g, 0.27 mol),
cesium fluoride (38.0 g, 0.25 mol) and dry diglyme (300 ml) was
stirred at -20C to -10C for 2 hours, then kept at -10C or be-
low whlle perfluoroallyl fluorosulfate (46.o g, 0.20 mol) was
added. The mlxture was stirred at -10C for 2 hours, at 0C for
2 hours, then at 25C overnight. The mixture was warmed under
a 511ght vacuum, and the volatile distillate (11 ml of liquid
collected at -80C) was redlstilled through a low temperature
~tlll to give 2-trifluoromethoxypropene (3.2 g, 2.0 ml at -80C,
0.014 mol, 7~) bp 11-12C. ~he structure was established by
i~s spectra: ~ (gas pha~e) 5.55 (CF=CFa), 8-9 (CF, C-O) and
5.35 ~m (weak COF impurlty band); ~9F NMR (CCl~), -56.5
(t J ~ 9.2 Hz) 3F, CF30, -74.6 (d J - 25.8 ~z, each member
-51-

1 15580 1
d J = 13.6, q J = 9.2 Hz, d J = 7.1 H~) 2F, OCF~C=C; -92.2
(d J = 53.4 Hz, each member d J a 39.2 Hz, t J ~ 7.1 Hz)
lF, cis ~CFaC~-CFJ -105.5 (d J - 118.0 Hz, each member
d J = 53. 4 Hz, t J = 25 . 8 Hz ), lF, trans-CFa C~CF, and
-190.9 ppm (d J = 118.0 H7,, each member d J = 39.2 ~z,
t J = 13.6 Hz ) lF, CFa C~C .
- EXAMPLE 21
Pcrfluoro-6-(?-~1openyloxy)hex~noic Aci.d and Its ~iethyl Ester
FCO ( Cl~'2 )4COF + l'~ CF~ = CFCF~OS02F ~
(C~ = CFCF~OC~cF2cF2)2 ~ C~2 CFCF2 ( 2)5
CF~ - CI; CF~O ( C~, ) 5COF 2 > 2 2 (- 2 ) 5 ~' ~
3 2 2 2 2C1~33 -d ' t 4 > C~2 = CFcF2o(cF2)5co2H ~-
C~i 2 = Cl~ CF20 ( CF2 ) 5C02CH3
A mlxture of potassium fluoride (11.7 g, 0. 20 mol),
diglyme (250 ml) and octafluoroadipoyl difluoride (PCR 58.8 g,
0.20 mol) was stirred at 0-5C for 30 min. The mixture was
kept at 0-5C while perfluoroallyl fluorosulfate (~xample 2A,
46.0 g, 0.20 mol) was added dropwise. When the addition was
¢omplete, the mlxture was stirred at 0-5C for 2 hours, then it
wa~ allowed to warm to 25C and the stirring was continued
for a further 4 hours. Evacuation of the reaction mixture to
35C (3 mm Hg) removed 45 ml of liquid. The higher boiling
residue was poured in water ~ 1.); the lower layer (10 ml)
was combined with the volatile fraction from above and treated
with a mixture of water (100 ml) and diglyme (20 ml). After the
resultlng exothermic reaction, the mixture was allowed to cool,
and the lower layer was separated and distilled to give perfluoro-
1,6-bis(2-propenyloxy)hexane (Example 13, 13.6 g, 0.023 mol, 23~)
-52-

1 1558~ 1
bp 61 (6 mm Hg) and the 2:1 complex of perfluoro-6-(2-propenyloxy)
hexanoic acid wlth diglyme (Example 13, 52.8 g, 0.109 mol, 54.5%)
bp 82-84C (O.8 mm Hg).
The diglyme complex of the higher boiling fraction
was distilled from concentrated sulfuric acid (40 ml) to
give perfluoro-6-(2-propenyloxy)hexanoic acid containing
12% of its methyl ester. The ester arises from the action
of sulfuric acid on the diglyme present in the complex.
These products were identi~ied by infrared ~max 2.82 and
3-4 (OH,CH3), 5.58 (C~=CF2), 5.61 (C-O) and 7-10 ~m
(CF,C-O,CH) and by lH NMR, ~ 3.92 (OCH3) and 11.33 ppm (OH)
signals in the ratio of 1:7.2; the 19F NMR spectrum was
also in accord with these structures.
EXAMPLE 22
Perrluoro-6-(2-propenyloxy)hexanoic Acid
A reaction was carried out as described in
Example 21. The crude reaction mixture was poured into
water (750 ml), and the lower layer was washed with water
(100 ml). The same two products were obtained as
ln Example 21 by distlllatlon o~ the crude lower layer.
The ~ractlon bp 45-53~C (6 mm H~) was freed o~ di~lyme by
water washlng to leave crude perfluoro-l, 6-bis(2-propenyl_
oxy)hexane (9.5 g, 0.016 mol, 16%).
The hlgher boiling complex of perfluoro-6-(2-pro-
penyloxy)hexanoic acid with diglyme was dissolved in
1,1,2-trlchloro-1,2,2-trifluoroethylene (50 ml) and
extracted in turn with 50 ml and 25 ml of concentrated
sul~uric acid. The organic layer was treated with
calclum sul~ate, filtered, and distilled to give pure
3o
perfluoro-6-(2-propenyloxy)llexanoi.c acid (42.2 g,
-53-

1 15580 1
o.og88 mol~ 49%) bp 75C (1.0 mm Hg). This material was
ldentified by infrared ~max 2.85-4.0 (H-bonded 0~),
~.57 (CF=CF2), 5.63 (sh,C=O) and 8-9 ~m (C~,C-O),
and by its lH and 19F NMR spectra.
Anal. Calcd. for C HF1503: C, 24.45; H, 0.23; F, 64.66
Found: C, 24 . 48; H, 0.45; F, 65.76
The following examples illustrate the preparation
of useful copolymers ~rom the polyfluoroallyloxy comonomers
of this invention. m e general properties of these co-
polymers were discussed above.
UTILITY EXAMPLES
Example A
Solution P~ erization of Tetrafluoroethylene with 2-El-
(Pèntafluoro-2-~ro~en~lox~)]tetrafluoroethanesulfon~l Fluoride
n x CFa 8 CFa + xCFa ~ CFCFaOCF2CFaSOaF (C-
~ (cFa-cF~)n -CF2CF
L CF~OCFaCF~SO~FJ x
An 80-ml stainless steel-lined tube was charged with
a cold mixture (-45C) of 1,1,2-trichloro-1,2,2-trifluoro-
ethane (Freon~ 113) (10 ml), 8% 1,1,2-trlchloro-1,2,2-tri-
fluoroethane solution of pentafluoroproplonyl peroxide (3P
lnitlator) (1 ml), and 2-[1-(pentafluoro-2-propenyloxy)~-
tetrafluoroethanesulfonyl fluoride ~Example 7, 17.5 g,O.053 mol).
m e tube was closed, cooled to -40C, evacuated, and charged
wlth tetrafluoroethylene (20 g, 0.20 mol). The tube was warm-
ed to 25C and shaken at this temperature for 20 hour~.- The
volatile materials were allowed to evaporate, and the product
3o
-54-

1 155801
polymer was evacuated to 0. 5 mm Hg. The product was then
extracted wlth l,1,2-trichloro-1J2,2-trlfluoroe~hane, and dried
under vacuum to give the solid white copolymer (16.9 g, 85%):
~max (KBr) 6.79 (SO~F) and 12.3 ~m (broad) ln additlon to the
usual polytetrafluoroethylene infrared bands, Gravlmetric
sulfur analysi~ gave o.48 and 0.2 ~ ~ corresponding to an
average of 0.34% S or 3.5 wt. % (1.1 mole %) of poly-
fluoroallyloxy comonomer corresponding to an equivalent
weight of 9400. Equivalent weight is the molecular weight
of the polymer per functional group (here -S02F).
Differential scanning calorimetry (DSC) showed a 12% depres-
sion of the endotherm peak (mp) compared to polytetrafluoro-
ethylene.
, ExamPle B
Solution Pol~erization of Tetrafluoroethylene with 1-[1-
LPentafluoro-2-~roPenvlox~)lhexafluoroproPane-2-sulfonyl Fluoride
x C~2=CFCF~OCFslF-SOaF ~ nxcFa=cFa -~ ~(CF2-CF2)n~CFaCF -
CF3 1 ¦ CF~
L CF~OCFSO~E x
The procedure of Example A was followed with 1,1,2-trichloro-
1,2,2-trl~luoroethane (10 ml), ~ pentafluoropropionyl
peroxide ln l,1,2-trichloro-1,2,2-trifluoroethane (2.0 ml),
l-~l-(pentafluoro-2-propenyloxy)~hexafluoropropane-2-sulfonyl
fluoride (Example 9, 17.4 g, o.o46 mol) and tetrafluoro-
ethylene (20 g, 0.20 mol) to glve 16.7 g (7 ~ ) of copolymer.
Analy~ls by X-ray fluorescence showed 0.49 ~ S present, cor-
responding to 5.8 wt-% (1.6 mole %) of poly~luoroallyloxy
comonomer corresponding to an equilvalent weight of 6540.
The sample had a mp depression o~ 11C compared to poly~
3 tetrafluoroethylene by DSC.
-55-

1 155~0 1
Example c
Solution Polymerization of Tetr~fluoroethvlene with ~ l-
(Pent~fluoro-2-pro~en~loxy)tetrafluoropropionYl Fluoride
x CFa =CFCFa OCFa CFa COF + nxCF~ =CFa ~ ~ CFa -CF:~ )n~ CF:a CF
CF~ OCFa CFa CO Y x
NaOH
--F(CFa~CFa )n-CFa I F
L CF~ OCF2 CFa CC)2 N~
The procedure of Example A was used with 3-[-l(penta-
fluoro-2-propenyloxy)]tetrafluoropropionyl fluoride
(Example 5, 13.3 g, 0.045 mol) in place of 2-
[l-(pentafluoro-2-propenyloxy)]-tetrafluoroethane-
sulfonyl fluorlde to give 17.8 g (86%) of copolymer:
~max (KBr) 5.62 (C02H, weak) and 9.7 ~m bands in
addition to the polytetrafluoroethylene bands; mp
depression (DSC) was 14C compared to polytetra-
fluoroethylene; gravimetric analysis showed 3.7 wt %
of polyfluoroallyloxy comonomer corresponding to an
equivalent weight of 7900.
A sample of the polymer was stirred with
a solutlon of sodlum hydroxide in 33% ethanol for
2 days, filtered, and washed with water until the
extracts were no longer basic. The resulting polymer,
now readily wetted by water, was dried under vacuum.
Analysis by atomic absorption spectroscopy showed
0.29% Na, corresponding to 3.7 wt-% (1.3 mole %)
of the original comonomer.
3o
-56-

1 15S80 1
Example D
Solution Polymerization of Tetrafluoroeth~lene with 1-
~ ~1,2,3,3~Hexafluoro-3-chloro-2-pro~oxy)pentafluoro-2-pro~ene
x CF,=CFCF,OCFCF,Cl + xncFa=cF~ CF,-CFa) -CF,CF ~
CF2OIFCF~C x
CF~
The procedure of Example A was used with
1-~1,1,1,2,3,3-hexafluoro-3-chloro-2-propoxy)penta-
fluoro-2-propene (Example 2, 14.3 g, 0.043 mol) in
place of 2-~1-(pentafluoro-2-propenyloxy)]-tetra-
fluoroethanesulfonyl fluoride to give 18.3 g (87%) of
copolymer: mp depression (DSC)14C compared to
polytetrafluoroethylene, gravimetric analysis ga-~e
0.61 and 0.61% Cl, corresponding to 5.7 Wt-% of poly-
fluoroallyloxy comonomer and an equivalent weight of
5800; more accurate analysis by X-ray fluorescence gave
0.53% Cl corresponding to 5.0 wt-% (1.56 mole %) of
polyfluoroallyloxy comonomer. The mp depression of 14C
compared to polytetrafluoroethylene corresponds to a
depression o~ 1C per 0.1 mol % of poly-fluoroallyloxy
comonomer present. In contrast to this result, the
smaller branch in hexafluoropropene gives a mp depression
correspondlng to about 1C per 0.3 mol-% of comonomer in
lts copolymer wlth tetrafluoroethylene. This means that
the copolymers prepared from the polyfluoroallyloxy
comonomers have better molding properties for the same
mol-% incorporation of comonomer than those prepared from
hexafluoropropene comonomer.

1155801
ample E
Solution Pol,Ymerization of Tetrafluoroeth,vlene with 2~
Pentafluoro-2-propen,yloxy¦hexafluo~E~ a_e-1-sulfon,yl Fluoride
CF3
X CF2 =CFCFa OCFCFz SOa F + xn CFa = CF2 - >
--F' CFa -CFa ~ CF2 CF
L CFs~OCFCF~ SO~ F~ x
~Fs
The procedure of Example A was used with 2~ penta-
fluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl ~luoride
(Example 3, 16.1 g, 0.042 mol) in place of 2-~1-(pentafluoro-
2-propenyloxy)]tetrafluoroethanesulfonyl fluoride to give
18.5 ~ (88~) of copolymer: mp depression (DSC) 8C compared
to polytetrafluoroethylene; analysis by X-ray fluorescence
showed 0.43% S, corresponding to 5.1 wt-% (1.4 mole %) of
polyfluoroallyloxy conomomer and an equivalent weight of
7460.
EXamP1e F
Solutlon Pol,ymerlzation of Vin,ylidene_Fluoride with 2-[1-
(Pentafluoro-2-proPen,Ylox~)ltetrafluoroethanesul~onyl Fluoride
CHa-CF~ + CFa = CFCF~OCF~CFaSO~F > Copolymer
The procedure of Example A was used with vinylidene
fluoride (20 g, 0.32 mol), 2-[1-(pentafluoro-2-propenyloxy)]-
tetrafluoroethanesulfonyl fluoride (Example 7, 16.5 g,
0.05 mol), 1,1,2-trichloro-1,2,2-tri~luoroethane tlO ml), and
8~ 1,1,2-trlchloro-1,2,2-tri~luoroethane solution of penta-
fluoropropionyl peroxide (5 ml). The mixture was shaken
o~ernight, the maximum recorded temperature being 31C. The
solid copolymer produced (21.5 g, 60%) contained 46 wt %
(14.2 mol %) of poly~luoroallyloxy comonomer with an equivalent
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1 15~80 1
weight oî 71. 9 DSC showed no thermal events between 25C and 400C .
Anal . Calc d for ~ CF~ )~, . O ~ ( CFa =CFCF2 0CF2 CF:~ SO~ F):
C, 28.62; H, 1~70; S, 4.47
Found: C, 28.49; H, 1.71; S, 4.46
Solution Pol~erization of Vinylldene Fluoride with l-~He~ta-
fluoro-2-pro~oxy)-1~1,3,3-tetrafluoro-2-chloro-2-propene
CH~-CF~ + CFa = CClCF20CF~CF3 )a ~ Copolymer
1 The procedure o~ Example F was used with l-(hepta-
fluoro-2-propoxy)-1,1,3,3-tetrafluoro-2-chloro-2-propene
(Example 1, 10.5 g, 0.032 mol) ln place of 2-[1-(pentafluoro-
2-propenyloxy)]tetrafluoroethanesulfonyl fluoride to give a
solld copolymer (20.6 g, 73~). This material contained
36 wt-% (9.8 mol-%) of polyfluoroallyloxy comonomer with an
equlvalent weight of 878. DSC confirmed the structure as a
copolymer and indlcated its stability, because ~o thermal events
were observed in the range 25-400C.
Example H
Solution Pol~merization Or Tetrafluoroethxlene with
Per~luoro-~-(butoxy)propene
CFa~CFa + CF3 (CFa )30CFaCF=CFg ~ Copolymer
m e procedure of Example A, when used with perfluoro-
3-(butoxy)propene (Example 1~., 19.0 g, 0.052 mol), tetra-
~luoroethylene (20 g, 0.20 mol), 1,1,2-trichloro-lJ2,2-tri-
f~uoroethane (10 ml) and 8% penta~luoropropionyl peroxide in
1,1,2-trichloro-1,2,2-trifluoroethane (2 ml) gave 18.9 g of
solid copolymer. mis crude material was chopped in a
blender with more solvent, rinsed, and dried to give 16,5 g
o~ copolymer with a mp of 309C, lndicating that it was a true
copolymer.
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1~S5~01
Solution Pol~merization of Tetra luoroeth~lene wlth Per~luoro-
1,6-bis(2-propenYloxv)hexane _ _
CFa -CF2 + ( CF:~ CFCF~ OCF2 CF~ CF~ ) ~ - ---~ Copol-ymer
The procedure of Example H was ~ollowed, using per-
fluoro-1,6-bis(2-propenyloxy)hexane (Example 13, 20 g, 0.20 mol)
for the polyfluoroallyloxy comonomer. This gave 16.3 g of dry
pulverized polymer with ~max 5-55 ~m (CF=CFa); the remalnder
of the infrared spectrum resembled that o~ poly(tetrafluoro-
ethylene). DSC showed a pronounced exotherm Tp 315C follow- -
ed by an endotherm Tp ~ 333C and 339C on the flrst heating;
the second heating showed no exotherm and a broad endotherm
Tp ~ 326C. Infrared spectra indicated that pyrolytic re-
actions of pendant pentafluoroa~lyloxy groups had occurred
during the first heating; the broad DSC endotherm near the
normally sharp mp of poly(tetrafluoroethylene) indicates that
cro~slinking had occurred.
Example J
Solution Polymerizatlon of Vinylidene Fluoride and
PerrluorO-1.3-bis(2-~ropenyloxy)propane
CH~ ~ CF~ ~ (CFa=CFCF~OCF~)aCF~ ~ Copolymer
A mlxture of perfluoro-1,3-bls(2-propenyloxy)-
propane (Example 17, 5.7 g, 0.013 mol), 1,1,2-trichloro-
1,2,2-trlfluoroethane (25 ml), and 8~ pentafluoropropionyl
peroxide in 1,1,2-trlchloro-1,2,2-tri~luoroethane (5 ml) was
held at -40C ln a stalnless steel-llned shaker tube whlle
vlnylidene fluorlde (20 g, 0.32 mol) was condensed into the
tube. m e mlxture was shaken overnight at room temperature,
and the product was isolated as descrlbed above. m e crude
polymer was drled under vacuum, pulverized ln a blender
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l 15580 1
wlth 95~ ethanol, filtered and dried to glve 24.0 g of solld
copolymer. DSC showed an endotherm Tp 124~C, stable to at
least 300C, indicatlng that a true copolymer had been form-
ed since poly(vinylidene ~luoridej has mp 171C. The in-
solubility of thls product in acetone and the lack of absorp-
tion bands in the infrared for pendant CF=CF8 groups in-
dicates that crosslinking had occurred.
EXAMPLE K
Copolymer of TFE with Methyl Perfluoro-3,6-dioxanon-8-enoate
45 g of methyl perfluoro-3,6-dioxanon-8-enoate and 0.04
g o~ pcrfluoroproplonyl peroxlde were reacted at 50C ~or 4 hr.
under a 10 psl pressure of tetrafluoroethylene. Filtration
gave a solid which on drying at 50C in a vacuum oven
weighed 0.71 g. The amount of ~F~ a~ded was 4 g. Equivalent
wei~ht by titration gave 1176; therefore the amount of the
ester incorporated in the polymer was 28~ and the yield based
on TFE was 20~. A transparent film was obtained by heating
at 220C in a Carver press.
EXAMPLE L
~eable Fluorocarbon Pol~mers
Samples of the polymers of Examples B and E were
treated with aqueous alcoholic ~mmonia 301ution for one day
at 25C, filtered, washed with aqueous ethanol and dried un-
der vacuum.
A ~ample of the polymer Or Example C was simllarly
treated with aqueous alcoholic sodlum hydroxide.
m e above partly hydrolyzed polymers were immersed
ln aqueous ethanol solutions o~ Se~ron~ Red GL (Se~ron~ is a
llne of catlonic dyes especially suited for dyeing Orlon~
and other acrylic fibers, having outstandlng fastness and
3~ brilliance - Du Pont Products Book, January 1975, p. 34)
at 25C ~or 1-3 hours, then they are extracted until the ex-
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1 1~580 1
tracts no longer contalned dye. All three samples dyed well
to an orange-red color.
EXAMPLE M
Wettable Fluorocarbon Polymer
A sample o~ the polymer of Example C was treated
wlth aqueous alcoholic sodium hydroxide as described in
Example L. The resulting fluorocarbon polymer contained
carbonyl groups and was wettable with water.
EXAMPLE N
Emulsion Polymerization of Tetrafluoroeth.~lene with 2~L~
(PerLtal'luoro-2-Propenylox~v)1t;ctr;lrluoroctllatlesuli`ol~yl_Fluor:L(lc
Cli~a =Cli`a + Cl;'2 =CFCl~`a OCIi ~ CI-'`2 SOa li' ~, COpOlyl~lCr
A stainless steel shaker tube was charged with
water (1l~0 ml), 1,1,2-trichloro-1,2,2-trifluoroethane (10 ml),
2-[1-(pentafluoro-2-propenyloxy)ltetrafluoroethanesulfonyl
fluoride (Example 7, 6.o g), potassium perfluorooctane-
sulfonate (0.16 g), ammonium car~on~e (0.50 g) and ammonium
persulfate (0.50 ~). The mixture was brought to an internal
pressure of 200 p.s.i.g. with tetrafluoroethylene and heated
to 70C. Tetrafluoroethylene pressure was maintained at
200 p.5.i.~. for 45 min at 70C. l~le polymeric product thus
obtained was filtered, washed and dried to give 43.2 g of
whito solld which contained approxim~t~ly 1.4 wt % (0,43 mol ~)
of polyfluoroallyloxy comonomer by lnfrared analysls.
Differentlal thermal analysls (DTA) showed a crystalline
transltlon at 10C, a recycle freezing temperature of 293C
and a recycle meltlng point of 311C from which the
polyfluoroallyloxy comonomer content is estimated as
3.5 wt % (1.09 mol %).
3o
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1155801
EXAMPLE O
nulsion Poly1ncri%atlon Or 'rc~rafluoroc~Ylenc wi~}l 2~
(~entarluoro-?-~ro~env~oY,y)ltetrafluoroe~llanesulfoll~l Fluor:ide
CF2=CF2 ~ CF2=Cl;'CF2OC~2Cl~2S02F ~ Copolymer
The procedure of ~xample N was rollowed using ~, O g
of 2-[l-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl
fluoride, 0.20 g of potassium pcrf`luorooctancsulfonate and
tetrafluoroethylene at a pressure Or 3O p.s.i.g. at; 7OC ror
a reaction period of 8 hours. The amounts of the other reagents
were no~ changed. This gave 45 g of solid polymer whose
infr~r¢d spectrum showed stron~ ~OaF absorption. D'l'~ showed
a crystalline transition at 5C, a recycle rreezin~ tcmpera-
ture of 282C, and a recycle meltine point of 300C, cor-
responding to a polyfluoroallyloxy comonomer content of
5.9 wt % (1.86 mol %).
EXAMPLE P
Emulslon Polymerization of Tetrafluoroethylene with 2-[1-
(Pentafl_oro-2-propenyloxy)]tetrafluoroethanesulfonyl
Fluoride
The procedure of Example N was followed using
10.7 g of 2-~1-pentafluoro-2-propenyloxy)]tetrafluoro-
sulfonyl fluorlde, 0.20 g of ammonium persulfate~ and
ketrafluoroethylene at a pressure of 50 p.s.i.g. at
70C for a reactlon perlod of 5 hours. The amounts
of other reagents were not changed. This gave 28.6 g
of white polymer whose infrared spectrum showed the
presence of S02F groups corresponding to 3.5 wt %
(1.08 mol %) polyfluoroallyloxy comonomer. DTA showed
two melting peaks at 290C and 317C, with an estimated
conomomer content of 5.5 wt % (1.73 mol %).
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1155801
UTILITY EXAMPLE Q
CoPol.Ymeri.zation of Tetrafluoroeth.Ylene_and 2-[1-(Pentafluoro-
2-ProPenYlox.Y~]tetra~fluoroethanesulfon~l Fluoride, and
Prer~aration Or ElectrlcallY Conductive Films from the
Co~ol.Ymer Product
nxCF2=CF2 ~ xCF2=CFCF20CF2CF2s02F
~CF2-CF2 )-CF2CF'
CF2OCF2CF2SO~F
x
~ steel tube charged with 2-[1-pentafluoro-2-
propenyloxy)~tetrafluoroethanesulfonyl fluoride (Example 7,
52.8 g) and 6~ 1,1,2-trichloro-1,2,2-trifluoroethane solution
of pentafluoropropionyl peroxide initiator (0.19 g). The
mixture was heated to 40C and brought to aninternal pressure
of 10 psig with tetrafluoroethylene (TFE). TFE pressure
was maintained at 10 psig for 6 hours at 40C. The polymeric
product thus obtained was filtered, washed and dried to
give a white solid (9.82 g): ~max (K~r) 8.65 ~ (SO2F) and 8-10 mm
(broad) in addition to the usual polytetrafluoroethylene IR
bands. The DSC melting point depression was 91C compared
with polytetrafluoroethylene. Sulfur analysis by x-ray fluor-
escence gave 2.7% S or 28.0 wt. ~ (8.5 mol ~) of poly-
fluoroallyloxy comonomer, corresponding to an equivalent
weight of 1180.
The product was pressed into a clear 4-5 mil film
~t 220-240C. Four inch diameter film samples were
reacted for 1 hour at 90C with 13-15~ potassium hydroxide
solution and dried to give a copolymer of TFE and
CF2=CFCF20CF2CF2S03-K+. IR spectra showed
essentially complete conversion of -S02F functions to
sulfonate salt.
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11~5801
The four-lnch diameter, 4-5 mil film was inserted
~s the lon exchange membr~ne in a chlor-alkali electrolysis
cell operated at 2.0 amps/in2. Cell voltage and current
efficiency were measured as a function of cell operating
time and sodium hydroxide concentration. The following
results were obtained for a 15-day test:
Sodium HydroxideCurrent EfficiencyCell Voltage
Da~ Product (~ ) (volts~_ _
1 21.5 70.7 ~-35
21.5 71.2 3.45
~0.0 65.2 3.60
UTILITY ~XAMPLE R
Co~olYmerization of Tetrafluoroeth~lene and Perfluoro-
6-oxsnon-8-enoic acid. and PreParation of Electrlcall~
Conductive Films from the CoPolYmer Product
nxCF2=CF2 + xCFz=CFCF20(CF2)4COOH
~ CF2CF2)n-CF2-CF - '-
L CF20( CF2 )4
The procedure of Example Q was followed with
perfluoro-6-oxanon-8-enoic acid (47.5 g), 8~ pentafluoro-
propionyl peroxide in l,1,2-trichloro-1,2,2-trifluoroethane
(0.05 g), and TFE at 10 pslg (40C) to give 2.41 g of solid,
white copolymer: DSC melting point depression was 157C
compared with polytetrafluoroethylene. Analysis of
carboxyl groups by titration showed 36.8 wt. ~ (9.3 mol ~)
of polyfluoroallyloxy comonomer, corresponding to an
equivalent weight-of 1070.
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115S801
The copolymer product was pressed lnto 4-5 mil
film and hydrolyzed as described in Example ~. IR spectra
showed essentially complete conversion of -COF functions
to carboxylate salt, indicating a copolymer of TFE and
CF2=CFCFzO(CF2)4CO2 K~.
A four-inch diameter sample of the 4-5 mil film
was inserted as the ion-exchange membrane in a chlor-alkali
- cell operated at 2.0 amps/ln2, and the following results
were obtained in a 76 day test:
Sodium Hydroxide Current Efficiency Cell Voltage
Da.vProduct (~ ) (volts)
1 37.1 93.3 4.02
39.2 90.9 4.60
39.4 ~7.7 4-25
32.9. 92.0 4.11
76 34.6 85.8 4.67
The application is a division of copending Canadian
Application Serial No. 292 106, filed 1976 November 30.
3o
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