Note: Descriptions are shown in the official language in which they were submitted.
~ ~t~ 3 ~
~1--
The present invention relates to monomers suitable
for copolymerization yielding polymers having modified
physical properties, such as lower melting point which
facilitates fabrication.
The application is divided for applicants co-
pending application Serial No. 379,491 filed on June 10,
1981 which relates to a method for preparing compounds of
the formula
Y(CF2)a-(CFRf)b-CFRf - O - ~CF-CF2- ~ CF-C=O
~F2X ' J CF2
which comprises reacting a compound of the formula
X'CF2 - CF - CF2
with a compound of the formula
,f
Y(CF2)a - (CFRf)b - C = O
for a sufficient time and sufficient temperature to form
said compound where
a = is O or an integer greater than O;
b = is O or an integer greater than O;
n = is O or an integer greater than O;
Rf and Rf are independently selected from
the group consisting of F, Cl, per-
fluoroalkyl radicals and fluorochloro-
alkyl radicals;
X' = Cl or Br or mixtures thereof when n>l;
Y = Cl, Br, I or F.
The present invention, together with that of
aforementioned Serial No. 379,491 and also Serial No.
455,616 (filed May 31, 1984 and also divided from Serial
No. 379,491) will now be further described.
U.S. Patent 3,~36,733 teaches the preparation
of compounds represented by the general formula
~ 28,981-F (Dj~T A) -1-
3~
.
YCF/-\CF
where Y is F or CF3.
UOSu Patents 3,214,478 and 3,242,218 teach a
process for preparing compounds having the general ~ormula
~ F
3 2)2 - ~ F - CF2 ~ ~ - CF C O
~ F3 ~ CF3
where n is O or an integer greater than 0.
28,981-F (~iv. A) -la-
.l.q~3~34
--2--
U.S. Patent 3,250,806 teaches fluorocarbons
having the general formula
S Y
X ' Rf - O - ( CF2 - CF2 - ~ ) n - CF2 - C = O
where
10 ~ = 0 to 20;
Rf = perfluoroalkylene radical
COY is a carboxylic acid group or a carboxy-
15lic acid fluoride; and
X' is halogen or hydrogen.
German Patent 1,238,458 teaches the reactionof iodo substituted perfluorocarboxylic acid fluorides
with hexafluoropropylene oxide to make acid fluoride
intermediates which can be pyrolyzed in the presence of
an inorganic compound such as ZnO to produce vinyl
ether compounds. The vinyl ether products, when co-
polymerized with tetrafluoroethylene form melt pro-
2S cessable polymers that can be crosslinked by thermal
decomposition of the perfluoro alkyl iodide.
'~
-(CE2)n+l-O-(CF2CF20)p-(CFCF20~-CF=CF2
~CF3 / m
where n = 1-8
p = 0-5
m = 0-5
28,981 F -2-
903~
A specific example being
F O\ F
ICF2C=o + CF3CF-CF2 CsF ~ ICF2CF20CF-C=o
CF3
ZnO ~ ICF2CF20CF=CF2
U.S. Patent 3,450,684 teaches the preparation
of vinyl ethers by reacting an acid fluoride with hexa-
fluoropropylene oxide followed by decarboxylation using
an activator such as ZnO or silica according to the
following reactions:
X F A
XCF2CF20~FCF20) -CF~C=O + CF3CF-CF
~ n-l
2~
XCF2CF20(CFC~2~ -CF-C=O AchtiavtatOr
~ CF3
XCF2 CF2 O~CFCF2 O~ -CF=CF2
~X Jn
where X is F, Cl, H, CH3, CF2Cl or CF3
n is at least l.
Copolymerization of these monomers with
tetrafluoroethylene forms polymers having lower melt
viscosity than the parent tetrafluoroethylene polymer.
28,981-F -3-
,
~ -
~ 34 ' ~
--4~
U.s. Patent 3,114,778 teaches the formation
of vinyl ethers by reacting an acid fluoride with hexa-
fluoropropylene oxide to produce an intermediate com-
pound which may be decarboxylated to a vinyl ether
according to the following reactions:
F o F
RfC=O + CF3CF-CF2 ~ RfCF2OCFC=O
CF3
decarb _ ylat1on RfCF2OCF=CF2
where Rf is, for example, a perfluoroalkyl radical.
Homopolymers and copolymers, with tetrafluoroethylene,
of the vinyl ethers is taught.
Fearn, et al, Journal of Polymer Science:
Part A-1, Vol. 4, 131-140~1966) discloses that in the
pyrolysis of sodium salts of carboxylic acids which
contain fluorine and chlorine in the beta position,
sodium chloride is preferentially, but not exclusively
eliminated. For example:
ONa
ClCF2CFClCF~CFClCF2C=O h5e0a,0t, ~
ClCF2CFClCF2CF=CF2 + CFCF2CFClCF2CCl=CF2
U.S. Patent 3,282,875 shows decarboxylation
of intermediates to form various vinyl ethers. At
higher temperatures of around 300C, vinyl ether yields
of about 80,~ were obtained. When, however, lower
temperatures of about 200C were used to decarboxylate,
yields of about 20-30% were obtained.
23,981-F -4-
s~
--5--
R. D. Chambers, in his book, Fluorine in
Organic Chemistry, published by John Wiley & Sons,
1973, pages 211-212, teaches that carboxylic acid
derivatives may be converted to olefins. The con-
version involves the loss of carbon dioxide and
forms an intermediate carbanion. The intermediate
then looses NaF to form the resulting olefin.
Evans et al., in the Journal of Organic
Chemistry, Vol. 33, page 1838, (1968) describes
catalysts useful for the reaction between acid
fluorides and epoxides.
M. Hudlicky in Chemistry of Organic Fluorine
Compounds - 2nd Edition, John Wiley & Sons, New York,
pages 20-21, teaches the well-known reaction between
tetrafluoroethylene and perfluoroalkyl iodides to form
telomeric perfluoroalkyl iodides according to the
following reaction:
RfCF2I ~ CF2= CF2 peroxide ~ RfCF2(CF2CF2!nI
Various methods for polymerication are
taught in the following references: Emulsion Polymeri-
zation - Theory and Practice by D. C. Blackley, John
Wiley & Sons; U.S. 3,041,317; U.S. 2,393,967; U.S.
2,559,752; and U.S. 2,593,583.
The present invention resides in a method
for preparing compounds of the formula
~ ~' ~ F
Y(CF2)a(CFRf)bCFRfO - ~CFCF2O~ - ~CFCF2O~ - CFC=O
~ J n~l ~ J m
28,981-F -5-
3~
--6--
which comprises reacting compounds of the formula
/o~
X'CF2 - CF - CF2
with compounds of the formula
~ ~ F
Y(CF2)a(CFRf)bCFRfOfCFCF20~ - CFC=O
~F2X J C 2
for a sufficient time and sufficient temperature to
form said compound
where
a is O or an integer greater than O;
b is O or an integer greater than 0,
n = O or an integer greater than O;
m = O or an integer greater than O;
Rf and Rf are independently selected
from the group consisting of F,
Cl, perfluoroalkyl radicals and
fluorochloroalkyl radicals;
X = F, Cl or Br or mixtures thereof
when n>O;
X' is independently Cl or Br;
Y = I, F, Cl or Br.
The invention further resides in a method of
producing a compound of the formula
Y (CF2 ) (CFRf ) b (CFRf ) CO -~CF2~
~ 2X J ~ F2X J C 2
28,981-F -6-
3~
which comprises reacting a compound of the formula
Y(C~2)a(CFRf)b CF~fo- ~FCF20~ - ~ FCF20~ - CFC-O
~CF2X J 1 ~;F2 ~ CF2X '
with a compound of the formula PZ' for a sufficient
time and a sufficient temperature to form said compounds
where
a is 0 or an integer greater than 0;
b is 0 or an integer greater than 0;
m = 0 or an integer greater than 0;
n is 0 or an integer greater than 0;
Rf and P~f are independently selected
from the group consisting of F,
perfluoroalkyl radicals and
fluorochloroalkyl radicals;
X = F, Cl, Br or mixtures thereof
when n>0;
X'= Cl or Br;
Y is I, ~r, Cl or F;
P = a cation or a qroup capable of
forming a cation;
Z'= OH, NRR' or OR;
R and R' are independently selected
from alkyl having one or more
than one carbon atom and an aryl.
In addition, any one or more of the monomers
represented by the general formula I or IV may be
copolymerized with any one or more of the monomers
selected from the group consisting of tetrafluoroethylene,
trifluoromonochlorethylene, trifluoroethylene, vinylidene
fluoride, 1,1-difluoro-2,2-dichloroethylene, l,l-difluoro-
2-chloroethylene, hexafluoropropylene, 1,1,1,3,3-penta-
; ~ 28,981-F (Div. A) -7
~9~3~
--8--
fluoropropylene, octafluoroisobutylene, ethylene, vinyl
chloride, trifluoronitrosomethane, perfluoronitroso-
ethane and alkyl vinyl ether.
For example, when Y = C1, Br, F or I, the
monomer incorporated (by copolymerization) into polymers
of well known monomers such as tetrafluoroethylene,
chlorotrifluoroethylene or the like, impart useful
properties. The copolymers are lower melting, thus
facilitating fabrication. This property becomes
extremely important in the case where the parent polymer
is derived from tetrafluoroethylene. It would be
difficult, if not impossible, to fabircate the polymer
by conven-tional means such as melt extrusion without
incorporation of a second component such as the above
monomer. In addition to modifying physical properties,
incorporating monomers derived from the intermediates
where Y - Cl or Br in polymers of tetrafluoroethylene
can be useful for introducing a site for further reaction
of the polymers either before or after the fabrication,
but preferably after. It is well known that perfluoro-
polymers such as Teflon~ are for most practical purposes
inert. Only extreme reaction conditions such as
reaction with sodium vapor affect their chemical integrity.
Introduction of controlled amounts of the present
monomers in
28,981-F (Div. A) -8-
`:
r-S
LQ~(~3~ ~ ~
`~
. , .
the polymers having a group more chemically reactive
than is the case with the perfluoropolymers. Reaction
with strong bases such as alkyl alkali metals can lead
to intermedl~tes useful for chemical modification such
as introducing sulfonate groups for wettability of the
polymers. In addition to the above uses, addition of a
monomer derived from the present invention to copoly-
mers of monomers having ion exchange functionality and
tetrafluoroethylene to form terpolymers, for example
when Y = Cl, that have
r ( I )h r (CFCI23i - (CF2CF2)j~
CF2 CFz
XCF2CF n XCF2CF n
O O
~CF2)a (CF2)a
Cl SO2OH
superior electrical properties compared to the copolymers
alone when used as ion exchange membranes in chlor-alkali
cells.
The radical X is chosen from the halogens Cl,
Br or F, while X' is chosen from Cl or Br. While
iodine would also be a useful radical for X or Xl,
formation of the ethers by the chemistry taught herein
is hampered by side reactions causing low or non-
existant yields to the desired compounds.
The intermediate compounds of the present
invention are conveniently prepared by reacting an
acylfluoride or ketone of the general formula
R'f
Y(CF2)a - (CFRf)b - C = O
28,981-F -~ ~
with a perhaloflu~ro propylene epoxlde of the formula
/o\
XCF2 - CF - CF2
where Y, Rf, Rf, and X are as defined above, the reactions
are done ln the presence of a fluorlde ion yielding
compound (MF-catalyst) at from below about -20C to
above about 50C, in the liquld state, deslrably in a
liguid solvent for the intermediate fluoroalkoxide
Y(CF2)a - (CFRf)b - CFRfO M formed between the acid
fluoride or ketone
R'f
Y(CF2~a - (CFRf)b - C = O
and the metal or ammonium fluoride ion yieldiny
catalyst (MF). The reactions proceed generally according
to the equation
o Rf
(X' )XCF2-CF-CF2 + Y(CF2 )a-(CFRf)~,-C=O
Y(CF2)a - (CFRf)b - CFRf - O -~CF - CF2 - O ~ CF - C ~ O
~F2X ~nCF2X'
where a = 0 or integer greater than 0;
b = 0 or integer greater than 0;
n = 0 or an integer greater than 0;
Rf and Rf are independently selected
from the group consisting of F, Cl,
perfluoroalkyl and 1uorochloroalkyl;
X = F, Cl, Br or mixtures thereof when n>1;
28,981-F -~-
~0
X' = Cl or Br;
Y = I, Br, Cl or F
In the special case where a = 2, b = o,
Rf = F, Y = X = X' - Cl or Br, and Z = F the
reaction can be done in either one or two steps. In
this case, the first reaction of the fluoride ion is
with the halofluoropropylene oxide compound rather than
with the carbonyl of the substituted fluorocarbon acid
fluoride. A fluorocarbon alkoxide is produced by this
reaction which can either react with additional epoxide
or lose fluoride ion to produce an acid fluoride.
/o\
F + XCF2~F-CF2 - XcF2cF2cF2o
F ~ ~ /0\
XCF2CF2C=O + F l XCF2CF-CF2
2~ ~
F + XCF2CF2CF20~FC=O -, XCF2CF2cF20cFcF2o
CF2 X CF2 X
As can be seen from the above scheme, it is
possible to rearrange the epoxide to acid fluoride with
fluoride ion and then use the acid fluoride as demon-
strated by the general scheme or one can simply react
the epoxide in the presence of fluoride ion in a single
step without isolation of the intermediate acid
fluoride.
Conversion of acid halides such as the acid
fluorides described herein to carboxylic acids and
28,981-F -~3'-
3~
derivatives by reac-tion with nucleophiles are well
known to those skilled in the art. For example, con-
version of the acid fluoride to the corresponding
carboxylic acid is easily accomplished by reaction with
water. Conversion to esters ox amides is accomplished
by reaction with alcohols or amines, respectively. The
carboxylic acid intermediates (Z=OH) are easily con-
verted to acid chlorides and bromides (Z = Cl, Br~ by
reaction with appropriate halogenation agents such as
PCl5 and PBr5.
Optional, additional reactions of the
carboxylic acid fluorides proceed according to the
following equation-
F
Y(CF~2)a ~ (CFRf)b - CFRf - O -~CF - CF2 - O ~ CF - C = O
\~F2X ,,~ CF2X '
+ pz~ .
Y~CF2)a - (CFRf)b - CFRf - O - ~F - CF2 - O~ - CF - C = O
~F2~ ~n CF2X'
where a = is 0 or an integer greater than 0;
b = is 0 or an integer greater than 0;
n = is 0 or an integer greater than 0;
Rf and Rf are independently selected from
the group consisting of F, Cl,
perfluoroalkyl and fluorochloroalkyl;
X = F, Cl, Br or mixtures thereof when n>1;
- 28,981-F -~A~-
/~
J;~ ~9~34
,,~
X' = Cl or Br;
is I, Br, Cl or F;
Z' = OH, NRR' or OR;
R and R' are independently selected from
the group consisting of hydrogen,
an alkyl having one or more
than one carbon atom and aryl; and
P is a cation or capable of forming a cation,
such as Na , K , H , etc.
It is of course to be understood that the
ratio of reactants, the temperature of reaction, the
amount of catalyst, as well as the amount and kind of
solvent, influence the course, speed and direction of
the reaction. Naturally the ratio of reactants bears
more directly on the value of n in the generic formula
than the other factors noted. For example, employing 1
or more moles of acid halide compound per mole of per-
halofluro epoxide results in a product rich in the n=O
product, i.e., greater than 1.5 n=O to n=l, respec-
tively and if the ratio is 2 to 1, respectively, then=O product, respectively, is about 92 to 1, respec-
tively, whereas e~.ploying greater than 1 mole epoxide
compound per mole of acid fluoride compound, i.e., 2 to
l, respectively, results in a product having a 3:9:1
ratio of n=2: n=l:n=O products. The ratio of reactants
thus can range, for practical purposes, from about 2 to
3 moles of the acylfluoride per mole of the halofluoro
epoxide to 1 to 20 moles of the epoxide per mole of the
acyl fluoride, the high acyl fluoride to epoxide pro-
ducing predominantly the n=O and the high epoxide to
acyl fluoride producing the n=2-12 ether, respectively,
and mixtures thereof.
28,981-F
, " 1~ 3~
Solvents employed in accordance with the
present invention should be nonreactlve (i.e., do not
contain hydroxyl groups) and have at least a solubility
for the reactants and the intermediate fluoroalkoxide
formed between the acyl fluoride or ketone compound and
the catalyst~ Whether or not the products are signifi-
cantly soluble in the solvent is a matter of choice and
can be used as a controlling factor for selectively
controlling the n value in the final product. For
; 10 example, if a high n value is desired, it is advan-
tageous that the product having at least n=O to 1 be
soluble in the solvent to give the intermediates (n=O
and n=l) time to react to produce the final n=1, 2 or
higher product. In addition, the amount of solvent can
be adjusted to accomplish somewhat similar results.
Suitable solvents which may be employed to take ad-
vantage of the solubility plus amount factor are
tetraglyme, diglyme, glyme, acetonitrile, nitrobenzene
and the like. ~xemplary of a preferred solvent is
tetraglyme which has a suitable solvency for the
intermediate.
Substantially any fluoride ionizable at the
reaction temperatures may be used as a catalyst,
however, CsF and KF are the most preferred but ~gF,
tetra alkyl ammonium fluoride as well as others listed
in Evans, et al., J. Orq. Chem. 33 1837 (1968) may be
employed with satisfactory results.
The temperature of the reaction also ef-
fectuates a controlling factor on the end product
obtained. For example, low temperatures such as -20C
favor n=O products and higher temperatures, 50C and
above, favor higher n values.
28,981-F ~-
lY
~3~
,,~
It has been discovered -that the intermediates
discussed above decarboxylate under far milder condi-
tions and in excellent yields compared to those of the
prior art
F
~OCF-C=O
CF2 X '
where X' = Br, Cl AS opposed to ~' = F.
~t has repeatedly been taught that prefer-
ential methods for the decarbo~ylation of compounds where
X1=F involve pyrolysis with activators such as ZnO at
temperatures between 300 and 600C. While it is taught
that these reactions do proceed at lower temperatures
with some bases, these methods are generally inferior
20 to the high temperature methods because of lower yields
(U.S. Patent 3,282,875). While the intermediates of the
present invention decarboxylate readily by the extreme
conditions reported in the prior art, such conditions
are neither required or desirable. These intermediates
~S decarbo~ylate in near quantitative yields to the
desired vinyl ether monomers at conditions as mild as a
suspension of sodium carbonate in a solvent and tem-
peratures at or below 100C.
In addition to the ease of reaction as
discussed above, the near quantitative yield to only
the fluorine substituted olefin group is surprising.
It is generally accepted that conversion of carboxylic
acid derivatives to olefins involves loss of carbon
28,981-F
3'~
,~,,,
, ~ -;L~--
dioxide to form an intermedia-te carbanion. In the
present invention, this reaction could conceivably
produce the intermediate shown below.
S ~OCF Na where X'=Cl or Br
CF2X'
This intermediate then loses NaX' to form the resulting
olefin.
~OCF ~a ~OCF=CF2 ~ NaX'
CF2X '
In this intermediate, it is possible to eliminate
either NaX' or NaF. Elimination of NaF would result in
another olefin, ~OCF=CFX', which would not be particu-
larly useful for subse~uent polymerization reactions
and would thus require a tedious purification procedure
for its removal. While it is not particularly sur-
prising that loss of NaX' predominates in the reaction,
it is surprising that loss of NaX', particularly when
X'=Cl, as opposed to NaF is the sole detected course of
the reaction. As discussed previously, Fearn reports
that elimination of both F and Cl occur in the fol-
lowing pyrolysis, though elimination of NaCl pre
dominates.
-NaCl
- ~ ClCF2CFClCF2CF=CF2 (84%)
ONa
ClCF2CFClCF2CFClCF2C=O
~ ClCF2 CFClCF2 CCl=CF2
NaF
28,981-F -.~-
/~
Analytical resul-ts from I.R. (Infra Red),
VPC-MS (Vapor Phase Chromatography-Mass Spectrometer~
and F19NMR have shown no evidence of a second vinyl
ether (namely ~OCF=CFCl) component in the olefins
prepared by decarboxylation of the acid fluoride inter-
mediates of the present invention.
In general, the polymerizatlon procedures and
techniques followed in the present invention are known.
A very good reference for polymerization techniques is
~ by D. C.
Blackley, published by John Wiley & Sons.
Additionally, the copolymer used in the
present invention may be prepared by general polymeri-
zation techniques developed fox homo- and copolymer-
izations of fluorinated ethylenes, particularly
those employed for tetrafluoroethylene which are
described in the literature. Non-aqueous techniques
for preparing the copolymers of the present invention
include that of U.S. Pat. No. 3,041,317, to H. H.
Gibbs, et al, that is by the polymerization oE a
mixture of the major monomer therein, such as tetra-
fluoroethylene, and a fluorinated ethylene containing
sulfonyl fluoride in the presence of a free radicalinitiator, preferably a perfluorocarbon peroxide or azo
compound, at a temperature in the range 0-200C and at
pressures in the range 1-200 atmospheres, or more. The
non-aqueous polymerization may, if desired, be carried
out in the presence of a fluorinated solvent. Suitable
fluorinated solvents are inert, liquid, perfluorinated
hydrocarbons, such as perfluoromethylcyclohexane,
perfluorodimethylcyclobutane, perfluorooctane, per-
fluorobenzene and the like.
28,981-F -~*r-
Q;3
,~
,~
Aqueous technique~ which may also be used for
preparing the copol-ymer used ln this invention include
contacting the monomers with an aqueous medium con-
taining a free-radical initiator to obtain a slurry of
polymer particles in non-waterwet or granular form, as
disclosed in U.S. Pat. No. 2,393,967 to Brubaker or
contacting the monomers with an aqueous medium contain-
ing both a free-radical initiator and a technologically
inactive dispersing agent, to obtain an aqueous col-
loidal dispersion of polymer particles and coagulating
the dispersion, as disclosed, for example, in U.S. Pat.
No. 2,559,752 to Berry and U.S. Pat. No. 2,593,583 to
Lontz.
It is particularly beneficial to form polymexs
from the vinyl ether monomers of the present invention
where Y=Cl and Br and not iodine. It is well known, M.
Hudlicky, Chemistry of Organic Fluorine Compounds, 2nd
Edition, John Wiley & Sons, New York, pages 420-~21,
that perfluoroalkyl iodides react under mild conditions
with fluorovinyl compounds, such as tetrafluoro-
ethylene, to form telomeric perfluoroalkyl iodides.
R CF I + CF =CF Peroxlde~ R CF (CF CF ) I
This reaction can be iniated with either
peroxide compounds or heat. The prior art teaches
copolymers of tetrafluoroethylene and iodoperfluoro-
alkyl vinyl ethers as useful since on heating they loseiodine and form crosslinked fluorocarbon resins.
~ormation of high molecular weight, linear polymers
from iodo substituted monomers is severely restricted,
at best, because of competing reactions of the alkyl
1~
28,981~ r-
34
".
iodide moiety with the olefinic moiety entering into
the polymerization reaction. ~t least, highly
branched, low molecular weight pol meric materials can
be formed using conventional po]ymerization techniques.
Formation of strong flexible films or structural
materials, from the polymers, usually associated with
high molecular weight plastic materials, would be
essentially eliminated.
Peroxide or heat iniated reactions of per-
fluoroalkyl chlorides or bromides, particularly
chlorides, with olefins does not take place nearly as
readily as perfluoroalkyl iodides. In fact, fluoro-
chloro compounds are not known to take part, via the
lS chloro substituent, in this reaction. -Thus, it is
possible, using the vinyl ether monomers of the present
invention, to form high molecular weight, plastic type
materials by copolymerizing with other vinyl monomers,
such as tetrafluoroethylene, by conventional poly-
merization techniques known for producing fluoropolymers.The resulting polymers have the added feature of having
a reaction site (Y), known to be more reactive than
perfluoropolymers where any additional reaction would
have to take part on a fluoro substituent. Only few
reactions and these requiring extreme conditions are
known to take place at a C~F linkage. In fact, the non
reactivity of this linkage accounts for the commercial
significance of known fluoropolymers. Fluorocompounds
having C1, Br, and I substituents are known to take
part in metallation reactions with such metallating
reagents as alkyl alkali metals to produce reactive
intermediates that undergo a variety of reactions.
I~j
28,981-F -,~I-
-?-2--
Example 1
50 ml dry tetraglyme and 8.35 gm CsF were
added to a 100 ml 3-nec~ flask equipped with a stirrer,
thermometer, (-78C) reflux conclenser and an inlet
port. Two cold traps in series and maintained at a
temperature of -78C were connected downstream of the
reflux condenser. A slight back pressure ~as maintained
on the system with dry N~. The tetraglyme and CsF were
mixed for 45 min. to 1 hour. The reactor was cooled to
0C to 10~C and 7.26 gm ClCFzCOF was added slowly
through the inlet port, controlled to barely observed
condensation on the reflux condenser. The mixture was
stirred for 1 hour at room temperature.
/o\
Ten grams of ClCF2CF CF2 were added to the mixture
limiting the addition by observing the reflux off the
condenser. The mixture was allowed to stir ~or an
hour. The product which separated as a bottom layer,
after stirrlng was stopped, and contained
3.0 gm ClCF2CF2OCFCOF,
CF2Cl
.38 gm ClCF2CF2OCFCF2OCFCOF
CF2Cl CF2Cl
and .05 gm ClCF2CF2OCFCF2OCFCF2OCFCOF identlfied by vPc
CF2Cl CF2Cl CF2Cl
peaks at 1.00 min., 5.82 min. and 9.39 min. on 6 ft.
l/8" columns 20% Viton~ A on 80-100 mesh Celite~ at
20ml/min. carrier flow and temperature programmed at
min. at 60C to 220C at 16~min. Mass spectroscopy
confirmed the structures shown above.
28,981-F -~2'
3~
Example 2
50 ml dry tetraglyme and 4 gm Na2CO~ were
added to a 100 ml three-neck flask fitted with a
stirrer, heating mantle, thermometer, an addition
funnel and stillhead with a vacuum take off adapter
with a collection vessel in a (-78C) bath. ~ dry N2 pad
was used to maintain dry conditions prior to adding of
the acid fluoride addition products. The acid fluoride
addition product mixture from Example 1 containing 3 gm
lo n=0, .7 gm n=1 and a small amount (0.1 gm) n=2 acid
fluorides was added dropwise to the stirring reactor
mixture with accompanying evolution of gas. Following
the completion of the addition, the reactor contents
were stirred until no further gas evolution was
observed at which time the heating mantle was turned on
and the temperature in the vessel was raised slowly to
120C with a vacuum of 20 in. Hg applied. Further gas
evolution was observed over the range of 60C-80C.
The reactor was cooled back down a~d 1.4 gm of product
was collected in the container, the VPC showed a peak
at .59 min. which was identified as ClCF2CF2OCF=CF2.
The product has an I.R. band @ 1835 cm l and a Fl9 NMR
spectrum consistant with the trifluorovinyl-oxo group.
Example 3
Dry tetraglyme (25 ml) and 20.8 gms of CsF
were added to a 200 ml, 3 neck flask equipped with
magnetic stirrer, reflux condenser maintained at a
temperature of -78C, thermometer and gas inlet tube.
The contents were allowed to mix for 40 minutes.
The reactor contents were then cooled
/ \ '
to 0-5C and 25 gms of ClCF.CF -CF2 added slowly after
28,981-F -~-
~1
~9~3~
~?
which the contents were mixed for an additional 40
minutes. Another 25 gms of epoxide was then added in
the same manner as described above. Two hours af-ter
the epoxide addition, with the contents at 0~5C, the
product was distilled from the flask at 30 inches of
vacuum while heating the flask up to 150C. The
maximum overhead temperature was 129C. The product
distilled in this manner (20.9 gms) was analyzed by vPC
using the same column and program as described in the
above examples.
Peak
time Wt.
(min) Ra-tio Com~osition
1.35 4 ClCF2CF2CF2OCFC
' F
CF2Cl
6.79 2 ClCF2CF2CF2O ~FCF2O~ CFC
2 2 2
~ O
9.86 1 ClCF2CF2CF20 ~CFCF20~ CFC~5Z
~CF2Cl ) CF2Cl
Example 4
17 gm of a mixture containing 68%
ClCF2CF2CF~OCF(CF2Cl)C~ and higher homologs as analyzed
by GC-mass spectrography was added dropwise to a stirred
3 neck reaction vessel containing 50 ml dried tetra-
glyme and 7.1 gm dried Na2 C03 and fitted with a thermometer,
heating mantle, and a stillhead with vacuum takeoff and
double dry ice acetone trap under inert purge. Gas
evolution was observed and a temperature ri.se from 25C
28,981-F
3~
".,-~
up to 33C was observed during addition. After
continued stirrir.g for l hour, a 5 mm vacuum was applied
and the temperature was raised slowly up to 100C in
the vessel. Seven grams of material was collected in
the primar~l collection receiver and identified as 97.1%
ClCF2CF.CF~OCF=CF2. Raising the temperature under
vacuum, up to 145C, resulted in collection of an addi-
tional 2 gm material which was analyzed by GC mass
spectrography and I.R. as 22.35% ClCF2CF2CF2OCF=CF2
representing an 81% yield of ClCF2CF2CF~OCF=CF2. VPC
analysis of the solvent in the reaction vessel showed
some ClCF~CF2CF2OCF=CF2 remaining along wi-th higher
homologs.
Com~arative Exam~le 4
A mixture ~35 gms) containing 31.7% of
CF3CF~CF2OCFCFO plus higher homologs was added to a
CF3
mixture of 15.5 gms Na~CO3 in 50 ml of tetraglyme at
room temperature. After several hours and cessation of
CO2 evolution, the mixture was raised to 120C where
upon there was indications of some slow CO2 evolution.
After several hours at this condition, pulling a vacuum
on the system to remove product resulted in little or
no evidence, by VPC and I.R., of vinvl ether formation.
The temperature of the reactor was then raised to
160-170C under atmospheric pressure. Under these
conditions, boiling of the mi~ture resulted. The product
collected (8 gms) showed a VPC peak at 0.74 min.
retention time and absorption in the I.R. at 1840 cm 1
indicating formation of the vinyl ether.
~3
28,9~
,~7,0 ~ ~9Q3f~L
Example ~
To a 100 ml 3 neck flask were added 50 ml of
dry tetraglyme and 9.75 gms of anhydrous Na2 C03 . The
flask equipped with a stirring bar, reflux condenser,
thermometer, and inlet port. Two, cold traps maintained
at a temperature of -78C in series were located down-
stream of the reflux condenser. A slight back pressure
was main~ained on the system with a dry N2 bubbler.
15.9_ gms of
ClCF2CF2CF2OCFCFO,
CF2Cl
were added slowly at room temperature. There was a
small temperature rise, to about 35C and an evolution
of CO2, upon addition of the acid fluoride. The tempera-
ture was increased to 67-68C and held there for 2.5
hours. The product was then distilled from the reactor.
12.59 gms of product was collected and analyzed to
contain 97.37% ClCF2CF2CF2OCF=CF2. This gave a 0.60
minute peak on the VPC and represents a 99.3% yield for
the vinyl ether.
The product was analyzed by IR and showed the
-OCF = CF2 at 1830 wave number.
Analysis of the product by El NMR verified
the ClCF2CF2CF2OCF = CF2 structure. A proton scan on
the NMR showed only a negligible amount of proton
containing material.
Example 6
Tetraglyme ~60 ml) and 7.5 grams of anhydrous
Na2CO~ were added to a 100 ml 3 neck flask equipped
~ith an air cooled reflux condense~, thermometer,
f;~
28,981-F -2~-
9(~
~s
2,~?~
~i
masnetic stirrer and dropping funnel. Cold traps were
located downstream of the reflux condenser. 20.9 grams
of a mixture of acid fluorides cons1sting of 35.9%
ClCF2CF2CF2OCFCFO, 9.15% ClCF~CF2CF2OCFCF2OCFCFO
,
CF2Cl CF2Cl CF2Cl
and higher homologs was added dropwise at room temper-
ature. The temperature was maintained at no higher
than 30C during the addition and until no further
evolution of CO2 occurred. The temperature was then
ralsed to 70C and held there until no further
evolution of CO2. A 30 inch vacuum was then applied to
the system and the pot temperature raised gradually to
142C while collecting the material boiling overhead.
No appreciable CO2 evolution ocurred during the
distillation. 8.2 gms of material were collected that
analyzed by VPC as
Peak
time Yield
(min) % Composition
0.6731.9 ClCF2CF2cF2OcF=cF2
3.3930.4 ClCF2CF2CF2OCFCF2OCF=cF2
CF2Cl
5.983.9 ClCF2CF2CF2 ~ FCF2 ~ CF= CF2
~F2Cl J2
The balance of the material being predominately
solvent. Higher vlnyl ether homologs remained in the
flask.
28,981-F
99~34
,~
Example 7
An example o the pol~merization of
Cl(CF2)~-0-CF=CF2 with fluorocarbon olefins is as
follows: 3.7 gm of Cl(CF2)3-0-CF=CF2 was added -to 400
ml deoxygenated water containing 3 gm K2S208, 0.75 gm
NaHSO3, 1.5 gm Na2HP04 and 3.5 gm C~F15C0zK under 60
psi applied tetrafluoroethylene pressure in a glass~lined
stainless steel reactor with stirring a-t 20C. After 2
hours, the reacto' was vented, evacuated and heated to
lo 50c to rem~ve residual monomer. The remalning material
was then frozen, thawed, filtered, washed repeatedly
and then vacuum dried for 16 hours at 120C. The
resulting polymer readily pressed into a flexible,
tough, transparent film and was analyzed to contain 3
percent chlorine.
Example _
As a further example of polymerization of
Cl(CF2)30CF=CF2 with fluorocarbon olefins:
4.8 gms of Cl(CF2)3OCF=CF2
were added to 30 ml of ClCF2CFCl2 in a stainless steel
reactor. Two drops of a 2-tert. butylazo-2-cyano-4-
-methoxyl-4-rnethylpentane initiator solution were added
and the reactor contents frozen to -78~C. The reactor
overhead was evacuated and ~1 gms of tetrafluoroethylene
was condensed into the reactor. The reactor was heated
to 55C and shaken for 16 hrs. After venting the
reactor and evaporation of the solvent, 14 gms of dried
polymer, analyzing as containing 2.36% Cl, was recovered.
28,981-F ,2~-
