CA1259336A - Preparation, decarboxylation and polymerization of acid fluorides and resulting monomers - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A method of preparing a monomer of the formula (I) which comprises reacting a compound of the formula for sufficient time and at a sufficient temperature to form said compound (I) wherein a = 0 or an integer greater than 0;
b = 0 or an integer greater than 0;
n = 0 or an integer greater than 0;
m = 0 or an integer greater than 0;
Rf and Rf are independently selected from the group consisting of F, C1, perfluoroalkyl radicals and fluorochloroalkyl radicals;
X = F, C1, Br, or mixtures thereof when n>1;
X' is independently C1 or Br;
Z = F, C1, Br, OH, NRR' or OA;
R and R' are independently selected from the group consisting of hydrogen, an alkyl having one or more than one carbon atom and an aryl;
A = alkali metal, quaternary nitrogen, or R;
Y = I, Br, C1, or F, the monomer thus produced being suitable for copolymerisation to yield poly-mers with desirably modified physical properties, such as lower melting point to facilitate fabrication.

Description

933~

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 from applicants co-pending application Serial No. 379,491 filed on June 10, 1981 (Patent No. 1,187,099) which relates to a method for preparing compounds of the formula Y(CF2)a~(CFRf)b-CFRf - O - ~CF-CF2 ~~ CIF-1=O
2X ' J CF2X ' which comprises reacting a compound of the formula F
X' CF2 - C -- CF2 with a compound of the formula ~Rcf Y(CF2)a - (CFRf)b - = 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.

;~

28,981-F (Div. C) -1-~la ~ z59336 ~ he present invention, together with that of aforementioned Serial No. 379,491 and also Serial No.
438,464, filed October 5, 1983 (Patent No. 1,199,034) and Serial No. 455,616 (filed May 31, 1984) both of which are divisionals from application Serial No.
379,491, will now be further described.
U.S. Paten~ 3,536,733 teaches the pr~paration of compounds represented by the general formula /0\

~-he_e Y is ~ or C~3.
U.S. Paten.ts 3,214,478 and 3,2 2,218 teac:~ a proceC~ ~or pre?arin compour.ds hz~irg the general ~ormula F
. 3 2)2 o - ~ F - C?2 - ~ - CF

: ~ 3 ~ CF3 wnere n is O or an in~eSer sre2ter tnan O.

~' `' 28,981-F (Div. C) -la-~.~53~336 U.S. Patent 3,250,8C6 teaches fluorocarbons having the gPneral formula X'Rf ~ o - (CF2 - CF2 ~ ~) n ~ CF2 - C = O

where o n = 0 to 20;
F.f - perfluoroalkylene radical .

~OY is a carboxylic acid group or a carboxy-lic acid fluoride; and X' is halog~n or hydrogen.

German Patent 1,238,458 teaches the r~action of iodo substitute~ perfluorocar~oxylic 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 wi~h tetrafluoroethylene form melt pro-

2 cessable polymers that can be crosslinked by thermal decomposition of ~he perfluoro alkyl iodide.
-(CF2)n+l O-(CF2C~2O)p-~CFCF2~ -CF=CF~

~CF3 m where n = 1 8 p = 0-5 m = 0-5 ~8,~81-F (Div. C~ -2 ~ 2 59 3 3 6 A specific example being F O F
~ \ CsF
ICF2C=O + CF3CF-CF2 - ~ ICF2CF20CF-C=O
CF~
ZnO ~ ICF2CF20CF=C~2 Eeat U.S. Paten~ 3,450,684 ~eaches the preparation of vinyl ethers by reacting an acld fluoride with hexa-fluoropropylene oxide followed by decarboxylation using an ac~ivator such as ~nO or sili~a according to the following reactions:
X F /
XCF2CF2~ (FCF20~ CF-C=O + CF3CF-CF
~ In-l F
~CF2CF2o~cFcF23 -CF-C=O Activator ~ CF3 XCF2 CF2 O~CFCF2 0~ -CF=CF2 ~X Jn where X is F, Cl, ~, CH3, CF2C1 or CF3 n is at least 1.

Copolymerization of these monomers with tetrafluoroe~hylen forms polymers havirg lower melt ~iscosity than the parent tetrafluoroethylene polymer.

28, 9al-F (Div. C) -3_ ~;259336 U.S. Paten~ 3,'~14,778 teaches the formation of vinyl ethers by reactlng an acid fluoride with hexa-fluoropropylene oxide to produce an intermediate com-pound which may be decar~oxylated to a vinyl ether according t~ the fo~lowing reactions:

F O F
~ \ , RfC=O ~ CF3 CF-CF2 -~ RfCF2 OCFC=O

~h9~ RfCF2 OcF=cF2 where Rf i5, for example, a perfluoroalXyl radical.
Homopolymers and copolymers, w1th tetrafluoroethylene, of the vinyl ethers is taught.

Fearn, et al, ~ournal of Polymer Science:
Part A- , Vol. 4, i31-140(1966) discloses that in the pyrolysis of sodium salts of carboxylic acids whlch con~ai~ fluorin~ and chlorine in the beta position, sodium cbloride is preferentially, but not exclusively eliminated. For example:

ONa ClCF2CFClCF2CFClCF?C=O ~
ClCF2CFClCF2CF=CF2 + CFCF2CFClCF2CCl=CF2 U.S. Patent 3,282,875 shows decarboxylatlon 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 o~ta-ned.

28,981-F (~i~i. C) -4-R. D. Chambers, in his book, Fluorine in Orqanic Chemi~ , published by John Wiley & Sons, 1973, pages 211-212, teahes that carboxylic acid derivativesmay be converted to oleinfs. The conversion involves the loss of carbon di~xide and forms an intermediate carbanion. The intermediate then looses NaF to form the resulting olefin.
Evans et al., in the Journal of Orqanic Chemistry, Vol~ 33, page 183B, (1968) describes catalysts useful for the reaction etween acid fluorides and epoxides.
M. Hudlicky in ChemistrY of Or~anic Fluorine Compounds - 2nd Edition, John Wiley 6 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:

peroxide RfCF2I + CF2 = CF2 > RfCF2I + CF2 = CF2 Various methods for polymerization are taught in the following references: Emulsion Polymerication -Theory and Practice by D. C. Blaceley, John Wiley &

3 Sons; U.S. 3,041,317; U.S. 2,393,967; U.S. 2,559,752, U.S. 2,593,583.

28,981-F (Div. C) -5-1;25~33 The present invention resides in a method or preparing a compound of the formula:

Y ( CF2 3 a ~ CFRf ) bCFR ' fO --~CFCF2(~--~CFCF2~ -- CF = CF2 ( I

~ Jn+l ~ Jm which comprises reacting a compound of the formula:

z Y ( CF2 ) a ( CFRf ) bCFR ' fO --~CFCF2~--~CFCF2~-- CFC = O

~ Jn+l ~ Jm for a sufficient time and at a sufficient temperature to form said compound (I);
where:
a = 0 or an integer greater than 0;
b = 0 or an integer greater than 0;
m = an integer of from l to 6;
n = 0 or an integer greater than 0;
Rf and R ' f are independently selected from the group consisting of F, Cl, perfluoroalkyl radicals and fluorochloroalkyl radicals;
X = F, Cl, Br, or mixtures thereof when n>l;
X' is independently Cl or Br;
Z = F, Cl, Br, OH, NRR' or OA;
R and R' are independently selected from the group consisting of hydrogen, an alkyl having one or more than one carbon atom and an aryl;
A = alkali metal, quaternary nitrogen, or R;
Y = I, Br, Cl, or F.

28,981-F (Div. C) -6-.. ,. ~, ....
!

--7-- ....
~25~336 The present invention relates to a method of polymerizing at least two compounds, wherein at lezst one compound is selected from a first group of compounds represented by the general formula:

2)a( )~ ~ 2 where a = O to 3;
b = O to 3;
RI æ~.d ~r are indepencently selec~ed from ~ie grou? consis.ing of F znd Cl; .
~ = Cl cr Br;
and at least one o~ier compc~nd is selected from e sccond srou~ o~~ csmpounds s21 ected from t~e grou~
corsisti~g o~: trifluoromonochloroe~hylene, trifluoro-e iyiene, vinylicene ~luoride, l,l-difluoro-2,2-di .
c:~lo~oethylene, l,l-dlfluoro-2-c:~loro~e:cz~luoropropy-lene, l,1,1,3,~-penta~luoropropylene, oc~-~luoro~ropy-lene e~ylene, vinyl chloride, zna alkyl vir.yl et~er;
said me_hod consis.ing essentially of ~ezcting at least one compound.from the first group with zt lezst one compound from the second group in the presence o an initiator for a su~icient time ~nd a suf,~icient temperature to ~olymerize said compounds.

28,981~F (Div. C) -7-. . , . ~ . .

~;~59336 -7a-For example, when Y - Cl, Br, F or I, the monomer of the general formula ~ when incorpora,ed (by copolymerization~ into polymers of such as tetrafluoro-ethylene, chlorotrifluaroethyiene or t;ne like, impart use~ul properties. The copolymers are lower melting, tnus facilitating f~brication. This property becomes e~t-emelv ~mportant in the case where the parent polymer is derived from te~rafluoroe~hylene. It would be dif~-icult, if not impossible, to fabricate the polymer by conventionzl means such as melt e~trusion without incorporation of 2 second component such as the abo~e moncmer. In addition to modifyina pnysical propexties, incorporatin~ monomers 2erived from the intexmediaates where Y = Cl or ~r in polymers cf 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 wi~h sodium vapor affect their chemical integrity. Introduction of controlled amounts of the present monomers result in ~8,981-F (Div. C) -7a-:3 %5~336 ~he polymers having a group more chemically reactive ~han is the case wi~h the perfluoropolymers. Reaction wlth strong bases such as alkyl alkali metals can lead to intermediates useful for chemical modification such as i~troducing sulfonate ~roup~ for we~tability of the polymers. In addition to the above uses' addition of a monomer deriv~d fro~ ~he prese~t invention ~o copoly-mers of monomers having ion exchange func~ionality and tetrafluoroethylene to form terpolymers, for example when Y = C1, that ha~e )h ~ 2)i ( 2 2) F2CF n F2CF n O O
(CF2)a(CF2)a Cl SO2O~

superior electrical properties compared ~o the copolymers alone when used as ion e~change membranes in ~hlor-alkali cells.

The radical X is chosen from the halogens Cl, Br or F, while X' is chosen from C1 or Br. While iodi~e would also be a useful radical for X or X', formation of the ethers by ~he chemistry taught herein is hampered by side reactions causing low or non-existant yields to the desir~d compounds.

The intermediate compounds of the present in~e~tion are con~eniently prepared by reacting an acylfluoride or ketone of the gener~l formula R f Y(CF2)a - (CFRf.)b - C = o 28,981~F (Div. C)-8_ w1th a perhalo1uoro propylene epoxide o the fonrula / \

s .where Y, R~, Rf, and X are as defined above, the reactions are done in the presence of a fluoride ion yielding compound (MF-catalyst) at from below about -20C to above about 50C, in the li~uid state, desirably in a liquid sol~ent for the intermediate fluoroalkoxide Y(CF2 )a ~ (CERf)b - CFRfO M formed between th~ acid fluoride or ke~one R f Y(CF2 )a ~ (CFRf)}~ - 'C = o and the metal or ammonium fluoride ion yielding catalyst (MF ) . The reac~ions proceed generally according to the equation o R~
(X' )XCF~-CFCF2 + Y(C~2 )a-(CFE~f)b-C=O
F

Y(CF2)a - (CFRf)b - CFRf - O -~CF - CF2 - O -)CF - C = O
\~,F2X ' ~,CF2X' where a = 0 or integer greater t~an 0;
b ~ Q or integer greater than 0;
n = O or an integer greater than O;
Rf and Rf are independently selected from the group consisting of F, Cl, perfluoroalkyl and fluorochloroalkyl;
X = F, Cl, Br or mixtureC thereof when n>1;

g 2 8, 98 1 ~F ( Div . C ) ~;~5~3336 x ~ = cl or ~ri 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 = ~ the reaction can ~e done in either one or two steps. In this case, the flrst reaction of the fluoride ion is with the halofluoropropylene oxide compound rather than with the carbonyl of the subs~ituted fiuorocarbon acid ~luoride. A fluorocar~on alko~ide is produced by this reac~ion which can either react wi~h additional epoxide or lose fluoride ion to produce an acid fluoride.

- / \ .
F ~ XCF2CF-CF2 ~ XCF2cF2cF20 // ' F
XCF2CF2C=O I F ~ ~cF2cF-cF2 F + XCF2CF2CF~OCFC=O = XCF2CF2CF20CFCF20 As can be seen from the above scheme, it is possible ~o re~rrange the epoxide to acid fluoride with fluoride ion and then use the acid fluoride as demon~
stra~ed by the gene.ral scheme or one can simply react the epoxide in the presence of fluorlde ion in a single step withou~ isolation of the intermediate acid fluoride.

Conversion of acid halides such as.the acid fluorides described herein to carboxylic acids and 2a, 981-F (Div. C) : LZS9336 derivatives by re~cticn with nucleophiles are well known to those sXilled in the art. For example, con-~ersio~ o~ the ac~d fluoride to ~he corresponding car~oxylic acid is easily accomplished by reaction with water. Conversion to esters or amides is accomplished by reaction wi~h alcohols or amines, respecti~ely. The carboxylic acid intermediates (Z=OH) are easily con-verted to acid chlorides and bromides (Z = Cl, Br) by reaction with appropriate hàlogenation agents such as PC15 and PBr5.

Optlonal, additional reactions of the carboxylic acld fluorides proceed according to _he following equation:

F
Y(CF2)a - (CFRf~b - CFRf - O -~CF - CF2 - O ~ CF - C = O
~CF2 X ,,~ CF2 X ' 20, + PZ' Y(CF2)a - (CFRf)b - CFRf - O - ~F CF2 - ~ - CF - C - o ~F2X Jn OE2x where a = is 0 or an integer greater tha~ 0;
b = is 0 or an integer greater th~n 0;
n = is 0 or an integer greater than 0i Rf and Rf are independently selected from the group consisting of F, Cl, perfluoroalkyl and fluorochloroalkyl;
X = F, C1, 3r or mixtures thereof when n>L;

28,981-F (~iv. C) ~;~5~3`36 X' = C1 or Bri Y is 1, Br, C1 or F;
Z' = OH, NRR' or OR;
R ~nd R' are independently selected from the group consisting of hydrogen, an alkyl havi~g one or more than one carbon atom and aryl; and P is a cation or capable of forming a cation, ~ uch as Na , ~ , H , etc.

It is of course to be understood that the ratio of' rea~tants, t~he temperature of reac~lon, the amvunt of ca~alys~, 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 th~ value of n in the g~neric 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.~ 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 employlng greater than 1 mole epoxide compound per mole of acid fluoride compound, i.e., 2 to 1, respectively, results in a product having a 3:9.1 ra~io of ~=2: n=l:n=O products. ~he ratio of reactan~s thus can ra~ge, for practical purposes, from about 2 to 3 moles of the acylfluoride per mole of the ha1ofluoro epoxide to 1 to 20 moles of the epoxide per mole of the 3a acyl fluoride, the high acyl fluoride to epoxide pro-ducing predominan~ly the n=O and the high epoxide toacyl fluoride producing the n=2-12 ether, respectively, and mixtures thereof.

2~,981-F (Div. C) - 12 -~;~5~333~

Solvents employed in accordance with the present invention should be nonreact~ve (i.e., do not conta1n hydroxyl groups) a~d have at least a solubility for the reactants and the intermediate fluoroalkoxlde foLmed ~etween the acyl fluoride or ketone c~mpound and the ca~ lyst. Whe~her or not the products are signifi-cantly soluble in t~e solvent is a matter of choice ar.a can be used as a controlling factor for selectlvely control1ing the n value in the final product. For example, _f 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 intermedlates (n=0 and n=1) time to react to produce the fin~l n=l, 2 or higher product. In addition, the amount of solvent can be adjusted to acco~plish somewhat s1milar results.
Sultable sol~ents which may be employed to take ad-vantag~ of ~e solubility plus amount factor are tetraglyme, diglyme, glyme, acetonitrile, nitrobenzene and the like. Exemplary of a preferred solvent is tetraglyme which has a suitable solvency for the intermediate.

Substantially any fluoride ionizable at the reaction temper~tures may be used as a catalyst, however, CsF and KF are the most preferred but AgF, tetra alkyl ammonium fluoride a~ well as others listed in Evans, et al., ~ L~ 33 1837 (1968) may be employed wlth satisfactory results.

The temperature of ~he reaction also ef-~ec~uates a controlling factor on the end product obt ined. For example, low temperatures such as -20C
favor n=0 products and higher temperatures, 50C and above, favor higher n valuPs.

28,981-F (Div. C) - 13 -:1~2593~6 It has been discovered that the intermediates discussed aDOVe decarboxylate under far milder ccndi-tion3 and ln excellent ylelds compared to those of the pr-or art F
~OCF-C=O
CF2 X ' where X' = Br, Cl as opposed to X' = F.

It has repeatedly been taught that pr~fer-entlal methods for the decar~oxylation of compounds whereX'=F involve pyrolysis with activators such as ZnO at temper~tures between 300 and 600C. While it is taught that these reactions do proceed at lower temperatures wi~h some bases, these me~hods are generally inferior to the high temperature methods beca~se of lower yields (U.S. Patent 3,282,875). While the intermediates of the present in~ention decarboxylate readily by the extreme .
conditions reported in tXe prior art, such conditions are neither required or desirable. These intermediates decarboxylate 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.

rn addition to the ease of reaction as discussed above, the r~ear quantitative yield to only the fluorine substituted olefin group is surprising.
It is generally accepted that convers.ion of carbo~Yylic acid derivatives to olefins involves loss of carbon 28,981-F (Div. c) - 14 -3L'~S933~

dioxide to form an intermediate carbanion. In the .
present inventlon, this reaction could conceivably produce the intermediate shown below.
~OCF Na where X'=Cl or Br CF2 X ' ~ is intermediate then loses NaX' to form the resulting lQ olefin.

~OCF Na ~OCF=CF2 ~ NaX' CF2X ' In th.is intermediate, it is po.sslble to eliminate either NaX' or NaF. Elimination of NaF would result in ano~her olefin, ~OCF=CFX', which w~uld not be particu-larly useful for subsequent polymerization reactions and would thus re~uire a tedious purification procedure for its removaL. While it is not particularly sur-prising that loss of NaX' predominates in the reactio~, 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 f~l-lowing pyrolysis, though elimina~ion of NaCl pre-dominates.
-NaCl ~ ClCF2CFClCF2CF-CF2 (84%) ONa ClCF2CFClCF2CFClCF2C=O
~ ClCF2CFClCF~CCl=CF.
-NaF

2a, 981-F (Div. c! - 15 -~'~ S~ 3 3~

Anal~tical results 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 clefins s prepared by decarboxylation of the aci~ f~uoride 1nter-mediates of the pxesent lnvention.

In general, the polymerization procedures ~nd techniques followed ln the present invention are known.
A very good reference for polymerizatibn techniques is Emulsion Pol~merlzation - TheorY_and Practice, by D. C.
~lackley, published by John Wiley & Sons.

Additionally, the ccpolymer used in the pr~sent i~ve~tion may be prepared by general polymeri zation technigues developed for homo- and copolymer-iza~ions 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 ~1, that is by the polymerization of a mixture of the major monomer therein, such as tetra-fluoroethylene, and a fluorinated ethyle~e containing sulfonyl fluoride in the presence of a free radical initiator, 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 carri~d out in the presence of a fluorinated solvent. Suitable fluorinated solvents are inert, li~uid, perfluorinated hydrocar~ons, such as perfluoromethylcyclohexane, perfluorodimethylcyclobutane, perfluorooctane, per-fluorobenzene and the like.

28,981-F (Div. C) - 16 -~'~S9336 Aqueous technlques which may also be used fo~
preparlng the copolymer used in ~his invention inclu~e contacting the monomers with an aaueous medlum con-talning a free-radical initiator to obtain a slurry of polymer particles in non-waterwet or granular form, as disclosed in U.5. Pat. No. 2,~9~,967 to Brubaker or conta~ting the monomers with an aqueous medium contain-ing both a free-radical initiator and a technologically inactive dispersing agent, to obtain an aqueous col-loid~l dispersion of polymer particles and coagulatingthe dispersion, as disclosed, for exam~le, in U.S. Pat.
No. 2,559,752 to Berry and U.S. Pat. No. 2,5~3,583 to ~ontz.

It is particularly benefici~l to form polymers from ~he vinyl ether monomers of the present inventlon where Y=Cl and Br and not iodine. It is well known, M.
~udlicky, Chemistry of Organic Fluorine Compounds, 2nd Edition, John Wiley & Sons, New York, pages 4~0-421, that perfluoroalkyl iodides react under mild cond~tions with fluorovinyl compounds, such as tetraflu~ro-ethylene, to form telomeric perfluoroalkyl iodides.
q RfCF2I + CF2=CF2 PeroxideJ RfCF2(CF2CF2)nI

This reaction can be iniated with either peroxide compounds or heat. The prior art teaches copolymers of tetrafluoroethylene and iodoperfluoro-alkyl vinyl ethexs as useful since on heating they loseiodine and for~ crosslinked fluorocarbon resins.
Formation of high molecular weight, linear polymers ~rom iodo substituted monomers ls severely restricted, at best, because of competing reactions of the alkyl 28,981-F (Div. C) - 17 -:~2S933~

iodide moiety wlth the olefinlc molety enter1ng into the polymerizat1on reactlon. At least, highlv branched, low molecular weight polymerlc materials can be formed using conventional polymerization techni~ues.
Format~on o~ strong flexible films or structural materials, from the polymer~, usually associated with high molecular weight plastic materials, would be essentially eliminated.
Peroxide or heat iniated reactions of per-fluoxoalkyl chlorides or bromides, particularly chlorides, with olefins does not take place nearly as readily as perfluoroalkyl iodides. In fact, fllloro-chloro compounds are not known to take par~, via the chloro substituen~, in this reaction. Thus, it ls possible, using the vinyl ether monomers of the present i;lven~ion, to form high molecular welght, plastic type materials by copolymerizing with other vinyl monomers, such as tetrafluoroethylene, by conventional poly-merization techniques; known for producing fluoropolymers.The resulting polymexs have the added feature of having a reaction site (Y), known to be more reactive than perfluoro~olymers where any additional reaction would have to take part on a fluoro substituent. Only few reactions and these requiring extreme conditlons are known to take place at a C-F linka~e. In fact, the non reactivity of this linkage accoun~s for the commercial significance of known fluoropolymers. Fluorocompounds having C1, ~r, and I substituents are known to take 3~ part in metallation reactions with such metallating reagents as alkyl alkali metals to produce reactive intermediates that undergo a variety of reactions.

Z8,921-F (Di~7. C) - 18 -.~ 5~ 33 6 Ex~mole 1 50 ml dry tetraglyme and 8.35 gm CsF were added to a 100 ml 3-neck flask equipped wit~ a stirrer, thermometer, (~78C) reflux con~enser and an lnlet port. Two cold ~raps ;n serLes a~d maintal~ed at a temperature of -78C were con~ected downstre~m of the reflu~ condenser. A sl_gh~ back pressuxe was maintained on the system wl~h dry N2. The ~etraglyme and CsF were mixed for 45 min. to 1 hour. The reactor was cooled to 0C to 10C and 7.26 gm ClCF~COF was added slowly through ~he inlet port, controlled to barely observed condensation on the re~lux condenser. The ml.Y~ur~ was stlrred for 1 hour at room ~.:emperature.

/ \
Ten ~ram~ of ClCF2CF---C~2 were added to the mlxture limiting the addition by observing the reflux off ~.e condenser. The mixture was allowed to stir for an hour. The product which separated as a ~o~tom layer, after stirring was stopped, and contained 3.0 gm ClCF2CF20CFCOF, . CF2Cl .38 gm ClCF2CF20;CFCF20CFCOF
CF2Cl CF2Cl and .05 gm ClCF2CF20CFCF20CFCF20CFCOF i dentifi ed by ~PC
, - CF2Cl CF2Cl CF~Cl peaks at lo 00 min., 5.82 min. and 9.39 min. on 6 f~.
1/8" columns 20% Viton~ A on 80-100 mesh Celite~ at 20ml/min. carrier flow and temperature programmed at 4 min. at 60C ~o 220C a~ 16/mln. Mass sp~ctroscopv confirmed the structures shown above.

~a,gal-F (~-v. c) - 19 -9~36 Exam~le 2 50 ml dry tetraglyme and ~ gm ~a2CO~ were added to a 100 nl three-neck flask fitted with a stirrer, hea~ing mantle, thermometer, an additlon funnel and stillh ad with a vacuum ~ake off adapter with a collec~io~ vessel in a (-78C) bath. A dry N2 ~ad was used to maintaln dry conditions prior to adding of the acid fluoride additlon products. The acid fluorlde addition product mixture from Example ~ containing 3 gm n=0, .7 gm n=l and a small amount (0.1 sm) n=2 acid f ! uorides was added dropwise to the stirrin~ reactor mixture with accompanying evolution of gas. Following the completion of the addition, the reac~or con_ents were s~irred until no further gas evolution was observed at which tlme the heating mantle was turned on and the temperature in the vessel was raised slowly to 120C with a vacuum of 20 in. ~g applied. Further gas evolutlon was obser~ed over the range of 60C-80C.
The reactor was cooled back down and 1.4 gm of product was collected in the container, the VPC showed a peak at .59 min. which was identified as ClCF~CF~.OCF=CF2.
The product has an I.R~ band @ 1835 cm l and a Fl~ NMR
spectrum consistant with the trifluorovinyl-oxo group.

Example 3 Dry tetraglyme (25 ml) and 20.8 gms of CsF
were added ~o a 200 ml, 3 neck flask equipped wlth magnetic stirrer, reflux condenser maintained at a temperature of -73C, thermometer and gas inlet tube.
The contents were allowed to mix for ~0 minutes.

~he reactor contents were then cooled o / \
to 0-5C and 25 gms of ClCF CF ~F2 added slowly after 28;981-F (Div. c) - 20 -~2S~33~

which the contents were mixed for an addltional 40 minutes. Another 25 gms of epoxide was then added in the same manner as described above. Two hours after the epo~ide addition, with the contents at 0-5C, the product was distilled from the flask at 30 inches of vacu~m while heating the flask up to ~50C. The maximum o~erhead temperature was 129C. The produc~
distilled in this manner (20.9 gms) was an lyzed by VFC
uslng ~ie same column and program as described in the 1~ a~ove examples.

Peak tlme Wt.
(min) Ratio comPosition lS l . 3 5 4 ClCF2 CF2 CF2 OCFCO~
CF2 Cl F

6 . 79 2 ClCF2CF2CF20 (~FCF~O) CFCC~

9 . a 6 1 Cl CF2 CF2 CF2 0 ~CFCF2 O~ CFC:~
~CF2 Cl J CF2 Cl F

Exam~le 4 Z5 17 gm of a mixture containing 68%

ClCF2CF2CF2OCF(CF2Cl)C~F and higher homologs as analyzed by GC-mass spectrography was added dropwise to a stirred 3 nec~ reaction vessel con~aining 50 ml dried tetra-glyme and 7 .1 gm dried Na2 C03 and fitted with a thermometer, heatin~ mantle, a~d a stillhead with vacuum takeoff and double dry ice acetone trap under inert purge. Gas evolution was obser~,~ed and a tempe~ature rise from 25C
.

28,981-F (Div. C) 21 -up to.33C was observed during addltion. After continued stirring for 1 hour, a 5 mm vacuum was applied and the t~mper~ture was raised slowly up to 100C in the ~Tessei. Seven grams of matPrial was collected in the ~rima~y collection receiver and identified as 97.1%
ClCF2CF2C~2OCF=CF2. Raising the temperature under vacuum, up to 145C, resulted in collection of an addi-tiona.l 2 sm material which was analyzed by GC mass spe~trography and I.R. as 22.35% ClCF2CF2CF20CF=CF2 representing an 81% yield of ClCF2CF2CF20CF=CF2. VPC
. anal~-sis of the solvent in the reaction vessel showed some ClCF2CF~CF2OCF=CF2 remaining along wi~h higher homologs.
Compara~iv~ E~ample 4 A mix~ure (35 gms) containing 31.7% of CF3CF2CF20CFCFO plus higher homologs was added to a ~F3 mixture of 1$.5 gms Na2CO3 in S0 ml of tetraglyme at room temperature. After several hours and cessa~ion of CO2 e~olution, the mixture was raised to 120~C 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 ~esulted in little or no evidence, by VPC and I.R., of vinyl ether formation.
The temperature of the reactor was then raised to 160-170C under atmospheric pressure. Under these conditions, boiling of the mixture resulted. ~he 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.
, 28, 981~F (Div. C) - 22 -~5~6 Exam To a 100 ml 3 neck flask were added 50 ml of dry tetraglyme and 9.75 gms of.anhydrous Na2CO~. The flask equipped with a stirring bar, reflux condenser, thermometer, and inlet port. Two, cold tra~s malntalned at a temperature of -78C in series were locat2d downw ~tream of thP reflux condenser. A slight baok pressure ~as maintained on the system with a dry N2 bubbler.
1~.95 gms of ClCF2CF2CF2OCFCFO, CF2Cl were added slowly at room ~emperature. There was a small temperature rise, to about 35C anc an e~olution of CO2, upon addition of the acid fluoride. ~he tempera-ture was incxeased to 67-68C and~ held there for 2.S
hours. The product was then distill~d from the reactor.
12.5~ gms of product was collected and analyzed to ~o~tain 97.37% ClCF2CF2CF2OCF=CF2. This gave a 0.60 minute peak on the VPC and represents a 9g.3% yield for the ~inyl ether.

The product was analyzed by IR and showed the -OCF = CF2 at 1830 wave number.

Analysis of the product by F NMR ~er,ified the ClCF2CF2CF20CF = CF2 s~ructure. A proton scan on the NMR showed only a negligible amount of proton contalninq material.

Example 6 Tetraglyme (60 ml) and 7.5 grams o~f anhydrous Na2 C03 were added to a 100 ml 3 neck flask equipped wlt~ an air cooled reflux ccndenser, _hermometer, 28,981-F (Di~. c) ~;~3336 magnetic stirrer and dropplng funnel. Cold traps ~ere located downstream of the reflux condenser. 23.9 grams of a mix~ure of acid fluorides consistins of 35.9%
CiCF2CF2CF2OCFCFO, 3O15% ClCF2CF2CF20CFCF2OCFCFO
CF Cl CF2Cl CF2C' and higher homologs was added dropwise at rGom temper-ature. T~e temperature was maintained at no higher than 30C duriny the addition and untll no further evolutlon of CO~ occurred. The temperature was then raised to 70C and held there until no further evolution of CO2. A ^0 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 ~ms of ma~erial were collected that analyzed by VPC as Peak time Yield ~min~ Co~m~osition 0.6731.9 ClcFzcF2cF2ocF=cF2 3.3930.4 ClcF2cF2cF2ocFcF2ocF=cF2 f ~
5.98 3.9 ClCF2CF2CF20_7'CFCF2 ~ CF= CF2 ~F2Cl J2 The balance of the material being predominately solvent. ~lgher vinyl ether homologs remained in the flask.

28,981-F (Div. C~ - 24 -. .

l;~S33~6 Exam~le 7 An example of the polymerizatlon of Cl(CF,)~-0-CF=CF2 with fluorocarbon olefins is as follows: 3.7 gm of Cl(CF~)3-o-CF=CF2 ~as added to 400 S ml deoxygenated water containing 3 gm K~S~8~ 075 gm NaHS03, 1.5 gm Na2HP04 and 3.5 ~m C7Fl5CG2K under 60 psi applied tetrafluoroethylene pressure in a glass-lined stainless steel reactor with stirring at 20aC. After 2 hours, the reactor was vented, eva~uated and heated to 50C to remove residual monomer. The remainlnq material was then frozen, ~hawed, filtered, washed repeatedly and then vacuum dried for 16 hours a~ 120~C. The resulting polymer readlly pressed into a flexible, tough, transparent film and was analyzed to contain 3 percent chlorine.

ExamPle 8 As a further ex~mple of polymerization of Cl(CF2)30CF=CF2 with fluorocarbon olefins:

4.8 gms of Cl(CF2)30CF=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-methylpentane initiator solution were added and the reactor contents frozen to -78C. The reactor overhead was evacuated and 21 gms of tetrafluoroethylene was condensed into the reactor. ~he reactor was heated to 55C and shaken for 16 hrs. After ventin~ the reactor and evaporation of the solvent, 14 gms or dried polymer, analyziny as containing 2.36% Cl, was recovered.

28,981-F (Div. C) 25 -

Claims (12)

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

1. A method of preparing a compound of the formula:

(I) which comprises reacting a compound of the formula:

for a sufficient time and at a sufficient temperature to form said compound (I);

where:
a = 0 or an integer greater than 0;
b = 0 or an integer greater than 0;
m = an integer of from 1 to 6;
n = 0 or an integer greater than 0;
Rf and R'f are independently selected from the group consisting of F, C1, perfluoroalkyl radicals and fluorochloroalkyl radicals;
X = F, C1, Br, or mixtures thereof when n>1;
X' is independently C1 or Br;
Z = F, C1, Br, OH, NRR' or OA;
R and R' are independently selected from the group consisting of hydrogen, an alkyl having one or more than one carbon atom and an aryl;
A = alkali metal, quaternary nitrogen, or R;
Y = I, Br, C1, or F.

2. The method of Claim 1 where a = 0-3;
b = 0-3; and n = 0-6.

3. The method of Claim 1 where Rf and R'f = F.

4. The method of Claim 1 where n = 0 and m = 0.

5. The method of Claim 4 where X = F.

6. The method of Claim 1 where Y = C1 or F.

7. The method of Claim 1 where Z = F.

8. The method of Claim 1 where the reaction is conducted in the presence of a base.

9. The method of Claim 1 where the base is sodium carbonate.

10. The method of Claim 1 where the reaction temperature is less than 300°C.

11. The method of Claim 1 where the reaction temperature is less than 200°C.

12. The method of Claim 1 where the reaction temperature is less than 100°C.