DE2753886A1 - POLYFLUORALLYLOXY COMPOUNDS AND METHOD FOR PRODUCING THE SAME - Google Patents

Description

December 2, 1977 CR 7704 A

EGG. DU PONT DE NEMORS AND COMPANY 10th and Market Streets, Wilmington, Delaware 19 898, V.St.A.

Polyfluoroallyloxy compounds and methods of making the same

809823/0878

CR 7704 A 10

The invention relates to polyfluoroallyloxy compounds, processes for making the same and copolymers made from the compounds.

State of the art

1. US Pat. No. 2,856,435 describes the preparation of perfluoroallyloxy-1,1-dihydroperfluoroalkanes from 3-chloropentafluoropropene and 1,1-dihydroperfluoroalkanol in an alkaline medium, for example CF ₂ = CFCF _{2 Cl + HOCH 2} CF ₃ - CF ₂ = CFCF ₂ OCH ₂ CF ₅ .

2. US Pat. No. 2,671,799 describes a process for replacing the chlorine atom in perfluoroallyl chloride (3-chloropentafluoropropene) by methoxy, cyano, iodine and nitrate groups, e.g.

CF ₂ = CFCF ₂ Cl + NaOCH ₃ > CF ₂ = CFCF ₂ OCH ₃ .

3. NE Redwood and CJ. Willis describe in "Canad. J. Chem. ¹¹ , Volume 45, Page 389 (1967), the reaction of allyl bromide with cesium heptafluoro-2-propylate to form 2-allyloxyheptafluoropropane:

CH ₂ = CHCH ₂ Br + (CF ₃ J ₂ CFO ^- Cs ⁺ > CH ₂ = CHCH ₂ OCF (CF ₃ ) ₂ + CsBr.

4. J.A. Young gives in "Fluorine Chemistry Reviews", Volume 1, Pages 389-393 (1967), an overview of the formation of perfluoro alcoholate anions by the action of alkali fluorides on perfluoroketones, perfluoroalkyloxiranes, perfluorocarboxylic acid fluorides and perfluoroalkyl fluorosulfates. The following References Nos. 5 to 9 are examples of the nucleophilic reactions of perfluoro alcoholate anions.

5. US Pat. No. 3,450,684 describes the preparation of fluorocarbon polyethers and their polymers by reaction

809823/0878

of perfluoroalkanoyl fluorides with potassium or quaternary Ammonium fluoride and hexafluoropropene epoxide, i.e.

R _f COF ♦ CF ₃ -CF- ^ CP ₂ -> R _f CF ₂ OCFCOF

Ό CF ₃

6. U.S. Patent 3,674,820 describes the reaction of fluoroketones with an alkali fluoride and an ω-haloalkanecarboxylic acid ester to give a cj- (perfluoroalkoxy) alkanecarboxylic acid ester, e.g.

(CF ₃ ) ₂ CO + KF + Br (CH ₂ J _{4 CO 2} CH ₃ >

(CFj) ₂ CFO (CH ₂ J ₄ CO ₂ CH ₃ .

7. US Pat. No. 3,795,684 likewise describes the reaction of hexafluoroacetone with potassium fluoride and an ω-haloalkanecarboxylic acid ester.

8. U.S. Patent 3,527,742 describes the reduction of the compounds described in Reference No. 6 to the corresponding alcohols and their esterification to polymerizable acrylic acid esters.

9. US Pat. No. 3,799,992 describes the preparation of (perfluoroalkoxy) vinyl compounds by reacting a perfluoroketone with an alkali fluoride and a 1,2-dihaloethane and then splitting off hydrogen halide from the intermediate 2-perfluoroalkoxyhaloethane, e.g.

(CF ₃ J ₂ CO + KF + BrCH ₂ CH ₂ Br - *

(CF ₃ J ₂ CFOCH ₂ CH ₂ Br (CF ₃ J ₂ CFOCH-CH ₂

10. US Pat. No. 3,321,532 describes the rearrangement of perfluoro-2-alkoxyalkanoyl fluorides into perfluoroalkopcyolefins by Passing over a metal oxide at 100 to 400 ° C, e.g.

809823/0878

CR 7704 A

OCF ₃

ZnO + CF ₃ CF-COF - CF ₃ OCF-CF ₂ + ZnF ₂ + CO ₂ .

The invention

The invention relates to a polyfluoroallyloxy compound the general formula

VD
CF-C-CF-O-CG

ZX E »

in the

X has the meaning -Cl or -F,

W and Z independently of one another have the meaning -F and

together can form the radical -CF ₂ -, D independently means -F,

CF ₂ -CFCF ₂ O

2 2

or -Rp, where -R "is a linear or branched- chain perfluoroalkyl radical with 1 to 10 carbon atoms , which must not be interrupted by 1 to 4 oxygen atoms more often than at every second carbon atom , and which has 0 to 2 functional groups of the composition - SO ₂ F, -COF, -CO ₂ H, -CO ₂ R ³ , -Cl, ^ OCF ₂ CF-CF ₂ or -OCF ₂ CO ₂ R ³ , where R ^{3 is} -CH ₃ or -C ₂ Hc has

independently has the meaning -F, -CF ₃ , -CF ₂ Cl, -CF ₂ CO ₂ R or -RpOCF (G) ₂ , in which R ^{3 has} the above meaning , and and E together is a 5- or 6-membered ring can form from members -Rp-, where R _{p is} a perfluoroalkylene chain of 4 or 5 members, which may only be interrupted by 1 or 2 oxygen atoms and 0 to 2 -CF ₃ groups

809823/0878

may have as substituents, or a remainder of the composition

CFf ^

means while G has the meaning -F or -CF.

The invention also relates to a process for the preparation of polyfluoroallyloxy compounds, which consists in that man

(1) a carbonyl compound represented by the general formula

O A-C-B,

in the

A can independently have the meaning -F, -COCF, or -Rp, in which Rp is a linear or branched-chain perfluoroalkyl radical with 1 to 10 carbon atoms, which may not be interrupted by 1 to 4 oxygen atoms more often than at every second carbon atom and 0 to 2 functional groups of the composition -SO ₂ F, -SO ₂ OCF ₂ CH ,, -COF, -Cl, -OCF ₂ CF = CF ₂ or -CO ₂ R, where R is -CH, or -C ₂ H ^ has,

B is independently a radical -F, -CF ₁ , -CF 2 Cl, CF ₂ CO ₂ R, where R is as defined above, or -CF ₂ ORp, where Rp is as defined above, and

A and B together can form a 5- or 6-membered ring of members of the composition -R _p -, in which Rp is a 4- to 5-membered perfluoroalkylene chain which is interrupted only by 1 or 2 oxygen atoms

809823/0878

CR 7704 A

may, means, and the 0 to 2 trifluoromethyl groups may have as a substituent,

mixed with a metal fluoride of the general formula KF and lets react, in which M has the meaning K-, Rb-, Cs- or R ^ N-, where the radicals -R are identical or different can be and are alkyl radicals having 1 to 6 carbon atoms, and

(2) The mixture obtained in (1) with a perfluoroallyl compound of the general formula

Z CF = C-CF

I Il

WXY

mixes in the

X has the meaning -Cl or -F, W and Z independently have the meaning -F or together

form a -CF ₂ radical, and Y is -Cl or -OSO ₂ F.

The invention also provides a copolymer of the above-mentioned polyfluoroallyloxy compound and at least one Ethylenically unsaturated monomers are available.

The invention relates to compounds of the following general formula 4, which ^{are prepared from starting materials 1_ ȣ and} 3 ^{according to the} following equation:

Z 0 WD j

% -CCF + MP + ACB > SCCOCG + Iff

809823/0878

CR 7704 A _f5

In the above equation, the starting materials 1 ,, 2 and 3 react to form the product f »and a metal salt £. The letters A, B, D, E, G ₁ H ₁ W, X ₁ Y and Z have the above meanings. Products of general formula 4 can be converted into valuable copolymers in particular with tetrafluoroethylene, trifluoroethylene, vinylidene fluoride and monochlorotrifluoroethylene.

The preferred polyfluoroallyloxy compounds of general formula 4 are compounds in which D and E have the meanings given for the independent radicals, where D preferably the meaning -F or R ₁ , and E preferably the meaning

B-X -x

tung -F, -CF ,, -CF ₂ Cl or CF ₂ CO ₂ R, where R ^ is a methyl or ethyl radical. In the preferred compounds, W and Z also have the meanings given for the independent radicals, and X is a fluorine atom. Rp is preferably a linear or branched-chain perfluoroalkyl radical with 1 to 8 carbon atoms, which must not be interrupted by more than one oxygen atom and 0 or a functional group of the composition -SO ₂ F ₉ -COF, -Cl, -CO ₂ H, -CO ₂ R, - OCF ₂ CF-CF ₂ or -OCF ₂ CO ₂ R- *, where R * denotes the methyl or ethyl radical.

Particularly preferred polyfluoroallyloxy compounds according to Invention have the general formula

D t

CF ₉ -C CF ₉ -O-CF

X E

in the

X is chlorine or fluorine (preferably fluorine), E is -F, -CF ,, -CF ₂ CO ₂ R ⁵ , where R * is a methyl or ethyl radical, or -CF ₂ Cl (preferably -F,

-CF, or -CF ₀ CO ₀ R ^) and

• 2 ^£ * LL L

D has the meaning -CF ₂ R or CFR, in which R is a radical of

CF

809823/0878

* 3 3

Composition -F, -SO ₂ F, -COF, -CO ₂ H, -CO ₂ R, -OCFCOR

wherein R ^{5 is} a methyl or ethyl radical, or fC ^ wherein χ is a number from 1 to 6 and R is a radical CF ,, -COF, -CO ₂ H, -CO ₂ R ³ , -SO ₂ F or -OCF _{2 means} CF = CF ₂ . R is preferably a radical -SO ₂ F, -COF, -CO ₂ H or CO ₂ R ³ , in which R ^{3 is} a methyl or ethyl radical.

The polyfluoroallyl group of product 4 is derived from the corresponding polyfluoroallyl chloride or fluorosulfate (1_) by nucleophilic replacement of the chloride or fluorosulfate group by a previously prepared polyfluoroalcoholate anion, which in turn is derived from the metal fluoride (2) and the carbonyl compound (35) . The synthesis can therefore be carried out in a single reaction vessel by successively adding the reactants 3_ and Λ_ to a suspension or solution of 2_ in a suitable solvent.

Polyfluoroallyl fluorosulfates are those for this displacement reaction preferred reactants and can be prepared in a conventional manner by treating polyfluoroalkenes with Sulfur trioxide according to B.E. Smart, Journal of Organic Chemistry, Volume 41, page 2353 (1976) and U.S. Patent Application Serial No. 718 337 dated August 27, 1976. Typically, such reactions are in one Carius tube was melted shut at temperatures of 25 to 95 ° C for a period of 16 hours to 4 days and the resulting fluorosulfates are purified by fractional distillation. One way of making the preferred Perfluoroallyl fluorosulfate (namely pentafluoro-2-propenyl fluorosulfate) is given in Example 2 below.

Stable metal polyfluoro alcoholates are formed by reacting certain metal fluorides with polyfluoro-substituted ketones

809823/0878

CR 7704 A

and acid fluorides (J.A. Young, op. cit.) as follows:

CF ₃

(CPa) aCO + KP CF ₃ -fc-O ~ K

F i

CP ₃ COP + KP. ., CP ₃ -CO K

1 !

The technical value of such intermediate polyfluoro alcoholates is measured by their stability the ease of their thermal decomposition. Since their formation is reversible, the equilibrium concentrations of various types of compounds in a given reaction mixture are important quantitative parameters that determine whether the subsequent displacement with the formation of the product 4 takes place or not. Solutions in which the balance on the right hand side (high anion concentrations) are more effective than those where the equilibrium is on on the left side (high concentrations of the carbonyl compound).

The formation and chemistry of polyfluoroalcoholate anions depends on the following four conditions detailed by J.A. Young, op. Cit., F.W. Evans, M.H. Litt, A.M. Weidler-Kubanek and F.P. Avonda in Journal of Organic Chemistry, Volume 33, page 1837, 1839 (1968), and by M.A. Redwood and CJ. Willis in "Canad. J. Chem.", Vol. 45, p. 389 (1967), have been discussed.

(1) Stable polyfluoro alcoholate anions are formed when the carbonyl compound is highly fluorine-substituted because the electron-withdrawing effect of the fluorine atoms the negative

809823/0878

tive charge distributed over the entire anion. When some of the fluorine atoms are replaced by chlorine, other fluoroalkyl groups or If hydrogen is replaced, the anion loses its stability because these groups are less electron-withdrawing and the negative charge cannot be easily retained.

(2) Large cations, such as K ⁺ , Rb ⁺ , Cs ⁺ and R ^ N ⁺ , favor the formation of stable polyfluoroalkoxides more than small cations, such as Li ⁺ and Na ⁺ , because the lattice energy of metal fluorides is inversely proportional to the cation size. In other words: large cations and low lattice energy favor the breakage of the metal fluoride crystal structure with the formation of the anion.

(3) Solvents that have a high heat of dissolution for the polyfluoro alcoholate have, favor its formation. Aprotic polar solvents such as N, N-dimethylformamide (DMF), acetonitrile and 1,2-dimethoxyethane (glyme) are very effective for this purpose.

(4) When fluorine atoms are in α-position to the oxygen atom in the Anion, the elimination of the fluorine ion can compete with the desired reactions, e.g .:

CF, CF,

I I has no fluorine atom in the α position

o-c-c-o

j j and forms many stable derivatives

CF ₃ CF-j vate.

CF,

J requires a responsive

CF - C - O

3 j bond, like allyl bromide, for the

F nucleophilic substitution.

809823/0878

CR 7704 A ,, 2 ^{? 53886}

CF, 0 "usually splits off F"; nucleo-

Phile substitution is known for perfluoroallyl fluorosulfate.

In the context of the invention, the polyfluoro alcoholate anion is preferably initially added by adding the carbonyl compound a mixture of the metal fluoride in a suitable aprotic solvent with stirring. The completeness of the formation of the anion is generally evident noticeable to the extent to which the metal fluoride goes into solution in the solvent as the reaction proceeds. The stoichiometry of the formation of the polyfluoroalkoxide anion requires a molar equivalent of metal fluoride for each Carbonyl group that is converted into the anion, e.g .:

CP ₃

(CPa) ₂ CO + KP CPa - C - θ "Κ ⁺ ^ I

0 0 FP

FO (CPa) ₄ CP + 2KP ■ K ⁺ O * "- C (CPa) ₄ C - θ""Κ ⁺

F F

Up to a two-fold molar excess of the metal fluoride is generally not harmful. Two side effects of excess metal fluoride are as follows: (1) Observation of the end point of the reaction is hindered because the reaction mixture contains undissolved solids, and (2) excess fluorine ions may be in the solution directly with Perfluoroallyl fluorosulfate with formation of hexafluoropropene react.

In view of the limited heat resistance of polyfluoroalkoxides, their production usually takes place between -20

- 10 -

809823/0878

and + 60 ° C, preferably with external cooling and pause from temperatures between 0 and 10 C.

The time it takes for the polyfluoro alcoholate to form required varies depending on the carbonyl compound, but is preferably 0.5 to 2 hours, wherein one has to determine in each individual case how long it takes for the reaction mixture to become homogeneous.

Ν, Ν-dimethylformamide (DMF), acetonitrile, Ν, Ν-dimethylacetamide (DMAC), r-butyrolactone, 1,2-dimethoxyethane (glyme), 1- (2-methoxyethoxy) -2-methoxyethane (Diglyme), 2,5,8,11-tetraoxadodecane (Triglyme), dioxane, sulfolane, nitrobenzene and benzonitrile are examples of aprotic polar solvents that are used to Production of polyfluoro alcoholates and their further reaction with the polyfluoroallyl chloride or fluorosulfate are suitable. DMF, diglyme, triglyme, and acetonitrile are preferred solvents for these reactions.

Device, reactant and solvent should be used for the process according to the invention can be dried sufficiently because polyfluoro alcoholates are hydrolyzed by water:

(Rp) ₂ CFO "+ H ₂ O > (Rp) ₂ C (OH ₂ ) + F"

RpCF ₂ O "+ H ₂ O> RpCO ₂ H + HF ₂ "

Metal fluorides which are suitable in the context of the invention are potassium fluoride (KF), rubidium fluoride (RbF), cesium fluoride (CsF) and tetraalkylammonium fluoride (R ^ NF), such as tetraethylammonium fluoride [(C ₂ Hc) ^ NF] and tetrabutylammonium fluoride [(C ^ Hq) ^ NF]. The radicals R, which can be the same or different, are alkyl groups having 1 to 6, preferably 1 to 4, carbon atoms. Potassium fluoride is preferred because of its ready availability, economic advantage and ease of handling.

- 11 -

809823/0878

CR 7704 A

Polyfluoro-substituted carbonyl compounds, which are included in the Ketones and carboxylic acid fluorides as well as a perfluoro-substituted lactone, namely 3,6-bis (trifluoromethyl) -3,5,5,6-tetrafluoro-1,4-dioxan-2-one. Ketones and the lactone make branched-chain fluorocarbon products, while acid fluorides predominantly form of fluorocarbon products where the new Aether bond is at the primary or secondary center:

(R _F ) _a CO> (RpJaC-O-CPaCP-CPe (ketone)

-OCFaCF-CFa (lactone)

p V

RpCOF> RpCFaOCFaCF-CFa (acid fluoride))

Examples of polyfluoro-substituted ketones which can be used according to the invention are hexafluoroacetone, monochloropentafluoroacetone, 1,3-dichlorotetrafluoroacetone, 1,1-difluoroethyl-2-oxopentafluoropropanesulfonate, dimethyltetrafluoroacetone-1,3-dicarboxylate, 1,3-bis- (2-propoxy-pano) -tetrafluoro-tetrafluoro) Octafluorobutanone, decafluoro-2-pentanone, dodecylfluoro-2-hexanone, tetradecafluoro-2-heptanone, hexadecafluoro-2-octanone, Octadecafluoro-2-nonanone, eicosafluoro-2-decanone and hexafluoro-2,3-butanedione.

Hexafluoro-2,3-butanedione is a special case (Example 12), because the perfluoro alcoholate that is initially formed not only

- 12 -

809823/0878

with perfluoroallyl fluorosulfate, but also with another one molar equivalent of hexafluoro-2,3-butanedione to form a Mixture of two heterocyclic compounds reacts.

Polyfluoro-substituted acid fluorides, which are suitable in the context of the invention, are carbonyl fluoride, trifluoroacetyl fluoride, Pentafluoropropionyl fluoride, heptafluorobutyric acid fluoride,

Nonafluoropentanoyl fluoride, tetrafluorodiglycol difluoride 0 0

FCCF ₂ OCF ₂ CF Undecafluorhexanoylfluorid _1, Tridecafluorheptanoylfluorid, Pentadecafluoroctanoylfluorid, Heptadecafluornonanoylfluorid, Nonadecafluordecanoylfluorid, Difluormalonyldifluorid, Tetrafluorsucainyldifluorid, hexafluoropropane-1,3-dioyldifluorid (Hexafluorglutarsäuredifluorid), octafluorobutane-1,4-dioyldifluorid (Octafluoradipinsäuredifluorid) decafluoropentane dioyldifluorid-1,5-( Decafluorpimelinsäuredifluorid) dodecafluorohexane-1 _t 6-dioyldifluorid (Dodecafluorsuberonsäuredifluorid) Fluorsulfonyldifluoracetylfluorid, 2- (fluorosulfonyl) -tetrafluorpropionylfluorid, 2- (1-heptafluoropropoxy) -tetrafluorpropionylfluorid, 2- [2- (1-heptafluoropropoxy) -hexafluorpropoxy] -tetrafluorpropionylfluorid, 2- ] 2- [2- (1-heptafluoropropoxy) hexafluoropropoxy] hexafluoropropoxy 1-4 tetrafluoropropionyl fluoride and carboxymethoxydifluoroacetyl fluoride.

The ketone 1, i-difluoroethyl-2-oxopentafluoropropane sulfonate (Example 3) is a special case as a starting material because it is a source of 2-Oxopentafiuorpropansulfonylfluorid which forms in situ is because the latter has not been isolated.

P "CP ₃ COCPaSOaOCPaCH ₃ > [CP ₃ COCPaSOaP]>

CP ₃ PSOaCP ₂ CPOCPaCP-CPa

- 13 -

809823/0878

CR 7704 A g

Many of the above starting materials are commercially available; e.g. the company PCR, Gainesville, Florida, V.St.A., fluorine-substituted ketones and carboxylic acids. In Examples 2, 3, 4, 5, 7, 9, 10, 11, 12, 13, 16 and 19 sources are and Preparation methods for some not commercially available compounds are given. In general, perfluoroketones from the esters of perfluoroalkanecarboxylic acids and by reacting carbonyl fluoride with perfluoroalkenes [w.A. Sheppard and CM. Sharts, "Organic Fluorine Chemistry, "pp. 365-368, W.A. Benjamin, New York, 1969; H.P. Braendlin and E.T. McBee," Advances in Fluorine Chemistry ", Volume 3, Page 1 (1963)]. Perfluoroalkanecarboxylic acid fluorides and perfluoroalkan-α ^ -dicarboxylic acid difluorides are by treating the corresponding acids with sulfur tetrafluoride, by adding carbonyl fluoride to perfluoroalkenes [F.S. Fawcett, CW. Tullock and D.D. Coffman, "Journal of the American Chemical Society ", Vol. 84, p. 4275, 4285 (1961)] and by electrolysis of alkane carboxylic acids in hydrogen fluoride (M. Hudlicky," Chemistry of Fluorine Compounds ", p 86, MacMillan Co., New York, 1962). Perfluoroalkanedicarboxylic acids are produced by oxidation of ο, 6 -dialkenes or fluorine-substituted cycloalkenes (Hudlicky, op. Cit., Pages 150-152). Perfluoroalkyl polyethers with a terminal acid fluoride group can be prepared from hexafluoropropene oxide and its oligomers formed by the action of fluorine ions, such as in U.S. Patent 3,450,684 and by P. Tarrant, CG. Allison, K.P. Barthold and E.C Stump, Jr., in "Fluorine Chem. Rev.", Volume 5, page 88 (1971).

The stoichiometry of displacement with polyfluoroallyl chloride or fluorosulfate requires a molar equivalent of this reactant for each reactive center in the Polyfluoro alcoholate anion. In the case of a bifunctional polyfluoro

- 14 -

. 8098? 3 / D878

CR 770, A.

alcoholate, on the other hand, the stoichiometry can be adjusted in such a way that that either a mono- or a disubstitution product is obtained:

00 0

PCCP ₂ OP + KF + CPa = CPCP ₂ OSO ₂ P- ⁱ > PCCP ₂ CPeOCPaCP-CPa

(Example 5) 0 0
FCCFaCF + 2KP + 2CPa = CFCP ₂ OSO ₂ F> (CFa = CFCFaOCF ₈ ) a CFs

(Example 17) FCO (CF ₂ J ₁₁ COF + KF + CF ₃ - CFCFgOSOgF »CF ₃ » CFCF ₂ O (CF ₂ J ₅ COF

(Examples 21, 22) FCOiCFp ^ COF + 2KF + 2CF ₂ - CFCF ₂ OSO ₂ F - »(CF ^ CFCFgOCFgCFgCFg ^

(Example 13)

The formation of the polyfluoro alcoholate and its subsequent reaction with the polyfluoroallyl chloride or fluorosulfate can sequentially without isolating the intermediates in a glass apparatus at atmospheric pressure under normal precautions to exclude moisture. By using cooling baths and cryogenic coolers (e.g. those loaded with mixtures of solid carbon dioxide and acetone) the reactions moderate, and the remaining volatile reactants and products in the reaction mixture is facilitated. The progress the displacement reaction is expedient on the appearance of a precipitate of the salt MY (J5) by gas-liquid partition chromatography (Glpc) and followed by nuclear magnetic fluorine resonance spectroscopy (F NMR).

- 15 -

809823/10878

CR 7704 A

The displacement reaction can be carried out between -20 and +80 C and is preferably carried out between 0 and 30 C. The reaction mixture is typically removed from the outside when the polyfluoroallyl chloride or fluorosulfate is added Hereafter cooled to 0 to 15 ° C, whereupon it is allowed to warm to 25 to 30 ° C for the remainder of the reaction time.

The time required for the displacement reaction to be completed varies from 1 to 24 hours, and is preferably from 2 to 4 hours. Typically will the reaction mixture is cooled from the outside for 5 to 45 min when the polyfluoroallyl chloride or fluorosulfate is added, and then Stirred for 2 to 3 hours at room temperature.

The reaction products are isolated by conventional methods. In some cases the reaction product is much more volatile than the high boiling solvent used (Diglyme bp 162 ° C, DMF bp 153 ° C) and can be distilled into a receiver cooled to -80 ° C by heating the reaction vessel to 30 to 50 ° C under reduced pressure of 1 to 200 mm of mercury. But you can also use the reaction mixture in 5 to 10 times its volume of water pour, whereupon the insoluble lower layer of the fluorine-substituted product is separated off by washing with more The water is freed from solvent, dried and subjected to fractional distillation over phosphorus pentoxide or concentrated sulfuric acid.

The polyfluoroallyloxy compounds according to the invention are unsaturated monomers that can be converted into new and valuable polymers. Monomeric polyfluoroallyloxy compounds can be homopolymerized under high pressure to give oligomeric products. An expensive monomer from an economic point of view and the need to work under

- 16 -

809823/0878

CR 7704 A 9 /

However, it is preferable to use these monomers with less high pressure expensive, ethylenically unsaturated monomers, e.g. olefins such as ethylene or propylene, halogen-substituted ones Olefins such as tetrafluoroethylene, trifluoroethylene, hexafluoropropylene, Vinylidene fluoride, vinylidene chloride, trifluoromethyl trifluorovinyl ether and monochlorotrifluoroethylene, or with acrylic or methacrylic acid esters, to be processed into copolymers. Halogenated olefins, especially tetrafluoroethylene, Monochlorotrifluoroethylene, trifluoromethyl trifluorovinyl ether, hexafluoropropylene and vinylidene fluoride are preferred. Such copolymers have either more advantageous or completely new properties, which e.g. in the case of poly (tetrafluoroethylene), Poly (trifluoroethylene), poly (vinylidene fluoride ), Poly (monochlorotrifluoroethylene) or polyethylene cannot be found. Copolymerization refers to processes understood in which two or more monomers are incorporated as integral components in a high polymer. That Copolymers is the product of such a process. It is not necessary that the relative numbers of the different Types of units in different molecules of the copolymer or even in different parts of a single one Molecule are the same.

Copolymers containing the polyfluoroallyloxy comonomer in amounts of about 5 to 55% by weight (about 1 to 25 mol-96) have lower melting points than the corresponding polyfluoroolefins and are therefore easier to shape into valuable products. Copolymers containing a comonomer having Polyfluorallyloxy-SO ₂ F or COF side groups in amounts of from about 0.1 to 10, preferably from 1 to 10 wt.% (About 0.3 to 5 mol%), can be prepared by partially convert hydrolysis into a copolymer with SO ₂ OH or COOH groups, which have an affinity for cationic dye molecules. So it is possible to use fluorocarbon polymers with the different

- 17 -

809823/0878

CR-7704 A

to dye the most diverse dyes. This is not possible with polyfluoroolefins ^ which contain no (^ monomer units of this type. Copolymers which contain a polyfluoroallyloxy comonomer with SO ₂ F or COF side groups in amounts of about 5 to 35% by weight (about 1.0 to 10 Mol%) can also be partially or essentially hydrolyzed to form copolymers which _{contain hydrophilic SO 2} OH groups and COOH groups. Such a copolymer has an affinity for water and is wettable by water Contain comonomer units, cannot be wetted and are impermeable to water.A second important feature of the copolymers, the polyfluoroallyloxy comonomer units with -SO ₂ OH or -COOH groups or ionized forms thereof, for example -SO ₂ O ^- Na ⁺ or C0 ₂ "Na ⁺ , contained in amounts of about 1.0 to 10 mol%, is their ion exchange capacity. A particular use of such polymers is their use in a chlor-alkali cell according to DE-OS 2 251 660, published published on April 26, 1973, and NL-OS 72.17598, published June 29, 1973, according to which a polymer capable of ion exchange in the form of a film membrane or a diaphragm is used to separate the anode compartment and the cathode compartment of the cell from one another, in which Chlorine or caustic soda is produced from saline solution that flows through the anode compartment of the cell.

The properties of each copolymer depend on the distribution of the monomer units along the polymer chain, as a copolymer is not a physical mixture of two or more polymers, each of which is derived from the respective monomers, but is a new substance that contains the various monomer units as constituents. It is known that the composition of such a copolymer is also quite different from that of the monomer mixture (Initial good) can be from which it is formed. Furthermore applies

- 18 -

809823/0878

CR 7704 A

the phrase: "The relative tendencies of monomers to turn into polymer chains Having to store does not only suit everyone

their relative rates of polymerization, the

Reaction properties of a growing polymer chain depend primarily on the monomer unit at the growing end and does not depend on the length and composition of the chain as a whole. ", see C. Walling," Free Radicals In Solution ", Pages 99-100, published by John Wiley & Sons, Inc., New York (1957).

The copolymerization reaction for making the copolymers according to the invention can in non-aqueous or aqueous medium, wherein the reactants and initiator can be in solution, suspension or emulsion, in a closed Through the vessel while stirring. This type of reaction is known to the person skilled in the art.

The copolymerization is initiated by a radical chain initiator which is generally contained in the reaction mixture in a concentration of from 0.001 to 5% by weight and preferably from 0.01 to 1.0% by weight. Reaction systems with such radical chain initiators work preferably at or below 25 ° C, and examples of such radical chain _{initiators are pentafluoropropionyl peroxide (C 2} FcCOO) ₂ , dinitrogen _{difluoride (N 2} F ₂ ), azobisisobutyronitrile, ultraviolet radiation and ammonium or potassium persulfate, mixtures of iron (II) sulfate with hydrogen peroxide, ammonium or potassium persulfate, cumene hydroperoxide, tert-butyl hydroperoxide, mixtures of silver nitrate and ammonium or potassium persulfate, mixtures of trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid or pentadecafluorooctanoic acid with ammonium or potassium persulfate. The peroxide reaction systems can also contain sodium sulfite, sodium tetabisulfite or sodium thiosulfate.

- 19 -

809823/0878

CR 7704 A

If the copolymerization is carried out in an aqueous emulsion, emulsifiers are added in the form of the sodium or potassium salts of saturated aliphatic acids with 14 to 20 carbon atoms or of perfluoroalkanoic acids and perfluoroalkanesulfonic acids with 6 to 20 carbon atoms, e.g. potassium stearate or potassium pentadecafluorocaprylate. These emulsifiers can be used in the reaction mixture in concentrations of 0.1 to 10.0 wt. # and are preferably included therein Contain concentrations of 0.5 to 5 wt.96.

Aqueous emulsions are usually buffered to a pH of 7 or above by adding reagents such as disodium phosphate, sodium metaborate or ammonium metaborate, in amounts of about 1 to 4% by weight of the reaction mixture.

For the preparation of the copolymers according to the invention, the following three types of copolymerization systems are preferred:

1) Solutions of two or more comonomers in 1,1,2-trichloro-1,2,2-trifluoroethane (Freon 113) with a content of pentafluoropropionyl peroxide are about 20 hours at 25 ° C in Shaken autoclave. The crude polymer is isolated by evaporation of the solvent and washing with freed further solvent from the monomers and lower oligomers.

2) An aqueous emulsion of two or more comonomers that an emulsifier such as potassium perfluorooctanesulfonate, and an initiator, such as ammonium persulfate, is shaken in an autoclave at about 70 ° C. and an internal overpressure of 2.1 to 14 kg / cm 2 for 0.75 to 8 hours. The polymer is filtered off or centrifuged off.

3) In method (1), instead of 1,1,2-trichloro

- 20 -

809823/0878

CR 7704 A

1,2,2-trifluoroethane, the polyfluoroallyloxy comonomer as Solvents are used if it is to be incorporated into the polymer in a high proportion (up to 25 mol%).

The following examples illustrate possibilities for carrying out the invention. Unless otherwise stated, all parts and percentages therein relate to weight. In the structure confirmation analyzes, the values for the chemical shifts in fluorine magnetic resonance are in parts per million (ppm) with respect to monofluorotrichloromethane as the internal standard, and in the proton nuclear magnetic resonance analysis, the chemical shifts are in parts per million with respect to tetramethylsilane as internal standard specified. Unless otherwise specified, ultrared and nuclear magnetic resonance spectra are recorded from undiluted liquid samples.

example 1

1- (heptafluoro-2-propoxy) -1.1 _t 3,3-tetrafluoro-2-chloro-2-propene

(CF,) ₂ CO + KF + CF ₂ = CClCF ₂ Cl> (CFj) ₂ CFOCF ₂ CCI = CF ₂

16.6 g (0.10 mol) of hexafluoroacetone are distilled into a mixture of 5.80 g (0.10 mol) of potassium fluoride and 100 ml of 1- (2-methoxyethoxy) -2-methoxyethane (hereinafter referred to as "diglyme") , whereby the mixture is stirred and a homogeneous solution is formed. This mixture is kept at 25 to 30 ° C and with 18.3 g (0.10 mol) 1,2-dichloro-i, 1,3,3-tetrafluoropropene [prepared according to JE Bissey, H. Goldwhite and DG Rowsell, "Journal of Organic Chemistry", Volume 32, page 15 ^ 2 (1967)]. The mixture is stirred overnight and then poured into 500 ml of water. The lower layer is washed with 250 ml of water, dried and distilled. 13.0 g (0.039 mol) of 1- (heptafluoro-2-propoxy) -1,1,3,3-tetrafluoro-2-chloropropene are obtained; Yield 39,96; Bp 82-83 ° C. The structure is as follows

- 21 -

809823/0878

CR 7704 A

confirmed: X _mav 5.72 (CCl = CFp) and 7.5-10 µm (CF, CO); 1 ο max. £. ι

^y F NMR, -64.9 (m) 2F, -OCF ₂ C = C; -76.0 (2nd order m) 2F, C = CF ₂ ; -81.2 (t J = 5.7 Hz, each term d J = 2.2 Hz) 6F, CF ₃ and -146.7 ppm (t J = 22.9 Hz each term septet J = 2.2 Hz ) 1F, CFO.

analysis

Calculated for C ₆ ClF ₁₁ O: C - 21.67 ft Cl = 10.66 ft found: C = 21.43 ft Cl = 10.89 %.

Example 2

1- (1 »1» 1 »2,3,3-hexafluoro-3-chloro-2-propoxy) -pentafluoro-2-propene

A. Pentafluoro-2-propenylfluorosulphate (perfluoroallylfluorosulphate) CP ₈ CP - CP «+ SO ₃ -! >

A mixture of 10 ml of commercially available liquid sulfur trioxide and 45 g (0.30 mol) of hexafluoropropene is at the temperature of the liquid nitrogen melted in a Carius tube, mixed well at 25 ° C, left to stand at 25 ° C for 4 days and finally heated in the steam bath for 6 hours. 3- (Trifluoromethyl) -3,4,4-trifluoro-1-oxa-2-thiacyclobutane-2,2-dioxide is obtained by distillation from two such tubes ^ -Hydroxy-i-trifluoromethyl-i ^^ - trifluoroethanesulfonic acid sulton, see D.C. England, M.A. Dietrich and R.V. Lindsey, Jr Journal of the American Chemical Society, Vol. 82, p. 6181 (1960)]; Yield 25 g - 22 ft bp 44 ° C, and 73 g pentafluoro-2-propenylf fluorosulfate (hereinafter referred to as perfluoroallyl fluorosulfate designated); Yield 63 ft bp 58-60 ° C.

- 22 -

809823 ^ 0878

CR 7704 A

The perfluoroallyl fluorosulfate is characterized by the following analytical values: i__ "5.55 (OC) and 6.75 µm (SO-); ¹⁹ F NMR, 46.1 (t J - 8.5 Hz, each term d J «1.8 Hz) 1F, SO ₂ F, -74.0 (d J = 28.2 Hz, each term d J» 13.9 Hz, d J »8.5 Hz, d J = 7.8 Hz) 2F, -91.2 (d J» 50 Hz, each term dJ _s 40.5 Hz, t J - 7.8 Hz ) 1F, -104.7 (d J = 119.4 Hz, each link d J = 50 Hz, d H - 28.2 Hz) 1F and -192.4 ppm (d J - 119.4 Hz, each link dJ = 40.5 Hz, t J - 13.9 Hz, d J * 1.8 Hz) 1F.

B. 1- (1,1,1,2,3,3-hexafluoro-3-chloro-2-propoxy) pentafluoro 2-propene

CFsCOCFeCl + KF +

CFcCl

A suspension of 5.80 g (0.10 mol) of potassium fluoride in 100 ml of diglyme is stirred at 20 ° C. in a cooling bath, 18.3 g (0.10 mol) of monochloropentafluoroacetone being distilled into it. After the potassium fluoride has dissolved, 23.0 g (0.10 mol) of perfluoroallyl fluorosulfate are quickly added while cooling the reaction mixture. During the exothermic reaction that takes place, a solid material precipitates. The mixture is stirred for one hour at 25.degree. C., after which the volatile constituents are transferred to a receiver cooled to -80.degree. C. by heating the reaction mixture to 42.degree. C. under a pressure of 5 mm Hg. Distilling the liquid product over phosphorus pentoxide gives 19.6 g (0.059 mol) of 1- (1,1,1,2,3,3, · hexafluoro-3-chloro-2-propoxy) pentafluoro-2-propene; Yield x 59 %; Bp 85-86 ° C; the compound is characterized by the following analytical values: ^ _{m & x} 5.55 (CF - CF ₂ ) and

^19th

7-10 µm (CF, CO); ¹⁹ F NMR, -68.6 (m) 2F, CF ₂ Cl, -69.1 (■) 2F, CF ₂ O, -78.8 (m) 3F, CF ₃ , -93.2 (d J - 54.7 Hz, each link

- 23 -809823 / Ü878

CR 7704 A 33

d J - 39.8 Hz, t J ■ 7.5 Hz), 1F, CiS-CF ₂ -CF = CF, -105.9 (d J = 116.7 Hz, each term d J = 54.7 Hz , t J - 24.0 Hz) 1F, trans-CF ₂ -CF = CF, -141.2 (t J »22.8 Hz, each term m) 1F, CF and -190.4 ppm (d J« 116.7 Hz, each term d J - 39.8 Hz, t J - 13.4 Hz) 1F, -CF ₂ CF-C.

analysis

Calculated for C ₆ ClF ₁₁ O: C * 21.67 %; Cl = 10.66 %; found: C = 21.34 %; Cl - 10.21 %.

Example 3

2- (1-pentafluoro-2-propenyloxy) -hexafluoropropane-1-sulfonyl fluoride (2-perfluoroallyloxypropane-1-sulfonyl fluoride)

A. 2-Oxopentafluoropropane sulfonic acid

OCcHs 0 0

I 11

CF ₃ C-CF ₂ + SO ₃ ^ CF ₃ CCF _s SO ₂ OC _c Hs + CF ₃ CCF ₂ SO ₂ OH

0 0

I 1

CF ₃ CCF ₂ SO ₂ OC ₂ Hs + CF ₃ CO ₂ H> CF ₃ CCF ₂ SO ₂ OH +

CF ₃ CO ₂ C ₂ Hs

(i) When 12.8 g (0.16 mol) of sulfur trioxide are added dropwise to 29.0 g (0.165 mol) of 2-ethoxy-1,1,3,3,3-pentafluoropropene (cf. DW Wiley and HE Simmons, "Journal of Organic Chemistry ¹¹ , Volume 29, 1964, page 1876), an exothermic reaction takes place. The black reaction mixture is distilled, 6.3 g (0.036 mol) of 2-ethoxy-1,1,3, -3 , 3-pentafluoropropene (yield 22 J6; identified by IR) and 20.2 g (0.078 mol) of 2-oxopentafluoropropanesulfonic acid ethyl ester (degree of conversion 49 #; yield 63 %, b.p. _{12 m} - 47-48 ° C) wins: X _max 3 , 34 and 3.41 (saturated CH), 5.60 (C-0), 7.09 (SO ₂ O) and 7.6-8.5 Jim

- 24 -

809823/0878

(CF, SO ₂ ); H NMR, f4.59 (q J = 7.2 Hz) 2H, OCH ₂ and 1.51 ppm (t J = 7.2 Hz) 3H, CH ₃ ; ¹⁹ F NMR, -75.0 (t J · 8.3 Hz) 3F, CF ₃ and -107.4 ppm (q J * 8.3 Hz) 2F, CF ₂ .

(ii) The reaction described above is repeated at 0 to 5 ° C. with 88 g (1.1 mol) of sulfur trioxide and 176 g (1.0 mol) of 2-ethoxy-1,1,3,3,3-pentafluoropropene. The colorless reaction mixture, which darkens on standing overnight, is distilled. 28.6 g (0.16 mol) of 2-ethoxy-1,1,3,3,3-pentafluoropropene are obtained (yield 16 %; b.p. 46-48 ° C.), 145.1 g (0.57 mol) 2-oxopentafluoropropanesulfonic acid ethyl ester (degree of conversion 57 96; yield 68 96; bp _{12 mm} = 48-52 ° C) and a higher-boiling fraction, which mainly consists of 2-oxopentafluoropropanesulfonic acid. The crude acid is redistilled under a pressure of 6.2 mm Hg at 81-82 ° C. and gives a yield of 35.6 g (0.16 mol; degree of conversion 16,96; yield 19,96) of pure acid: A (CCl ₄ , CaF ₂ plates) 3.3 and 4.2 (wide) (SOH), 5.58 (C = O), 7.13 (SO ₂ O) and 7.5-9 / am (CF, SO ₂ ); ¹ H NMR, 6 10.2 ppm (s) SO ₂ OH; ¹⁹ F NMR, -76.2 (t J "7.5 Hz) 3 F, CF ₃ and -108 ppm (q J" 7.5 Hz) 2F, CF ₂ . analysis

Calculated for

C 1 HF.-0-S: C = 15.80 %; H = 0.44 96; F - 41.65 96;

^ ⁵ * S «14.06 96;

found: C = 15.95 96; H ■ 0.55 96; F - 41.55 96; S = 13.89 96.

(iii) 25.6 g (0.10 mol) of ethyl 2-oxopentafluoropropanesulfonate are stirred at 25 ° C., and 17.1 g (0.15 mol) of trifluoroacetic acid are added. The mixture is left to stand overnight and then heated to reflux temperature (60 ° C.) in a spinning band column. Fractional distillation of the mixture at a flask temperature below 100 ° C. gives 18.4 g (0.081 mol) of 2-oxopentafluoropropanesulfonic acid (yield 81,96; bp ₂ g

73 ° C).

- 25 -

809823/0873

B. 2-Oxopentafluoropropanesulfonic acid-1 «1-difluoroethyl ester

0 O

1 ^ I

CP ₅ CCPeSOeOH + CPe-CHe " ^ CPaCCPeSOeOCPeCH ₃

A metal tube containing 23.8 g (0.10 mol) of 2-oxopentafluoropropanesulfonic acid is cooled to -40 ° C., whereupon 13 g (0.20 mol) of vinylidene fluoride (1,1-difluoroethane) are added. The mixture is shaken and warmed to 25 ° C. and kept at this temperature for 4 hours. Distillation of the liquid product gives 20.4 g (0.07 mol) of 1,1-difluoroethyl 2-oxopentafluoropropanesulfonate; Yield 70,96; ^K P50 mm ^{β 62} " ⁶ 3 ° C: ^ _x (CCl ₄ ) 5.54 (CO), 6.96 (SO ₂ O) and 7.5-9 _{µm (CF, SO 2} ); ¹ H NMR, <f 2.06 ppm (t J "14.3 Hz) CH ₃ ; ¹⁹ F NMR, -58.3 (q J" 14.3 Hz, Each term t J "7.1 Hz) 2F, OCF ₂ , -75 , 0 (t J - 8.0 Hz) 3F, CF ₃ and ^ 106.1 ppm (q J - 8.0 Hz, Each term t J - 7.1 Hz) 2F,

analysis

Calculated for

C ₅ H ₃ F ₇ O ₄ S: C - 20.56 96; H - 1.03 96; F - 45.52 %; Found: C - 20.73 96; H - 1.03 96; F- 45.72 96.

A similar experiment on a scale of 0.8 mol gives an 86 percent product ^{yield (κ} Ρκλ η »" 6 ° C). This material is kept in polytetrafluoroethylene bottles so that it does not decompose.

C. 2- (1-Pentafluoro-2-propenyloxy) -hexafluoropropane-1- sulfonyl fluoride '

CPsUCPeSOeOCFeCHa + KF + CPe-CPCFeOSOaF CFa-CPOCPeCF-CFe + CHaCOF + KOSOeP

- 26 809823/0878

CR 7704 A

A suspension of 5.80 g (0.10 mol) of dry potassium fluoride in 100 ml of 2,5,8,11-tetraoxadodecane (triglyme) is cooled to 0 ° C. with stirring, whereby 29.2 g (0.10 mol ) 2-0xopenta fluoropropanesulfonic acid 1,1-difluoroethyl ester (prepared according to Example 3B) is added. When the potassium fluoride has almost completely dissolved, 23.0 g (0.10 mol) of perfluoroallyl fluorosulfate (prepared according to Example 2A) are added at 0 ° C. and the mixture is stirred for 3 hours at 20-26 ° C. The volatile constituents are distilled off at a flask temperature of 25 C and a pressure of 1 mm Hg. The distillate is washed with cold, dilute ammonium hydroxide solution, dried and distilled again, 13.0 g (0.034 mol) of 2- (1-pentafluoro-2-propenyloxy) -hexafluoropropane-1-sulfonyl fluoride being obtained (yield 34%; _{boiling point 60 ff} »47-48 ° C), the structure of which is confirmed by the following analysis values: λ_ _ν 5.59 (CF = CF ₅ ), 6.80 (SO ₉ F) and 7.5-10 μm (CF, CO, SO ₂ ); ^iy F NMR, +45.4 (m) 1F, SO ₂ F, -70.0 (m) 2F, OCF ₂ , -78.0 (quintet J. 10.7 Hz) 3F, CF ₃ , -91, 5 (d J >> 51.5 Hz, each term d J - 39.5 Hz, t J = 7.5 Hz) 1F, cis-CF ₂ CF - C £, -104.8 (d J - 117.0 Hz, each term dJ. 51.5 Hz, t J 25.5 Hz) 1F, trans-CF ₂ CF - CF, -107.0 and -108.4 (AB J 225 Hz, each term q J - 10, 7 Hz, m) 2F, CF ₂ SO ₂ F, -138.7 (t J - 20.2 Hz, each term m) 1F, CF and -190.8 ppm (d J 117.0 Hz, each term d J = 39.5 Hz, t J »13.0 Hz) 1F,

CF ₂ CF = C. for C - 18 96 96; F> 59, 98 96; S. - 8th, 43 96; analysis C - 19 24 96; F - 60, 06 96; S. - 8th, 26 %. Calculated C ₆ F ₁₂ O ₃ S: found:

In a reaction similar to that of Example 3C , it is shown by ultra-red analysis that the developing gases consist mainly of acetyl fluoride and small amounts of hexafluoropropene and sulfuryl fluoride.

- 27 -

809823/0878

Example 4 3>

1- [1,3-bis (2-heptafluoropropoxy) -2-pentafluoropropoxy] pentafluoro-2-propene ;

A. 1,3-bis (2-heptafluoropropoxy) tetrafluoropropanone

O!

A mixture of 21.0 g (0.36 mol) of dry potassium fluoride, 150 ml of dry Ν, Ν-dimethylformamide (DMF), 59.8 g (0.36 mol) of hexafluoroacetone and 35.8 g (0.18 mol) ) 1,3-dichlorotetrafluoroacetone is heated to reflux temperature (40-60 ° C.) for 3 days. Distilling in a receiver cooled to -80 ° C. gives 16.5 ml of hexafluoroacetone (yield 46,96) and 63 g of a liquid with a boiling range of 30 to 145 ° C. The higher-boiling material is redistilled over sulfuric acid, and 18 is obtained , 7 g (0.037 mol) of 1 _f 3-bis (2-heptafluoropropoxy) tetrafluoropropanone; Degree of conversion 21 96; Yield based on hexafluoroacetone, 39,96; Bp 117-118 ° C: Λ _max (CCl ^) 5.51 (C = O) and 7.5-9 fira (CF, COC); MS m / e 479 (MF) ⁺ , 313 (MF-CF ₃ COCF ₃ ) ⁺ , 263 (MF-CF ₃ COCF ₃ -CF ₂ ) ⁺ , 235 [(CFj) ₂ CFOCF ₂ I ⁺ , 169 (C ₃ F ₇ ) " ¹ ", 147 (CF ₃ CO _{CF 2} ) ⁺ , 97 (CF ₃ CO) ^+, and 69 (CF ₃ ) " ¹ "; ¹⁹ F NMR, -75.0 (d J - 21.5 Hz ₁ each link septet J »5.5 Hz) 2F, OCF ₂ , -81.4 (m) 6F, CF ₃ and -145.3 ppm ( t J »21.5 Hz,

each link septet J » 2 ,1 Hz ) 1F, CF. 68 , 66 96; analysis 68 , 59 96 Calculated for C _q F-jq0 ₃ : C. a 21st , 70 96; F - found: C. at 21st , 60 96; F -

B. 1- [1,3-bis (2-heptafluoropropoxy) -2-pentafluoropropoxy] pentafluoro-2-propene

(CFa) aCFOCFaCCFaOCF (CFa) a + KF + CFa ■ CFCF ₈ OSOaF

CFa - CFCFaOCF [CFaOCF (CFa) a] a - 28 -

809823/0878

A mixture of 20.0 g (0.04 mol) of 1,3-bis (2-heptafluoropropoxy) tetrafluoropropanone, 100 ml of diglyme and 2.32 g (0.04 mol) of potassium fluoride is heated to 55 ° C. with stirring . The originally present two liquid phases and the solid substance become homogeneous and remain homogeneous when cooled. 10.0 g (0.043 mol) of perfluoroallyl fluorosulfate (prepared according to Example 2A) are quickly added at 10 ° C. and the mixture is allowed to warm up. The slightly exothermic reaction is accompanied by the formation of a solid precipitate and the appearance of a second liquid phase. The mixture is stirred for 2 hours and then poured into 350 ml of water. The lower layer is washed with 75 ml of water, dried over phosphorus pentoxide and distilled. This gives 16.1 g (0.024 mole) of 1- [1,3-bis (2-heptafluoropropoxy) -2-pentafluoropropoxy] pentafluoro-2-propene (yield 62%; b.p. _{25 mm} = 64-67 ° C), the structure of which is confirmed by the following analytical values: \ 5.57 (CF ₂ = CF) and 7.5-9 µm (CF, CO); ¹⁹ F NMR, -69.4 (m) 2F, OCF ₂ C = C; -80.3 (broad) 4F, CFOCF ₂ -81.5 (s) 12F, CF ₃ , -93.7 (dJ- 54.0 Hz, each term dJ = 39.6 Hz, t J «7.8 Hz) 1F, CiS-CF ₂ - CF = CF, -106.3 (d J = 117.4 Hz, each term d J = 54.0 Hz, t J = 23.7 Hz) 1F, trans-CF ₂ CF = CF, -145.8 (m) 3F, OCF and -190.9 ppm (dJ »117.4 Hz, each term d J» 39.6 Hz, t J - 16.6 Hz) 1F, CF ₂ CF »C.

analysis

Calculated for C ₁₂ F ₂₄ O ₃ : C · 22.24%; F · 70.35 % i found: C = 22.66 % \ F »70.27 %.

Example 5

3- (1-Pentafluoro-2-propenyloxy) tetrafluoropropylfluoride A. Difluoromalonyl difluoride

SO ^ Il M

CH ₃ OCF ₂ CF ₂ COF - FCCF ₂ CF

- 29 -

809823/0878

ca 770, a ₅₅

81 g (0.45 mol) 3-methoxytetrafluoropropionyl fluoride (cf. FS Fawcett, CW. Tullock and DD Coffman, "Journal of the American Chemical Society ¹¹ , Volume 84, 1962, page 4275) slowly become 80 g at 40 ° C (1.0 mol) of sulfur trioxide is added and the product, namely difluoromonyl difluoride (bp -9 ° C), is constantly distilled off through a low-temperature column; yield 58 g * 90 96 »0.40 mol. The structure of the product is as follows Analysis values confirmed: J _max 1860 cm " ¹ (COF), ¹⁹ F NMR (without solvent), +17.1 ppm (t J = 10 Hz) 2F, COF and -114.2 ppm (t J - 10 Hz) 2F , CF ₂ .

B. 3- (1-pentafluoro-2-propenyloxy) tetrafluoropropionyl fluoride

0 0 0

FCCFaCF + KF + CFs-CFCFsOSOaF> FCCF ₉ CFa OCFa CF-CFa

A mixture of 7.5 g (0.13 mol) of dry potassium fluoride and 100 ml of diglyme is stirred at 10 ° C., 18.5 g (0.13 mol) of difluoromalonyl difluoride (prepared according to Part A) being distilled into it. After 20 min, almost all of the potassium fluoride has dissolved, and 29.9 g (0.13 mol) of perfluoroallyl fluorosulfate (prepared according to Example 2A) ^{are added dropwise at 10 to 15 ° C.} The mixture is stirred for 3 hours, after which the volatile constituents are distilled off at a flask temperature of 32 ° C. under a pressure of 4.8 mm Hg. Fractionation of the distillate gives 14.9 g (0.051 mol) of 3- (1-pentafluoro) -2-propenyloxy) tetrafluoropropionyl fluoride (yield 39 % at a boiling point of 70-71 ° C.) and slightly higher-boiling material. The structure of the product is confirmed by the following analytical values: ληβχ ^{5 '33} < ^COF > » ⁵ · ⁶⁰ ( ^CF - ^CF 2> *** 7.5-10 µm (CF, CO); ¹⁹ F NMR 23.7 ( apparent quintet, J ^ 7.5 Hz) 1F, COF, -71.9 (d J - 24.6 Hz, each term t J - 13.9 Hz, d J - 13.9 Hz, d J - 7, 4 Hz) 2F, OCF ₂ CC, -86.7 (m) 2F, CF ₂ O, -91.6 (d J -51.8 Hz, each term d J - 39.4 Hz, t J - 7, 4 Hz) 1F, CiS-CF ₂ CF - CF, -105.1 (d J - 117.1 Hz, each link dJ -

- 30 -

809823/0878

CR 770, AY, ^{275388 (} 5th

51.8 Hz, T j = 24.6 Hz) 1F, trans-CF ₂ -CF = CF, -122.0 (d J 8.2 Hz, Each term t J >> 3.1 Hz) 2F, FCOCF ₂ and -191.0 ppm (d, J = 117.1 Hz, Each term d, J - 39.4 Hz, t J - 13.9 Hz, t J -1.6 Hz) 1F, CF ₂ -CF = C .

analysis

Calculated for C ₆ F ₁₀ O ₂ : C = 24.51 96; found: C = .24.56 %.

Example 6

Perfluoro-3,6-dloxanone-8-enoylfluoride A. Tetrafluorodiglycolylchloride

Cl Cl

^mn ° * . ^H * ^S0 * _v , HO ₈ CCF ₈ OCF ₈ CO ₈ I. ^!

y ι

ο ο ι / ^socl «i

Il II

ClCCFaOCF ₂ CCl |

A mixture of 307.6 g (1.46 mol) of dichlorotetrafluorodihydro furan, 157.8 g (3.9 mol) of NaOH, 312 g (1.97 mol) of potassium permanganate and 1500 ml of water is heated to boiling for 17 hours on a reflux condenser . A short steam distillation, 10.6 g of dihydrofuran (3 wins? 0 · The reaction mixture is filtered and the filter cake was stirred twice with 400 ml of water. The combined aqueous solutions are concentrated ml to 1500 cold 300 ml of concentrated sulfuric acid and continuously Extracted with Xther for one day. The extracts are evaporated until no more ether develops at 25 ° C. (0.5 mm Hg). 5 g (0 0.06 moles) of pyridine and 416.5 g (3.5 moles) of thionyl chloride, at which point some gas and considerable amounts of oas are evolved

- 31 -

809823/0878

CR 7704 A

develop when the mixture is stirred and warmed above 40 ° C. The evolved gases are through a 0 C cold template headed. After 4 hours at about 40 ° C, the evolution of gas slows down, and so does the contents of the template (10 ml) is returned to the alembic. The mixture is then heated to reflux temperature, the contents of the cold initial charge being occasionally returned to the reaction mixture until a head temperature of 81 ° C. is reached is and no more gas develops. Fractionation gives 215.2 g of tetrafluorodiglycolyl chloride; Yield 61 96, based on dihydrofuran; Bp 94-97 ° C. The structure is through

1Q

confirmed the following analytical values. NMR: ¹⁷ F -77.0 ppm (s, -CF ₂ O-).

Tetrafluorodiglycolyl chloride (boiling point 96.5 ° C) has previously been used by R.E. Banks, E.D. Burling, B.A. Dodd and K. Mullen, "Journal of the Chemical Society (C) ", 1969, p. 1706, prepared in a different way.

B. tetrafluorodiglycolyl fluoride

0 0 0 0

ClCCPaOCFaCCl PCCF _a OCF _a CF;

The conversion of the diacid chloride into the corresponding fluoride (bp 32-33 ° C) takes place according to the method of RE Banks, ED Burling, BA Dodd and K. Mullen, "Journal of the Chemical Society (c)" _f 1969 »page 1706, on a larger scale. A mixture of 215 g (0.885 mol) of tetrafluorodiglycolyl dichloride, 140.5 g (3.35 mol) of NaF and 1200 ml of anhydrous acetonitrile is stirred overnight and then distilled, a fraction passing over at 35 to 79 ° C. being collected. The distillate is mixed with 20 g of NaF and distilled, 105 g of tetrafluorodiglycolyl difluoride being obtained; Bp 32-33 ° C, by adding a further 100 g (2.38 mol) of NaF to the reaction

- 32 -

809823/0878

CR 7704 A lft

mixing and slow distillation gives another fraction; Bp 35-81 ° C. By adding 10 g of NaF and fractionating, a further 37.0 g of difluoride are obtained; Bp 32-33 ° C, a total of 142 g; Yield 76 %.

C. Perfluoro-3.6-dioxanone-8-enoylfluorld

ο ο j

FCCF ₂ OCFaCF + KF + CFa = CFCF ₂ OSO ₂ F

0 II CF ₂ = CFCF ₂ OCF ₂ CF ₂ OCf ₂ CF

A mixture of 38.9 g (0.67 mol) of KF, 141.5 g (0.67 mol) of tetrafluorodiglycolyl difluoride and 500 ml of dry diglyme is stirred for 30 minutes at 5 ° C., during which time almost all of the KF goes into solution. Then added rapidly at 5 ° C 154.1 g (0.67 mol) Perfluorallylfluorsulfat added and stirred the mixture for 3 hours at 0 to 5 ⁰ C, 2 hours at 25 ° C and let it stand overnight. The volatile substances are driven off at temperatures up to the reflux of the diglyme at 38 C under a pressure of 3 mm Hg. The distillation of the volatile substances over 20 g of NaF gives a yield of diacid fluoride of 28.2 g (20 %; boiling point 32-33 ° C.) and 125.0 g of mono-acid fluoride (yield 52 %) , which is almost completely at 93-94 ° C is boiling. The structure is confirmed by the following analytical values: IR (CCl ^): 5.30 (COF), 5.59 (C = C), 8-9 u (CF, CO). NMR: F 13.3 (m, 1F, COF), -72.0 (d of d of t of d, J _pp 25, 13, 13, 7.7 Hz, 2F, -CFCF ₂ ), -77, 5 (t of d, J _pF 11.5, 2.7 Hz, 2F, CF ₂ CO ₂ F), -88.8 (t, J _pp 11.5 Hz, 2F, CF ₂ OCF ₂ COF), - 89.4 (t, J _pp 12.7 Hz, 2F, -CFCF ₂ OCF ₂ ), -91.9 (d of d of t, J _pp 52.7, 39.3, 7.7 Hz, 1F, cis-CF ₂ CF = CF), -105.3 (d of d of t, J _pp 117.6, 52.7, 24.6 Hz, 1F, trans-CF ₂ CF = CF) and -190.8 ppm (d of d of t of t, J _pp 117.6, 39.3, 13.7, 1.6Hz, 1F, CF ₂ CF-).

- 33 -

809823/0878

CR 7704 A

Example 7

2- (1- pentafluoro-2-propenyloxy) tetrafluoroethanesulfonylfluoride

0 FSOaCF ₈ UF

+ KF + CFe-CFCF ₈ OSOeP- ^ FSO ₈ CF ₈ Cf ₈ OCF ₈ CF-CF ₈

A suspension of 5.8 g (0.10 mol) of potassium fluoride id. in 100 ml of diglyme is cooled with stirring, 18.0 g (0.10 mol) of fluorosulfonyl difluoroacetyl fluoride being added rapidly; See DC England, MA Dietrich and RV Lindsey, Jr., Journal of the American Chemical Society, Vol. 82, p. 6181 (1960). The mixture is stirred for 15 min at 20 to 30 ° C., the potassium fluoride going into solution, and then in the course of 5 min at 20 to 25 ° C. with 25.0 g (0.11 mol) of perfluoroallyl fluorosulfate (prepared according to Example 2A ) offset. The mixture is stirred for 2 hours, a solid precipitate separating out and the temperature rising to 28 ° C. and falling again. The volatile constituents are transferred to a receiver cooled to -80 ° C. by heating the solution at a pressure of 5 mm Hg to the reflux temperature of 38 ° C. The distillate is mixed with 10 ml of concentrated sulfuric acid to remove the diglyme and then distilled. 19.9 g (0.06 mol) of 2- (1-pentafluoro-2-propenyloxy) tetrafluoroethanesulfonyl fluoride are obtained; Yield 60 %; Kp ^ ₅₀ »55-56 ° C. The Structure of the product is confirmed by the following analysis _values : Λ Μχ 5.53 (CF ₂ -CF), 6.79 (SO ₂ F) and 7-10 µm (CF, CO, SO ₂ ); ¹⁹ F NMR, + 44.9 (t J - 6 Hz, Each term t J «6 Hz) 1F, FSO ₂ , -71.8 (d J - 25.3 Hz, Each term t J -13.8 Hz , d J - 13.8 Hz, d J - 7.3 Hz) 2F, OCF ₂ CC, -83.0 (m) 2F, CF ₂ CF ₂ O, -90.9 (d J - 50.6 Hz , Each term d J - 39.5 Hz, t J - 7.3 Hz) 1F, CiS-CF ₂ CF-CF, -104.5 (d J - 117.6 Hz, each term d J - 50.6 Hz, t J - 25.3 Hz) 1F, trans-CFgCF-CF, -113.0 (d J - 5.6 Hz, Each term t J - 2.9 Hz) 2F, FSO ₂ CF ₂ and -190 , 9 ppm (d J - 117.6 Hz, Each term d J - 39.5 Hz, t J - 13.8 Hz, t J - 3.2 Hz) 1F, CF ₂ CF-C.

- 34 -809823/0878

CR 7704 A

analysis

Calculated for

C ₅ F ₁₀ O ₃ S: C = 18.19 %; F = 57.55 % i S = 9.71 96; found: C = 18.35 96; F = 57.40 96; S - 9.69 96.

Example 8

2- (1-pentafluoro-2-propenyloxy) tetrafluoroethanesulfonyl fluoride

O
PSOaCP ₈ CP + KP + CPa-CFCFaOSO ₈ P _> PSOaCPaCFaOCP _- CF-CP ₈

The procedure is as in Example 7, except that acetonitrile is used as the solvent instead of the diglyme. The acetonitrile is not extremely pure, and the yields of 2- (1-pentafluoro-2-propenyloxy) tetrafluoroethanesulfonyl fluoride (bp _{150 mm} = 54-55 ° C) are in the range from 40 to 50 96.

Example 9

1- [1- (Pentafluoro-2-propenyloxy)] hexafluoropropane-2-sulfonyl fluoride

FSO ₂ CFCOF + KF + CF ₂ = CFCF ₂ OSO ₂ F

FSo ₂ CFCF ₂ OCF ₂ CF-CF ₂

A mixture of 5.80 g (0.10 mol) of potassium fluoride and 100 ml of diglyme is added at 10 ° C. with the addition of 23.0 g (0.10 mol) of 2-fluorosulfonyl tetrafluoropropionyl fluoride (cf. DC England, MA Dietrich and RV Lindsey , Jr., Journal of the American Chemical Society, Vol. 82, 1960, p. 6181). The solution is then (prepared according to Example 2A) at 10 ° C with Perfluorallylfluorsulfat added, and after completion of the addition the mixture is stirred for 3 hours at 25 ° C and then in

- 35 -

809823/0878

CR 7704 A

Poured 500 ml of water. The lower layer is washed with 100 ml of water, dried and distilled. 25.7 g (0.068 mol) of 1- [i- (pentafluoro-2-propenyloxy)] -hexafluoropropane-2-sulfonyl fluoride are obtained; Yield 68 %; Bp _{60 mm} = 50 ° C;

purely by gas-liquid partition chromatography (Glpc). The structure of the product is confirmed by the following analytical values: 1 "5.55 (CF-CFp), 6.78 (SO ₂ F) and 7.5-10 pa (CF, CO, SO ₂ ); '* F NMR, 54.9 (d J = 20.7 Hz, each term q of J - 10.4 Hz, d J = 3.6 Hz) 1F, SO ₂ F, -71.8 (d J = 25.0 Hz, each term t J = >> 13.8 Hz, d J = 13.8 Hz, d J >> 7.4 Hz) 2F, OCF ₂ C = C, -72.1 (m) 3F, CF ₃ , -75.5 (m) 2F, CFCF ₂ O, -91.0 (dJ> 50.7 Hz, each term d J >> 39.4 Hz, t J - 7.4 Hz) 1F, CiS-CF ₂ CF = CF, -104.6 (d J * 117.6 Hz, each term d J = 50.7 Hz, t J »25.0 Hz) 1F, trans-CF ₂ CF =» CF, -166, 4 (d J = 14.6 Hz, each term q J = 7.2 Hz, d J = 3.6 Hz) 1F, CF and -191.1 ppm (d J = »117.6 Hz, each term d J »39.4 Hz, t J - 13.8 Hz, t J = 1.7 Hz) 1F, CF ₂ CF = C.

analysis

Calculated for

C ₆ F ₁₂ O ₃ S: C »18.96%; F = 59.98 %; S - 8.44 %; found: C * 18.70 %; F - 60.09 % \ S = 8.08 %.

Example 10

2- [i- (1,2,3,4,4-pentafluoro-2-cyclobutenyloxy)] tetrafluoroethanesulfonyl fluoride

OSQaF

+ KP + PCOCFaSO ₈ P

-OCFaCFaSOaF

^S F r >

A suspension of 5.80 g (0.10 mol) of potassium fluoride in 100 ml of diglyme is kept at 15 ° C. with stirring and cooling from the outside, with 18.0 g (0.10 mol) of fluorosulfonyl difluoro-

- 36 809823/0878

CR 7704 A IfQ

acetyl fluoride can be added. The mixture is mixed at 10 to 15 ° C with 24.2 g (0.10 mol) 1- (1 ^^^^ - pentafluoro ^ -cyclobutenyl) fluorosulfate (see BE Smart, "Journal of Organic Chemistry", Volume 41, 1976, page 2353) and then stirred for 3 hours at 25 ° C and poured into 500 ml of water. The lower layer is washed with 100 ml of water, dried and distilled. 24.0 g (0.07 mol) of 2- [i- (1,2,3,4,4-pentafluoro-2-cyclobutenyloxy)] tetrafluoroethanesulfonyl fluoride are obtained; Yield 70 % \ Kp ₁₀₀ ^ = 62 ° C. The structure of the product is confirmed by the following analysis values: A _max 5.53 (C = C), 6.80 (SO ₂ F) and 8-9.5 pm ( CF, CO, SO ₂ ); ¹⁹ F NMR, 44.8 (t J = 6.0 Hz, each term t J = 6.0 Hz, m) 1F, SO ₂ F, -80.3 and -83.8 (AB J = 146 Hz, each link m) 2F, OCF ₂ , -112.7 (m) 2F CF ₂ SO ₂ F, -117.6 and -119.7 (AB J = 190 Hz, each link m) 2F, Ring-CF ₂ , -121.8 (m) 1F, CF, -127.1 (m) 1F, CF and -128.4 ppm (m) 1F, CF.

analysis

Calculated for C ₆ F ₁₀ O ^ S rounded : C - 21.07 Ji; S = 9.37 %; + CPa-CFCPaOSOaP - F. T. i s ρ i e 1 11 : C ■ 21.38 %; Ss CFa-
-> \ - ρ
CF ₉ B e CPa-CFCPaC-- 2- (1
2.3, * 9.44 56. CF * - 0 -Pentafluoro-2-propenyloxy) -3,6-bis (trifluoromethyl) -
5,5,6-pentafluoro-1,4-dioxane P. U ⁰ \ P.
I + KP ^ CPa

A mixture of 5.8 g (0.10 mol) of potassium fluoride and 100 ml of diglyme is added at 25 ° C with 31.0 g (0.10 mol) of 3,6-bis (trifluoromethyl) -3.5.5, 6-tetrafluoro-1 _t 4-dioxan-2-one added (cf. US Pat. No. 3,321,517). The mixture is stirred for 1 hour, whereupon

- 37 -

809823/0878

CR 7704 A

23.0 g (0.10 mol) of perfluoroallyl fluorosulfate (prepared according to Example 2A) are added dropwise and the reaction mixture, in which an exothermic reaction takes place, is kept at 35 to 40 ° C. by cooling in an ice bath. The mixture is stirred overnight at 25 ° C., no evolution of gas being observed and an orange-yellow color developing. The mixture is poured into 500 ml of water, the lower layer is washed with 100 ml of water, dried and distilled under a pressure of 180 to 140 mm Hg at 73 to 74 ° C. The distillate is mixed with a little phosphorus pentoxide and fractionated again, with 2- (1-pentafluoro-2-propenyloxy) -3,6-bis (trifluoromethyl) -2,3,5,5,6-pentafluoro-1,4 -dioxane is obtained as a mixture of isomers; Kp ^ _{0 mm} = 55-57 ° C. The structure of the product is confirmed by the following analysis values: _max 5.57 (CF = CF ₂ ) and 7.5-10 µm (CF, CO); ¹⁹ F NMR, -70.7 and -71.8 (AB J - 159 Hz, each link m) 2F, OCF ₂ CC, -77.3 and -87.91 (AB J = 153 Hz, each link m) 2F, Ring-0CF ₂ , -81.4 (m) 4F, CF ₃ + OCFO, -82.4 (m) 3F, CF ₃ , -92.3 (d J «52.0 Hz, Each link d J > 39.3 Hz, t J - 7.2 Hz) 1F, cis-CFgCF-CF, -105.3 (d J = 117.1 Hz, each term d J- 52.0 Hz, t J - 25, 4 Hz) 1F, trans-CF ₂ CF «CF, -123.3, -124.7, -1.26.2 ,. -152.2 ~ "-1J2.9 and -134.1 (m) 2F, CF ₃ CFO, -190.5 (d J - 117.1 Hz, each term d J = 39.3 Hz, t J« 13.7 Hz) 1F, CF ₂ -CF-C. Small subordinate signals, which are caused by the presence of isomers, are observed at -92.1, -105.3 and -190.5 ppm.

analysis

Calculated for C ₉ F ₁₆ O ₃ : C - 23.50 96; F - 66.07 96; Found: C-23.71 96; F - 66.17 96.

- 38 -

809823/0878

CR-7704 A example 12

2- [1- (pentafluoro-2-propenyloxy)] - 2,3,5,6-tetrakis- (trifluoromethyl) -5-fluoro-1,4,7-trioxabicyclo- [2.2.1] -heptane and 2- [1- (pentafluoro-2-propenyloxy) tetrafluoroethy1] -4- [1- (pentafluoro-2-propenyloxy]) -2,4,5-tris- (trifluoromethyl) -5-fluoro-1,3-dioxolane

OO

in the

CPaCCCP ₃ +

KP

U CP ₃ C

0 "

K CFa

CP ₃ = CFCPaOSOaP

-Ά /

F ₃

P-CCF2CP-CP2 CF *

A suspension of 5.80 g (0.10 mol) of anhydrous potassium fluoride in 100 ml of diglyme is stirred at 10 ° C., during which process 19t4 g (0.10 mol) hexafluoro-2,3-butanedione (hexafluorobiacetyl, see L.O. Moore and J.W. Clark, Journal of Organic Chemistry, Volume 30, 1965, page 2472). The mixture is stirred until almost all of the potassium fluoride has dissolved, and then 23.0 g (0.10 mol) of perfluoroallyl fluorosulfate (prepared according to Example 2A) are quickly added at 15 ° C. As a result of a somewhat exothermic reaction, the temperature rises to 30 ° C. The pale yellow mixture is stirred overnight at 25 ° C. and then distilled. That at 49 to 54 ° C under one Two-phase distillate which has passed over under pressure of 10 mm Hg is shaken with 8 ml of concentrated sulfuric acid, treated with anhydrous calcium sulfate and fractionated in a spinning band column. 3.0 g (0.0055 mol) of 2- [1- (penta-

- 39 -

809823/0878

CR 7704 A

fluoro-2-propenyloxy)] - 2,3,5,6-tetrakis- (trifluoromethyl) -5-fluoro-1,4,7-trioxabicyclo [2.2.1] heptane (b.p. ₁₅ ^ _n - 50-51 ° C; yield 11,96) as a main component, determined by Glpc. The analytical sample of this product is made by preparative Glpc and the structure is confirmed by the following analytical values: ^ _max 5.58 (CF-CF ₂ ) and 7.5-10 µm (CF, CO); ¹⁹ F NMR, -65.6 and -71.0 (AB J »155 Hz, each term m), 2F, OCF ₂ , -74.7 (m) 3F, CF ₃ , -78.5 (m) 3F , CF ₃ , -79.3 (s) 3F, CF ₃ , -79.9 (d J - 13 Hz, each term septet J = 4 Hz), 3F, CF ₃ , -92.0 (d J - 52 , 1 Hz, each term dJ »39.5 Hz, d J» 8.3 Hz, d J - 6.6 Hz) 1F, CiS-CF ₂ CF-CF, -105.5 (d J »117.2 Hz, each term d J - 52.1 Hz, d J - 27.0 Hz, t J - 21.8 Hz, q J = 3.0 Hz) 1F, trans-CF ^ F-CF, -121.7 (q J = 20.5 Hz, each term q J - 13.1 Hz) 1F, CF and -191.2 ppm (d J = 117.2 Hz, each term d J »39.5 Hz, t J - 13.8 Hz) 1F, CF ₂ -CF-C.

analysis

Calculated for C ₁₁ F ₁₈ O ₄ : C - 24.55 96; F - 63.55 96; Found: C - 24.57 96; F - 63.60 96.

The second fraction is an isomer mixture of 2- [1- (pentafluoro-2-propenyloxy) -tetrafluoroethy1] -4- [1- (pentafluoro-2-propenyloxy)] - 2,4,5-tris- (trifluoromethyl) -5 -fluoro-1,3-dioxolane, which is obtained in an amount of 7.2 g (0.01 mol; yield 21,96) and, according to the Glpc, contains only small amounts of impurities. The structure of this product is confirmed by the following analytical values: ^ n _0x 5.56 (CF-CF ₂ ) and 7-10 pm (CF, CO), ¹⁹ F NMR -72.8 ppm (AB) 2F, OCF ₂ , -75.4, -76.8, -78.3, -78.7 and -79.1 (m) 12F, CF ₃ , -93.1 (m) 2F cis-CF ₂ CF-CF, -105 , 8 (m) 2F, trans _{-CF 2} CF »CF, -121.0, -136.5 and -141.6 (m) 2F, CF and 190.8 ppm (m) 2F, CF ₂ CF-C .

analysis

Calculated for C ₁₄ F ₂₄ O ₄ : C - 24.44 96; F - 66.26 96; Found: C - 24.73 96; F - 66.48 96.

- 40 -

809823/0878

CR 7704 A

SO

Example 13

Perfluoro-1 _t 6-bls- (2-propenyloxy) -hexane

0

I 'Il'

FC (CFa) ₄ CF + KF + CFa = CFCFaOSO ₃ F ► (CFa = CFCFaOCFaCFaCFa) a

+ CFa «CFCFa0 (CFa) e COF

DLglyme CFa = CFCF ₃ O (CFa) e COF + HaO > CFa = CFCF ₈ O (CFa J ₈ CO ₈ H * niglyme

A mixture of 11.62 g (0.20 mole) potassium fluoride, 200 ml diglyme and 28.2 g (0.096 mol) of octafluoroadipoyl difluoride is stirred for 1.5 hours at 5 ° C. The mixture is heated to 5 to 10 ° C held, 46.0 g (0.20 mol) of perfluoroallyl fluorosulfate (prepared according to Example 2A) are added dropwise. After finished In addition, the mixture is stirred for 30 min at 5 ° C., after which it is allowed to warm to 25 ° C. and for a further 3 hours stirs. After standing overnight, the mixture is poured into 1 l of water and the lower layer with 150 ml of water washed, dried and distilled to give two products.

The lower-boiling fraction consists of 21.1 g (0.0355 mol) of perfluoro-1,6-bis (2-propenyloxy) -hexane (yield 37 % at _{boiling point 20} , J _11n = 84-86 ° C.), its structure is confirmed by the following analytical values: λ _max 5.59 (CF = CF ₂ ) and 7.2-9.5 µm (CF, CO); ¹⁹ F NMR, -72.1 (d J - 25.7 Hz, each term t J - 13.3 Hz, d J - 13.3 Hz, t J - 7.6 Hz) 2F, OCF ₂ CC, - 84.2 (m) 2F, CF ₂ O, -92.3 (d J - 52.7 Hz, each term d J 39.5 Hz, t J - 7.6 Hz) 1F, cis-CF ₂ CF = CF, -105.5 (d J » 117.8 Hz, each term d J = 52.7 Hz, t J - 25.7 Hz) 1F, trans-CF ₂ CF = CF, -122.9 (m) , CF ₂ , -126.2 (m) 2F, CF ₂ and -191.0 ppm (d J = 117.8 Hz, each term d J - 39.5 Hz, t J - 13.8 Hz) 1F, CF ₂ -CF = C.

- 41 -

809823/0878

CR 7704 A for found: C -
C - I. ; * 96;
96; F »
F » 70
70 , 35
»38 2753886 analysis
Calculated 24
24 , 26
, 43 96

The higher boiling fraction is a complex compound made from 2 moles of perfluoro-6- (2-propenyloxy) -capronsäure and 1 mole of diglyme and falls in an amount of 7 _f 9 g (0.0155 mol; yield 16 96) to; Bp ₉ ^ _n »109-110 ° C. This product was formed by hydrolysis of perfluoro-6- (2-propenyloxy) -hexanoyl fluoride in the aqueous diglyme washing solutions. This complex compound shows: A _031x 3-4 (OH, CH), 5.59 (with shoulder, CF ₂ -CF, CO ₂ H) and 7.2-9 pm (CF, CO, CH); ¹ H NMR, J * 11.93 (s) 1H, CO ₂ H, 3.75 (s) 4H, OCH ₂ and 3.52 (s) 3H, OCH ₃ ; ¹⁹ F NMR, -71.9 (d J - 25.1 Hz, Each term tJ = 13.4 Hz, d J = 13.4 Hz, d J = 7.5 Hz) 2F, OCF ₂ C = C, -83.1 (m) 2F, CF ₂ CF ₂ O, -92.0 (d J - 52.3 Hz, each link d J = 39.3 Hz, t J - 7.4 Hz) 1F, CiS- CF ₂ CF-CF, -105.2 (d J - 117.7 Hz, each term dJ »52.3 Hz, t J - 25.1 Hz), 1F, trans-CFgCF-CF, -119.6 ( t J = 12.6 Hz, Each term t J * 3.2 Hz) 2F, CF ₂ , -122.6 (m) 2 F, CF ₂ , -123.5 (m) 2F, CF ₂ , -126 , 1 (m) 2F, CF ₂ and -190.9 ppm (d J >> 117.7 Hz, Each term d J = 39.3 Hz, t J - 13.8 Hz, t J - 1.8 Hz 1F , CF ₂ CF-C.

Example 14 Perfluoro-3,6-dloxanone-8-enoic acid methyl ester

2 CH, OH
CF ₂ = CFCF ₂ OCF ₂ CF ₂ OCF ₂ CF 2> _CF2 -CFCF ₂ OCF ₂ CF ₂ OCF ₂ CO ₂ Ch ₃

A suspension of 42 g (1.0 mol) of NaF in 100 ml of methanol is rapidly admixed with 114 g (0.317 mol) of acid fluoride at 5 ° C. while stirring. When the addition is complete, the mixture is stirred overnight at 25 ° C., filtered and the solid residue is washed with ether. Distillation gives 102.0 g of methyl perfluoro-3,6-dioxanone-8-enoate (yield 86,96;

- 42 -

809823/0878

CR 7704 A

Bp ₂₀ = 60-61 ° C), which contains small amounts of impurities. Redistillation gives a somewhat purer ester (1 to 2 % impurities, determined by gas chromatography; bp _{20 mm} = 61-62 ° C). The structure is determined by Ultrarotanalyse (undiluted) as follows: 3t32, 3 "37, 3, 9 ^ (CH,), 5.57 (C = O) ₁ 8-9.5 μ (CF, CO). NMR: H 3.95 ppm (s) with minor impurities at 3.53 and 3.33 ppm; ⁷ F -72.0 (d of d of t of d, J _pp 24, 13, 13, 7.5 Hz, 2F, = CFCF ₂ ), -78.0 (t, J _FF 11.6 Hz, 2F , CF ₂ CO ₂ CH ₃ ), -89.0 (t, J _pp 11.6 Hz, 2F, CF ₂ OCF ₂ CO ₂ CH ₃ ), -89.5 (t, J _pp 12.6 Hz, 2F , = CFCF ₂ 0CF ₂ ), -92.3 (d of d of t, J _pp 53.2, 39.2, 7.5 Hz, 1F, CiS-CF ₂ CF = CF), -105.2 ( d of d of t, J _pp 117.3, 53.2, 24.3 Hz, 1F, trans-CF ₂ CF ₂ -CF) and -190.8 ppm (d of d of t of t, J _pp 117 , 3, 39.2, 14.0, 1.6 Hz, 1F, CF ₂ CF =).

analysis

Calculated for

C ₈ H ₃ F ₁₁ O ₄ : C = 25.82 %; H - 0.81 %; F = 56.17 % i found: C = 26.17 % ', H = 0.66 96; F = 56.24 %.

Example 15

Dimethyl perfluoro-3-alloxyglutarate A. Bls- (2-methoxytetrafluoroethyl) ketone

The synthesis of bis (2-methoxytetrafluoroethyl) ketone from dimethyl carbonate, tetrafluoroethylene and sodium methylate is described in US Pat. No. 2,988,537. A further development of this synthesis gives 1,3,3,5-tetramethoxyoctafluoropentane in a one-step reaction

0 0 "Ne ⁺

Il _v I CH ₃ ONa + 2 CP ₈ = CF ₂ + CH ₃ OCOCH ₃ > CH ₃ OCP ₈ CPeCCPaCFeOCH ₉

OCH ₉

CH ₃ OSO ₂ OCH ₃

CH ₃ OCP ₂ CP ₈ Ci OCH ₃ J ₈ CPaCP ₈ OCH ₃

- 43 -809823/0878

CR 7704 A 53

A mixture of 27.0 g (0.50 mole) sodium methylate, 56.0 g (0.62 mol) of dimethyl carbonate and 100 ml of dry tetrahydrofuran is kept in motion in a 350 ml tube under a tetrafluoroethylene pressure of 1 to 3 atm. Tetrafluoroethylene is reduced to the extent that it is consumed Pressure was initiated until 110 g (1.1 moles) had been added. The temperature remains as a result of the slightly exothermic reaction near 35 ° C; after the addition, the reaction mixture is heated to 40 ° C. for 1 hour. The viscous solution obtained in this reaction is directly heated to 40 ° C. for 15 hours treated with 75.6 g (0.60 moles) dimethyl sulfate. Filtration and distillation give 87.6 g of 1,3,3,5-tetra- methoxyoctafluoropentane (yield 52 %; bp _n , = 54 ° C;

24 »^

n _ß = 1.3605), the structure of which is confirmed by the following analysis values: IR 3.29, 3.33 and 3.42 (sat. CH), 8-9 μ (CF, COC). NMR (CCl ₄ ) ¹ H ιί 3.68 (s, 1, CF ₂ OCH ₃ ) and 3.57 (p, J _Hp 1.3 Hz, 1, C (OCH ₃ ) ₂ ); ¹⁹ F -88.2 (m, 1, CR ₂ O) and -116.5 ppm (m, 1, CF ₂ ).

analysis

Calculated for

C ₉ H ₁₂ F ₈ O ₄ : C = 32.16 96; H - 3.60 96; F - 45.21 %; found: C = 32.57 %; H - 3.72 %; F - 44.61 96.

B. tetrafluoroacetone-1,3-dlcarboxylic acid dimethyl ester

conc. H ₂ SO ₄

0 0 0

1 I I

CHaOCCFaCCFaCOCH ₃ !

33.6 g (0.10 mol) of the tetraether are added dropwise to 50 ml of concentrated sulfuric acid. When the mildly exothermic reaction has subsided, the mixture is under a pressure of 50 mm Hg heated to 70 ° C to remove the volatile substances.

- 44 -

809823/0878

CR 7704 A S

ben, and then distilled under a pressure of 1 mm Hg at about 50 C. The crude distillate is fractionated. 16.9 g of tetrafluoroacetone-1,3-dicarboxylic acid dimethyl ester are obtained; Yield 69 %; Bp _{2 jm} = 58 ° C; n _D ²² = 1.3713. The structure is confirmed by the following analysis values: IR 3.28, 3.34 and 3, ^ 8 (sat. CH), 5.57 (C = O), 5.64 (shoulder ~ C = O), 8-9 u (CF, COC). NMR (CCl ₄ ) ¹ H «f 4.00 (s, OCH ₃ ); ¹⁹ F -113 ppm (s, CF ₂ ).

analysis

Calculated for

C ₇ H ₆ F ₄ O ₅ : C -34.16 96; H - 2.46 Si; F - 30.88 96

Molecular weight 246;

found: C = 34.18 %; H = 2.66%; F = 30.95 %

Molecular weight 246 (mass spectrum).

The same reaction, carried out with 0.56 moles, gives the diester in a yield of 82 %.

C. Dimethyl perfluoro-3-alloxyglutarate

0 0 0
Il Il II
CaI ₃ OCCFaCCF ₂ COCH ₃ + CoF + CFa = CFCF ₂ OSOaF

0
II
(CH ₃ OC-CFa) ₂ CFOCFaCF-CFa

27.3 g (0.18 mole) of dry CsF in 100 mL of diglyme at 5 to 10 ° C with 43.5 g (0.18 mol) of O = C (CF ₂ COOCH _{3) 2} and stirred for 1 hour; 41.4 g (0.18 mol) of CF ₂ = CFCF ₂ OSO ₂ F are then added at 5 to 10 ° C. and the mixture is stirred for a further 3 hours. The reaction mixture is poured into 1 l of water and the lower layer is separated off and washed twice with water. After treating with 20 ml of sulfuric acid at 0 ° C and

- 45 809823/0878

CR 7704 A

Extracting with 1,1,2-trichloro-i, 2,2-trifluoroethane, the extract is distilled in a short-path evaporator. 4.54 g of product are obtained; Yield 7.2 %; Kp _{n Λ wmm} «51-53 ° C. The structure

Λ Q ^ f uUD

is confirmed by ^iy F NMR (F11): -68.48 ppm (OCF ₂ CF =); -93.45 ppm CiS- (CF-CFF); -105.91 ppm trans- (CF-CF); -117.10 ppm (CF ₂ COOCH ₃ ); -142.78 ppm (CF ₂ CF ₂ OCF-); -190.35 ppm (CF-CF ₂ ). ¹ H NMR (F11 / TMS): 3.96 (singlet, CH ₃ ). IR (neat): 3.37 u, 3.49 u (sat. CH); 5.60 2 (; C-O, CF ₂ = CF); 8-10 ρ (CF, CO).

analysis

Calculated for

C ₁₀ F ₁₀ H ₆ O ₅ : C = 30.32 96; F - 47.96 96; H = 1.53 96; found: C = 30.45 96; F - 48.10 96; H = 1.48 96.

Example 16 Perfluoro-3- (2-propoxy-2-methylethoxy) propene CF ₃ CF ₂ CF ₂ OCFCOf + KF + CF ₂ = CFCF ₂ OSO ₂ F CF ₃ CF ₂ CF ₂ OCFCF ₂ OCF ₂ CF = Cf ₂

A mixture of 6.96 g (0.12 mol), potassium fluoride, 150 ml diglyme and 29.4 g (0.089 mol) 2- (1-heptafluoropropoxy) tetrafluoropropionyl fluoride (dimer of hexafluoropropene oxide, prepared by treating with fluorine ions) is 1 Stirred at 5 ° C. for an hour. 27.6 g (0.12 mol) of perfluoroallyl fluorosulfate (prepared according to Example 2A) are then added dropwise at 5 ° C. and the mixture is stirred for 3 hours at 5 ° C. and overnight at 25 ° C. The reaction mixture is poured into 1 l of water, the lower layer is separated and the volatiles are driven off at 25 ° C. under a pressure of 0.5 mm Hg. Distillation of the volatile components over concentrated sulfuric acid gives 25.2 g (0.052 mol) of perfluoro-3- (2-pro poxy-2-methylethoxy) propene (yield 59,96; ^K P- | oo mm * ^ ^{2 bis}

- 46 -

809823/0878

CR-7704 A

63 ° C), the structure of which is confirmed by the following analysis values: A _max 5.57 (CF = CF ₂ ) and 7.5-9 μm (CF ₁ CO); ¹⁹ F NMR, -72.2 (d J = 25.5 Hz, each term t J - 13.3 Hz, d J - 13.3 Hz, d J - 7.4 Hz) 2F, OCF ₂ C = C , -81.0 (m) 3F, CF ₃ , -82.3 (m) 5F, CF ₃ + OCF ₂ , -84.1 (m) 2F, CF ₂ O, -92.1 (d J 52, 7 Hz, each term d J = 39.7 Hz, t J = 7.4 Hz) 1F, cis- CF ₂ CF = CF, -105.5 (d J = 117.8 Hz, each term d J = 52 , 7 Hz, t J = 25.5 Hz), 1F, trans-CF ₂ CF = CF, -130.4 (s) 2F, CF ₂ , -145.9 (m) 1F, CF and -191.0 ppm (d J = 117.8 Hz, each term d J = 39.7 Hz, t J = 13.6 Hz) 1F, CF ₂ CF = C.

analysis

Calculated for

C ₉ H ₁₈ O ₂ : C = 22.42 %; F = 70.94%; found: C = 22.18 %; F = 70.96 %.

Example 17 Perfluoro-1,3-bis (2-propenyloxy) propane

0 0
FCCF ₂ CF + KF + CF ₂ = CFCF ₂ OSO ₂ F > (CF ₂ = CFCF ₂ OCF ₂ J ₂ CF ₂

A mixture of 15.3 g (0.26 mol) of potassium fluoride, 200 ml of diglyme and 17.3 g (0.12 mol) of difluoromalonyl difluoride (prepared according to Example 5A) is stirred at 5 ° C. for 15 minutes. Is reacted in the course of 45 min at 5 to 10 ° C 57.5 g (0.25 mol) Perfluorallylfluorsulfat added and stirred the mixture for an additional hour at 5 ° C and then 2 hours at 25 ° C. The reaction mixture is poured into 1 Poured 1 water and washed the lower layer with 100 ml of water, dried and distilled. 12.0 g (0.027 mol) of perfluoro-1,3-bis (2-propenyloxy) propane are obtained (yield 23 % i ^κ £ 00 mm " ⁸⁸ ""90 ° C.), the structure of which is determined by the following analytical values the following is confirmed : k _max 5.59 (CF = CF ₂ ) and 7.2-9.5 pm (CF, CO); ¹⁹ F NMR, -72.2 (m) 2F, OCF ₂ CC, - «'■ ), 6 (m) 2F, CF ₂ CF ₂ O, -92.3 (d J 53.0 Hz, each term d J - 39.5 Hz, t J - 7.2 Hz) 1F,

- 47 -

809823/0878

CiS-CF ₂ CF = CF, -105.6 (d J = 117.8 Hz, each term d J. 53.0 Hz, t J = 25.2 Hz) 1F, trans-CFgCF-CF, -130, 0 (s) 1F, CF ₂ and -191.0 ppm (d J = 117.8 Hz, each term d J >> 39.5 Hz, t J -13.5 Hz) 1F, CF ₂ CF-C.

analysis

Calculated for C ₉ F ₁₆ O ₂ : C - 24.34%; F = 68.45 %; found: C = 24.67 96; F = 68.36 %.

Example 18 Perfluoro-3- (butoxy) -propene CF ₃ CF ₂ CF ₂ COF + KF + CF ₂ = CFCF ₂ OSO ₂ F CF ₃ CF ₂ CF ₂ CF ₂ OCF ₂ CF = Cf ₂

A mixture of 7.50 g (0.13 mol) of dry potassium fluoride, 100 ml of diglyme and 28.1 g (0.13 mol) of heptafluorobutyroyl fluoride (prepared from the acid by reaction with sulfur tetrafluoride) is stirred at 5 ° C. for 30 minutes. Perfluoroallyl fluorosulfate is then added dropwise at 5 ° C. and the mixture is stirred for one hour at this temperature and for 3 hours at 25 ° C. The volatile components are distilled off at 40 ° C. under 8 mm Hg, washed with 100 ml of water and poured over a small amount concentrated sulfuric acid distilled. 30.3 g (0.083 Molji perfluoro-3- (butoxy) -propene (yield 64 %; boiling point 80-84 ° C.) are obtained, the structure of which is confirmed by the following analytical values: X _av 5.57 (CF-CFo) and 7.2-9.5 µm (CF, • in max €, 1

CO); ¹ ^ F NMR -72.1 (d J = 25.2 Hz, each term t J = 13.5 Hz, d J = 13.5 Hz, d J = 7.4 Hz) 2F, OCF ₂ C = C , -82.1 (t J = 8.1 Hz, each term m), 3F, CF ₃ , -84.5 (m) 2F, CF ₂ O, -92.1 (d J = 52.3 Hz, each term d J »39.4 Hz, t J = 7.4 Hz) 1F, CiS-CF ₂ CF = CF, -105.5 (d J» 117.5 Hz, each term d J -52.3 Hz , t J = 25.2 Hz) 1F, trans-CF ₂ CF = CF, -127.3 (m) 4F, CF ₂ and -191.0 ppm (d J = 117.5 Hz, each term d J = 39.4 Hz, t J - 13.7 Hz, m) 1F, CF ₂ CF = C.

- 48 -

809823/0878

CR 7704 A
analysis for C ₇ F ₁₄ O: C = 22 St. F = 72 .66 % 2753886 _# Calculated found: C = 23, 97 %; F = 72 , 80 % 20 %;

Example 19 Perfluoro-3- (octyloxy) -propene

F (CF ₂ ) ₇ COF + KF + CF ₂ = CFCF ₂ OSO ₂ F> F (CF ₂ J

A mixture of 5.80 g (0.10 mol) of potassium fluoride, 150 ml of diglyme and 25.0 g (0.06 mol) of pentadecafluorooctanoyl fluoride (prepared by reacting commercial perfluorocaprylic acid with sulfur tetrafluoride) is stirred at 5 ° C. for 1 hour. After the dropwise addition of 23.0 g (0.10 mol) of perfluoroallyl fluorosulfate, the mixture is stirred at 5 ° C. for 4 hours and then at 25 ° C. for a further 3 hours. The mixture is poured into 1 l of water, separated into layers and the lower layer is distilled over concentrated sulfuric acid. 27.1 g (0.048 mol) of perfluoro-3- (octyloxy) -propene are obtained (yield 80 %; _{b.p. 20 mm} = 69-70 ° C.), the structure of which is confirmed by the following analytical values: 5.59 (CF = CF ₀ ) and 7-9 µm (CF CO); ^iy F NMR -71.8 (d J = 25.1 Hz, each term d J >> 13.4 Hz, t J = 13.4 Hz, d J = 7.7 Hz) 2F, OCF ₂ C = C, -81.6 (t J >> 10.0 Hz) 3F, CF ₃ , -83.8 (m) 2F, CF ₂ CF ₂ O, -92.3 (d J >> 53.6 Hz, Each term d J = 39.9 Hz, tJ = 7.7 Hz) 1F, cis-CF ₂ CF = CF, -105.5 (d J = 117.8 Hz, each term dj »53.5 Hz, t J - 25, 1 Hz) 1F, trans-CF ₂ CF = CF, -122.2 (m) 6F, CF ₂ , -122.9 (m) 2F, CF ₂ , -125.7 (m) 2F, CF ₂ , - 126.5 (m) 2F, CF ₂ and -190.8 ppm (dJs 117.8 Hz, each term d J = 39.9 Hz, t 13.7 Hz, t 1.7

Hz) 1F, CF ₂ CF = C. C = 23 , 34 %; F = 73 , 84 % 't analysis C = 22nd , 99 F » 73 , 94 Calculated for C ₁₁ F ₂₂ O: found:

- 49 -

809823/0878

CR 7704 A

Example 20

2-trifluoromethoxypentafluoropropene [perfluoro (allyl methyl ether)]

COF ₂ + CsF + CF ₂ = CFCF ₂ OSO ₂ F> CF ₃ OCF ₂ CF = CF ₂

A mixture of 18.0 g (0.27 mol) of carbonyl fluoride, 38.0 g (0.25 mol) of cesium fluoride and 300 ml of dry diglyme is stirred for 2 hours at -20 to -10 ° C and then to -10 ° C or below while adding 46.0 g (0.20 mol) of perfluoroallyl fluorosulfate. The mixture is stirred at -10 ° C. for 2 hours, at 0 ° C. for 2 hours and then at 25 ° C. overnight. The mixture is then heated under a weak vacuum and the volatile distillate (11 ml of liquid which is collected at -80 ° C.) is redistilled in a low-temperature column. 3.2 g (2.0 ml at -80 ° C.; 0.014 mol) of 2-trifluoromethoxypropene are obtained; Yield 7%; Bp 11-12 ° C. The structure is confirmed by the spectra: X (gas phase) 5.55 (CF = CF ₂ ), 8-9 (CF, CO) and 5.35 pm (weak COF impurity band); ^ F NMR (CCl ₄ ), -56.5 (t J = 9.2 Hz) 3F, CF ₃ O, -74.6 (d J >> 25.8 Hz, each term d J = 13.6, q J «9.2 Hz, d J = 7.1 Hz) 2F, OCF ₂ C = C; -92.2 (d J = 53.4 Hz, each term d J = 39.2 Hz, t J = 7.1 Hz) 1F, CiS-CF ₂ CF = CF, -105.5 (d J = 118 , 0 Hz, each term d J = 53.4 Hz, t J - 25.8 Hz), 1F, trans-CF ₂ CF = CF and -190.9 ppm (d J = 118.0 Hz, each term d J = 39.2 Hz, t J = 13.6 Hz) 1F, CF ₂ CF = C.

Example 21 Perfluoro-6- (2-propenyloxy) -caproic acid and its methyl ester

. ■ · ι

KCOF + KF + CF ₉ ■ CFCP ₀ OSO-F - *!

- CFCF ₂ OCF ₂ CP ₂ CP ₂ J ₂ + CF ₂ · CPCF ₂ O (CF ₂ J ₅ COF j

? _? " CFCF ₂ O (CF ₂ ) ₅ COF ^H 2 ⁰ · ^ CFg - CFCF ₂ O (CF ₂ J ₅ CO ₂ H ^ (OT OCIIgCHgOCHgCHgOCH) ^H g ^S0 4 ν CP - CFCF ₂ O (CF J CO H +

Distillery / °

CP ₂ - CPCP ₂ O (CF ₂ J ₅ CO ₂ CH ₃

- 50 -809823/0878

CR 7704 A 60

A mixture of 11.7 g (0.20 mol) of potassium fluoride, 250 ml of diglyme and 58.8 g (0.20 mol) of octafluoroadipoyl difluoride is stirred at 0 to 5 ° C. for 30 minutes. The mixture is kept at 0 to 5 ° C., 46.0 g (0.20 mol) of perfluoroallyl fluorosulfate (prepared according to Example 2A) being added dropwise. When the addition is complete, the mixture is stirred at 0 to 5 ° C. for 2 hours, then allowed to warm to 25 ° C. and stirred for a further 4 hours. 45 ml of liquid are distilled off from the reaction mixture at 35 ° C. under a pressure of 3 mm Hg. The higher-boiling residue is poured into 1 l of water and the lower layer (10 ml) is combined with the volatile fraction obtained in the above-mentioned distillation, and a mixture of 100 ml of water and 20 ml of diglyme is added. After an exothermic reaction has taken place, the mixture is allowed to cool, the lower layer is separated off and it is distilled. Han receives 13.6 g (0.023 mol) of perfluoro-1,6-bis (2-propenyloxy) -hexane (Example 13; yield 23 %; bp _{6 mm} = 61 ° C) and 52.8 g (0.109 mol) a complex compound of 2 moles of perfluoro-6- (2-propenyloxy) -caproic acid and 1 mole of diglyme (Example 13 »yield 54.5 %; b.p. _{0 8} ^ = 82-84 ° C).

The diglyme complex compound of the higher-boiling fraction is distilled over 40 ml of concentrated sulfuric acid, whereby perfluoro-6- (2-propenyloxy) -caproic acid, which contains its methyl ester in an amount of 12,96, is obtained. The ester was formed by the action of sulfuric acid on the diglyme contained in the complex compound. The products are identified as follows: By ultrared analysis X _max 2.82 and 3-4 (OH, CH ₃ ), 5.58 (CF = CF ₂ ), 5.61 (C = O) and 7-10 μm (CF, CO, CH) and by ¹ H-NMR, ^ 3.92 (OCH,) and 11.33 ppm (OH) signals in the ratio 1: 7.2; the

F-NMR spectrum is also in agreement with these Structures.

- 51 -

809823/0878

CR 7704 A

Example 22 *

Perfluoro-6- (2-propenyloxy) caproic acid

The reaction is carried out according to Example 21. The crude reaction mixture is poured into 750 ml of water and the lower layer is washed with 100 ml of water. Distillation of the crude lower layer gives the same two products as in Example 21. The fraction boiling at 6 mm Hg at 45 to 53 ° C. is freed from diglyme by washing with water, giving 9.5 g (0.016 mol) of crude perfluoro -1,6-bis (2-propenyloxy) hexane remain; Yield 16 %.

The higher-boiling complex compound of perfluoro-6- (2-propenyloxy) -caproic acid and diglyme is dissolved in 50 ml of 1,1,2-trichloro-1,2,2-trifluoroethylene and extracted successively with 50 ml and then with 25 ml of concentrated sulfuric acid . The organic layer is treated with calcium sulfate, filtered and distilled to give 42.2 g (0.0988 mol) of pure perfluoro-6- (2-propenyloxy) -caproic acid; Yield 49 % 1 bp ₁ Q «75 ° C. This material is determined by ultra-red analysis ^ I 84 () () 6 (

2.85-4.0 (Η-bonded OH), 5.57 (CF = CFp), 5.63 (shoulder, C = O) and 8-9 pm (CF, CO), and by its H- and ¹⁹ F-NMR spectra identified.

analysis

Calculated for C ₉ HF ₁₅ O ₃ : C »24.45 %; H - 0.23 %; F «64.66 %; found: C - 24.48 %; H - 0.45 % ', F - 65.76 %.

The following examples explain the preparation of valuable copolymers from the polyfluoroallyloxy comonomers according to Invention. The general properties of these copolymers are described below.

- 52 -

809823/0878

CR 7704 A ,,

Application examples Example A

Solution polymerization of tetrafluoroethylene with 2- [i- (Penta fluoro-2-propenyloxy)] - tetrafluoroethanesulfonyl fluoride

η χ CFa »CFa + xCFa * CPCPaOCFaCFaSO ₃ P

- (CPa-CPa) _n -CPaCP

I. CPaOCFaCFaSOaF

A 80 ml capacity, lined with stainless steel tube is with a cold (-45 ° C) mixture of 10 ml 1,1,2-trichloro-1,2,2-trifluoroethane, 1 ml of an 8 percent solution of pentafluoropropionyl peroxide in 1,1,2-trichloro-i, 2,2-trifluoroethane (3P initiator) and 17.5 g (0.053 mol) of 2- [1- (pentafluoro-2-propenyloxy)] tetrafluoroethanesulfonyl fluoride (see Example 7) loaded. The tube is closed, cooled to -40 ° C., evacuated and charged with 20 g (0.20 mol) of tetrafluoroethylene. The tube is heated to 25 ° C. and shaken at this temperature for 20 hours. The volatiles are allowed to evaporate and the resulting polymer is held under a vacuum of 0.5 mm Hg. The product is then extracted with 1,1,2-trichloro-i, 2,2-trifluoroethane and dried under vacuum, 16.9 g of a solid white copolymer being obtained; Yield 85 % i A _mev (KBr) 6.79 (SO ₅ F) and 12.3 pm (broad) apart from the usual ultrared bands of polytetrafluoroethylene. The gravimetric sulfur analysis shows 0.48 and 0.20% S, corresponding to an average of 0.34% S or 3.5 wt.% (1.1 mol%) of the Polyfluorallyloxy comonomers, which corresponds to an equivalent weight of 9400. The equivalent weight is the molecular weight of the polymer per functional group (here —SO ₂ F). Differential scanning calorimetry (hereinafter abbreviated to DSC) shows a 12 percent

- 53 -

809823/0878

CR 77OA A

ge reduction of the endothermic maximum (melting point) compared to polytetrafluoroethylene.

example

Solution polymerization of tetrafluoroethylene with 1- [1- (penta-fluoro-2-propenyloxy)] - hexafluoropropane-2-sulfonylfluoride

x CFaOCFCFaOCF ₈ CF-SOaF + IUcCF ₈ -CF ₈ CFa

- (CFa-CFa) _n -CFaCF

CFa CF ₈ OCFSOaF

It works according to Example A with 10 ml of 1,1,2 trifluoroethane, 2.0 ml of an 8 percent solution of pentafluoropropionyl peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane, 17, ^ g (0.046 mol ) 1- [1- (Pentafluoro-2-propenyloxy)] -hexafluoropropane-2-sulfonyl fluoride (see. Example 9) and 20 g (0.20 mol) of tetrafluoroethylene and receives 16.7 g of copolymer; Yield 79 %. The analysis by X-ray fluorescence shows 0.49 96 S, corresponding to 5.8 wt. # (1.6 mol%) of the polyfluoroallyloxy comonomer, which corresponds to an equivalent weight of 6540. The sample shows a lowering of the melting point by 11 ° C compared with polytetrafluoroethylene, determined by DSC.

Example C

Solution polymerization of tetrafluoroethylene with 3- [i- (penta fluorine-2-propenyloxy) 3-tetrafluoropropionyl fluoride

X CF ₈ -CFCF ₈ OCF ₈ CFa COF + nxCFa-CFa

(CFa-CFa) _n -CF ₈ CF.

CFaOCF ₈ CFaCOF

NaOH

809823/0878

CR 7704 A

-T (CPa-CPa) _n -CPaCP

CFaOCFaCPaCO ₈ Na

Example A is used with 13.3 g (0.045 mol) of 3- [i- (pentafluoro-2-propenyloxy)] tetrafluoropropionyl fluoride (See. Example 5) instead of 2- [i- (pentafluoro-2-propenyloxy)] - tetrafluoroethanesulfonyl fluoride and receives 17.8 g of Co-

IDcIjC

(KBr) 5.62 (CO _? H, weak)

polymer; Yield 86 %;
and 9.7 µm bands other than the polytetrafluoroethylene bands; the lowering of the melting point (DSC) compared to polytetrafluoroethylene is 14 ° C .; the gravimetric analysis shows 3.7% by weight of polyfluoroallyloxy comonomer, corresponding to an equivalent weight of 7900.

A sample of the polymer is stirred with a solution of sodium hydroxide in 33 percent ethanol for two days, filtered and washed with water until the extracts no longer react alkaline. The polymer can now easily be wetted by water and is dried under vacuum. Analysis by atomic absorption spectroscopy shows 0.29 % Na, corresponding to 3.7% by weight (1.3 mol%) of the original comonomer.

Example D

Solution polymerization of tetrafluoroethylene with 1- (1,1,1,2, 3,3-hexafluoro-3-chloro-2-propoxy) -pentafluoro-2-propene

CPa
X CFa ¹⁹ CFCFaOCPCFaCl + XnCF ₈ ⁰¹ CPa

- (CPa-CPa) _n -CP ₈ CP

CFaOCFCFaCl CFa

- 55 -809823/0878

CR 77OA A £

Example A is used with 14.3 g (0.043 mol) of 1- (1,1,1,2,3,3-hexafluoro-3-chloro-2-propoxy) pentafluoro-2-propene (see Example 2 ) instead of 2- [1- (pentafluoro-2-propenyloxy)] - tetrafluoroethanesulfonyl fluoride and receives 18.3 g of copolymer; Yield 87% · The lowering of the melting point (DSC) in comparison to polytetrafluoroethylene is 14 ° C. The gravimetric analysis gives 0.61% Cl and 0.61, corresponding to 5.7 wt.% Of Polyfluorallyloxy comonomers and an equivalent weight of 5800 ; a more detailed analysis by X-ray fluorescence gives 0.53% Cl, corresponding to 5.0 wt.% (1.56 mole 96) of the Polyfluorallyloxy comonomers. The reduction in the melting point compared to polytetrafluoroethylene is 14 ° C., which corresponds to a reduction in the melting point by 1 ° C. per 0.1 mol% of the polyfluoroallyloxy comonomer contained in the copolymer. In contrast to this result, the lower branching in hexafluoropropene leads to a lowering of the melting point, corresponding to about 1 C per 0.3 mol-96 of the comonomer in its copolymer em with tetrafluoroethylene. This means that copolymers which are produced with the polyfluoroallyloxy comonomers have a better deformability than copolymers which are produced with hexafluoropropene as comonomer with the same mol% content of comonomer.

Example E.

Solution polymerization of tetrafluoroethylene with 2- (1-pentafluoro-2-propenyloxy) -hexafluoropropane-1-sulfonyl fluoride

χ CFa-CFCFa

CF. .

OCFCFaSOaF + xn CFa ^β CFa

t (CFa-CFa) _ir CF ₈ CF -L CFaOCFCFaSOaF I Af. ^J

- 56 -

809823/0878

CR 7704 A iU

Example A is used with 16.1 g (0.042 mol) of 2- (1-pentafluoro-2-propenyloxy) hexafluoropropane-1-sulfonyl fluoride (see Example 3) instead of 2- [i- (pentafluoro-2-propenyloxy) )] - tetrafluoroethanesulfonyl fluoride and receives 18.5 g of copolymer; Yield 88 %; the lowering of the melting point (DSC) compared to polytetrafluoroethylene is 8 ° C; the analysis by X-ray fluorescence gives 0.43 % S, corresponding to 5.1% by weight (1.4 mol%) of polyfluoroallyloxy comonomer and an equivalent weight of 7460.

Example F

Solution polymerization of vinylidene fluoride with 2- [i- (pentafluoro-2-propenyloxy)] - tetrafluoroethanesulfonyl fluoride

CH ₂ = CF ₂ + CF ₂ = CFCF ₂ OCf ₂ CF ₂ SO ₂ F> · Copolymer

Example A is used with 20 g (0.32 mol) of vinylidene fluoride, 16.5 g (0.05 mol) of 2- [i- (pentafluoro-2-propenyloxy)] tetrafluoroethanesulfonyl fluoride (see Example 7), 10 ml 1,1,2-trichloro-1,2,2-trifluoroethane and 5 ml of an 8 percent solution of pentafluoropropionyl peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane. The mixture is shaken overnight with a maximum temperature of 31 ° C being recorded. This gives 21.5 g of solid copolymer (60% yield) containing 46 wt.% (14.2 mol%) Polyfluorallyloxy-comonomer having an equivalent weight of 71.9. The DSC shows no thermal processes between 25 and 400 C.

analysis

Calculated for

(CH ₂ = CF ₂ ) _{6 # 05} (CF ₂ = CFCf ₂ OCF ₂ CF ₂ SO ₂ F):

C - 28.62 96; H = 1.70 %; S - 4.47 % found: C - 28.49 %; H - 1.71 % i D * 4.46 %.

- 57 -

8098 2 3/0878

CR 7704 A
Example G

Solution polymerization of vinylidene fluoride with 1- (heptafluoro- 2-propoxy) -1,1,3,3-tetrafluoro-2-chloro-2-propene

2 = CF ₂ + CP ₂ ■ CCICF ₂ OCF (CFj) ₂ > copolymer

Example F is used with 10.5 g (0.032 mol) of 1- (heptafluoro-2-propoxy) -1,1,3,3-tetrafluoro-2-chloro-2-propene (cf. Example 1) instead of 2- [i- (pentafluoro-2-propenyloxy)] tetrafluoroethanesulfonyl fluoride and contains 20.6 g of solid copolymer; Yield 73%. This material contains 36% by weight (9.8 mol-96) polyfluoroallyloxy comonomer with an equivalent weight of 878. DSC confirms the structure as a copolymer and indicates heat resistance because in the range of 25 to 400 ° C no thermal processes are observed.

Example H

Solution polymerization of tetrafluoroethylene with perfluoro- 3- (butoxy) -propene

CF ₂ = CF ₂ + CF, (CF ₂ ), OCF ₂ CF = CF ₂ > copolymer

Example A is used with 19.0 g (0.052 mol) of perfluoro-3- (butoxy) propene (cf. Example 18), 20 g (0.20 mol) of tetrafluoroethylene, 10 ml of 1,1,2-trichloro-1 , 2,2-trifluoroethane and 2 ml of an 8 percent solution of pentafluoropropionyl peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane and receives 18.9 g solid copolymer. This raw material is crushed in a mixer with additional solvent, rinsed and dried. 16.5 g of copolymer with a melting point of 309 ° C, which means that it is a real copolymer.

- 58 -

809823/0878

Example I.

Solution polymerization of tetrafluoroethylene with perfluoro -1,6-bis- (2-propenyloxy) -hexane

CF ₂ = CF ₂ + (CF ₂ = CFCF ₂ OCF ₂ Cf ₂ CF ₂ ) 2> copolymer

The procedure is as in Example H. using 20 g (0.20 mol) of perfluoro-1,6-bis (2-propenyloxy) hexane as the polyfluoroallyloxy comonomer (cf. Example 13). This gives 16.3 g dry powdery polymer with A 5.55 µm (CF = CF ₂ ); the rest of the infrared spectrum resembles that of polytetrafluoroethylene. The DSC shows a pronounced exothermic maximum at 315 ° C. and then an endothermic maximum at approximately 333 ° C. and at 339 ° C. on the first heating; on the second heating there is no exothermic maximum and a broad endothermic maximum at about 326 ° C. The ultrared spectra show that on the first heating pyrolytic reactions of the pentafluoroallyloxy side groups have taken place; the broad endothermic maximum in the DSC near the normally sharp melting point of polytetrafluoroethylene indicates that crosslinking has taken place.

Example J

Solution polymerization of vinylidene fluoride and perfluoro- 1,3-bis (2-propenyloxy) propane

CH ₂ = CF ₂ + (CF ₂ = CFCF ₂ OCF ₂ ) ₂ CF ₂ > copolymer

A mixture of 5 _f 7 g (0.013 mol) of perfluoro-1 _t 3-bis (2-propen yloxy) propane (see Example 17), 25 ml of 1,1 , 3-trichloro 1,2,2- trifluoroethane and 5 ml of a θ percent solution of pentafluoropropionyl peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane is kept at -40 ° C. in a stainless steel-lined shaker tube, with 20 g (0.32 mol ) Vinylidene fluoride are condensed into the tube. Daa Ge

- 59 -809823/0878

CR 7704 A £

the mixture is shaken overnight at room temperature and the product is isolated as described above. The crude polymer is dried under vacuum, powdered with 95% ethanol in a blender, filtered and dried. 24.0 g of solid copolymer are obtained. The DSC shows an endothermic maximum at 124 ° C and stability up to at least 300 ° C, which shows that a true copolymer has formed, since polyvinylidene fluoride has a melting point of 171 ° C. The insolubility of this product in acetone and the fact that no absorption bands for CF = CF ₂ side groups appear in the ultrared analysis indicate that crosslinking has taken place.

Example K

Copolymer of tetrafluoroethylene and perfluoro-3 _t 6-dioxanone- 8-enoic acid methyl ester

45 g of methyl perfluoro-3,6-dioxanone-8-enoate and 0.04 g of perfluoropropionyl peroxide are reacted for 4 hours at 50 ° C. under a tetrafluoroethylene pressure of 0.7 kg / cm. Filtration gives a solid which, after drying at 50 ° C. in a vacuum oven, weighs 0.71 g. 4 g of tetrafluoroethylene have been added. An equivalent weight of 1176 is determined by titration; therefore, the amount of ester groups in the polymer is 28 % and the yield based on tetrafluoroethylene is 20 %. A transparent film is obtained by heating in a Carver press to 220 ° C.

Example L

Colorable fluorocarbon polymers

Samples of the polymers produced in Examples B and E are treated for one day at 25 ° C. with aqueous alcoholic ammonia solutions, filtered, washed with aqueous ethanol and dried under vacuum.

- 60 -

809823/0878

CR 7704 A ^ O

A sample of the polymer produced according to Example C is treated in a similar manner with aqueous-alcoholic sodium hydroxide solution.

These partially hydrolyzed polymers are immersed in aqueous-ethanolic solutions of "Sevron Red GL" for 1 to 3 hours at 25 ° C. have excellent fastness and luminosity; cf. Du Pont Products Book, January 1975 _f page 34) and then extracted until the extracts no longer contain any dye. All three samples are colored well orange-red.

Example M Wettable fluorocarbon polymer

A sample of the polymer prepared according to Example C is Treated according to Example L with aqueous-alcoholic sodium hydroxide solution. The fluorocarbon polymer thus obtained contains carbonyl groups and is wetted by water.

Example N

Emulsion polymerization of tetrafluoroethylene with 2- [i- ( pentafluor-2-propenyloxy)] - tetrafluoroethanesulfonylfluorld

CF ₂ = CF ₂ + CF ₂ = CFCF ₂ OCf ₂ CF ₂ SO ₂ F> copolymer

A stainless steel shaking tube is filled with 140 ml of water, 10 ml 1,1,2-trichloro-1,2,2-trifluoroethane, 6.0 g 2- [i- (pentafluoro-2-propenyloxy)] tetrafluoroethanesulfonyl fluoride (cf. Example 7), 0.16 g of potassium perfluorooctanesulfonate, 0.50 g of ammonium carbonate and 0.50 g of ammonium persulfate are charged. The mixture is brought to an internal overpressure of 14 kg / cm by introducing tetrafluoroethylene and heated to 70 ° C

- 61 -

809823/0878

heats. The tetrafluoroethylene pressure is maintained at 14 kg / cm overpressure at 70 ° C. for 45 minutes. The polymeric product is filtered off, washed and dried. 43.2 g of a white solid material are obtained which contain approximately 1.4 parts by weight (0.43 mol%) of polyfluoroallyloxy comonomer, determined by ultrared analysis. The differential thermal analysis (hereinafter abbreviated as DME) shows a crystalline transition at 10 ° C, one cycle freezing temperature of 293 ° C and a cycle melting point of 311 ° C, resulting in the content of the PoIyfluorallyloxy comonomers to 3.5 wt.% (1, 09 mol%) is determined.

example

Emulsion polymerization of tetrafluoroethylene with 2- [i- ( pentafluoro-2-propenyloxy)] tetrafluoroethanesulfonyl fluoride

CF ₂ = CF ₂ + CF ₂ = CFCF ₂ OCf ₂ CF ₂ SO ₂ F ^ copolymer

It works according to Example BE with 8.0 g of 2- [i- (pentafluoro-2-propenyloxy)] - tetrafluoroethanesulfonyl fluoride, 0.20 g of potassium perfluorooctanesulfonate and a tetrafluoroethylene excess pressure of 2.1 kg / cm at 70 ° C for a reaction time of 8 hours. The amounts of the other reactants are not changed. This gives 45 g of solid polymer, the ultra-red spectrum of which shows _{strong SO 2 F absorption.} The DTA shows a crystalline transition at 5 ° C, a cycle freezing temperature of 282 ° C and a cycle melting point of 300 ° C, corresponding to a content of the Polyfluorallyloxy comonomers of 5.9 wt.% (1.86 mol%).

Example P

Emulsion polymerization of tetrafluoroethylene with 2- [1- (penta- fluoro-2-propenyloxy)] - tetrafluoroethanesulfonylfluorld

You work according to Example Ni with 10.7 g of 2- (1-pentafluoro-2-propenyloxy) tetrafluorosulfonyl fluoride, 0.20 g of ammonium persul-

- 62 -

809823/0878

CR 7704 A

fat and a tetrafluoroethylene excess pressure of 3.5 kg / cm 70 ° C in a reaction time of 5 hours. The amounts of the other reactants are not changed. Here 28.6 g of a white polymer are obtained, the infrared spectrum of which has the presence of SC ^ F groups, corresponding to 3.5 % By weight (1.08 mol% of the polyfluoroallyloxy comonomer, shows. The DTA shows two melting points at 290 ° C and 317 ° C with an estimated comonomer content of 5.5% by weight (1.73 mol-90.

example

Copolymerization of tetrafluoroethylene with 2- [i- (pentafluoro-2-propenyloxy)] - tetrafluoroethanesulfonyl fluoride and making electrically conductive films from the copolymer

1IxCF ₂ = CF ₂ + XCF ₂ = CFCF ₂ OCf ₂ CF ₂ SO ₂ F

("CF

₂ -CF ₂ ) -CF ₂ CF

CF ₂ OCF ₂ CF ₂ SO ₂ F

A steel tube is filled with 52.8 g of 2- [1- (pentafluoro-2-propenyloxy)] tetrafluoroethanesulfonyl fluoride (see Example 7) and a 6 percent solution of 0.19 g of pentafluoropropionyl peroxide in 1,1,2-trichloro 1,2,2-trifluoroethane charged as initiator. The mixture is heated to 40 ° C. and brought to an internal overpressure of 0.7 kg / cm with tetrafluoroethylene. The tetrafluoroethylene pressure of 0.7 kg / cm is maintained at 40 ° C. for 6 hours. The polymer product thus obtained is filtered off, washed and dried. Nan receives 9.82 g of a white solid substance: A fflax (KBr) 8.65 u (SO ₂ F) and 8-10 mm (wide) in addition to the usual _{ultra-red bathing of polytetrafluoroethylene.} The reduction in the melting point determined by DSC compared to polytetrafluoroethylene is

- 63 -

809823/0878

CR 7704 A / 3

91 ° C. The sulfur analysis by X-ray fluorescence gives 2.7 % S or 28.0% by weight (8.5 mol-96) of polyfluoroallyloxy comonomer, corresponding to an equivalent weight of 1180.

The product is pressed at 220 to 240 ° C to a clear, 0.1 to 0.125 mm thick film. Foil samples 10 cm in diameter are reacted with 13 to 15 percent potassium hydroxide solution for 1 hour at 90 ° C. and dried _{to form a copolymer of tetrafluoroethylene and CF 2} = CFCF ₂ OCF ₂ CF ₂ So ^ ^- K ^+. Ultrared spectra show an essentially complete conversion of the ~ S0 ₂ F functions into sulfonate salt groups.

The 0.1 to 0.125 mm thick film with a diameter of 10 cm is used as an ion exchange membrane in a chlor-alkali electrolysis cell, which has a current density of 0.31 A / cm is operated, cell voltage and current yield are determined as a function of the working time of the cell and the sodium hydroxide concentration. In a 15 day trial the following results are obtained:

Day Sodium hydroxide
(Product), % Current yield,
% Cell voltage,
V 1 21.5 70.7 3.35 10 21.5 71.2 3.45 15th 30.0 65.2 3.60 B e i s ρ i e 1 R Copolymerization of tetrafluoroethylene with
8-enoic acid and making an electrically
from the copolymer PerfIuor-6-oxanone-
conductive foil

nxCF _a -CF _a + xCF _a -CFCF _a O (CF ₈ UCOOH

• tCF _a CFa) _n -CF _a -CF

CF _a O (CF _a ) 4COOH

- 64 -809823/0878

You work according to Example Q with 47.5 g of perfluoro-6-oxanone-8-enoic acid, 0.05 g of an 8 percent solution of pentafluoropropionyl peroxide in 1,1,2-trichloro-i, 2,2-trifluoroethane and one Tetrafluoroethylene overpressure of 0.7 kg / cm at 40 C and is maintained 2.41 g of a solid, white copolymer. The lowering of the melting point determined by DSC compared to polytetrafluoroethylene is 157 ° C. The analysis of the carboxyl groups by titration shows 36.8% by weight (9.3 mol #) of polyfluoroallyloxy comonomer, corresponding to an equivalent weight of 1070.

According to Example Q, the copolymer is 0.1 to 0.125 mm thick film is pressed and hydrolyzed. The ultrared spectra show an essentially complete conversion of the

-COF functions in the carboxylic acid salt, resulting in the formation of a copolymer of TFE and CF ₂ = CFCF ₂ O (CF ₂ ) ACO ₂ ^- K ⁺ .

A 0.1 to 0.125 mm thick film sample of the polymer of 10 cm diameter is used as an ion exchange membrane in a Chlor-alkali cell is used, which is operated at a current density of 0.31 A / cm. In 76 days you will get the following Results:

Sodium hydroxide Current yield, Cell voltage, Day (Product), % % V 1 37.1 93.3 4.02 20th 39.2 90.9 4.60 35 39.4 87.7 4.25 50 32.9 92.0 4.11 76 34.6 85.8 4.67

End of description

- 65 -

\ 809823/0878

Claims (38)

CR 7704 A December 2, 1977 claims 1. Polyfluoroallyloxy compound, characterized by the general formula W D CF = C-CF-O-CG t I I ZX E in the X has the meaning -Cl or -F, W and Z independently of one another have the meaning -F or together can form the radical -CF ₂ -, D independently has the meaning -F, p. j ^CP3 "?" ° V ' T> CP ₂ = CPCP ₂ O or -Rp may have, wherein -R _{p is} a linear ^ outer branched-chain perfluoroalkyl radical with 1 to 10 carbon atoms, which must not be interrupted by 1 to 4 oxygen atoms more often than at every second carbon atom, and which has 0 to 2 functional groups of the composition - SO ₂ F, -COF, -CO ₂ H, -CO ₂ R, -Cl, -OCF ₂ CF = CF ₂ or -OCF ₂ CO ₂ R ³ , where R * is -CH, or -C ₂ Hc has, independently the meaning -F, -CF ,, -CF ₂ Cl, -CF ₂ CO ₂ R or -RpOCF (G) ₂ , wherein Br has the above meaning, and
and E together form a 5- or 6-membered ring ORIGINAL INSPECTED 809823/0878 Members -Rp- can form, where Rp is a perfluoroalkylene chain of 4 or 5 members, which may only be interrupted by 1 or 2 oxygen atoms and 0 to 2 -CF, groups as substituents, or a radical of the composition means while G has the meaning -F or -CF ₃ , optionally in the form of a copolymer with at least one ethylenically unsaturated monomer. 2. A compound according to claim 1, characterized in that D and E the meaning given for the independent residues where D is -F or R " according to claim 1 and E is -F, -CF ,, -CF ₂ Cl or CF ₂ CO ₂ R ³ . 3. A compound according to claim 2, characterized in that W and Z have the meanings given for the independent radicals to have. 4. Compound according to claim 3, characterized in that X is a fluorine atom. 5. A compound according to claim 4, characterized in that 2
Rp is a linear or branched-chain perfluoroalkyl radical with 1 to 8 carbon atoms, which must not be interrupted by more than one oxygen atom and 0 or a functional group of the composition -SO ₀ F, -COF, -Cl, -CO ₂ H, -CO ₂ R, -OCF ₂ CF = CF ₂ or -OCF ₂ CO ₂ R- ', where R is the methyl or ethyl radical. 809823/0878 6. A compound according to claim 1, characterized in that X means -Cl or -F. LL L. D has the meaning -CF ₀ R or -CFR, in which R is a radical ^ t CF ₃ -F, -SO ₂ F, -COF, -CO ₂ H or fCF ₂ ) ^ l and χ has a value from 1 to 6, where R is -CF ,, -OCF ₂ CF = CF ₂ , COF, -CO ₂ CH ₃ or -SO ₂ F, E is -F, -CF, or -CF ₂ Cl, and G, W and Z are fluorine atoms. 7. A compound according to claim 6, characterized in that R ^{5 is} a radical -CF, or -OCF ₂ CF = CF ₂ . 8. A compound according to claim 7, characterized in that X is -F, D is -CF ₂ R, E is -F and R is -SO ₂ F. 9. polyfluoroallyloxy compound according to claim 1, characterized by the general formula CF ₉ = C-CF ₅ -O-CF ¹ · in the χ E ' X signifies chlorine or fluorine, LL L. D has the meaning -CF ₅ R or CFR, in which R is a radical CF ₃ of the composition -F, -SO ₂ F, -COF, -CO ₂ H, -CO ₂ R, -OCF ₂ CO ₂ R ³ , in which Br is a methyl or ethyl radical, or ^ CFg) _x R, in which χ is a number from 1 to 6 and R is a radical CF ₃ or -OCF ₂ CF = CF ₂ , and E has the meaning -F, -CF ₃ or -CF ₂ CO ₂ R ', where R * has the above meaning. 10. A compound according to claim 9 _f, characterized in that X is a fluorine atom. 11. A compound according to claim 10, characterized in that E is the trifluoromethyl group. 12. A compound according to claim 10, characterized in that R ^ means -SO ₂ F, -COF, -CO ₂ R ³ , -OCF ₂ CO ₂ R ⁵ , where R ^{3 is} a methyl or ethyl radical, or -CO ₂ H has. 13. Compound according to claim 10, characterized in that E is a fluorine atom. 14. A compound according to claim 13, characterized in that 2
D has the meaning -Rp. 15 · Compound according to claim 14, characterized in that -Rp denotes the radical -CF ₂ OCF ₂ COF. 16. A compound according to claim 14, characterized in that -Rp denotes the radical -CF ₂ OCF ₂ CO ₂ CH. 17. A compound according to claim 10, characterized in that E is the radical -CF ₂ CO ₂ CH. 18. A compound according to claim 17, characterized in that 2
D has the meaning -Rp. 19. A compound according to claim 18, characterized in that -Rp denotes the radical -CF ₂ CO ₂ CH. 20. Polyfluoroallyloxy compound according to claim 1, characterized by the general formula D.
CF ₉ = C-CF ₅ -O-CG XE »
in which X has the meaning -Cl or -F, 809823/0878 2 2 D has the meaning -F or -Rp, where -R “is a linear one or branched-chain perfluoroalkyl radical with 1 to carbon atoms, which must not be interrupted by 1 to 4 oxygen atoms more often than at every second carbon atom and 0 to 2 functional groups of the composition -SOpF, -COF, -CO ₂ H, -CO ₂ R, - OCF ₂ CO ₂ R ³ , where R ^{3 is} a methyl or ethyl radical, -CO ₂ CH ^, -Cl or -OCF ₂ CF = CF ₂ , E is a radical -F, -CF ^ or -CF ₂ CO ₂ R ³ , in which R ^{3 has} the above meaning, -CF ₂ Cl or -RpOCF (F) ₂ , and G has the meaning -F or CF. 21. A compound according to claim 1, characterized in that the ethylenically unsaturated monomer is selected from the class of olefins, halogenated olefins, trifluoromethyl trifluorovinyl ether, acrylic acid esters and methacrylic acid esters. 22. Compound according to claim 1, characterized in that the polyfluoroallyloxy compound is the compound according to claim 6. 23. A compound according to claim 21, characterized in that it contains units of the polyfluoroallyloxy compound in amounts of Contains about 0.1 to 55% by weight. 24. A compound according to claim 22, characterized in that it contains units of the polyfluoroallyloxy compound in amounts of Contains about 0.1 to 55% by weight. 25. A compound according to claim 23, characterized in that the ethylenically unsaturated monomer vinylidene fluoride, monochlorotrlfluoroethylene, trifluoromethyl trifluorovinyl ether, Is tetrafluoroethylene or hexafluoropropylene. 809823/0878 CR 7704 A 26. A compound according to claim 25, characterized in that the ethylenically unsaturated monomer vinylidene fluoride, Monochlorine fluorine or tetrafluoroethylene is. 27. A compound according to claim 24, characterized in that it contains units of the polyfluoroallyloxy compound in amounts of Contains about 1 to 10% by weight. 28. Process for the preparation of polyfluoroallyloxy compounds according to claim 1, characterized in that one (1) a carbonyl compound represented by the general formula It A — C — B ' in the A can independently have the meaning -F, -COCF, or -Rp, in which Rp denotes a linear or branched-chain perfluoroalkyl radical with 1 to 10 carbon atoms, which must not be interrupted by 1 to 4 oxygen atoms more often than for every second carbon atom and 0 to 2 functional groups of the composition -SO ₀ F, -SO ₀ OCF ₀ CH ,, -COF, -Cl, 3 - ^ 3 -OCF ₂ CF = CF ₂ or -CO ₂ R, in which R has the meaning -CH, or -C ₂ Hc, B independently represents a radical -F, -CF ,, -CF ₀ Cl, CF ₀ CO ₀ R, 3 T where R has the above meaning, or -CF ₂ ORJ, where Rp has the above meaning, and A and B together can form a 5- or 6-membered ring of members of the composition -Rp-, where R ₁ -, a h- to 5-membered perfluoroalkylene chain, 809823/0878 interrupted only by 1 or 2 oxygen atoms may be, means, and can have 0 to 2 trifluoromethyl groups as substituents, with a metal fluoride of the general formula MF mixes and allows to react, wherein M has the meaning K-, Rb-, Cs- or R ^ N-, where the radicals -R is the same or can be different and denote alkyl radicals having 1 to 6 carbon atoms, and (2) The mixture obtained in (1) with a perfluoroallyl compound of the general formula CF = C-CF WXY mixes in the X has the meaning -Cl or -F, W and Z independently have the meaning -F or together form a -CF ₂ radical, and Y has the meaning -Cl or -OSO ₂ F. 29. The method according to claim 28, characterized in that Vf and Z have the meanings given for the independent radicals, X is a fluorine atom and Y is a radical -OSO ₂ F. 30. · The method according to claim 29, characterized in that M Means potassium. 31. The method according to claim 30, characterized in that A and B have the meanings given for the independent radicals. 32. The method according to claim 28, characterized in that steps (1) and (2) are carried out in an anhydrous aprotic polar solvent. 809823/0878 33. The method according to claim 32, characterized in that step (1) at a temperature in the range from -20 to + 60 ° C and step (2) at a temperature in the range from -20 to + 80 ° C. 34. The method according to claim 31, characterized in that steps (1) and (2) in an anhydrous aprotic polar solvent, namely step (1) at a Temperature in the range from 0 to 10 ° C and step (2) at a temperature in the range from about 0 to 30 ° C, be performed. 35. The method according to claim 34, characterized in that the solvent used is N, N-dimethylformamide _f 1- (2-methoxyethoxy) -2-methoxyethane, 2,5,8,11-tetraoxadodecane or acetonitrile. 36. Use of hydrolyzed or ionized copolymers of the perfluoroallyloxy compound according to claim 1 and 9, wherein R ^{4 is} -COF, -CO ₃ H, -CO ₂ R ³ , -SO ₂ P or -OCF ₂ CO ₂ R ³ or E die Meaning -CF ₂ CO ₂ R ³ , with at least one ethylenically unsaturated monomer, for the production of an electrically conductive membrane, in particular for the production of alkali hydroxide in a chlor-alkali cell. 37. Use according to claim 36, characterized in that the ethylenically unsaturated monomer is tetrafluoroethylene, Monochloritrifluoroethylene, vinylidene fluoride or TrifluormethyItrifluorvinylather is. 38. Use according to claim 37, characterized in that X is a fluorine atom. 809823/0878