JPS5896630A - Electroconductive film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyfluoroallyloxy compounds, processes for their production, and copolymers produced therefrom.

1. E, S, Lo tl) US Patent & 85a4ss
describes the preparation of fluoropryloxy-1,1-dihydroperfluoroalkane from 3-chloropentafluoropropene and 1,1-dihydroperfluoroalkanol in an alkaline medium, e.g. CF, =CH"CF
, C1-) HOCIiNCF.

-''Elephant L-→C^=CFC^ocBird CF.

is disclosed.

US Patent to λ W, TOM Iliede 2. @TL? l
I9 describes methods for replacing chlorine in non-fluoroallyl chlorides with methoxy, cyano, iodo and nitrate groups, e.g. CF*=CFCF*C1+Na0CHs →CF, -
CFC^0CH1 is disclosed.

& M, E, Redwood, and C1J, fj
jj4a.

Canat LJ, Cham, 48.389 (19
G? ) is allyl bromide and cesium butafluoro-2-
React with glopoxide to form 2-allyloxy! The reaction that produces tafluoroglopane, i.e. CH, -CH
CH, Br-1-(CF, ), CFO-Cm” →CH
, -CHCH, 0CF (CFs), -4-CBr.

4 J, A, Yosng, FiI&uring
ChatstryReviews, 1, 38
*-898 (19g?) is alkali metal fluoride perfluoroketone, /#-fluoroalkyloxirane, perfluorocar? This paper outlines the production of Δ-fluoroalkoxide anions by acting on phosphoric acid fluoride and non-fluoroalkyl fluorosulfate.

U.S. Patent Turtle 4S to Wh, R, A, Darky 6
84 is an arm-fluoroalkanoyl fluoride and 7
A process for the preparation of fluorocar I/polyethers and their polymers by reaction with potassium fluoride or quaternary ammonium fluoride and hexafluorogropene epoxide is disclosed.

Turtle A, G, Pittnan and W, L, Wa
U.S. Pat. No. 4,674,820 to Aleg describes the reaction of a fluoroketone with an alkali fluoride and an omega-haloalkanoate to produce an omega-(/#-fluoroalkoxy)alkanoate, for example (CF,) , CO+ KF -1-By(CH,), C
O, CHl-+ (C8), CFO (CM, )4CO,
C.B.

is disclosed.

7. E. Dosba U.S. Patent & 795,6
No. 84 also discloses the reaction of hexafluoroacetone with potassium fluoride and omega-haloalkanoic acid esters.

& A, G, Pittmtxn and W, L, Wa
U.S. patent for s l # y & 527.74 g
discloses the reduction of the compound of 6 above to the corresponding alcohol and the esterification of the alpool to a polymerizable acrylate.

& A, G, Pittma% and W, L, W
U.S. Patent No. 9&99g to aalay involves reacting a fluoroketone with an alkali metal fluoride and a 1,2-dihaloethane and then dehydrohalonating the intermediate 2-perfluoroalkoxyhaloethane. A process for producing (perfluoroal;
Discloses Br −+ (CF, ), CFOCR, C Bird B Day 25 J Munina (CF, ), CFOCH=C Parrot.

1 aCoE, US patent to Love%s & 3! L83
The meaning is the rearrangement of the parent fluoro-2-alkoxyalkanoyl fluoride to the fluoroalkoxyolefin by passing over 10 to 400 tons of metal oxide, such as OCF.

■ 2%0 + CFsCF-COF "'-""→CF,
0CF=CF, 10ZnF, 10Co.

is disclosed.

According to the invention, compounds of the formula -FlCFr-CFCF, 0 or -Rp, -RJ, can be interrupted with 1 to 4 oxygen atoms for every second and lower carbon atoms;
-8o, F, -COF, -Co, H, -Co, Ra
', -CI, -0CF, CF=CF* Oyohi-0
CF, Co, E' color, t il L * O ~ C 1-10 linear or branched perfluoroalkaline alcohol having 2 functional groups, R8 is -CH1 or -C3 Ashi~E is independently -F, -CF,, -C^C1゜-C^CO, R"jtasha-IJ, 0CF(G), and Bs is defined above. Torideashi, and D and E
- together form a 5- or 6-membered ring whose ring members are -Rp-, and RF is 1
or can be interrupted by two oxygen atoms, O-2
4 to 5 true/#-fluoroalkylene chains with -C^ substituents,
or, and G is -F or -C.

Furthermore, according to the present invention, (1) a set (in which A is independently +F, '-COCF, t or -R
ν, Rν is 1 to 4 for each second and subsequent carbon atoms.
can be interrupted by eight oxygen atoms, -so, eight -
so goose OCF goose CH.

-CO8 -C1, -QC^CF=C^ and -Co,
is a straight or branched chain C1-10 /4-fluoroalkyl having O-2 functional groups selected from R@, R1 is 109 or -hekarasu, and B is ,Independently,-F,,CF,,-C^C1,-CF,
CO, R Hatake, or -CF, ORν deshi, Bs and RY
is as defined above, and A and B together form a 5- or 6-membered ring in which the ring members are -Rp- and RF is interrupted by 1ial or 2 oxygen atoms. A compound having the formula (where y is 1Rh +, C#- or R,N-, each -R is the same or different, and has 1 to 1 carbon atoms
6 is an alkyl of and Z are independently -F, and together are -C8-, and Y is -ct or -8O,F). A method for producing a polyfluoroallyloxy compound is provided.

Furthermore, copolymers of the aforementioned polyfluoroallyloxy compounds and at least one ethylenically unsaturated monomer are provided.

The present invention uses starting materials 1.2- and 1 according to the following reaction formula.
For a compound of formula prepared from: Y D In the above reaction scheme, starting materials 1.2 and 3 react to form product 4 and its Jinpeng salt 5. Letters A, B
, D, E, G, M, W, X, Y and Z are as defined above. The products represented by the general structure can be converted into useful copolymers, especially with tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, and chlorotrifluoroethylene.

Preferred polyfluoroallyloxy compounds of formula 4 have D and E being independent, D is preferably -F or Rp, E is preferably -F1-CF, -CF
, Cl1ftli-CF, Co, Ra and hF), and Rs is 10H, or -C,H,. Preferred compounds also have W and Z which are independent, and X is -
It is F. Rv can preferably be interrupted by up to one oxygen atom, -80,F.

-COF, -Cj, -CO,HX-CO,Ra
, -0CF.

CF=CF, oj hee-0CFICO! RI is a straight-chain or branched perfluoroalkyl having 0 to 1 functional groups, Rs is -CH, and M9 is -C,H.

Particularly preferred 4-trifluoroallyloxy compounds according to the invention are of the formula
FICl, preferably -F1-CF, or -CJ%
CC)t R"teh'), R"bar"s t
Taher C is HI and D is R4 or -CFR4 to 10 and R4CF.

is -F, -80,F, -CUP', -Co,
H.

-CO, Ra, -〇CF, Co, R", -5, Ril
-1+C^)gR", R1 is 10H island or -C
, H, and R1 is -CF, -COF,
-CO, H, -Co, Rm, -80,F or -OC80F=C^. R4 is preferably -so, y,
-co8 -CO, H or -ocp', co, Rs
-t's ri, -t t, teRs is -CH, or -C
, Hl). The polyfluoroallyl group of product A is a preformed polyfluoroal derived from a metal fluoride and a carbonyl compound (1) from the corresponding polyfluoroallyl chloride or fluorosulfate (1);
Derivatized by nucleophilic substitution of the chloride or fluorosulfate group with an oxide anion. Therefore, the synthesis is the sequential addition of one container of reactants 1 and 1 to a suspension of 1 or solution #1 in the appropriate solvent.

Polyfluoroallyl fluorosulfate is the preferred reactant for this substitution, B,E.

5tnart, J, Or, Chum, 4 1,
23 5Jl (111 Chome 6) and 1976 8
May 27, 2003, can be conveniently prepared by treating a 14-lifluoroalkene with sulfur trioxide as described in US Patent Application No. 71 &337. Such reactions are typically carried out in sealed Carius tubes at 25 to 95
C. for 16 hours to 4 days, and the product fluorosulfate is purified by fractional distillation. The preparation of the preferred no#-fluoroallylsulfate (pentafluoro-2-probenylfluorosulfate) is described in Example 2.

Stable metal fluoroalkoxides are produced by the reaction of certain metal fluorides with tetrafluorinated carbon and acid fluorides, i.e. The usefulness of intermediate polyfluoroalkoxides is determined by their stability, as measured by their ease of thermal decomposition.Since their formation is reversible, the equilibrium of the various components in a given reaction mixture is determined by their stability. Concentration is the critical quantity that determines whether a subsequent Solutions of car/nyl compounds) may also be effective.

The production and chemistry of polyfluoroalkoxide anions depends on four conditions, which are detailed in J. A. Young.

1oe, tit, F.W., Evana, M.H.
, Litg, A.M.

Wgidlar-Kubanek and F. P. Avo.
nda, J.

h, 9km, , 33, 183? , 183
@ (1968), and M, A, Redwood and C0J.

Willia, Canad, J. Chum, 45
, 3811 (196 guns).

(1) Stable polyalkoxide anions are generated when cal-niyl compounds are highly fluorinated, since the electron withdrawal effect of the fluorine atom distributes negative charges across all interstitial ions. Chlorine, other fluoroalkyl t'#:
, some replacement of fluorine by hydrogen destabilizes the anion. This is because these groups have a low ability to withdraw electrons and are not easily replenished with negative charges. (2) Large cations, such as Ni+, Rh+, Ca
+ and R4N+ are more likely to form stable polyfluoroalkoxides than small cations, such as Li+ and (jNa+, because the lattice energy of metal fluorides is inversely proportional to the size of the cation. In other words: For example, the large cation size and small lattice energy are favorable for disrupting the metal heptadide crystal structure to generate cations.

(3) Solvents that have a high heat of dissolution for polyfluoroalkoxide tend to generate anions.

Aprotic polar solvents such as N,N-dimethylformamide (DMF), acetonitrile, and 1.2-
Dimethoxyethane (ylttma) is very effective for this purpose. (4) If an alpha fluorine atom is present relative to the oxygen atom in the anion, the loss of fluorine ions can be accompanied by the desired reaction. An example is: generate.

F allyl is required for parent substitution.

CF, O- is commonly known as F-rich nucleophilic substituted hano-fluoroallyl fluorosulfate.

In the practice of the present invention, the carzanyl compound is combined with a metal fluoride in an aprotic solvent. It is preferred to preform the -lifluoroalkoxide anion by adding it to the combined mixture. The completeness of the formation of the kuma ion is generally indicated by the extent to which the gold maple heptadide dissolves in the solvent as the reaction progresses. Stoichiometrically, the formation of a polyfluoroalkoxide anion requires an equivalent amount of tk 1 mole of metal fluoride for each cal-nyl group that is converted into the anion. For example: 鵠−FC(C^)40F+2KF□ The presence of up to a two-fold molar excess of metal fluoride generally does not give negative results. Two side effects of excess metal heptadide are:
(1) Preventing observation of the end point of the reaction due to the presence of undissolved solids in the reaction mixture; and (2)
) Excess dissolved fluoride ions can react directly with perfluoroallyl fluorosulfate to form hexafluoropropene.

Since the thermal stability of polyfluoroalkoxy Y is limited, its formation is usually -! ! It is carried out between 0°C and +60°C, preferably with external cooling to maintain the temperature between 0-10°C.

The time required to complete the formation of the 4-trifluoroalkoxide varies with the cal content, but is preferably o,s-g hours and is usually determined by the time each individual pigeonhole reaction mixture becomes homogeneous. .

N, N-5
C), r-butyrolactone, 1.2-N methoxyethane (glyme), 1-(2-methoxyethoxy)-2
-Methoxyetay (dtglyma), 2, 5,
8.11-f5o #'rYr力y (tri-gly
me ), N-oxane, sulfolane, nitrobenzene and benzonitrile are examples of suitable aprotic solvents for the preparation of the 4-lifluoroalkoxide and its subsequent reaction with polyfluoroallyl fluoride or fluorosulfate.

The equipment, reaction components, and solvent should be suitably dry for use in the method of the invention. This is because polyfluoroalkoxides hydrolyze in the presence of water.
: <RF)*CFO-+ H*O→(RF)mc (OH
) 懺+FRpCF, 0-100-4RFCO2H+H^
One metal fluoride useful in the present invention is potassium fluoride (KF), rubidium fluoride (RbF), cesium fluoride (CsF), and tetraethylammonium fluoride (RlNF), such as tetraethylammonium fluoride ((CoHs >*NF) and tetrabutylammonium fluoride ((CoH*)aNF'J.R
are the same but different, alkyl having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Potassium fluoride is highly valued due to its availability, economical advantages, and ease of handling.
preferable.

Polyfluorinated carmenyl compounds useful in the present invention include:
Ketone fluoride, carboxylic acid fluoride and perfluorinated lactone 3,6-bis(trifluoromethyl)3,5,
5.8-tetrafluoro-1,4-dioxan-2-one. Ketones and lactones give branched fluorocarbon products, whereas acid heptadides give primary fluorocarbon products with a new ether linkage in the first or second center. : (Rp;), Co→(R1), C-0-C^CF=CF
.

(ketone) (Lactone) RyCOF −+ RyC＾oc＾CF=CF.

Acid Fluorides Examples of useful 4-reflated ketones are: hexafluoroacetone, chloropentafluoroacetone, 1,3-dichlorolotiderafluoroacetone, 1.
1-difluoroethyl-! -oxypentafluoroderonodane sulfonate, dimethyltetrafluoroacetone-1,3-t/carxylate, l,3-bis(2-
Hebutafluorozolo-4xy)tetrafluoropropanone, octafluorotutanone, decafluoro-2-pentanone, dodecafluoro-2-hexanone, tetradecafluoro-2-heptanone, hexadecafluoro-2-octanone, octadecafluoro -2-nonanone, eicosafluoro-2-decanone, and hexafluoro-2
, 3-butanedione.

Hexafluoro-2,3-butanezoone is a hexafluoro-2,3-butanezoone, which is formed by converting the initially formed fluoroalkoxide into fluoroallyl fluorosulfate and other molar equivalents of hexafluoro-2,3-butanzoone.
A special case in which two types of heterocyclic compounds are produced by reacting with both luoli-2,3-butanezoone (Reference Example 11)
It is.

Examples of useful polyfluoroyl sulfides are: heptafluoride, trifluoroacetyl fluoride, pentafluoroglopionyl fluoride, heptafluorobutyroyl heptafluoride, nonafluorofluoride. Pentanoyl, tetrafluoroVFCCF, OCk', CF fluorohexanoyl, tridecafluoroheptanoyl fluoride, pentadecafluorooctanoyl fluoride, hebutadecafluorononanoyl fluoride, nonadecafluorodecanoyl fluoride , V7 k 0 malonyl difluoride,
Tetrafluorosuccinyl difluoride, hexafluoropronotan-13-dioyl difluoride, hexafluoroglutaryl fluoride), 2-tafluorobutane-1 difluoride
, 4-octafluoroadipoyl fluoride in sea oil)
, decafluoropentane-1,! ! -1' oil (decafluoropimelyl niffluoride), dodecafluorohexane-1,6-t) oil (dodecafluoroberyl difluoride), fluorosulfonyl fluoride v
Fluoroacetyl, 2-(fluorosulfonyl) fluoride
-Tetrafluorogropionyl, fluoride*-(1-hebutafluorogropoxy)-tetrafluorogropionyl, 2-(2-(1-hegtafluoroproxy) fluoride)
hexafluoropropoxy]tetrafluorogropionyl, and g-(g-(2-(t-heptafluoropropoxy)hexafluoropropoxy]hexafluoropropoxy)tetrafluorogropionyl fluoride, and methoxydifluoroacetyl fluoride.

The ketone 1,1-difluoroethyl 2-oxobentafluoropropanesulfone) (Example 3) is a special case as a starting material. This is because it is an in situ source of the 2-oxopentafluoroglonodansulfonyl fluoride, and the 2-oxopentafluoroglonodansulfonyl fluoride was not isolated.

− C1 busy-cocp', so, ocノ'i, CB.

[CF, C0CF”, 80.F] CF'.

FSO, C^CFOCF, CF=CF.

Many of the starting materials are commercially available, e.g. PC
R0 Gat%eavilla, Florida is a supplier of fluorinated ketones and fluorinated carboxylic acids.

Examples 2, 3, 4, 5, 7, 9, 10, 11.12.1
3.18 and 19 are sources of some compounds and methods that are not commercially available. General example - Fluoroketone is perfluoro 71kfJ'/carcanoic acid,
(W.

A, 5happard and C0M, 5harts,
”OrganieFluorine Chemises
try', p, 365-368°W, A, Ba
*jamis, New Yor″h, 1e6s, h
, p.

Bram*dL4*> and E, T, MeBaa,
Advances Fluorine Chemt
atr s, s (1963)).

Fluoride/blue-fluoroalkane carboxylic acid and difluorinated perfluoroalkane-α,ω-dicaric acid can be prepared by treating the corresponding acid with sulfur tetrafluoride. By adding (F, S, Fawc a t t , C0W, Tul
lock, D, C (1/hannn, J, k
netech-^Son, , 84 41! 75,
428.5 (19@2)) and by electrolysis of alkanecarboxylic acid in hydrogen heptadide (A/, Hsdliak4.
” Chamiatry of Fluorine C
ornpos*da"tj'-86, Mg2-Mill
an(llvo, , HasDYork, 196
2) Manufactured by Rel. /4-Fluoroalkanedicanic acids are produced by oxidation of fluorinated α,--sialkenes or fluorinated cycloalkenes (H%dltck4
．． j maba (t,, 7.150-1551). Arm-fluoroalkyl polyethers with terminal acid fluoride groups are described in R6A, Darby O U.S. Patent 345a684 (
19g9) and P, Tarra%t, C, G, Al order #6S#, P, Barthold and E, C
0C05tu, Jr.

FLsorina Cha chicken Rav, , l, , 8
g (1971), hexafluoroglobene oxide and its fluoride ion-induced ori! - Can be manufactured from.

Stoichiometrically, substitution of polyfluoroallyl chloride or polyfluoroallyl fluorosulfate requires one molar equivalent of said reagent for each reactive center in the polyfluoroalkoxide anion.

However, with difunctional polyfluoroalkod-dPV, the stoichiometry can be adjusted to produce mono- or di-substituted products, i.e. O → FCC^CF, OCF, CF-CF, (Reference Example 5) → (C^-CFCF, QC^)tc^ (Reference example 1
? )FCO(CF,), COF 10KF +C＾諭CF
CF, F to O8 → C^-CFC^0 (C^), COF
(Reference example 21゜22) FCO (C^), COF +2KF + 2CF, =C
FC^080, F-+ (CFfCFCF, OCF,
CF, CF,).

(Reference Example 13).

The formation of the fluoroalkoxide and its subsequent reaction with polyfluoroallyl chloride or polyfluoroallyl fluorosulfate can be carried out sequentially in a glass apparatus at atmospheric pressure without separation of the intermediates, with precautions taken to exclude moisture. The use of cooling baths and cryogenic condensers (eg, packed with a mixture of dry ice and acetate) moderates the reaction and promotes retention of volatile reaction components and products. The progress of the W exchange reaction was determined by the salt MY(5
), gas-liquid chromatography (g
) and by fluorine nuclear magnetic resonance spectroscopy (1.FNMR).

The W exchange reaction is performed at 0°C to 10SO°C, preferably 0°C to 30°C.
It can be carried out at ℃. Typically, the reaction mixture is externally cooled to 0°C to 15°C during the addition of polyfluoroallylalkyl chloride or monolifluoroallyl fluorosulfate and then allowed to warm to 25°C to SO°C for the remainder of the reaction time. .

The time required to complete the substitution reaction varies between 1-24 hours, preferably 2-4 hours. Typically, the reaction mixture is externally cooled for 5-45 minutes during the addition of polyfluoroallyl chloride or polyfluoroallyl fluorosulfate and then stirred at room temperature for 2-3 hours.

The products of the reaction are isolated using standard procedures. In some cases, the reaction product is dependent on the high boiling solvent used (di
glym - boiling point 18 g"ClDMF boiling point 153 °C) to slightly more volatile To, by heating the reaction vessel to 30-50 °C under a vacuum of 1-1100 w #I.
It can be distilled into a trap cooled to °C. Alternatively, the reaction mixture can be poured into 5-'to times its volume of water to separate the insoluble lower layer of the fluoride-rich product, wash with additional water to remove the solvent, dry, phosphorus pentoxide or concentrated Fractionally distilled from sulfuric acid.

The 4-trifluorofluoroxy compounds of this invention are unsaturated monomers that can be converted into new and useful polymers. Polyfluoroallyloxy monomers can be homopolymerized under high pressure to form oligomeric compositions. However, for economic reasons of expensive monomers and the need for high pressure operation, it is preferred to copolymerize these monomers with cheaper ethylenically unsaturated monomers. Such ethylenically unsaturated mono! An example of - is
Niolefins such as ethylene or propylene-halonated olefins such as tetrafluoroethylene, trifluoroethylene, hexafluoropropylene, vinylidene fluoride, vinylidene chloride,
Trifluoromethyl trifluorovinyl ether, chlorotrifluoroethylene, and acrylic F11 or methacrylic acid. Halodanated olefins are preferred, especially tetrafluoroethylene, chlorotrifluoroethylene, trifluoromethyltrifluorovinyl ether, hexafluoropropylene and vinylidene fluoride. Such copolymers include -(tetrafluoroethylene), poly(trifluoroethylene), 't''J (vinylidene fluoride), and 4-(chlorotrifluoroethylene).
or have completely new or even more desirable properties that polyethylene does not have. Copolymerization can be defined as any method of incorporating two or more polymers as an integral part of a polymer. Copolymers are the products resulting from such processes. The relative numbers of different units need not be the same in different molecules of the copolymer or even in different parts of a single molecule.

About 5-5! A copolymer containing a polyfluoroallyloxy comonomer with an S weight of 96 (approximately 1 to 25 moles) has a lower melting point than the corresponding polyfluoroolefin;
As a result, they can be more easily molded and shaped into useful objects.

80,! or a copolymer containing about 0.1 to 10 wt., preferably about 1 to 10 wt. 80. which has an affinity for cationic dye molecules by being hydrolyzed to It can be a copolymer with OH1 or CQIH groups. That is, the fluorocarbon polymer can be dyed in a bright color. This is not possible with polyfluoroolefins that do not incorporate this type of co-monomer.

80, F! Friends are about 5 to 3 4-lyfluoroallyloxy comonomers with side groups of COF! s weight% (approximately 1.0 to 1
The copolymer containing 0 mol.
It can be a copolymer with H groups. Such copolymers have an affinity for water and are wettable by water. Polyfluoroolefins without this type of comonomer are non-wetting and impermeable to water. -80,OH4 or -CO,H or their ionized groups, such as -80,0-Ha+ or C01-Na+f, of polyfluoroallyloxy comonomers 1 containing about 1.0 to 10-E The second important feature is their ion exchange capacity. The special use of such a combination is as disclosed in German patent application λ25LI660, published on April 26, 1981, and Dutch patent application 7117598, published on June 29, 1973. This is in a lolo-alkali tank. In this cypress, an ion-exchange polymer in the form of a film-like membrane or septum is used to separate the anode and cathode parts of the cypress, and in these parts chlorine and water are removed, respectively, from the prine flowing within the anode part of the oak. Produces sodium oxide.

The properties of each copolymer depend on the distribution of heptanomeric units along the polymer chain. This is because a copolymer is a physical mixture of two or more polymers, each derived from a respective monomer.

It is well known that the composition of such copolymers is very different from the composition of the monomer mixture (feed) from which they are formed. Furthermore, [the relative tendency of monomers to be incorporated into a polymer chain does not correspond in any way to their relative polymerization rate...the relative properties of a growing polymer chain are primarily dependent on the monomer unit at the end of the growth. and overall independent of chain length and composition], C
oWalling, “Free Radicals I
n 5olstto*”99~Zoo Peso, John
Wilgy & 5ona.

1*a, New York (1957).

The copolymerization reactions to produce the copolymers of the present invention can be carried out using solutions, suspensions, or emulsions of the reactants and initiator in non-aqueous or aqueous media in a closed vessel with a stirring bar. This type of reaction is well known to experts in this field.

Copolymerization is initiated with free radical initiators. The initiator generally accounts for 0.001 to 5 g of the reaction mixture, preferably 0.0 g.
It is present at a concentration of 1 to 1°. Such free radical initiator systems can preferably be used at temperatures below 25°C, examples of which include, but are not limited to: pentafluorogropionyl peroxide (C
98000)*s Dithioric difluoride (N*Ft), azobisin butyronitrile, ultraviolet light and ammonium persulfate or potassium persulfate, monoferric sulfate (■), hydrogen peroxide, peroxyacid, Ammonium, potassium persulfate, cumenehydro/moxidide, t-butyl hydroperoxide
Mixtures with oligosilver nitrate and ammonium persulfate or potassium persulfate Mixtures with trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid or pentadecafluorooctanoic acid and ammonium persulfate or potassium persulfate.

The peroxide system can further contain sodium sulfite, sodium metabisulfite, or sodium thiosulfate.

When an aqueous emulsion system is used for the copolymerization, the system is a sodium or potassium salt of a saturated fatty acid having about 14 to 20 carbon atoms or a sodium salt of a perfluoroalkanoic acid and a fluoroalkanesulfonic acid having about 6 to 200 carbon atoms. or contain emulsifiers in the form of potassium salts, such as potassium stearate or potassium pentadecafluorooctanoate. These emulsifiers constitute 0.1 to 10.0 weight percent of the reaction mixture, preferably a5 to 5 weight percent.

Aqueous emulsion systems are usually buffered to a pH of 7 or above by adding disodium hydrogen phosphate, sodium metaborate, or ammonium metaborate in an amount of about 1 to 4 weight percent of the reaction mixture.

One of the following copolymerization systems is preferred for the preparation of the preferred copolymers of the invention: l) 1,1,2-trichloro-1,2°2-trifluoroethane containing pentafluoroglopionyl peroxide (Fraon@11.3) A solution of 11 or more comonomers in a solvent is heated at about 25°C in an autoclave.
At about 8 p.m., I lost my hearing.

The stock polymer is isolated by evaporation of the solvent, and monomers and lower oligomers are removed by washing with additional amounts of solvent.

g) an aqueous engineered malzoyone of two or more comonomers containing an emulsifier such as potassium fluorooctane sulfonate and an initiator such as ammonium persulfate;
Approximately 70℃ in an autoclave and! ! 0~200ps
A (1,4~1 ttKe/at) r - 0.
I lost track of it after 75-8 hours. The polymer is isolated by filtration and centrifugation.

3) When a large proportion (up to 25 mol %) of the polyfluoroallyloxy component is intended to be incorporated into the polymer in process l), the polyfluoroallyloxy comonomer f1,1,2-trichloro-1,2, It can be used as a solvent in place of 2-trifluoroethane.

The method of carrying out the present invention will be explained with reference to the following reference examples and examples. All parts and percentages are by weight unless otherwise specified. For structure confirmation analysis, the nuclear magnetic resonance chemical shifts of fluorine are ppm from internal fluorotrichloromethane and the nuclear magnetic resonance chemical shifts of protons are ppm from internal tetramethylsilane. Infrared and nuclear magnetic resonance spectra were recorded on undiluted liquid samples unless otherwise noted.

Reference example 1 Delonon (CF, ), CO-4-KF -)-CF, =CCIC
F, C1→ (C^), CFOCF, CC1=C^hexafluoroacetone (11!L6?, 0.10 mol) is distilled to produce potassium fluoride (&80F.

0.1 mol) and 1-(2-methoxyethoxy)-
Methoxyethane (hereinafter referred to as dilVrM) (lOO
*) to form a homogeneous solution. The mixture was maintained at 25-30°C and 1.2-
Dichloro-1,1,3,3-tetrafluoroglobene (
laar, o, xomol, H6Goldwkit-andori, G, Rowell, lselfemch-tortoise, sz, t
542 (manufactured according to LAS MA)). Mix this mixture for one night or one! Mix, then add this to water (soov).
) was injected. Wash the lower layer with water (250 m), dry,
When distilled, t-(heptafluoro-2-propoxy)
-t tl, 3. S-Tetrafluoro-2-chlorozolopey (13,Of, 0.019-El, 39%)
, a boiling point of 82-83℃ was obtained, and its structure is w1w! from the following data. i was: (CC1=CF,) and 7.5-10stn (CF,
C-0) Taika F NMR, -64,9 (m) 2F
, -0CF, C=C irises -7s, o(gjiku) 2F,
C=CF electric 1-81.1 (t J=r>'IHm,
Each member d J = LtHz) 6F.

CF, goalkeeper and 14a? 1ltx(tJ=22.
9Hi each member 111. Term J = t2Hs) tJF, CFOo
, Analysis C, CIF, , Calculated value for O: C, 2187: (1'l, 10.66 Actual value:
C,! 1.431Cj, 1a89 Reference Example 2 A) Pentafluoro-2-propenyl fluorosulfate (perfluoroallyl fluorosa OSO.

1 Goose-)-CFl=CF-CF! 080. F Commercially available liquid sulfur trioxide (10-) and hexafluoropropene (4S?
, α30 mol) was sealed in a Carius tube with a liquid gas atmosphere, mixed well at 25°C, and 1!
It was left at 5° C. for 4 days and finally heated in a steam bath for 6 hours. From two such tubes, a-(trifluoromethyl)-8,4,4-trifluoro-l-oxa-2-thiacyclobutane 2,2-8' oxide (
-Hydroxy-1-)lifluoromethyl-1,2,2
-) IJ fluoroethanesulfonic acid sulfonate) y, D,
CoEngland, M.A., Diatrieh
k and R0'%! , Lindsey, Jr.
, J., Amar, Chats.

, Soa, , at, stst (togo)) (gsr.

21%), boiling point 44°C, and pentafluoro-2-f
Ropenyl fluorosulfate) (hereinafter referred to as half-fluoroallyl fluorosulfate) (TSR, GS),
A boiling point of 58-60°C is obtained.

Non-fluoroallyl fluorosulfate is characterized by: Xmaz 5. ! S 5 (
C=C) and 6.7Hflm(So,)1'・FNM
R, 46, 1 (t J=&SH1, each member d J=L
BH Liao) IF.

So! F, -'14.0 (d J=2fLJHg, each member d J-IL9Hg, d J=&sHz, d
J=7.8H Liao) 2F, -91,2(d J==aO
HM, each member d J = 4α5Hz, t J = 7.8F
g) IJ', -1O47 (d J = 119.4H - error, each member d J = 50H wealth, d J = 2B, 2Hz)
IF, and -192,4pp 愼(d J=■44H
m, each member d J=40.5Hfl, t J=1&'
aHm.

dJe=1.8H atmosphere) IF.

B, 1-(1,1,1,2,3,3-hexafluoro-3-chloro-2-proxy)-pentafluoro-
2-Propene CF, COC^C1+KF+C^=CFC^080. F
C^Ct → CF, CFOCFtCF direct C^ Potassium fluoride (IL80fs 110 mol) todiQll bait * (X
The suspension with chloropentafluoroacetone (1 asr
, o, xo moles) are distilled and added. After the potassium heptadide was dissolved, perfluoroallylfluorosulfate (!&Of, 0.10 mol) was rapidly added while cooling the reaction mixture. The exothermic reaction that occurred was accompanied by sedimentation of the product. This mixture t-2! The volatile components were transferred by stirring at i'c for 1 hour and then heating the reaction mixture to −42° C. (swHg) in a tog cooled to -80° C. The volatile product is distilled from phosphorus pentoxide to give 1-
(1,1,1,2,3,8-hexafluoro-3-chloro-2-pro4xy)-penta7A/oro! -Propene (196F, (1089 mol, 59%) boiling point 85-8
6°C, and its properties were as follows: \mag
E[55(CI=CFt) and 'I-10l-10s
,C-',0)H"・FNMN,-gas(愼)t,F
, CFtCl , -69,1 (regular) 2F, CF, 0. −
'ItJ,, 8 (s) 8F, CF,, -11l thought (d
J-st'lHg, each member d J=89.8Fm,
tJ=7. ! ! Hm)tIFscis-CF, -CF
=CF, -1O41 (d J = 116.'lH dew, each member, d J = s table Ma Hg, t J = 44.0Fg)
IF,) Lance-CF Goose-CF=CF, -141,2(
t J = 22.8 Hz, each @, WL) IF, CF, and -19α4ppm (d J = 11s, tHs, each member d J = 39.8Hs, t J = 11t #g) l
F,-CF,Cχ=C1 Analysis C6CIF,,calculated value for 0:C,t! 1.6・7寥CJ, 10.116 Actual value: C, 21,34 rich (:'j, 10.1!1 Reference example 3 A) 2-oxopentafluoroglopanesulfonic acid CF, C=C^ 10 SO, → CF', CC^80. QC,
H1■ +C^CC^80. OH 1 C^CCF, 80. QC, 80 CF, CO, H → CF
, CCF, So, OR+ CF3Co, C, 搗 (+) Sulfur trioxide (tzsr, o, ts mol) is converted into 2-ethoxy-1,1,3,3,3-pentafluoropropropene 7 (D, W, Wi l l y and H,E.

S4wnona, Oh tn, JJ, 1
87 g (1964)) (29.0?, 0.165 mol), an exothermic reaction occurred. Distillation of the black reaction mixture yields the recovered 2-ethoxy-1,1,R
3,3-pentafluoropropene (tar, α03
6 mol, g2s, according to infrared analysis) and 2-oxo4
Ethyl fluoropronosulfonate (2o, gp
, 0.078 mol, 49% conversion and 63% yield) with a boiling point of 47-48°C (12ssmHy) and the characteristic values of the ester were: λmnz
& 34 and 141 (saturated CH), &1! O(C=0
), 7.01 (8090>e and 7.6-&5a
us(C-F, SO,)l ”HNMR, ats9(g
J-t, 2Hz) zH, OCH, and L51pp information (t J='1.2M-): R7, C#, 1凰"F
NMR,-'rFh,o(tJ=&3Hg)3F
.

CF, , and -107,4jlp (q J = Tortoise 3Hz) 9F, CF,.

(ii) using sulfur trioxide ($18f, 1.1 mol) and 2-ethoxy-1,1,3,3,3-pentafluoropropene (176f, 1.0 mol) at 0-5°C. , repeat the above reaction. A colorless reaction mixture was obtained which turned dark after standing overnight 9 and which was distilled to give the recovered 2-ethoxy-1,1,11,3,3-
Pentafluoropropene (2asr, a1s mol, 16
%), boiling point 46-48°C, ethyl 2-oxo-4-ntafluoropronopronosulfonate (141 Ltr, os fumol, 57 g conversion and yield of SSS), boiling point 48-s
2 DEG C. (tgsmHg) and a high boiling fraction consisting mainly of 2-oxopentafluoropropanesulfonic acid was obtained. When the crude acid is redistilled at 81-82°C (61 mHtl), the result is 35.6? (0.16 mol, conversion to 16q1 and 19% yield) of pure acid is obtained:
s (CC14, CaF, plate) 3.3 and 4.
Sparse (broad) (SOB), 5.58 (C=O).

7.18 (So, 0) and 7.5-9stn (CF
, SOB) 1”HNMRalo,t(ppm(a)8
0. OHI@*FNMR, -7r>x(*J-=r
,sH寥)sF,CF,.

and −t o s pp 愼(g J=′1.6H 廖)2F.

C.F.

Analysis C, HE”, for 0.S Calculated values: C, 15,80iH, 0,441F.

41.65iS, 14.06 Actual measurements: C, 1 & 951H, 0,551F.

41.56BS, 1&89 (i) Ethyl 2-oxopentafluoropronosulfonate (2&sf, o, tomol) t2B Stir at °C, trifluoroacetic acid (17,1f.

0.15 mol). This mixture was electrostatically charged overnight,
Then spinning band still (apt% sitag)
Heat to reflux (60°C) in a pot (hand atill).

This mixture was fractionally distilled at a temperature below 100°C, resulting in 2-oxopentafluoropropanesulfonic acid (1
&4f, 0.081 mol, 81 t), boiling point 73°C (!6
s+aug) was obtained.

11-difluoroethyl custom CF, CChSo, OH+ CF’, =CH, → Tsuba CF, CCP’, SO, OCF, CH.

2-oxopene-fluoroglopanesulfonic acid (2a,
A metal tube containing vinylidene fluoride (1,l-t/full k a
(13f% O-20mok) f
added. The mixture was shaken and warmed to 25°C where it was maintained for 4 hours. When the liquid product is distilled, 2
0.4 f (0,OTMok, 70%>(D2-oxypentafluoropropanesulfonic acid 1,1-difluoroethyl, boiling point 62-63°C i50smHtt>) was obtained:\mara(CCI,) LS4 (C=0)
, 6.96 (80,0) and 7.5-***(C
F, 80. )B'HNMR,aLO@ppm(t J
=143#g) CB, $ '・F NuR, -3as
(eJ=14.3H dew.Each member tJ='1.IHm)
2F, OCF.

-75,0 (t J = 8.OHm) 3F, CF, and -10 East ippm (q J = = 8., OH earthquake, each member t J = 1.1Hz) *F, CF@f; 0. .

Analysis C, H, F, 0. Calculated value for S: C, 10, 56; H, LO3 wealth F, 4,55! Actual value: C92α? 3gB, 1.03 wealth! , 4 rods 7! α8
Similar experiments on the molar scale gave a yield of 86% of the product, boiling point 60°C (SO2Ha). This material was stored in polytetrafluoroethylene bottles to prevent decomposition.

C,! -(1-pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl fluoride CF, CCF, SO, QC^C Bird 10KF -) CF
, TomiCFCF, 080. F ↓ CF, -CFoC1? , CF=CF, +CM, COF
+CF, SO, F KO8O, F 1, S”, s, tt-tetraoxadodecane (tr4g
Stir a suspension of dry potassium heptadide (a, sor, α 10 mol) in (100 d)
2-oxopentafluorozolonosulfonic acid 1 prepared as in Reference Example 3B.
, 1-difluoroethyl (29.2f, 0.10 mol) was added. When almost all of the potassium heptadide was dissolved, perfluoroallyl fluorosulfate (21O?, 0.10 mol) prepared as in Reference Example 2A was added at o'c and the resulting mixture was heated to gsC.
3 hours or tk mix nine. The volatile components were removed by distillation at a flask temperature of 25° C. and a pressure of 1 HQ. The distillate was washed with cold dilute ammonium hydroxide, dried, and diluted to yield 2-(l-penta7A/o-g-f ropenyloxy)hexafluorozolopane-l-sulfoelfluoride (11Of, 0.0S4 -% Le, 34ch), boiling point 47
~48°C (so-Bl) was obtained, and its structure was confirmed by the following data: input mataL69 (CF==x
CF, ), ale (80, F'p and 7.5-10
# Information (C-F, C-0, 80t) 1”F NMR, +
45.4 (m) IF, So, F, -7O, e (淋)z
F, oCFt , -q@, o (quadrut J=io, r11
) SF, CF, , -911 (d J=51.5#g
.

Each member d J=39L6HM, t J=1. IHm)
lF.

SisuCF嘗CF=CΣ, -104,8 (d J=1
17.6Ha, each member d J""5LSHz, g,
7=25.5#g) 1F, trans-CrtCF=Cj
:, -107,0 and -10&4 (AJB J-2
55H#, each member qJ=tαdingH1-”) Snow F, CF,
Flu! F, -131L (t J=2
0, 1! H customers, each! IIL) xF, CF, and -1
90.8pp (d J-117.0BM for each member)
J=39.6BM, tJ=1&OH Liao) IF, CF
Calculated value for electric CZ=C0 analysis C6FllOsS: C, 18,968F, 59.98 Wealth S, 114
B actual value: C, 19,! 4t F, 6α06t S, 1L2
6 In a reaction similar to Reference Example 3C, infrared analysis showed that the gas generated was mainly composed of acetyl heptafluoride and small amounts of hexafluoropropene and sulfuryl heptafluoride.

Reference example 4 A, 1. B-bis(2-hebutafluorozololoxy)tetrafluoroglopanone (CJ', ), GO+KF+CIF, CCCF
, C1→1 (CF, ), CFOC^CCF, 0CF (CFJ).

Dry potassium fluoride (gt, or, α36 mol),
Dry A/, 7V-dimethylformamide (DMF) (1
A mixture of hexafluoroacetone (S91F, 0.3 mol) and 1.3-$/chlorotetrafluoroacetone (3&8F, 0.18 mol) was heated under reflux for 3 days. Upon distillation into a trap cooled to -80°C, the recovered hexafluoroacetone (1a5m, 46
h) and 63f liquid with a boiling point of 30-145°C was obtained. Redistilling the high boilers from sulfuric acid yields 1,3-bis(2-hebutafluorozololoxy)tetrafluoropro/#non(satf, α017 mol, 21% conversion, 3g- based on hexafluoroacetone). yield), boiling point 1
1 to 118℃: %mam (CC14) 51 (C
, (j) and 7.5-9μ inertia (CF, C-0-C)r
彽inh/a 479 (jkf-Ji')",
313 (M-F -CF, C0CF,)", 263 (
MF, CJ', C0CF, -Cr)+, 23B[
(CF,), CFOC1i',]"91 all('s
'v)+e 14ma(CF, C0CF,)+, 97
(CF.

CO) + and as ((J',) 1"J' NM
R, -7 0 (d J-!IJ#g, each member septet J=
=tsH 廖)zF, OCF, , -81,4(m)sF,
CFm e and -14rLBpp (t J = 2L
511s, each member Te° doublet J=! IHg) IF, CF.

Analysis C0! ,, Calculated value for Ol: C, gtyo F, 5ass Actual value: C,! ! 110gF, @1L59B, 1-(1
, 3-bis(2-hebutafluoroguloxy)-2-pentafluorozolopoxy)-interfluoro-2-propene (CF, ), CFOCF, CCFtOCF (CF, ),
10KF-)CFt=CFC^080. F ↓ CF, = CFC＾0CFCCF, 0CF(CF,),)
.

1.3-bis(2-hebutafluorozololoxy)tetrafluoropronopronomonone (go, or, o, o4 mol),
A mixture of ds1y normal-(t o sg) and potassium fluoride (2.32f, 0.04 mol) was added to 1! Mix,
It was heated to 55°C. The two liquid phases and the initially present solid were homogeneously potassium and remained that way upon cooling. Sitaperfluoroallylfluorosulfate prepared as in Reference Example 2A (1(LOF, ao
43 mol) was rapidly added at 10° C. and the kernel mixture was allowed to boil. The somewhat exothermic reaction was accompanied by the precipitation of a solid and the appearance of a second liquid phase.

The mixture was stirred for 2 hours and then poured into water (SSOd). The lower layer was washed with water (7!Ss+/), dried over phosphorus pentoxide, and distilled to give 1-(t,S-bis(2-
fart! Tafluoro! -2-pentafluoropropoxy)-pentafluoro-2-guloin (ta, x
r, o, o2a2F, 62), boiling point 64~@7℃ (2
5w#g) was obtained and its structure was confirmed by the following data: kmam5.5? (Crt=CF) and '1.5-9p5-9p,C-0)1''F NM
R, -69,4(m)gF, OCF, C-C1-go,
s (wide > 4F, CFOCF, -81,5 (#) 1g
F, CFs, -93,7 (d J = 54.0Hl,
Each member d J = 39.6Hz, t J = 7.811)
)IF, cis-CF, -CF=C尤, -10as (
dJ=117. t#g.

Each member d J = 54.0Hz, t J = 23. 'lH
Liao) IF.

Trans-CF, CF=CF, -145,8(m)8F
, 0CF, and −190,9 ppm (d, 7=1
17.4 Fg.

Each member d J=39.6Hz, t J-46,6Fg
)IF.

CF, Cr=C.

Calculated value for analysis 'tlF140m: C, 22, 24; F, '10.35 Actual value: C
,2L66$F,? α27 Reference Example 5 3-methoxytetrafluoroglobionyl fluoride)
F (F, S, Fawctttt, C0W, Tull
ock andori, D., Coffman, J., Amgr.
,Cham, go c, .

84.4275 (1961) (81F, 0.45 mol) was added slowly to sulfur trioxide (80f, 1.0 mol) at 4°C and the product difluoroQ! Ronyl difluoride, with a boiling point of -9°C, was continuously taken out by distillation from a low-temperature distillation kettle, and 68f (0.40 mol, 90'f
A) was obtained. The structure of this product was confirmed from the following data: human emotion α1g1B60cm (CUFF,”
-FNMR (solvent-free).

+11.1pptlL (t J = 10Hz) x F, C
OF and one 11 table t, pp 愼(t J=1oH Liao)
2F, CF! .

La-(t-pentafluoro-2-propenyloxy)
Tetrafluoropropionyl fluora 1 FCCFCFOCFCF=CF.

Tomi! ! Dry potassium fluoride (7, sr, o, ts mol) and di
The mixture with gLymm (100 yd) was stirred at 10°C and difluoromalonylzofluoride (xasr, α13 moles) from Part A was distilled in. After 20 minutes, almost all of the potassium fluoride had dissolved and tano-fluoroallyl fluorosulfate (13 moles of go, or, α) prepared as in Reference Example 2A was added dropwise at 10-15°C. This mixture was stirred for 3 hours, then the volatile components were removed at a pot temperature of 32°C and 4 hours.
．． 8-H (1) was removed at a pressure of 1. Fractional distillation of the distillate yielded 3-(1-pentafluoro-2-propenyloxy)tetrafluoropropionyl fluoride (14,
The structure of the product was confirmed by the following data:
s(CoF), Fk, go (CF=CF,) and 7.6-10 μ inert (CF, C-0), l”F NMR2
&7 (apparent quartet, J=7.5Fg) IF, COF
.

-71,9 (d J-44,8H Liao, each member t J=
119H error * d J=l *sH glue, d
J=7.4H Liao) LF tOCF, C=C, -
3IL? (s)2F,CF,O,-@1.6(d
J=51.8Fg, each member d J==39.4HTl
t'J=7.4H fog) I F#cis-CF, CF=
CF, -101&,l(dJ=117.IHg, each member d, y=st, sHπ.

t J=24.6Hz) IFI) Lance-CF, -C
F-CF, -1tto(d J=agHg, each member t
J=&IH error) tF, FCOCFt, and -191
, Opp 愼(d, J=117.IHg, each member d, J=f
a9.4H customer, tJ=119#g, tJ=1.6H
z) IP, CF, -Cχ=C0 Calculated value for analysis C@FIfj°01: C, 24, 51 Actual value: C, 24, 1$ 6 Reference example 6 cscc＾OC＾CCl 5o f, @ICL4・mol )'s Jiku a, vxf) Lafuruo of human o7 run, 1M? ,8#(lLIMok)ON
@OH, a mixture of 3121 (1 mole Ll) of potassium permanganate and 1800111 moles of water was refluxed for 1 hour. When distilled for a short time (steam).

la@JF (3all recovered dihydrotura ν could be obtained, the reaction mixture was filtered and the filter cake was divided into 3×4
・Volatilize a total of nine Od solutions ground with Od water and '4hWc to give 1500-, and when cold, 5ooIIj@H,g
o4 and continuously extracted with ether for 1 day.

The extract was evaporated at 15° C. (α2 Htt) until no more ether evolved.

Crude solid 2III! , g7 reference I (ssl ma teno yield)
K.

5II (a06%&)F) viridine and 41111 (15
mol) of thionyl chloride was added. At this stage, a small amount of gas is generated and the mixture is mixed. ★A considerable amount of gas was generated as the temperature was increased to 40℃ or higher. 1. Pass the generated gas through a trap at 0℃ and leave it at about 40"Gk for 4 hours.
Gas evolution slows down and trap contents (lom)
The contents of the cold trap were then returned to the reaction from time to time until the head temperature reached 81°C and no gas was evolved, and this mixture was fractionally distilled at reflux. 111&g# (611 from dihydride field 7 run) Tetrafluorodiglycoyl talloy
, a boiling point of 94-9i°C was obtained. The structure was confirmed by NMRWC.

Tetrafluorodilicoil, boiling point 981℃
were previously produced by different routes (E, E,
Banks, E, D, 8% 714 mg, B, A.

D.dd, and 1M%lign, J, CAg5
．． Sem.

(C), 1-06 (191i19)).

Fluoride corresponding to diacid sugalide, boiling point s ~ s
Conversion to 8°C was achieved on a larger scale (R2
H, Banks, E, D, Baw14mg, B.

A, D.dd, and AfwjJgs, J.C.
Hew, Sea.

(C), 170G (11181)), 1116JF (a
ll 811 mol) of tetrafluoro aS/cricoyl ditarolide, 14α51 (& 3!$4 mol) (
DNd'.

and 1! Go- mixture of anhydrous acetonitrile [-1
The mixture was stirred overnight and then distilled to obtain a fraction collected at 3s to 9°C. This distillate was treated with 2 liters of A/a F and distilled to give 105N tetrafluoro V cricolyl V fluoride, S1-33°C.
00 J' (l3114 l) of N-Hatake F was added to the reaction mixture and slowly distilled, resulting in #maka fraction, boiling point 3s~81
'C can be obtained.

When treated with 161ONsF and distilled for 1 minute, other a y,
A difluoride product of OIi, boiling point 5 mN, 51°C was obtained, giving a total of 14211 (76 units).

1"ccF, OCI", CF + KF + CF, -
CF” (J', 08OJ→C^-CFC80F, C
F, QC^CF3111 (46 moles) 1.14L
A mixture of @1 (a6 moles) of tetrafluorodichloryl V fluoride and 500 m of dry digllate was stirred at 5'C for 30 minutes, during which time almost all of the KF was dissolved, and then 18411 (1187 mol) of perfluoroallyl fluoresulfate was added rapidly at 5°C and the mixture was stirred for 3 hours at O-5°C, 2 hours at 25°C and left overnight. Evaporate volatiles and digI
6 2tJION refluxed P# at ss℃ (s-Hg)
Distillation of volatiles from aF resulted in the recovered di[7F compound of sagy(go-), boiling point 31-38°C, and 1! IL
An acid fluoride of (ItSS-), almost all of which has a boiling point of 93 to 4°C, was obtained. The structure has been confirmed by the first order IR(CCEa)l180(COF)e! kl! *(
C-C), 8-1μCCF, C-0), NME*F1 turtle 3 (@IN@ *Fec()?')*-'ILOCda
dm g *I1mJFFlB, 13,13. γ, τH
z, 2F, vmcIPcF,).

-y y,s (t t ti e JF y t t
s e * y Zf m e t F mCI'@
Co@F ) m -8K8 (g * JJ'JP
1 t, tzrg e i! ! ,CF,OCF,C0
F) *-89,4(t, JFl' 117H*,s
r, fableCFCF, OCF, ), -1l1J (d, at.

t, Jyl B! ? #1G, s e 74ffg
, IP, vx-CI'.

CI"wmCI')*-1OLRCd*dateJl'
1117-6゜l117 m! 4@Jfg t 1j
P*)5yx-CFICFw, CF).

and -1lalPjlnawate (dads g e g Ja
y 1174°3 East 1, LfiHz, IF, CF
, CF-x).

Reference example 7 FSO, C^CF + KF + C^-CFC^OS
to F→FSO, C^C^OCF, F-C^digly
Potassium fluoride (&8L) in mac 100 m
Stir the soybean oil solution containing α10 mol).

Cool, while fluorosulfonyl difluorotetraacetyl fluoride (1 & (1, α10) (D, C6
JsgJasd, M, A, D E grtak and R
o V, Lindmay, Jv, , J.
Jbmav, Chasm.

5fes, 11! , 6181 (19@@)) were rapidly added. This mixture! Stir for 18 minutes at 0~30℃,
During this time, potassium fluoride was dissolved and this was then added to Reference Example I.
Perfluoroallylic 78 (2&0#) prepared as in A.

at 14) “t”gO-1! ! 'C for S minutes. The mixture was stirred for 3 hours during which solids precipitated and the temperature rose to 28°C.

It dropped again. The volatile components were transferred to a trap cooled to 0° C. by warming the solution to 38° C. and refluxing. The distillate was treated with concentrated sulfuric acid (XO*) to remove d (g l ym-) and then distilled to 2
-CI-pentafluoro-2-benyloxy)tetrafluoro42thanesulfol pw*94 P(1ti
e g, ao 8 mol, 609G).

A boiling point of 15 ~ l@℃ (is (ImHy) was obtained. The structure of the product was confirmed by the first order 11 ll51118# (CF, -CF), t 71 C8O,!") Oyobi? -10.ll5 (CF, (,0,So,) Liao1・F
NMR, +441 (t J 6H3, each member t J=
x6H Dew) IF.

FSO,, -71,11 (d, J=25.8H Liao,
Each member t J = LL8Hz, d J = IB, 8Hz,
dJ==7.3Fg)21? , OCF, C-C, -B
z6-2F, CF, CI? ,O,-kai a,eCd J
-sa, aHs.

Each member d Jtxs*, sHg, t Jxx'1. s
H Liao) 1F, xi-CF, CF=cz, -t O&!
! (d J-= 11?, ・Hm, each member d J
-B(L@Hg,t J-=-1!L8H Liao)IJ'
,) Lance-C^CFsCF, -111・(d J
=IL @ Hg *Each member t, ymzsHg) xF
, FSO, CF, , > and -11allFj1
m (d J=117.aHs, each member d J-39
, 14Hz, 處Jt=xl&8Hg, t J-L*
Hg')IJ', CF@C! Proverb C0 analysis C@F,,0
Calculated value for 1Si *C, 1 &111J', 5? , 1l
llS.

Koshiki 71 5iIIjIIJ Value IC, 11L3! I I F,
m'1.40 18゜169 Reference example 8 FSO, CF, CF + KF + C^=CFC^o
so,y→FSO,C^C^oc^CF-C^ The method of Reference Example F was repeated using acetonitrile instead of d4glymm as the solvent. Acetonitrile is not rigorously purified and is 2-(1-pentafluoro-gropenyloxy)tetrafluoroethanesulfonyl fluoride, boiling point! The yield of $4~ss'c (11 iomHg) was 4ONIs@%.

Reference example 9 C.F.

To FS CFCOF + Kl' + C^=CFC^0
80. ! cr.

→FSO, CFC^OC^CF-C^ Potassium fluoride A (!L8ON, aloe#) and dirt
lyma (* o o WJ) was stirred at 16 °C while 2-fluorosulfonyltetrafluorozolo♂onylfluoride)'(!L(1,alOmost
) (D, ClEngland, M, A, Diat
rimk and R, V, Z, (%damy, J de,
, J., Jhmaf, Cha Ming.

SOm,,a! 6181 (11@0)) was added.

Reference example of the nine solutions obtained at 10°C! After the addition was completed, the mixture was stirred for 3 hours at 15°C, then poured into water (100i1j), and the lower layer was mixed with water. (1001wj), dried, and distilled to form a gas-liquid liquid Elw) / Roughy Cylpm
> etc.] Pure 1-(1-(Pentafluor E1
-2-dep-benyloxy)]hexafluoropolysulfonyl fluorite (2L'r1.ao@I mol, 6111G), boiling point 50'C (go■H1) was obtained. What is the structure of the product?

next! 8λ-,,Lmm (CFxxCF
,), tYIC8O, ri>Lbi7.5-10s111(
CF, C-0,80,)l”・NMR, at@Cd
JexgayH Liao, each pg J=10.4Hm, d
J=31gHz)11', Sodo JF, -7l8(d
J hat>atoHm.

Feelings of each member J-1 &8##, d J-1 8Hged
J■T, 4Hg) Dew F, OCF, C=C, -7!1(
Moe) 3F, CF Hatake, -YLmCm) fltF, CF
Cj, 0. -9L0(d J=5a7Bgm each member d
ixs*ans, tJ='1.4H*) IF,
x-CF, CF-CF, -1O46 (d J-11
7JH Liao, each member d JsgsaγHa, tJ=2
1oHs)17'*)5yx-CF, CF-CF.

-134L4 (d, J-146Bg, each member q J-x
r, zBro, d J, = x2L8Hz) I J'
* CF e and -11111 ppm (d J=a
l17.6ffg, each member d J=x 31L 4 H
M ft Jc-1 turtle 8H, t J=xL'l
Hs) IF CF, C7l.

=C0 Analysis C1! ,, O, SK vs. Sur calculation value * Ce 1 & 961 F e 5 t 1
1 B! Se & 44 actual measurement value sC, 1 & 701J
Potassium fluoride CL11011 in ', 6α01NSt&O Hatake Reference Example 1O Stir the suspension of α10 mol).

3111s'' GK is maintained by external cooling, and at the same time fluoro tetrasulfonyl V fluoroacetyl fluoride (1&Oj
1, α10 mol) was added rapidly. Add this mixture to 10~
At 15°C, 1-(Is!e3@4e4-pentafluoro a-yuki-sikku■butenyl)fluorosulfate [4
gN, α10 mol) (B.

(117@)) and then heated to 25℃ for 3 hours or 1!
Mix, add water (100 d), and add water (10 d) to cover the bottom layer.
-), washed, dried, and distilled. ”[1-(1e1
1*3e4*4-pentafluoro4-3-citarotesteroxy)]tetrafluoroethanesulfonyl fluoride (240JI, 10 moles, 70%), boiling point @IC (
100-Hll) was obtained. The structure of this product was confirmed by the first order ftl-6,s,s s (C-C
) * a, go (So.

F) and 8-koshi 5μ duck (c-F, C-0,80,)t
l・FNME, 4 Table 8 (處 J-xLOH Liao, each member t
JzaOffg, tph) IF, 80. ! , -8al
Ojbi-311 (AB J=146Hm, each member concerned) 2
F, OCF snow.

-11! ? (fi)2J'C! ! ,So,! ,
−117,6 and one l117 (AJ? J=19
0B dew, each group 12F.

3JCF Snow, -13! L8 (inertia) I F , (J'
, -1117, ICm) IF, CF, and -1!1L
4pys(s)IJP.

C.F.

Analysis C1! ,・0. Calculated value for SK sc, 2i, o ma 嘗 S, * S d actual measured value C, 2L311S, 144 Reference example 11 Potassium fluoride (IIIJI, 0110 mol) on L dig
lyma(1·Om) in a mixture with 3.6-bis(trifluoromethyl)-m in %glc&c.

1, Is, 6-titrafluor a-1,4-s/oquinan-2-one (S, Sol music U.S. patent & 32L! $17
) (31,0', f, 0.10 mol).

The mixture was stirred for 1 hour and then treated dropwise with perfluoroallyl fluorosulfate (3 OI, α10 mole) prepared as in Reference Example 2A. The exothermic reaction was maintained at 35-40°C with an external water bath. This mixture was stirred at 25° C. overnight, during which time no gas evolution was detected and a yellow-orange V color developed. This mixture was mixed with water (50
011J), wash the lower layer with water (100wJ),
Dry.

Distilled at 73-74°C (180-140-Hy). The distillate is treated with food-type phosphorus, and when distilled for 8 minutes, 2-(
1-pentafluoro-2-propenyloxy)-3,6
-Bis(trifluoromethyl)-! , 8151516-
Pentafluoro-1,4-dioxane is an isomer mixture,
The boiling point was SS~5°C (60mH11). The structure of this product was confirmed by primary analysis of 311,115 units (CF-CFm)! Hif, s −1 @ as (CF
, C-0) 1 trout FNMR, -'Iα and 1 foot
s (AJ? Jヰ1511ff#, each member 5) 2F, O
CF, C==aC, -7'I:8>Lbi187', 91
CAB J-1113Hg, each member w+ ) 2 F
.

Soil OCF, -'81.4 (m) 4F, CJ', +
0CFO.

-s*a(s)sF,CF,*-9l3(d J-s
l・Hs, each member d Jwz3甑3Ht,,t Jm
7.1Fg)jJ" *Siss CF, CF=CL, -1
04a (dJ-11'1AIi, each member d J=x5
*OH dew, t J Tomi 25 41i m) t F e
) Lance-CFmCF 2CFe -i *'j48
*-124,7,-1! ! ILI-13L! , -1m
! I and -1341(s) $lJF CFsC,j
,0. -19CLSCdJm117. IHz, each member d
Jm3 @, 3Hz, t, J-xl &'
A small underlying point due to the presence of the IF, CF, CF-C0 isomer can be observed in the Ll, -1, and -tso4pp cells.

Calculated value wealth C9 for analysis C, F, ・O1#IC! Turtle SO 蓼! , @4LO ma actual measurement value wealth C11
&711J', 66.1 block reference example! ! To Rio Kisabi Shitaro (2elsl)! Tan and C.F.

Anhydrous potassium heptadide (!LIO1, al 0 mol) (D suspension) in dilytlLac 100 d) was heated at 10°C and at the same time hexafluoro-2,S-
j” tandione (hexafluoroat) acetyl, L,
O.

Moor- and J, W, Cl%ck, J, Or
g, C45m,.

1, 24 f! (196 vessels)) and put it in.

This mixture was stirred until almost all of the potassium heptafluoride was dissolved and then treated with perfluoroallyl fluorosulfate prepared as in Reference Example 2A.
Rapid treatment in s'cI/c.

The temperature rose to 30°C due to a somewhat exothermic reaction.

This pale yellow mixture was kept at 25℃ overnight or 1 day. The mixture was mixed and then distilled. The two-phase distillate collected at a boiling point of 49 DEG-54 DEG C. (10 wm HI) was treated with anhydrous calcium sulfate with 12 Km of sulfuric acid (IIIJ) and fractionated in a one-turn band still. g-(1-(pentafluoro4-
2-propenyloxy))-g*8, Is, 6-tetrakis(trifluoromethyl)-5-fluoro-1,4,
? -) Rioxabisik El (2,11) Hebuta/(&O
jj, 0.00511 mol, 1111 boiling point 50-51
°C (15 ■Hfi') contained t main components as determined by gas-liquid chromatography. An analytical sample of this product was obtained by 1-minute gas-liquid chromatography, and its structure was confirmed by the following: 10ss (C-F, C-0) as pupil F N
M.R.

-6L・and-Ding LO (AB J-18!!Hg, each member) -2F San〇CF Yuki, -74th (ta) 8F, C
F.

-7&S(m) 3J', CI'@e-7
9+, 3(a) SF, CF-.

−? t9 (d J-13H Liao, each member septet J = 4H dew).

sF, CF, -ttzocd JxszIHz, each member dJxs*5lls, d Jt8.8Fgod
J = e, sHm) IF-Siss CF society CF9G, [6-
10 & 1I (d J-11y, gHs I each member d
J=82hIKm, d J-27,011s, g
JmilL8ffs, (Jm3Loffg)IJ',)
Lance-CF, CF-CF, -1! L Ding Cq J helmet 2α 纂Ha, each member (J-IL1ff Russia) xF, C1j'
, and -19LPtpp5Cd/ml17JHg
, each member d J-3 & IB Liao, tJx=1λ8H glue)t
F, CF, -CF-C0 Analysis' It 'II 04 Calculated value for K 1G, 1
4181F* 6111 real side value sC, 1457IJ',
@L60 No. 60 Glopenyloxy)Nato9Fluotetraethyl)-4-C1
-C pentafluoro is -2-propenyloxy))-g,
4,s-tris(trifluoromethyl)-5-fluoro-1.3-1/oxolane (711 N. 0.0
1 mol, 21%) (7) Mixture tearing.

This contained only a small amount of impurities in the gas-liquid nib. The structure of this product was confirmed by first order)-λsagIL5・(CF 謡cy,) and Ding-10 voice vortex CCF,C-0), ts 7NMB-ma*spp愼(AE)! F,OCF,,-ding14.

-74La,-? JL? oh! Bi-79.1 (s) 11J
',CJ',.

-9l1 (regret) IF cis-CF, CF=CF, -10 Kanabatake (collection) 3F,) Lance-CF, CF-C1i', -
1! 10.

-1lSL! and -14l11CIII)i17'*
C'e> and -x*asppm<vi) tp, cr, c
Calculated value for z-c・Analysis CF, O, I C , 2 4 4 4 1 F m 6
11・Back measurement value IG,! 473 1F, a & 411 Reference Example 13 (CF!=CFCF!QCFICrtCF*)! +
Crt=CFCFtOrcF*)s C0F CF Snow-CFCF*0 (Crt)sCOF+Ht
O-≦1ノ■! [Nicho≦yms-110F*=CFCF
*0(Crt)scOIH-i diglyme potassium fluoride (11,62p, 0.20 mol), d Igl
yme (200m) and octafluoroaziboyl difluoride (PCB 28.2,9.0.096
mol) mixture was stirred at 5°C for 1.5 hours. The mixture was kept at 5-10 DEG C. and at the same time perfluoroallylfluorosulfate (46,0,9,0,20 mol) prepared as in Reference Example 2 was added dropwise. When this addition is complete, heat the mixture at 5°C for 30 minutes or t! This was then allowed to warm to 25° C. and stirring continued for a further 3 hours. - After storing for the night, pour the kernel mixture into water (1 t) and wash the lower layer with water (150 ml);
Drying and distillation gave two products.

The fraction with a lower boiling point is perfluoro-1,6-bis(2
-bubenyloxy)hexane (21,1,p, ,0
．． 0355 mol, 37111), boiling point 84-86°C (2
0■H1), and its structure was confirmed by: 1m1 electric 5.59 (CF=CFri and 7.2-9.
5Bm (C-F, C-0): "F NMR, -7
2,1 (dJ=25.7Hz, each member tJ-13,3Hπ
, dJ 13.3Hz % t J = 7-6 Hz
) 2 F s 0CFt C=C1B 4-2(f
fl)2F, CrtO,-92,3(dJ=52
．． 7 HE, each member dJ-39.5Hz, tJ depth 7.6H
π) IFl cis-CF, CF=CF, -I Q 5
:5 (dJ depth 117.8Ht, each member dJ=*52.7
Hz, tJs=2&7Hz) CF,, 126.2
(m) 2F, CFi and -191,0ppm (
dJ-117,8Hz, each member dJ-39,5H! ,t
J: 13.8 HE) IF, CF, -CF^1 = C0 Analysis C1, Calculated value for F□O8: C', 24.26
; F, 70.35 Actual value: C, 24.43 g F, 70.38 The higher boiling point fraction is a 2:1 complex of perfluoro-6-(2-propenyloxy)hexanoic acid and diglym@ (7 ,9
g, 0.0155 mol, 164), boiling point 109-110
(5a+HJ7), which was produced by hydrolysis of perfluoro-6-(2-propenyloxy)hexanoyl fluoride in an aqueous dIglyme wash solution. The structure of this complex was K11IIJ: λ 3-
4 (OH.

aK C-H), 5.59 (Shoulder, CF, -CF.

Cot H>, and 7.2-9 am (CF, C
-0,CH)t”HNMR,δ11.93 (S)I
H%Co, H,3,75(1)4B% OCH, and 3-52 (S) 3 H%0CRs 薖l”F N
MR, -71,9 (dJ-211H Tomi, each member tJ =
13.4 Hz%dJ = 13.4 Hz, dJ-7
,5Ht)2F,OCF'IC=C,-84,1(m
)2 F.

CF, 0FRO1-92,0 (dJ-52,3Hz, each member dJ-39.3Hz, tJ depth 7.4H depth) IF1cis-〇F, CF=CF, -105.2 (dJ=117.
7H dew, each member dJz52.3Hz, tJ=2&IHg
)% IF% trans-〇F, CF=CF, -119
, 6 (tJ -12,6Hπ, each member tJ = 3.2Hπ)
2F,CF,,-122,6Cm)2F%CF,,-
1=23.5 (rn)2F.

CF,, -126,1(fn)2F, CF, and -190,9ppm (dJ-117,7Hz, each@d
J-39, 3H! , tJ = 13.8H, tJ = 1.8
Hπ1F% CF, CF coC8 Reference example 14 Monoenoate CF! =CFCF*QCF*CFtOCF*COweH
A suspension of Nm1i'oII of 424F (1,0 mol) in 100 m1j of methanol was stirred at 5°C and at the same time 1
14II (0,317 mol) of acid fluoride was added rapidly.

After the addition was complete, the mixture was stirred at 25° C. overnight, filtered, and the solids were rinsed with ether. When distilled, 102.
0g (86%) of methyl perfluoro-3°6-thioxanone-8-dino'ate, boiling point 60-61°C (20%)
H,f'') was obtained, which contained small amounts of impurities. Redistillation yielded a somewhat purer ester (1-2 impurities by gas chromatography), boiling point 61
A temperature of ˜62° C. (20 μHg) was obtained. The structure was confirmed by =IR (pure)! 3.32.3.37.3.4
9 (CHI), s, 57 (C=O), 8-9.5 i
s (CF, C-0).

NMR: H3, 95ppm (8) Impurities 3.53 and 3°33ppm=”F 72-0 (6% d
s t s a 5JFF24.13.13.7.5
Hz, 2F, =CFCF*), -78,0
(t, JFFl 1.6 Hg, 2FSCFICOI
CI(l), -89,0(t, JFFI 1.6Hz,
2F.

CF20CF*CotCHs), -89,s
(t, JFFl 2.6 Hl, 2 F, =CF
CF, OCF, ), -92,3(d, d, t%J
FF53.2.39.2.7.5H! %IF, cis-CF, CF=CF), -105,2 (d, d.

t, JFF117.3.53.2.24.3 Shame, IF.

trans-cr, cr-cv'>, and -190,8
Dpm(d, d, t%t - JFF 117.3.39
．． 2.14.0.1.6Hz, IF, CF, CF=).

Analysis C, H, F, 10. Calculated value for: C, 25,
82$H, 0.81g F, 56.17 Measured value: C, 26,17$H, 0,668F, 56.
24° Reference Example 15 Ketone Synthesis of bis(2-methoxytetrafluoroethyl)ketone from dimethyl carbonate, tetrafluoroethylene and sodium methoxide is described in D and W.

U.S. Patent 188,537 (1961) K to W■ey
It is written and maintained. Extending the reaction with gave 1,3,3.5-tetramethoxyoctafluoropentane in a one-pot reaction.

CH,ONm+2CF,=CF,+CH,0COCH.

0”Na” CHsOCFt CF t C(0CHs) me
F*CFtOCHs A mixture of 27.0 g (0.50 mol) of sodium methoxide, 56.0 JF (0.62 mol) of carbon dimethyl, and 100% dry tetrahydrofuran was heated in a 350° tube at 1 to 3 atmospheres of tetrafluorocarbon Stir in ethylene. Tetrafluoroethylene was pumped in as it was consumed, totaling 110g (1,
1 mol) was added. A mild exothermic reaction reduces the temperature to 3
The temperature was maintained at around 5°C. After the addition, the reaction mixture was heated to 40°C for 1
Time was added. The viscous solution from this reaction was 75.6p (
0.60 mol) of dimethyl sulfate for 15 hours at 40°C. When heated and distilled, 87.6.9
(52 sounds) i.

3.3.5-tetramethoxyoctafluoro tetrapentane,
A boiling point of 54°C (0.3 mHg) and n%'1.360s were obtained, and its structure was confirmed as follows:! R3,29,
3,33 and 3.42 (saturated CH), 8-95 (C
F%COC)ONmr(CC14)'HJ3.68(1
*1 m CFloCHm) and 3.57CP-
JHFl, 3H! l 1 # C (OC
HI)rii weight01 8 8.2 (m +1
, CR,O) and −116,,5 ppm (m,
1.

CF, ).

Analysis Cm I (+2Fg04 Calculated value for K: C
, 32, 16; H, 3, 6Q, F, 45.21 Actual value: C, 32, 57s H13, 72: F-44
, 61° deep H, SO.

CH3QCFI CFIC(QCH8)l CFICF
Spirit QCHl -1 → 50- of concentrated H, SO, 33.6I
i (0.10 mol) of the above tetraether.

After the mild exothermic reaction has ceased, the mixture is heated to 70°C (50°C).
0 ■ Hg) to remove volatiles, then heated to approximately 50°C
Distilled at (1■HIi). The crude distillate was then fractionated to yield dimethyltetrafluoroacetone-1,3-dicarboxylate with a t of 6.1 (ss*) and a boiling point of 58°C (2
), n 111.3713 was obtained. The structure was confirmed by: IR3,2g, 3.34 and 3.4
8 (saturated CH), as7 (c = o) ae4 (sh = C
-0), 8-91 (CF, C0C), Nmr (CC14
)"Ha 4.00 (1,OCH,),'・F-11
3ppm(s, CFri.

Analysis Calculated value for CyHs F2O3K: C, 34,
16 $8, 2.46 t F, 30.88 B Molecular weight 246 Actual value: C, 34,18 Iris H, 2,66 Mu F30
．． 95 rich molecular weight 246 (mass spectrum) When the same reaction was carried out on a 0.56 mole scale, the diester yield was 82.

Dry CIFK of 27.3JF40.18mol) in old glyme with rate too-: 43.5,? (0.18 mol) of O=C(CF t COOCHs )t from 5 to 10
Add at C and stir for 1 hour. 41.1 (0°18 mol) of CF, -CFCF, 0801F from 5 to 10
℃ and the mixture was stirred for an additional 3 hours. The reaction mixture was injected with 1 t of H, OK, and the lower layer was separated.

This was washed twice with H and O. 2111 H, SO, 0
After treatment at 7 °C and extraction with 7 Freon 113, the extract was distilled in a molecular distiller, resulting in
4.54 g (yield of 7,296) product, boiling point 51~
A temperature of 53° C. (0.1 μm) was obtained. The structure was confirmed by: "F nmr (Fl 1) 68.48 ppf
il (OCF, CF-”)! -93,459pm
Cis-(CF=CFF) knee 105.91 ppm
) U/Sue (CF-CF) E -117,1Of)I
) m (CFICOOCHs) 1-142.78 ppm
(CF*CF*0CF= ) knee 190.35pp
m(CF-CF,). ' Hnmr (Fl 1/TM
S): 3.96 (singlet, CHI). IR (pure)
:3.37j.

3.49μ (saturated CH): 5.6o 2 (ゝC=O.

CF, -CF): 8-10μ (CF, , Co).

Analysis Cl6F1 (calculated value for IHllol: C,
30,32°F, 47.96 t H, 1,53 Actual value: C, 30,45: F, 48.10 t
H, 1,48° Reference Example 16? Fro CFscFtCF*0CFCOF+KF+CF! =C
FCF*O8owFCF.

□CF, CP, CF, 0CFCF, OCF, CF=CF
.

Potassium fluoride (6,96L O, 12 mol), dig
1YIns (150*) and 2-(1-heptafluoropropoxy)tetrafluoropropionyl fluoride (dimer of hexafluoropropene obtained by treatment with fluorine) (29°49.0. 089 mol) was stirred at 5° C. for 1 hour. Reference Example 2 Perfluoroallylfluorosulfate (27,6,9,0,12 mol) prepared as in AK was added dropwise at 5°C, and the mixture was then stirred at 5°C for 3 hours and at 25°C overnight. Ta.

The reaction mixture was poured with water (lt) K, the lower layer was separated and the volatile components were removed at 25° C. (0.5 μHg').

Distilling volatile components from concentrated sulfuric acid produces perfluoro-5-
(2-propoxy-2-methylethoxy)propene (2
5.2g, 0.052mol, 59%), boiling point 62-63
°C (toomuf) was obtained and its structure was confirmed by: λ 5.57 (OF1x-CF,) and 7.5-9 am (C-FSC-0
):”F NMR, -72,2 (dJ 25.5H 0,
Each member tJ-13,3Hz, dJ-13,3Hz, dJ
=7.4Hz) 2F,0CFtC=Cs
81. O(m) 3 FSCFs, 82.3 (”
) 5 F −C'F s + QCFt s-84
,i (m)2F,CF! O1-92,1(dJ-5
2.7Hz, each member dJ=39.7Hz, tJ=7.4H
z) IF, cis-cplcF'=cF'% -10S
, 5 (d J ; 117.8 Hz.

Each member dJz52.7Hz, tJs=25.5Hz)%
IF% Tonsu〇F, CF=C foot, -130,4(
s) 2 F% OP, -14 & 9 (m) I P, C
F% and -191,0 ppm (dJxl 17.8H
z, each member dJxa9.7HzstJ Wl 3-6 H
E) Z F s CFx CF”C.

Analysis Calculated values for c@F, , O, K: C, 22, 42
sF, 70.94 Actual value: C, 22, 18 Wealth F, 70.96 Reference example 17 e (CF, = CFCF, OCF,)! CFt potassium fluoride 15.3L O, 26 mol) 1, Hgly
me (200 m) and difluoromalonyl difluoride (17,3
g, 0.12 mol) at 5°C for 15 minutes9. Perfluoroallyl fluorosulfate (57,
Wl, 0.25 mol) was stirred at 5-10°C for 45 minutes, the mixture was stirred at 5°C for an additional hour, and then at 25°C for 2 hours. This reaction mixture was mixed with water (
11) After injecting K and washing the lower layer with water (100 m), drying, and distilling, perfluoro-1,3-bis(2-propenyloxy)propane (12,0 g, 0.027 mol, 23 ml), A boiling point of 88-90 °C (200-8 g) was obtained, the structure of which was confirmed by: λmat5,59
(CF”CFx) and 7.2-9.5gm (C-
F, C-0'): "F NMR, -72,2(m
)2 F.

0CFIC=C, -84,6(m) 2F%CF,C
F, O1 ~ -92,3 (dJ=53.OH!, each member dJ=39.5
)Tg, tJs-7,2Hg) IF, cis-CF
, CF=CJ.

-10 rods 6 (dJ=117.8H!, each member dJ=53.
0Ht −, t J =25−2 FIX ) I F
sFuy S-CFICF=CF, -130,
0 (a) I F1CF* and -191,0 ppm (d
J-117.8Hg, each member dJ-39.5Hz, tJ
tl3,! S lx ”)I F,eF*cF=00 analysis (:calculated value for 1Fl@Os: C, 24, 34
sF, 68.45 Actual value: C, 24, 67, F, 68.36 Reference example 18 CFsCF*CFtCOF+KF+CF*=CFCrt
080tFCF, CF, CF, CF, OCF, CFmC
F.

Dry potassium fluoride (7,50,9,0,13 mol),
A mixture of diglyme (10Qm) and heptafluoro-tetrabutyroyl fluoride (prepared from treatment of acid with sulfur tetra7ide) (28,1,f, 0.13 mol) was stirred at 5°C for 30 minutes. Perfluoroallyl fluorosulfate was added dropwise at 5°C and the mixture was stirred at this temperature for 1 hour and at 25°C for 3 hours. By distilling volatile components? Transfer at 40°C (8 t (l), water (toom)
When washed with water and distilled from a small amount of concentrated sulfuric acid, perfluoro
-3-(butoxy)propene (30,3f1.0.08
3 mol, 6411), boiling point 80-84 °C, whose structure was confirmed by: λmmg 5.57 (C
FmCF1) and 7.2-9.5 Am (C-F,
C-0) l'°FNMR-72,1(dJ-25,
2Hz, tJ for each member: a+13.5H, dJ=13.5
H! , dJ-7,4Hg)2F, OCF, C=C,
-82,1 (tJ=8.I Hg, each member m), 3 F
% CF8% -84,5(ffl)2 FSOF, 0
%-92,1 (dJ = 52.3 Hz, each member dJ =
39.4Hg, tJ=7.4Hz) IF, ShiX-CF
, CFmCF.

-1085 (dJ=117.5 Hz, each member dJ 5
2.3Hz s t J-2 & 2 HE) IF
s trans-cp, cp-CF, 127.3
(m) 4t% CF i and -191,0ppm (dJ
=+=117.5Hz, each member dJ-.

39.4 Hz, t J 璽i 3.7 Hz, m
) i Fs CF = C0 Analysis Calculated values for CF, F, 40: (?', 22.
97iF, 72.66 Actual value: C, 23, old 1F, 72.80 Reference example 19 F(CFs)ycOF+KF+CF! =CFCF! 0
8OtF-1→F(CFt)aOCFtCF-CF*
Potassium heptadide (s, soy% 0.10 mol), djg
lyme (150 m) and pentadecafluorooctanoyl fluoride (prepared by treatment of commercially available perfluorooctanoic acid with sulfur tetrafluoride) (25,0
A mixture of 11,0,06 mol) was stirred at 5° C. for 1 hour. Perfluoroallyl fluorosulfate (23,
0 g, 0.10 mol) was added dropwise and the kernel mixture was heated at 5°C for 4 hours.
hour, then stirred for an additional 3 hours at 25°C. The mixture was poured into water (1 t), separated, and the lower layer was distilled from concentrated sulfuric acid to produce perfluoro-5-(octyloxy).
Propene (27,11I, 0.048 mol, 80 ml),
A boiling point of 69-70°C (20 ■Hg) was obtained, and its structure was confirmed as follows: λmat 5-59 (CFmC
F, ') and 8-9 am (CF C-0):
"F NMR-71,8 (dJ-25,1H rich, each member dJ = 13.4H!, tJ-13,4Hz, dJ =
7.7Hπ)2F%OCF, C=C, -81,6(tJ
tl Q, OH Tom) 3F, CFs, -83,8(m)2
F% CFICF, 0, -92.3 (dJ=53.6H
Home, each member dJ = 39.9Hz, t J = = 7.7H
IF, cis-〇F, CF=CF, -105,5(d
J-117, 8H Atsushi, each member dJ-53, 3H Tomi, tJ
=25.1HriIF, ) uyx-OF, CF-CF, -
122,2(ffl)6F, CFI, -122,
9(m)2F, CFI, -12[7(m)2F,
CF, -126,5(ffl) 2F.

CF and -190.8ppm (dJ=117.8H
z, each member dJ -39.9Hz, t 13.7H
ll, tl, 7Hz) IF, CF, CF=00 Analysis Calculated values for CxtlttOK: C, 23, 34
:F, 73.84 Actual value: C, 22.99 stems? , 73.94 Reference Example 20 COF, 10@F+CF, =OFCF, O8O,F-
〉CF sOCF! CF = CF*carbonyl fluoride (18,0I!, 0.27 mol), cesium fluoride (38,0I!, 0.25 mol) and dry digl
A mixture of perfluoroallyl fluorosulfate (46,0
g, 0.20 mol) was added. The mixture was stirred at -10°C for 2 hours and 2 hours, at 0°C for 2 hours, and then at 25°C overnight. The mixture was warmed under slight vacuum and the volatile, distillate (11 m of liquid collected at -80°C) was recrystallized from a cold still, resulting in 2-trifluoromethoxypropene (3.2 g, 2 .0 m, at -30C, 0,0
14 mol, 7 parts) and a boiling point of 11-12°C were obtained. Its structure was established by spectroscopy = λmaK (gas phase)
5.55 (CF=CF*), 8-9 (CIP.

C-0) Oh! 5.35 am (weak COF' impurity band): "F NMR (CCI, ), -56,5 (
tJ=9.2H tom) 3F, CF30. -74.6 (d
J = 25.8Hπ, each member (dJ = 53.4I (maximum, each member dJ-39, 21'T-maximum, tJ-7, 1Hz) IF, cis-〇F, CF = CF.

-105,5 (dJ-118,0Hz, each member dJ-53
, 4H, tJ 25.8 Hz), IF, trans-
C.F.

CF-CF, and -190,9 ppm (dJ==11
8.0~Hx, each member dJ=39.2Hg, tJ-13,6Hz)
IF, CF, CF=00 Reference example 21 FCO (CFI) 4 COF+KF+CFt=CFC
F! 0801F→(CF@=CFCF*0CFxCFt
cFri! +CFl=CFCF! 0(CFI)scOF CF1=CFCF10(Crt)scOFJL→Cr
t=CFCF10(Crt)sCO*H-■Crt=
CFCFto(CFI)aCO*H+CF! =CFC
F*0(CFI)l CoICHI Potassium fluoride (11,7,p, 0.20 mol), d
A mixture of Iglyme (259m) and octafluoroaziboyl difluoride (58.8p PCB, 0.20mol) was stirred at 0-5<0>C for 30 minutes.

Perfluoroallyl fluorosulfate (Reference Example 2A) was added while maintaining the mixture at 0-5°C.

46.0 g, 0.20 mol) was added dropwise. When the addition was complete, the mixture was incubated at 0-5°C for 2 hours, then allowed to warm to 25°C and heating continued for an additional 4 hours. The reaction mixture was evacuated to 35°C (3■H9) and heated to 45°C.
− liquid was removed. The high boiling residue is poured into water (1 t), the lower layer (10 m) is combined with the volatile fraction from above and water (100 J) is poured into d 1 gl yme (=20
m).

After the exothermic reaction occurred, the mixture was allowed to cool, the lower layer was separated, distilled into a distillation funnel, and diluted with perfluoro-1,6-bis(2-propenyloxy)hexane (Nt3, 13.6L O,0
23 mol, 23 thi) and perfluoro-6-(2-)O
benyloxy)hexanoic acid and dIglyme 2:
1 complex (Reference Example 13.52.8II, 0.109 mol,
54.5 cm) and a boiling point of 82-84°C (0.8 ■Hg).

The high boiling fraction of dlglyme complex was dissolved in concentrated sulfuric acid (40
Distillation from m) gave its methyl ester t-containing perfluoro-6-(2-propenyloxy)hexanoic acid. This ester is the dlg present in the complex.
results from the action of sulfuric acid on lyme. These products were identified by infrared and NMR analysis: IR, λ
m,, lc2.82 and 3-4 (OH, CHs)
, 5.58 (CF=CFri, 5.61(C=O) and 7-10 sm (CF, C-0,CH>and'
HNMR, 83,92 (OCR,) Oh! h11.33
ppm (OH), 1 nia, ratio of 2:"F' NMR spectra were also consistent with these structures.

Reference Example 22 The perfluoro-0-6-(2-propenyloxy)hexanoic acid reaction was carried out as described in Reference Example 21.

The crude reaction mixture was poured into water (75oIIj) and the lower layer was washed with water (100m). By distillation of the lower layer, 4
4 The same two products as in Example 21 were obtained. Fraction, boiling point 45-53℃ (6 cabinets) I, f) Gara diglyme
When removed by washing with water, crude perfluoro-1,6-
Bis(2-propenyloxy)hexane (9,511s
0.016% Le, 161G).

High boiling perfluoro-6-(2-proveni).

The complex of 1.1.2-)lichloro-1,2,2-)lifluoroethylene (50 m) and dlglyme was extracted with 5o- and 25-concentrated sulfuric acid sequentially. . treating the organic phase with calcium sulfate;
After heating and distilling, pure perfluoro-6-(2-
propenyloxy)hexanoic acid C42,29,0,09
88 mol, 49 tatami), boiling point 75℃ (1,0asH, 17
)was gotten. This substance was analyzed by IR and NMR)
Identified: IRJm□2.85-4.0 (H-bond OR
), 5.57 (CF=-CFI), 5.63 (sh
, C=O) and 8-9 am (CF% CO), and IH and "F NMR spectra.

Analysis Calculated value for C5HFtsOsK: C,24,4
5 Wealth H, 0, 23: F, 64.66 Actual value: C, 24, 48: ■, 0.45. F, 65.76
The following examples illustrate the preparation of useful copolymers from the polyfluoroallyloxy comonomers of this invention.

Example A Tetrafluoroethylene and 2-(1-(bentaf nxC)
FH=CFI+XCFl"RCFCFjOCF,
CFISO,F (c,F,co,,o.

80m# pipe K lined with stainless steel.

1.1.2-)lichloro-1,2,2-)lifluoroether 7 (Freon 113) (10m), 1 of 8 pentafluoropropionyl peroxide (3P initiator)
．． 1.2-trichloro-1゜2.2-trifluoro-U ethane solution (t*), and 2-(1-(pentafluoro-
2-propenyloxy)]-tetrofluoroethanesulfonyl fluoride (Reference Example 7.17.5p, 0.05
A cold mixture (-45° C.) of 3 mol) was added. The tube was closed, cooled to -40°C, evacuated and charged with tetrafluoroethylene (20g, 0.20mol). This tube was heated to 25°C.
The sample was heated to a temperature of 100.degree. C. and left at this temperature for 20 hours.

Volatile substances were evaporated and the product polymer was reduced to 0.5 HI
Exhausted to I. The product was then extracted with 1.1.2-trichloro-1,2,2-trifluoroethane and dried in vacuo to yield the copolymer (16,9II, 851) as a white solid.
:λmax (KBr) 6.79 (SOIF) and 12.3. sm (broad) as well as the infrared band of normal polytetrafluoroethylene. Gravimetric sulfur analysis gives 0.4811 G and 0.20 S, which corresponds to an equivalent weight of 9400, with an average of 0.34 st or 3.
This corresponded to 9 g (1.1 mol) of polyfluoroallyloxy comonomer. Equivalent weight is the molecular weight of the polymer equivalent to one functional group (possibly -8o, F). Differential scanning calorimetry (DSC) showed a 12'l reduction in endothermic peak (mp) compared to polytetrafluoroethylene.

Example, B 1.1.2-trichloro-1,2,2-trifluoroethane (10j), 1,1.2-trichloro-1,2,2
-) solution of 84 pentafluoropropionyl peroxide in refluoroethane (2,0”)% 1 (t
(Pentafluoro a -2-y) CI's + propenyloxy)] Hexafluoro pprono (no 2-sulfonyl fluoride (Reference example 9% 17.4.9, 0.046 mol) and tetrafluoroethylene y (20 g, 0 According to several people's procedures, t6.y#(7
A copolymer of sl) was obtained. X-ray fluorescence analysis showed the presence of 0.49% S. This corresponds to an equivalent weight of 6540 5
, 8 weight units (1,ti moles) of polyfluorolyloxy comonomer. This sample was determined by DSCK to have an m of 11℃ compared to polytetrafluoroethylene.
It had a decrease in p.

Example C xCFl-CFCF10CFICF1COF+nxCF
1=CF1 → 2-(1-("e-entafluoro-2-flobenyloxy)] 3-(1-(pentafluoro-2-) instead of tetrafluoroethanesulfonyl fluoride
17.8Ii (861 g) using the procedure of Example A using Tetrafluorotetraprobionyl fluoride (Reference Example s, t3.sLo, 045 mol).
Copolymer of: λm, x (KBr) 5.152 (CO*
Hs weak) and 9.7 am band were obtained; mp decrease (
DSC) t-j compared to polytetrafluoroethylene
4°C; gravimetric analysis corresponds to an equivalent weight of 790G.
7 wt. of polyfluoroallyloxy comonomer.

A sample of this polymer was stirred for two days with a solution of sodium hydroxide in 33 ml of ethanol, allowed to cool, and washed with water until the extract was no longer basic. The resulting polymer wetted easily with water and was dried under vacuum. Atomic absorption spectroscopy showed an N1 of 0.29116, corresponding to 3.7 weight points (1.3 moles) of the original comonomer.

Example D C.F.

xCFt=CFCFtQCFCFtel+xnCF
t=CF1→2-(1-(pentafluoro-2-propenyloxy))-tetrafluoroethanesulfonyl fluoride [1-(1,1,1,2,3゜3-hexafluoro-3- Chloro-2-propoquine) Pentafluoro-2-propane 1 consideration N2.14.3Ii, 0.0
According to several people's procedures, 18.3
Copolymer of II (87m): 9 mp reduction compared to polytetrafluoroethylene (1) 3C) 14°C was obtained;
Gravimetric analysis gave a CI of 0.61 tatami and 0.611,
This corresponded to 5.7 wt. of polyfluoroallyloxy comonomer and 5800 equivalents; more precise analysis by X-ray fluorescence showed a C1 of 0.53116;
This corresponded to 1.0 weight (1.56 moles) of polyfluoroallyloxy comonomer. The 14°C reduction in mp compared to polytetrafluoroethylene corresponds to a 1°C reduction per 0.1 mole of poly-fluoroallyloxy comonomer present. In contrast to this result, the smaller branch in hexafluoropropene gives a mpO reduction equivalent to 0.3 mol-0 comonomer mb about 1° C. in its copolymer with tetrafluoroethene.

The fact is that copolymers made from polyfluoroallyloxy comonomers have better molding properties than copolymers made from polyfluorolyloxy comonomers, which are more effective against contamination with the same molar amount of comonomers. It means to have.

Example E O.F.

xCF1=CFCF10CFCP1SOgF + xn
CF1tgCF12-(1-(pentafluoro-2-propenyloxy)]?)5fluoroethanesulfonyl → fluoride glue! DK2-(1-pentafluoro4-2-p4benyloxy)hexafluoropropane-1
-Sulfonyl fluoride (Reference example 3, t 6.1, p
, 0.042 mol) according to Example A, 18.
Copolymer of 5N (881G): Analysis by X-ray fluorescence gave an mp reduction (DEC) of 8°C compared to polytetrafluoroethylene, showing an S of 0.4311, which is equivalent to polyfluoroallyloxy comonomer and 7460 equivalents.

Example F Vinylidene fluoride 1-(1-(pentafluoro CHI-
CF, +CF fable-1-CFCFI ocp, CFI s
o,? → Copolymer vinylidene fluoride (21,0,32 mol), 2-(1-
(Pentafluoro-2-propenyloxy)]-tetrafluoroethanesulfonyl fluoride (Reference example γ, x
a, sIi, 0.05 mol), 1.1.2-)lichloro1.2.2-trifluoroethane (lQs#), and 111 of pentafluoropropionyl peroxide.
．． The procedure performed by several people was followed using 1.2-trichloro0-1.2.2-)lifluoroethane solution (5-). This mixture was shaken overnight and the highest temperature recorded was 31°C. The solid copolymer produced (21,5,9°60
The composition contained 46 (14.2 moles) of polyfluoroallyloxy comonomer with an equivalent weight of 71.9. DSC showed no thermal events between 25°C and 400°C.

Analysis (CHm-CF!)s, oi (CFl-C
FCI'm QCF *OFlso, ii") Calculation for K: C, 28,621H, 1,70 less S, 4.4
7 Actual measurement value: C, 28, 4JH, 1,71ts, 4.46
Example G CH@=CF@+CF1=CCICF10CF(C
Fm) * → Copolymer 2-(1-(pentafluoro-2-7"ropenyloxy)) 1-(heptafluoro-2-poquine)-1 instead of tetrafluoroethanesulfonyl fluoride,
L, 3,3-tetrafluoro-2-propene (Reference Example 1
．． Example F using 10.51i, 0.032 mol)
Solid copolymer (20.6 g, 731)
I got it. This material was extracted with an equivalent weight of 878, 36 weight 1 (9
, 8 moles) of polyfluoroallyloxy comonomer.

DSC confirmed its structure as a copolymer, and the temperature was 25-400℃.
No thermal events were observed in the experiment, demonstrating its stability.

Example H CF, TSCF*+CFm (CFI) sOcF*cF FujiC
F.

→ Copolymer implementation According to several procedures, perfluoro-5-(butoxy)propene (Reference Example 18.19.OIi).

0.052 mol), tetrafluoroethylene (209,
0.20 mol), lel*2-trichloro-1,2,2
-)lifluoroethane (10m) and 8 pentafluoropropionyl peroxides (21Ij) in 1.1.2-trichloro-1,2,2-)realoloethane
Using t8. ．． A solid copolymer of 9p was obtained. This crude material was cut in a premix with a lot of solvent, rinsed and dried to a mp of 309°C.
An IiO copolymer was obtained and the mp showed it to be a true copolymer.

Example I Polymerization Crt=CF1+ (CFI-CFCFI 0CF1C
FtCFt )*→ Copolymer Following the procedure of Example H, perfluoro-1,6-bis(
2-propenyloxy)hexane (61 examples 13.20I
i, 0.20 mol) was used for the polyfluoroallyloxy comonomer. A dry powder polymer of 16.39 was obtained from this K: λmax 5.55 Am (C
FFCF,)! The remainder of the infrared spectrum was similar to that of poly(tetrafluoroethylene). DSC shows a pronounced exotherm T, 315°C, followed by an endotherm ~333°C.
9 (first heating); the second heating showed no exotherm and a broad endotherm T, ~326°C. Infrared spectra showed that the thermal decomposition reaction of pentafluoroallyloxy side groups occurred during the first heating.
Tetrafluoroethylene) usually has a sharp wide D near mp.
An SC endotherm indicates that cross-linking has occurred.

Example J CH*-CF* + (CF* = CFCF* QC
F*)mc Ft→Copolymer perfluoro-1,3-bis(2-purbenyloxy)
Propane (Reference example 17.5.7 g\o, ots mol),
1,1,2-trichloro-1,2,2-trifluoro-tetraethane (zsm), and 1.1°2-trichloro-1.
2.2-) A mixture of 8-pentafluoropropionyl peroxide (5-) in refluoroethane was maintained at -40°C in a stainless steel-lined shaker tube while vinylidene fluoride (20 g, 0.32 mol) was condensed into the tube. The mixture was shaken overnight at room temperature and the product was stripped as before. The combined mold was vacuum dried, crushed in a blender with 95% ethanol, heated in an oven,
Upon drying, 24.0 Il of solid copolymer was obtained.

DSC shows endotherm 'l'p 124°C, at least 30
It was stable up to 0°C, which indicates that a true copolymer was formed since poly(vinylidene fluoride) has m9171°C.

The product is insoluble in acetone and CF=CF,
The absence of infrared absorption bands for side groups indicates that cross-linking has occurred.

In an example, 45 g of methyl perfluoro-3,6-thioxanone-8-enoate and O,Q 417 perfluoropropionyl peroxide were mixed at 10 psi (0°7h/a).
50′ under the pressure of tetrafluoroethylene (m”)
The reaction was carried out for 4 hours at c. Upon heating, a solid was obtained which, when dried in a vacuum oven at 50°C, had a concentration of 0.7
It was 11i. The amount of tetrafluoroethylene added is 4
It was g. The equivalent weight by titration is 1176, so the amount of ester incorporated into the polymer is F i 281 & the yield based on tetrafluoroethylene is 2
There were 0 bites. 2 in Carver press
A transparent film was obtained by heating to 20°C.

EXAMPLES Samples of the polymers of Examples B and E were treated with aqueous alcoholic ammonia solution for one day at 25°C, oven-treated, washed with aqueous ethanol, and dried in vacuo.

A sample of the polymer of Example C was similarly treated with aqueous alcoholic sodium hydroxide.

The above partially hydrolyzed polymer is used as a series of Sevron Red GL (Sevron Red GL), known as KOrlon Red GL, which has remarkable fastness and brightness, and is suitable for dyeing KOrlon and other acrylic fibers. Du Pont Products Book.

January 1975, p. 34) in an aqueous ethanol solution at 25° C. for 1 to 3 hours and then extracted until the extract no longer contains dye. All three dyes were stained orange-red.

Example M A sample of the heavy body of Example C was treated with hydroalcoholic sodium hydroxide as described in Example LK. The resulting fluorocarbon polymer contained carbonyl groups and was water wettable.

Example N Polymerization CFm-CFl + CFm=CFCF'*OCF!
CFl 801 P → copolymerized ice water 140 m), 1.
1.2-tricloa-1.

2.2-trifluoroethane (10j), 2-(1-(
pentafluoro(0-2-7'ropenyloxy)]tetrafluoroethanesulfolylfluor((examples y, a,
o g ), potassium perfluorooctane sulfonate (0,16j'), ammonium carbonate (0,50Il)
and ammonium persulfate (0,501) were placed in a stainless copper loss tube. This mixture was brought to 200 pal (14,1 Kg/m") gauge with tetrafluoroethylene, and yOcK was added to 11 L9.
The gauge was maintained at 70°C for 45 minutes. The resulting polymer product was filtered, washed, and dried to yield 43.21i as a white solid. It contained approximately 1.4 wt (0.43 mole) of polyfluoroallyloxy comonomer according to infrared analysis. Differential thermal analysis C
According to DT K., it exhibited a crystal transition of 10°C, a recycle freezing temperature of 293°C and a recycle melting point of 311°C. From these, polyfluoroallyloxy comonomer content Fi3
．． 5 weight 1 (1,09 mole tatami).

Example 0 Polymerized Crt-CFm + Crt-CPCFt OCFt
CFt SO*F → According to the flow side of copolymer Example N,
s, op 2-(:1-(pentafluoro-2-propenyl, t+shi)]tetrafluorotetraethanesulfonyl fluoride, 0.201i potassium perfluorooctanesulfonate and 30p 1 (2,1!/country) Tetrafluoroethylene at a pressure of 3) was used at 70° C. for a reaction time of 8 hours. No other components were fed. The spectrum showed strong absorption of SO and F.

Differential thermal analysis showed a crystalline transition of 5°C, a recycle freezing temperature of 282°C, and a recycle melting point of 3°OO°C. These correspond to a polyfluoroallyloxy comonomer content of 5.9 g by weight (1,86 mol).

Example P Polymerization Example No. 10.7jp of 2-[1-(pentafluoro-2-propenyloxy)]te)9fluoroxulfonylfluoro')4) + 1.0.20JF· of ammonium persulfate, and 5Gpsl (3,5415
1”) gauge of tetrafluoroethylene at 7G°C.
used for a reaction time of hours. No other ingredients were supplied. This is K, right? A white polymer of 28.61i was obtained,
Its infrared spectrum is 3.5 wt-(1,08 mol)
So to the polyfluoroallyloxy comonomer of
, indicating the presence of F group. Differential thermal analysis is 290℃ and 317
It showed two melting peaks at 0.degree. C., and the content of 9 comonomers was estimated to be &5 weight 1s (1,73 mol).

Example Q nxCF, =+=CF, +xcF@xcF(J'@OC
F, CF, 801F+2-(1-(pentafluoro-2
-propenyloxy)] tetrafluoroethanesulfonyl fluoride (Reference Example 7.52.8N) and pentafluoropropionyl peroxide initiator 6111.1.
2-trichloro-1,! , 2-trifluoroethane solution (0,19Ii) was placed in a steel pipe. Add this mixture to 40″
Heated at cK and diluted with tetrafluoroethylene (TFE) for 10
The internal pressure of the tetrafluoroethylene was set to 10 ps I (0.7 Kg/as”) gauge.
(0.7 h/am”) gauge and maintained at 40° C. for 6 hours. The polymer product thus obtained was filtered, washed and dried to obtain a white solid (9.82 g). T:λ
m,, (KB r ) 8.65 xi (So, F
) and 8-10 ■ (broad) and the IR band of normal polytetrafluoroethylene. The reduction in melting point of DSC was 91° C. compared to polytetrafluoroethylene.

Sulfur analysis by X-ray fluorescence shows 27% Sl or 1
28.0 weight - (8.5 mol I) reduced to 1800 equivalents
II) polyfluoroallyloxy comono! − was given.

The product was pressed into a clear 4-5 L# (0.10-0.13 m2) 0 film at 220-240°C. Four 4-inch diameter (10,251) film samples were reacted with potassium hydroxide solution of 3-151 for 1 hour at 90 °C and dried to form tetrafluoroethylene and CF, -CFCF, OCF, CF.

A copolymer of SO, - and + was produced. The IR spectrum showed that the -80,F functionality was essentially completely converted to the pressure sulfonate.

This diameter is 4 inches (10,2 aw) and the thickness is 4 to 5 volts (
A film of 0.10 to 0.13 mm was placed at 2oO. Sliding voltage and current efficiency were measured as a function of seed run time and sodium hydroxide concentration.

For the 15 day test, the following results were obtained: Days Sodium Hydroxide Current Efficiency Sliding Voltage 1 21.5
70.7 3.3510 21.5
? 1.2 3.4515 30.0
65.2 3.60 Example R n xCFm = CFm + xCF', =CFC
FtO(CPI)4C0OH→Perfluoro-6-oxanone-8-enoic acid (47
,5,17),1,1.2-trichloro-1,2,2-
8th grade pentafluoropropionylper in trifluoroethane, tM? '/do(0,051i), and 10p
si (0.7 Kp/a+”) gauge tetrafluoroethylene was used at 40C to obtain a solid white copolymer of 2.41.9; the melting point reduction of D8C was 157 compared to polytetrafluoroethylene. °C.For titration 9
The analysis of the carboxyl group in
It showed 6.8 wt 1 (9.3 mol 4) of polyfluoroallyloxy comonomer.

This copolymer was pressed to 4-5 mils (0.10-0.
13) and hydrolyzed as described in Example QK. The IR spectra showed that the -C'OF functional group was virtually completely converted to carboxylate salts, indicating that the -C'OF functional group was virtually completely converted to carboxylate salts, with tetrafluoroethylene and CF, -CFCFmO (CFm
)4 showed a copolymer with Cot-K+.

A sample of film 4 inches (10,2 cm) in diameter and 4 to 5 nm thick (0°10 to 0.13 m+) was placed in a chloroform tube operated at 2.0 amps per square inch (0.3 amps 151"). Sodium hydroxide Current efficiency Sliding voltage 1 3 Sodium hydroxide Current efficiency Sliding voltage 1 3
7.1 93.3 4.0220 3
9.2 90.9 4.6035 3
9.4 87.7 4.2550 3
2.9 92.0 4,1176 3
4.6 85.8 4.67 Patent applicant
1 person outside of E.I. DuPont de Nemois & Company

Claims (1)

[Claims] The formula (wherein X is -ct or -F, D is -CFJt4t or -CFE4, R4CF. R
", -0CF, CO*B" -1: *Jri, Bs is -CH, or -〇, H, is, and E is -
and at least one
? An electrically conductive membrane formed from a hydrolyzate or ionized copolymer of 1.1 ml of an ethylenically unsaturated monomer. 2. The membrane of claim 1, wherein the ethylenically unsaturated monomer is tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride or trifluoromethyl trifluorovinyl ether. 3. The membrane according to claim 2, wherein 3L X is F. Table 9. Conductive membrane according to claim 1, which is used in a chloralkali bath for producing alkali metal hydroxide.