CA1274650A - Preparation, decarboxylation and polymerization of novel acid fluorides and resulting monomers - Google Patents

Abstract

ABSTRACT
The invention relates to a method of polymerizing at least two compounds, wherein at least one compound is selected from trifluoromonochloroethylene; trifluoroethylene; vinylidene fluoride; 1,1-difluoro-2,2-dichloroethylene; 1,1-difluoro-2-chloroethylene; hexafluoropropylene; 1,1,1,3,3-pentafluoro-propylene; octafluoropropylene ethylene; vinyl chloride; and alkyl vinyl ether and at least one second compound represented by the general formula:
Y(CF2)a(CFRf)bCFR'f-O-CF=CF2 where:
a = 0 or an integer of from 1 to 3;
b = 0 or an integer of from 1 to 3;
R'f and Rf are independently selected from F or Cl; and Y is selected from Cl or Br;
and reacting at least one compound from the first group with the second compound in the presence of an initiator for a period of time and a temperature sufficient to polymerize said compounds.
The process produces compounds useful in the preparation of poly-mers with improved properties.

Description

5~

The present invention generally relates to a method of polymerizing at least 2 components yielding copolymers having modified physical properties, such as lower melting point wnich facilitates fabrication The application is divided from applicants co-pending application Serial No. 479,654 filed on April l9, 1985. Application 479,654 being a divisional of Application Serial No. 379,491, filed on June 10, 1981, now Patent No. 1,187,099.
U.S. Patent 3,536,733 teaches the preparation of compounds represented by the general formula /o\

where Y is F or CF3.
U.S. Patents 3,214,478 and 3,242,218 teach a process for preparing compounds having the general formula CF3(CF2~2 - O - ~F - CF2 - O) - CF - C - O
\CF3 ~ n CF3 where n is 0 or an integer greater than 0.

28,981-F (Div. D) `~ 127~5 -la-The second compound represented by the general formula Y(CF2)a(CFRf)~,CFR'f-O--CF=CF2 is prepared by the method described in copending Application Serial No. 455,616, filed May 31, 1984, said application being a divisional of Application Serial No.
379,491, filed June 10, 1981, now Patent No. 1,187,099, granted May 14, 1985.

28,981-F (Div. D) -1a-~ -2- ~

: ,~
, U.S. Patent 3,250,8C6 t~aches fluorocarbons having the general formula :. ' ..
.. 5 ,, /
X ' R~ - O ~ (CF2 - CF2 ~ ~) n ~ CF2 - C ~ O

where 10 n = 0 to 29;
F.f = perfluoroalkylene radical . COY is a carboxylic acid group or a carboxy-lic acid fluoride; and . 15 : X' is halogen or hydrogen.
:
German Patent 1,238,458 teaches the reaction of iodo substituted perfluorocarboxylic acid fluorides with hexafluoropropylene oxide to make acid fluoride i~termediates which can be pyrolyzed in the presence of an inorganic compound such as ZnO to produce vinyl ether compounds. The vinyl ether produc~s, when co-polymerized with tetrafluoroethylene form melt pro-cessable polymers that can be ~rosslinked ~y thermal . decompositio~ of the perfluoro alkyl iodide.

I tCF2)n~1~~(CFZCF2O)p~(CFCF2~ -C~=CF2 .: F~ m ' 30 where ~ 8 : p = 0 5 .: m = 0~5 ., , . .

..
28, 981-F (Div . C) -2-. .
, -3-~ ~74~;5~ ~

A specific example being ICF2C=O + CF3CF-CF2 CsF - , ICF2CF~OCF-C=O
S

ICF~CF20CF-C~2 U.S. Pa~ent 3,450,684 teaches ~he preparation of vinyl ethers by reacting an acid fluoride wi~h hexa-fluoropropylene oxide followed by decarboxylaticn using a~ acti~ator such as ZnO or sili~a accoxding to the following .reacti~ns:
X F /
X~F2CF20 ( FCF20~ -CF-C=O + CF3CF-CF~
\~ /n-l F
XCF2CF20~CFCF2~ -CF-C=O Actlvator . ~ CF3 XCF2CFzQ~CFCF2 ~ -CF=CF2 wh~re X is F, Cl, ~, C~3, CF2Cl or C~3 n is at least 1.

Copolymerization of these monomers with tet~afluoroethylene forms polymers havir,g lower melt viscosity than the parent tetrafluoroethylene pol~mer.

... .

28,981-F (Div. C) _3_ _.' ~4~ ~2~js0 U.S. Patent 3,114,778 teaches the formation of vinyl ethers by react~ng an acid fluoride with hexa~
fluoropropylene oxide to produce an intermediate com-po~nd which may be decarboxylate~ to a vinyl ether according t~ ~he following reactions:

F O F
~\ , R~C=O ~ CF3CF-CF2 ~ R~CF2OCFC-O

RfCF20CF=CF2 where Rf is, for example, a perfluoroal3~yl radical.
~omopolymers and copolymers, with tetra1uoroethylene, of the vi~yl ethers is taught.

Fearn, et al, Journal of Polymer Science:
Part A-l, Vol . 4, 131-140 ( 1966 ) discloses that in the pyrolysis of sodium salts of carbo~cylic acids which con~ain fluorine and chlorine in the beta position, sodium chloride is pre~erentially, but not exclusively : eliminated. For example:

ONa ClCF2CFClCF2CFClCF2C=O
ClCF2CFClCF2CF=CF2 + CFCF?CFClCF2CCl=CF~

U.S. Patent 3,282,875 shows decarboxylation of inter~ediates ~o form various vinyl ethers. At high~r temperatures of around 300C, vinyl ether yields of about 80% were ob~ained. When, however, lower temperatures of about 200C were used to decarboxylate, yields of about 20~30% were obtained.
., .

: 28,981-F .(Dlv. c) -4-'''' .

,~ J Lf~ ~, j 5 ~

'' `

R. D. Chambers, in his book, Fluorine in Orqanic ChemistrY, published by Jshn Wiley & Sons, 1973, pages 211-212, teaches that caxboxylic acid derivativesmay be converted to oleinfs. The conversion involves the loss of carbon dioxide and forms an intermediate carbanion. The intermediate then looses ~aF to form the resulting olefin.
Evans et al.l in the Journal of Orqanic Chemistry, Vol. 33, page 1838, (1968) describes catalysts useful for the reaction etween acid fluorides and epoxides.
M. Hudlicky in ChemistrY of Orqanic Fluorine Compounds - 2nd Edition, John Wiley & Sons, New York, pages 20-21, teaches the well-known reaction between tetrafluoroethylene and perfluoroalkyl iodides toform telomeric perfluoroalkyl iodides according to the following reaction:

.:' . . .

,, RfCF2I ~ CF2 = CF2 peroxide > Rf~CF2I + CF2 = CF2 . . , . . .
Various methods for polymerization are taught in the following references; Emulsion Polymerication -Theory and Practice by D. C. Blaceley, John Wiley &
3 Son ; U.S, 3,041,317; U.SO 2,393,967; U.S. 2,559,752;
U.S. 2,593,5~3.

. - .
., ., 28,981-F (Div. C) -5-.

~27g~6i5~

In particular, the present invention resides in a method o~ polymerizing at least two compounds, wherein at least one com-pound of a first group is selected from trifluoromonochloroethy-lene, trifluoroethylene, vinylidene fluoride, l,l-difluoro-2,2-dichloroethylene, l,l-difluoro-2-chloroethylene; hexafluoroprop lene, 1,1,1,3,3-pentafluoropropylene, octafluoroisobutylene, et lene, vinyl chloride, and alkyl vinyl ether, and at least one second compound represented by the general formula:

Y(CF2)a(CFRf )bCFR' ~-O-C~=CF2 where:
a = 0 or an integer of from 1 to 3, b = 0 or an integer of from 1 to 3;
R'f and Rf are independently selected from F or Cl; and Y is selected from Cl or Br;
and reacting at least one compound from the first group with the second compound in the presence of an initiator for a period of time and at a temperature ~ufficient to polymerize said compounds.
For example, when Y = Cl, Br, the second compound of the general formula when incorporated (by copolymerization) into at least one compound of the first group impart useful properties.
The copolymerR are lower melting, thus facilitating fabrication.
This property become~ extremely important in the case where the first compound on is derived from ~etrafluoroethylene.

1~:7~6S~

It would be difficult, if not impossible, to fabricate the polymer by conventional 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 perfluoropolymers 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 result in .

28,981-F (Div. D) -7-~-8- ~ 6 ~

~he polymers having a group more chemically reacti~Je ~han is the case with the perfluoropolymers, Reaction with strong bases such as alXyl alk31i metals can lead ~o interm~diates useful for chemical modification such as introdu d ng sul~onate groups for wettability of the polymers. In addition to ~he above uses, addition of a monomer deri~ed from the prese~t invention to copoly-mers of monomers having ion ex~hange functionality and tetra~luoroethylene ~o foxm ~erpolymers, fo~ example whe~ Y = Cl, that have -(CFCF2~h [ (CFCFZ)i - (CF~CF2)j-F2CF n F2CF n O O
(CF2)a (CF2)a ~ 1 52OEI
"
superior electrical properties compared ~o the copolymers : 15 alo~e when used as ion exchange membranes i.n chlor-alkali cells.
. .
The radical X is chosen from the halogens Cl, Br or F, while X' is chosen from Cl or Br. While iodi~e would als~ be a useful radical for X or X', formation of the ~thers by the ch~mist~y taught herein is hampered by side reactions causing low or non-: e~istant yields to ~he desired compounds.

The intermediate compounds of the present .i~ventio~ are conve~iently prepared by reacting an .
acylfluoride or ketone of the general formula.
R
y~ cF2 ? a ~ ( cFRf )b .
. 28,981-F (Div. C) -8-:, ,:, ~z~s~

wi~h~a perhalofluoro p~opylene epoxide of the formula -. /o\

. 5 . where Y, R~, Rf, and X are as defined ~bove, the reactions ; are d~ne i~ the presence of a 1uoride ion yielding '............. compo~nd (MF catalyst) at from below ~bout ~20C to above abou~ 50C, in the liquid state, desirably in a liquid solvent for the i~ermedia~e fluoroalkoxide Y(CF2 )a ~ (CFR~)b - CFR~O M ~or~Tled betw~en the acid fluoride or ketone .; R' .; , f 15 y(CF2)a - (CFR~)b . .
and the metal or ammonium fluoride ion yi~lding catalyst (MF). The reactions proceed generally according .. to the equation . 20 o Rf ', (X' )X~F2 CF-CF2 + Y(C~2 )a-(CFRf)b-C=O
... .
. F
Y(CF2)a - (CFRf)b - CFRf - 0 ~CF - C~2 - 0 ~ CF - C = o ~F2X ~nCF2X' ., .
where a - O or integer greater than O;
b = O or integer greater than O;
. n = O or an integer greater than 0;
3 Rf ~d Rf are independently selected from the group consisting of F, Cl, . perfluoroalkyl and fluorochloroalkyl;
.. ; X - F, C1, Br or mixtures thereof when n>1;
.. O
. _ 9 _ .~

~ ~2~
.

. X' - Cl or Br;
Y = I, Br, Cl or F
' In the special case where a = 2, b = o, R~ ~ F, Y = X = X' = Cl or Br, and Z = F the reaction can be done i~ either one or two steps In this case, the ~irst reac~ion of the fluoride ion is : with th~ halofluoropropylene oxide compound rather than with the carbonyl of the substituted fiuorocarbon acid fluoxide. A fluorocar~on alkoxide is produced by this reac~ion which can either react with additional epoxide or lose ~luoride ion to produce an acid fluoride.
,............. /0\
15 F ~ XCF2CF-C~2 XCF2c~2cF20 .'.,` ~'. ~

~ ~O XCF2CF2C=O + F- j ~CF C~
.. . F
F ~ XCF2CF2CF20CFC=O --~ XCF2CF2CF2OCFCF20 .' ' . CF2 X CF2 X
As can be seen from the above scheme, it is possible. to rearrange the epoxide to acid fluoride with fluoride io~ and then-use the acid fluoride as demon-strated by the general scheme or one can simply react the epoxide i~ the presence of fluoride ion in a single 30 step without isolation o~ the intermediate acid fluoride.
.
Conversion of acid halides such as.the acid .. fluorides described herein to carboxylic acids and :............. .

2~,981-F (Div. C) s ,.
.

-6~

derlvatives by reactlcn with nucleophiles are well : known to those skilled in the art. For example, con-version of the ac~d fluoride to the corresponding carboxylic acid is e2sily accomplished by reac~ion ~ h water. Conversion to esters or amides is accompli~hed by re2ctio~ wi~h alcohols or amines, respectively. ~he carboxyllc acid intermediates (Z=OH) are easily con-: ver~ed to acid chlorides and bromides (Z = Cl, Br) by reac~i~n with approprlate halogenation agen~s such as PCl5 and PBr5.
. , : Optlonal, additional reactions of the carboxylic acid fluorides proceed ~ccording to ~ne ; followi~g eguatio~:
.. ~5 ; - F
. Y(CF2)a - (CFRf)b - CFRf - O -fCF - CF2 - O ~ C~ - C = O
... \~F2X ~CF2X' : 20, PZ' . z~
. Y(CF2)a - (CFRf)b - CFRf - o ~F - CF2.~ ~ - CF - C = o :. 25 ~F2X Jn cF2x~
.
where a = is 0 or an in~eger greater tban 0;
b = is 0 or a~ integer greater than 0;
n = is 0 or an in~eger greater than 0;
Rf and Rf are independently selected from the group consisting of F, Cl, perfluo~oalkyl and fluorochloroalkyl;
X = F, Cl, Br or mix~ures thereof whe~ n>l;
.
.. . -- 11 --.... .

28,981-F (~iv. C) .

; ~Z7~6~
.

X' = Cl or ar;
Y is 1, Br, C1 ox Fi . Z' = OH, NRR' or OR;
R ~nd R' are independently selected from the group consisting of hydrogen, an alkyl having one or more than one carbon atom and arvl; and P is a cation or capable of fo~ming a cation, cuch as Na , K , H , etc.
" 10 It is o~ course ~o be unders~ood that the ratio of reactants, the temperature of reac~ion, the amoun~ of catalyst, as well as the amount and kind of sol~Jent, i~fluence the course, speed and direction of the reaction. Naturally ~he rat~o of reactants bears more direc~ly on ~he value of n in the generic formula ~han the other factor~ 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
. 24 product, i.e., greater ~han 1.5 n=O to n=l, respec-tively and if the ratio i5 2 to 1, respectively, the n=O product, respectively, is about 92 to 1, respec-tively, whereas employing greater than 1 ~ole epoxide compound per mole of acid fluoride compound, i.e., 2 to 2S 1, respectively, results in a product having a 3:9:L
ratio of n-2~ n=O produc~s. The ratio of reactants - thus can range, for practical purposes, from about 2 to : 3 moles of the acylfluoride per mole of the halofluoro ep~xide to 1 to 2a moles of the epoxide per mole of the acyl fluoride, ~he high acyl fluoride to epoxide pro-ducing predomi~an~ly ~he n=O and the high epo~ide to acyl fluoride producing the n=2-12 ether, respectively, .
., and mixtures thereof.
. . .
., ... . . .
.:
~ 28,981-F (Div. C) : ::
.:

~ 2~ J
. .
Solvents employed in accordance ~ith the . presen~ invention should be nonreactive (i.e., do not . contain hydroxyl groups) and have at least a solubili~y for the reactants a~d the intermediate fluoroalkoxide : 5 formed between ~he acyl fluoride or ketone compound and- the catalyst. Whether or not the products are signifi-cantly ~oluble in the solvent is a ma~er of choice and ~ can be used as a controlling factor for selectively con~rolL1ng the n vaLue in the final product. For example, ~f a high n value is desired, it is advan-tageous that ~he product having at least n-0 to 1 be soluble in the solvent to give the intermeaiates (n=0 and r.=1) time to reac~ to produce the fin~l ~=1, 2 or higher product. In addition, the amount of solvent can be adiusted to accomplish somewhat similar results.
Suitable solvents which may be employed to take ad-vantage of ~e solubility plus amount factor are tetraglyme, diglyme, glyme, acetonitrile, nitrobenzenea~d the like. Exemplary of a preferred solvent is 20 tetraglyme which has a suitable solvency for the . intexmediate.
.. . .
Substantially any fluoride ionizable at the reaction temper~tures may be used as a catalyst, however, CsF and ~F are the most preferred but AgF, . tetra alkyl ~mmonium fluoxide as well as others listed . in Evans, et al., ~ L~ 33 1837 (1968~ may be employed wi~h satisfactory results.

30 The temperature of the reaction al~o ef~
fectuates a controlling fa~tor on ~he end product . obtained. For example, low temperatures such as -20C
favor n=0 products and higher temperatur~s, 50C and above, favor higher n values.
.. . .
.- - 13 -:..
. Z8, 9al-F (Div. C) :: ' 1274i5~ --.
, .
I~ has been disco~Jered that the intet~edia~es discussed above decarboxylate under far milder ccndi-; tions and in excellent yields compared to those o~ the pr_or art .. 5 .. F
: ~OCF-C-O
. CF2 X ' "
where X' = Br, Cl as opposed to X' = F.

It has repeatedly been taught that prefer-ential ~ethods for the dec~rboxylation of compounds where X'-F involve pyrolysis with activatoxs such as Zna at temper~ures between 300 and 6Q0C. While it is taught that these raactions do proceed at l~wer temperatures with some bases, these me~hods are generally inferior 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 tXe prior art, such conditions are neither required or desirable. ~hese intermediates decarboxylate in near quantitative yields to the desired vinyl ether monomers at conditions as mild as a suspension of sodium car~onate in a solvent and tem-- peratures at or below 100C.
. .
In addi~ion to the ease of reaction ~s discuss~d above, ~he near quantitative yield to only the fluorine substi~uted olefin group is surprising.
It is generally accepted ~hat con~ersion of carbo~ylic acid derivatives to olefins invol~es loss of carbon . .
.- - 14 -. .
28,981-F (Div. C) ' dioxide to fonn an intermediate carbanion. In ~h~
present inven~io~, this reaction couLd conceivably produce the in~ermediate shown below.
., ~OCF Na where X ' =Cl or Br , CF2 X ' "his intermediate then loses NaX ' to form t.~ resulting . 1~ ol~fi~.

~OCF Na ~OCF=CF2 + NaX ' ",, ' CF2 X ' '' 15 In this intermediate, it is possible to eliminate either Na~' or NaF. Elimination of ~aF would result in ano~her olefin, ~OCF=CFX', which would not be particu-larly useful for subsequent 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 surprisi~g 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 elimina~ion of bo~h F and Cl occur in the fol-lowing pyrolysis, ~hough elimination of NaCl pre-dominates.
:-NaCl ClCF2 CFClCF2 CF=CF2 ( 84~o ) . ONa .
ClCF2 CFClCF2 CFClCF,. C-O . -.
L~ ClCF2 CFClCF, CCl=CF~
-NaF
: ~ 15 -2a ~ 981-F (Div. C) ~.~7~
. .
: Anal~Itical results from I.R. (Inf--a P~edj, VPC-MS (Vapor Phase Chromatography-Mass Spectrometer) : a~d F19NMR have shown ns evidence of ~ second vinyl e~her (namely ~OCF=CFCl) component in ~he clefins prepared by decarboxylation of ~he acid f~oride inter-media~es of ~he present inventicn.
! .
. In general, the polymerization procedures ~nd : technigues followed in khe present invention are ~no,Jn A very good reference for pol~merization techniques is

3~y~ nLs9~y~ 33s y~ _r~ .c-i-e b~ D. C.
filackley, published by John Wiley & Sons.
... .
Additionally, the ccpolymer used in the . 15 present invention may be prepared by general polymeri-zation techniyues dev~loped for homo- and copolymer-izations of fluorinated ethylenes, particularly ~hose empLoyed or tetrafluoroethylene which are desc~ibed in ~he literature. Non-a~ueous techniques for preparing the copolymers of the present invention include that of U.S. Pat. No. 3,041,317, to H. H.
. Gibbs, e~ al, that is by the polymerization of a mixture of the major monomer therein, such as tetra-fluoroethylene, and a fluorinated ethylene containing 25 sulfonyl fluoride in the presence of a free radical initiator, preferably a perfluorocarbon peroxide or azo compou~d, at a temperature i~ the range 0-200C and at pressures in the range 1-20a atmospheres, or more. The non-aqueous polymerization may, if desired, be carried out in ~he presence of a fluorinated solvent. Sui~able fluorina~ed solve~ts are inert, liquid, perfluorinated hydrocarbons, such as perfluoromethylc~clohexane, perfluorodimethylcyclobut~ne, perfluorooctane, Der .. fluorobenzene and ~he like.

28,981-F (~iv. C) :'.

Aqueous techniques which ma~ alss oe used o.
prepari~g ~he copolymer used in this invention ir.clu~e contacting the monomers with an aaueous medium con-taining a free-radical initiator to o~tain a slurr~ Oc 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 con~ain-ing both a fr~e-radical initiator and a technologically inactive dispersing agent, to obtain an aqueous col-loidal dispersion of polymer particles and coagula~ingthe dispersion, as disclosed, for example, in U.5. Paf.
No. 2,559,752 to Berry and U.S. Pa~. No. 2,593,583 to Lontz.

It is particularly beneficial to form polym~rs from the vinyl ether monomers o~ the present i~vention where Y=C1 and Br and not iodine. It is well known, ~.
Hudlicky, Chemist~y of Organic Fluorine Compounds, 2nd Edition, John Wiley & Sons, New York, pages 420-421, that per~luoroalkyl iodides react under mild conditions with fluorovinyl compounds, such as tetrafluoro-ethylene, to form telomeric perfluoroalkyl iodides.
' ' q :
: 25 RfCF2I ~ CF2=CF2 ~ RfcF2(cF2cF2) This reac~ion can be iniated with either peroxide compounds or heat. The prior art teaches copolymers of tetrafluoroethyle~e and iodoperfluoro-alkyl vinyl ethers as useful since on heating the~ loseiodine and form crosslinked fluorocarbon resins.
~or~ation of high molecular weight, linear polymers ~rom iodo subs~ituted monomers is severely restricted, at best, because of compe~ing reactions of fhe alk~l ., .
. . .
~ 17 -, 28,981-F (Div. C)-:

74~5~

lodlde moiety with the oleflnic rno1e~y enterin~ into the polymeri~ation reaction. At least, highly bra~ched, low molecular weight polymeric materials c~n be formed using conventional polymerization techniques.
S Formatian of stro~g flexible films or structural materials, from the polymers, usually associated with high molecular weight plastic m~terials, wauld De essen~ially elimi~a~ed.
':
1~ Peroxide or heat iniated r~ac~ions of per-fluoroalkyl chlorides or brom~des, particularly chlorides, with olefins does not ~ake place nearly as readily as perfluoroalkyl iodides. In fact, fllloro-chloro compou~ds are no~ known to take par~, via the chloro substitue~t, i~ this reac~ion. Thus, it is possible, using the vinyl ether monomers of the present vention, to form high molecular weiqht, plastic type materials by copolymeri?ing with other vinyl monomers, . such as tetrafluoroethylene, by conventional poly-merization techniques known for producing fluoropolymers.
The resulting polymers have the added feature of havinga reactlon 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 re~uiring extreme conditions are known to take place at a C-F linkage. In fact, the non reactivi~y of this linkage accounts for the commercial signi~icance of known fluoropolymers. Fluorocompounds having C1, Br, and I substituents are known to take . part in metallatioa reactions with such metalla~ing ; reagents as alkyl alkali metals to produce reactiv~
.. int~rmediates that u~dergo a varie~y of reactions.

,..

28, 9al-F (Di~.~. C) , .

~ ~ ~7~5~ ~

Examol~ 1 50 ml ory tetraglyme and 8.35 gm Cs~ ~ér~
add~d to a 100 ml 3-nec~ flask equipped wi~h ~ s~ir~r, thermometer, (-78C) reflux con~enser and an inle~
S port. Two cold traps :n series and maintai~ed at a temperature of -78C were cor~ected downstream of ~.h~
reflu~ condenser. A sl_ght back pressure was maln~ined on ~he system with dry N2. The ~etragLyme and C~F ~e~e mixed ~or 45 mir. ~o 1 hour. The reac~or was ~oolea ~o 0C to 10C and 7.26 gm Cl~F~COF was added slowly ~hrough the inl~t pox~, co~t.olled to barely ooservea çond~sation Gn ~ha re1ux co~denser. The mi.Y~ure. was stirred for 1 hour at room '.:emperature.
/o\
Ten grams of C'CF2CF---CF2 were added to the mixture limiti~g the addition by ob~erving the reflux off ~e condenser. The mixture was allowed to stir for an hour. The product which separated as a bottom layer, after stirring was stopped, and contained . 3.0 gm ClCF2CF2OCFCOF, CF2Cl .3a gTn ClCF2CF20CFCF20CFCOF
~5 C~2Cl C~2Cl and .05 sm ClCF2CF20CFCF20CFCF2OCFCOF ldentitiea by ~PC
CF2Cl CF2Cl CF~Cl , peaks at 1.00 min., S.a2 min. and 9.39 mi~. on 6 ft.
1/8" columns 20% Viton~ A on 80-100 mesh Celite~ at .
20ml/min. carrier flow and temperature pro~rammed at min. at 60C to 220C at 16/min. Mass spçctroscoov con~irmed the struc~ures shown above.

' ' - 1 9 -2a, 98~ J . C) ~7~1~,.5 Exam~.le 2 50 ml dry te~raglyme and ~ grn Na2 CO ~ werP
atlded to a 100 :nl three-neck flas~ fi cted ~"ith a stirrer, heating mantle, the~momet~r, an additlon S funnel and stillhead with a vacuum ~ake off adapt~r ~ith a collec~io~ vessel i~ a (-78C) bath. ~ dry ~12 p~d was used to malntaln dr~ conditions prior ~o adding of the acid fluoride addition products. The acid fluoride addition produc~ mixture from Example 1 conlaining 3 ~m n-0, .7 gm n=l and a small amoun~ (O.1 gm) n=2 acid fluorides was added dropwise to the s~irring reactor mixture with accom~anying evolution of gas. Following the completion of the addition, the reactor con~ents were stlrred un~il no further gas evolution was observed at which time the heating mantle was turned o~
., .
: and the temper~ture 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 and 1.4 gm of product was collected in the container, the V~C showed a peak : at .59 min. which was identified as ClCF~CF~.OCF=CF2.
The product has an I.R. band @ 1835 cm 1 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 stixrer, reflux condenser maintained at a temperature of 78C, thermometer and gas lnlet tube.
The contents were allowed to mix for 40 minutes.
.
The reactor contents were then cooled / \ '' to 0-5C and 25 gms o ClCF,CF~F, added slow1ir after : -- 20 --28, 981-F (Div. C) ~ ~7~5 ''' .
which the contents were mixed fcr ar. additional ~0 minutes. Another 25 gms of epoxide was ~hen ~dded ir.
the same manner as described above. Two hours al~er : the epo~lde addition, with the contents at 0-5~C, the S product w2s distllled from thP flask at 30 inches Ot vacu~m while hea~ing the flask up ~o 150C. The maximum overhead temperature was 1Z9C. The produc~
dlstilled in this mannex (20.9 gms) was anal~zed by V~
using ~1e 5ame column and program as described in the above examples.
. Peak time Wc.
~ Ratio 1.35 4 ClCF2CF2CF20 FC~

6.79 2 ClCF2CF2CF20 ~FCF20~ CFC
~CF2Cl J2CF2Cl ' 20 0 9.86 l ClCF2CF2CF20 ~CFCF2~ CFC
~CF2Cl J CFzCl F

;..
.. '. ~ .
. 25 17 gm of a mix~ure containing 68%
.. , 'o CLCF2CF2C~20CF(CF2Cl)C~F a~d higher homoLogs as analyzed by GC-mass spectrography was added drop~ise to a s.irred 3~ 3 neck reac~ion vessel con~aining 50 ml dried tetra-glyme and 7.1 gm dried ~a2 C03 and fitted with a thermometer, heating mantLe, a~d a stillhead with vacuum takeoLf and double dry ice acetsne trap under lnert purge. Gas - ~voLution was observed and a tempe~ature rise from ~5C

. 28,981-F (Div. C) :' :
up to.33C was observed during ~dd1tion. A.~ter continued stlrring for 1 hour, a 5 mm vacullm ~,~as appl1ed and the temperature ~as raised slowly up to lOO~C in the ~essei. Seven grams sf material was collected in S the primary collection receiver and identified as ~7.1%
ClCF2CF2C~20CF-CF2. Raising the temperature under vacuum, up to 145C, result0d in collectio~ of an addi-tionzl 2 gm material which was analyzed by GC mass sp~Gtrography and I.R. as 22.35% ClCF2CF~CF20CF=CF2 repr~senting an 81% yield of ClCF2CF2C.20CF=CF2. VPC
. anal~-sis of the solven~ in the reaction vessel showed om~ ClCF2CF2CF20CF=CF2 remaining along wi~ h7gher homologs.
~
A mixture (35 gms) contalning 31.7% of CF3CF2CFzOCFCFO plus higher homologs was added to a . CF3 mixture of 15.5 gms Na2CO3 in 50 ml of tetraglyme at room temperature. After several hours and cessation of C02 e~olution, 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, ~y VPC and I.R., of vinyl ether formation.
The temperature of the reactor was then raised to 160-170C under atmospheric pressure. Under these c~nditions, boiling of the mix~ure resul~ed. The product collected (8 sms) showed a VPC peak at 0.74 min.
retention time and absorption in the I.R. at 1840 cm ; indicatiny formation of the vinyl ether.
, ,. -:
,, .

.
, 2a, sal-F (Div. C) :

~ Z 7 L~

.. Exam~le S
To a 100 ml 3 nec~ flask were added 50 ml c~f dry tetragl~me and 9,75 gms of anhydrous ~Ja2CO~. ~h~
flask equipped with a stirring bar, reflux condens2r, : 5 . ~hermometer, and inlet por~. TWO, sold txa~s mai~tained at a temperatuxe of -78C in series were loczt~d do~n-~ream of the reflux condenser. A slight ba~k pressure was maintained on the system with a dry N~ bu~bler.
: 1;.95 gms of ~ ClCF2CF2CF20CFCFO, ~F2Cl : . ~ere added slowly a~ room tempera~ure. There was a small tempera~ure rise, to abou~ 35C ana an evolution of CO2, upon addition of the acld fluoride. The tempera-ture was inereased to 67-68C and held there for 2.5 hours. The product was then distilled from the reactor.
12.59 sms of product was collected and analyzed to contain 97.37% ClCF2CF2CF20CF-CF2. This gave a 0.~0 :: 20 minute peak on the VPC and represents a ~9.3% yield for .. the vinyl ether.

The product was analyzed by IR and showed the . -OCF = CF2 at 1830 wave number.
. 25 19 Analysis o ~he product by F NMR ~er.ified the ClCF2CF2C~20CF = CF2 ~ructure. A proton scan on the NMR showed only a negligible amoun~ o pro~on . containing material.
: 3~

. Tetraglyme (60 ml) and 7.5 grams o~ anhydrous : Na2CO3 were added to a 100 ml 3 neck flask equipped wi~h an air cooled reflux ccndenser, ~hermomete,, . . - 23 -, ~8,981-~ (Di~J. c) ':

magnetic stirrer and dropping funnel. Cold traps "ere located downstream of the re~lux condenser. 2~.9 gr~m~
of a mixture of acid fluorides consi3tins of 35.~%
S ClCF2 CF2 CF2 OCFCFO, 9 . 15% ClCF2 CF2 CF~ OCFCF~, OCFCFO
CF~Cl CF2Cl CF2C' and higher homologs was added dropwise at rcom temper-atuxe. The ~emperat~lre was main~ained at no higher than 30C during the addition and until no ~urther evolution sf C0~ occurred.. The temperatuxe was then raised tQ 70C and held ~h~re until no further evolutio~ of C~2. A ~0 inch vacuum was ~hen applied to the system and the pot temperature raised gradually to 142C while collecting the material boiling overhead.
No appreciable CO2 evolution ocurred during ~he ; distillatio~. 8.2 gms of material were collected that analyzed by VPC as ., .

Peak~
time Yield 0.67 31.9 ClcF2cF2cF2ocF=cF2 3.39 30.4 ClcF2cF2cF2ocFcF2ocF=cF2 CF2Cl S.9~ 3.9 ClCF2CF2CF2 ~ 'CFCF2 ~ CF= CF2 ~F2Cl J2 The balance of ~he material being predominately 30 solvent. ~igher vinyl ether homologs remained in ~he .. flask.

. . .
... .
., .
. - 24 -: 28,981-F (Div. C) s~

Exam~le /
An example of ~he polymerization of Cl ( CF2 ) 3 ~0; CF=CF2 wi~ch fluorocarbon olefins is as .. follows: 3.7 gm of Cl(GF~)3-0-CF=CF2 ~a~ added to 40G S ml deoxyge~ated water containing 3 gm K~S~Oa, 0.75 ~m NaHS03, 1.5 gm Na2HP04 a~d 3.5 gm C~Fl5CG2K under 60 psi applled tetrafluoroethylene pressure in a glass-lined s~ainless s~eel reactor wi~h stirring a~ 20C. After 2 hours, ~he reactor was vented, eva~uated and hea~ed ts 50C to remove residual monomer. The remaining material was ~hen fxozen, thawed, fil~exed, washed repeatedl~
and then vacuum dried for 16 hours at 12~C. The : resulting polymer read~ly pressed into a flexib.le, . tough, transparent film and w~s analyzed to contain 3 lS percent chlorine.
., .
:. ~
As a fur~her example of polymerization of : Cl(CF2 )30CFaCF2 with fluorocarbon olefins:

4.8 ~ms Of Cl(cF2 ~30CF=cF2 . ' , .
were added to 30 ml of ClCF2CFC12 in a stainless steel reactor. Two drops of a 2-ter~. butylazo-2-cyano-4-: -methoxyl-4-methylpentane i~itiator solution were added and the reactor contents frozen to -78C. The reactor overhead was evacuated and 21 gms of te~rafluoroethylene 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 o~ dried pol~mer, a~alyzi~g as containing 2.36% Cl, was recovered.

.,.

.... .
. 28,981-F (Div. C) .

Claims (2)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method of polymerizing at least two compounds, wherein at least one compound of a first group is selected from trifluoro-monochloroethylene; trifluoroethylene; vinylidene fluoride; 1,1-difluoro- 2,2-dichloroethylene; 1,1-difluoro-2-chloroethlyne;
hexafluoropropylene; 1,1,1,3,3-pentafluoropropylene; octafluoro-isobutylene; ethylene; vinyl chloride; and alkyl vinyl ether; and at least one second compound represented by the general formula:
Y(CF2)a(CFRf)bCFR'f-O-CF=CF2 where:
a = 0 or an integer of from 1 to 3;
b = 0 or an integer of from 1 to 3;
R'f and Rf are independently selected from F or Cl; and Y is selected from Cl or Br;
and reacting at least one compound from the first group with the second compound in the presence of an initiator for a period of time and at a temperature sufficient to polymerize said compounds.

2. The method of Claim 1, wherein the compound selected from the first group is chlorotrifluoroethylene.