JPS5891708A - Copolymer - 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, U.S. Patent No. 2.856.435 to ELO ← 1, 3-chloropentafluoropropene and 1 in alkaline medium
, discloses a method for preparing perfluoroallyloxy-1,1-dihydroperfluoroalkanes from l-dihydroperfluoroalkanols, e.g.

2.W. T. U.S. Patent 2.671.7 to Miller
No. 99, for example, discloses a method for replacing chlorine in perfluoroallyl chloride with methoxy, cyano, iodo and nitrate groups.

3.M. E. Redwood and C.J., WiH4a
.

Canad, J. Chem, 45.389 (1967)
describes the reaction of allyl bromide and cesium heptafluoro-2-propoxide to produce 2-allyloxyheptafluoropropane, viz.

4. J. A. Young, Fluorine Chemi.
stryReviews, t, 389-393 (19a
7) outlines the action of alkali metal fluoride perfluoroketones, perfluoroalkyloxiranes, perfluorocarboxylic acid fluorides, and perfluoroalkylfluorosulfates to produce perfluoroalkoxide anions.

5, R. A. U.S. Patent No. 3.450.68 to Darby
No. 4 discloses a method for preparing fluorocarbon polyethers and polymers thereof by the reaction of perfluoroalkanoyl fluoride with potassium fluoride or quaternary ammonium fluoride and hexafluoropropene epoxide.

6, A.G., Ptttrnan and W. L. Waal
U.S. Pat. No. 3,674,820 to ey discloses, for example, the reaction of a fluoroketone with an alkali metal fluoride and an omega-haloalkanoate to form an omega-(perfluoroalkoxy)alkanoate.

7, U.S. Pat. No. 3,795 to E. Dormba. ss4
also discloses the reaction of hexafluoroacetone with potassium fluoride and omega-haloalkanoic acid esters.

8, A.G., Pittman and W.L., Wasle.
US Pat. No. 3,527,742 to ry discloses the reduction of the compound of 6 to the corresponding alcohol and the esterification of that alcohol to a polymerizable acrylate.

9.A. G, PiL1m4n and W, L, Wasle.
U.S. Pat. No. 3,799,992 to y discloses reacting a perfluoroketone with an alkali metal fluoride and a 1,2-dihaloethane and then dehydrohalogenating the intermediate 2-perfluoroalkoxyhaloethane. Method for producing (perfluoroalkoxy) vinyl compounds by,
For example, disclosing.

10, U.S. Pat. No. 3,321 to C.E. Loress.
No. 532 discloses, for example, the rearrangement of perfluoro-2-alkoxyalkanoyl fluorides to perfluoroalkoxyolefins by passing over metal oxides at 100-400°C. .

According to the invention, compounds of the formula , -F, or -RF, where -RF can be interrupted by 1 to 4 oxygen atoms, especially the second or lower carbon atoms, -
SO, R, -COF, -CO2H, -CotRa, -C
1, -r noCF', CF=CF2 and -OCF2CO
1 carbon number with O~2 functional groups selected from 2R3
~10 linear or branched perfluoroalkyl, R3 is -CH2 or -C2H3, and E is independently -F, -CF3, -CF2Cl.

-CF2CO2R3 or -RF2OCF(G)2, where R3 is as defined above, and D and E taken together are a 5-membered ring or a 6-membered ring whose ring member is -RF-. Forms a membered ring, RF is 1
or can be interrupted by 2 oxygen atoms, 0 to 2
a 4- to 5-membered perfluoroalkylene chain having ~CF substituents,
and G is -F or -CF.

Furthermore, according to the present invention, formula (1) (wherein A is independently -F, -COCF, or -Rγ
, and R'F is 1 to 1 for each carbon atom below the second.
Can be interrupted by 4 oxygen atoms, -SO,OC
F2CH, -COF, ~C1, -0CF, CF=CF2
and -CO2R8 is a linear or branched perfluoroalkyl having 1 to 10 carbon atoms and having 0 to 2 functional groups, R3 is -CH3 or -C2H5, and B is independently, -F, -CF3, -CF, CL, -CF2CO2R3
, or -CF2OR1F, F3 and R1F are as defined above, and A and B together form a 5- or 6-membered ring whose ring member is -RF-. , RF can be interrupted by 1 or 2 oxygen atoms and is a 4- or 5-membered perfluoroalkylene chain with O~2 substituents, a trifluoromethyl group). is a metal fluoride of the formula: mixing and reacting, and (2)
The mixture from (1) has the formula (wherein X is -CL or -F, W and Z are independently -F and taken together are -CF2-, and Y is -Ct or -SO2F) 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 relates to compounds of formula 4 prepared from starting materials 1, 2 and 3 according to the following reaction scheme: In the above reaction scheme, starting materials 1, 2 and 3 react to form product 4 and its metal Salt 5 is produced. Letters A, B, D, E, G, M,
W, X, Y and Z are as defined above. The products represented up to 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, where D is preferably -F or RF and E is preferably -F, -CF, -CF,C
L or -CF, CO, R3, and R3 is -C
H3 or -C2H3. Preferred compounds also have W and Z being independent, such that X is -F.

RF can preferably be interrupted by up to one oxygen atom, -SO,F, -COF, -Cl, -CO,H,
-CO, Ra, -0CF.

CF=CF2 and -COF2CO2R3 have 0 to 1 functional groups, R3 is -CH or -C
2H5 is a straight or branched perfluoroalkyl.

Particularly preferred polyfluoroallyloxy compounds of the invention have the formula (wherein X is -Cl or -F, preferably -F and E is -F, -CF3, -CF2CO2R3 or -CF
2Cl, preferably -F, -CF2 or -CF2CO
2R3, R3HA-CG2 or -C2H5, and D is -CF2F4 or, R4 is -F, -SO2F, -COF, -CO2H, -CO,
R8, -OCF2CO2R3, or -(CF2)XR
5, R3 is -cH3 or -C2H3, and R' is -CF3, -COF, -CO,H, -CO2
R3, -SO2F or -OCF2CF=CF2. R4 is preferably -SO2F, -COF, -CO,H
or OCF2CO2R3 and R8 is -CH
3 or -C2H5). The polyfluoroallyl group of product 4 is derived from the corresponding polyfluoroallyl chloride or fluorosulfate (1) by a preformed polyfluoroalkoxide anion derived from a metal fluoride (2) and a carbonyl compound (3). derived from the nucleophilic character of the chloride or fluorosulfate group. The synthesis is therefore the sequential addition of one vessel of reactive components 3 and 1 to a suspension or solution of 2 in a suitable solvent.

Polyfluoroallyl fluorosulfate is the preferred reactant for this substitution, and B. E. Smart, J.
Org, Chem, 41, 2353 (1976) and U.S. Patent Application No. 718.33, dated August 27, 1976.
No. 7, it can be conveniently prepared by treating polyfluoroalkenes with sulfur trioxide. This further reaction is typically carried out in a sealed Carius tube at 25-95°C for 16 hours to 4 days, and the product fluorosulfate is transferred by fractional distillation. Preferred perfluoroallyl sulfate (pentafluoro-2-propenylfluorosulfate)
The preparation of is described in Example 2.

Stable metal polyfluoroalkoxides are formed by the reaction of certain metal fluorides with polyfluorinated ketones and acid fluorides (J, A., Young, loc, cit), ie. The usefulness of such intermediate polyfluoroalkoxides is determined by their stability, as measured by their susceptibility to thermal decomposition. Since their formation is reversible, the average concentration of the various species in a given reaction mixture is an important value in determining whether subsequent substitution to produce product 4 occurs. Solutions with a mean to the right (high concentration of anions) will be more effective than solutions with a mean to the left (high concentration of carbonyl compounds).

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

1oc, cit, R.W., Evans, M. B. Lit
t, A.M.

Weidier-Kubanek and R. P. Avo
nda,,J.

Orf. Chem, 33, 1837, i839 (196
8), and M, A, Redwood and C, J.

willis, Canad, J. Chem, 45, 38
9 (1967).

(1) Safe polyalkoxide anions are formed when carbonyl compounds are highly fluorinated, since the electron withdrawal effect of the fluorine atom distributes the negative charge across all anions. Some substitution of fluorine with chlorine, other fluoroalkyls or hydrogen destabilizes the anion. This is because these groups have a low ability to withdraw electrons,
This is because negative charges are not easily replenished. (2) Large cations such as R+, Rb+, Cs+ and R
4N+ is a small cation such as Li+ and Nα+
It is easy to generate more stable polyfluoroalkoxide than the above. This is because the lattice energy of metal fluorides is inversely proportional to the size of the cation. In other words, the large cation size and small lattice energy are favorable for coating the metal fluoride crystal structure to generate cations.

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

Aprotic polar solutions such as N,N-dimethylformamide (DMF), acetonitrile, and 1,2-dimethoxyethane (glyme) are very effective for this purpose. (4) When an alpha fluorine atom is present relative to the oxygen atom in the anion, the loss of the fluorine ion can be completed with the desired reaction. An example is as follows: produces many stable derivatives with α-fluorine to be lost.

Reactive compounds, e.g. odors The allyl is necessary for the substitution of the parent nucleus. do.

loses Yujo F-; parent position The replacement is perfluoroarylfluor. known for orosulfate ing.

In the practice of this invention, it is preferred to preform the polyfluoroalkoxide anion by adding the carbonyl compound to an agitated mixture of metal fluoride in a suitable aprotic solvent. The completeness of anion formation is generally indicated by the degree of metal fluoride that dissolves in the solvent as the reaction progresses. Stoichiometrically, the formation of a polyfluoroalkoxide anion requires one molar equivalent of metal fluoride for each carbonyl group that replaces the anion. An example is as follows: 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 fluoride are:
(1) Preventing observation of the end point of the reaction due to the presence of undissolved solids in the reaction mixture; and (2)
) The dissolved excess fluoride ions can react directly with perfluoroallyl fluorosulfate to form hexafluoropropene.

Due to the limited thermal stability of polyfluoroalkoxides, their production is usually carried out at -20 DEG C. to +60 DEG C., preferably with external cooling to maintain the temperature between 0 DEG and 10 DEG C.

The time required to complete the formation of the polyfluoroalkoxide varies with the carbonyl component, but is preferably between 0.5 and 2 hours and is usually determined in each individual case by the time at which the reaction mixture becomes homogeneous.

N,N-dimethylformamide (DMF), acetonitrile, N,N-dimethylacetamide (DMAC), γ
-butyrolactone, 1,2-dimethoxyethane (gly
ma), 1-(2-methoxyethoxy)-2-methoxyethane (diglyme), 2.5,8.11-tetraoxadodecane (tri-glyma), dioxane,
Sulfolane, nitrobenzene and benzonitrile are
Examples of suitable aprotic solvents for the preparation of polyfluoroalkoxides and their subsequent reaction with polyfluoroallyl fluorides or fluorosulfates.

The equipment, reaction components, and solvent should be suitably dry for use in the method of the invention. The metal fluoride useful in the present invention is potassium fluoride (
KF), rubidium fluoride (RbF), cesium fluoride (csF) and tetraalkylammonium fluoride (
R4NF), such as tetraethylammonium fluoride [(C2H5)4NF] and tetrabutythylammonium fluoride [(C4H.)4NF]. R is the same or different and has 1 to 6 carbon atoms, preferably 1
~4 alkyl. Potassium fluoride is preferred from the viewpoints of its availability, economical advantages, and ease of handling.

Polyfluorinated carbonyl compounds useful in the present invention include:
Ketone fluoride, carbon content fluoride and perfluorinated lactone 3,6-bis(trifluoromethyl)3,5,
5,6-tetrafluoro1,4-dioxan-2-one. Ketones and lactones give branched fluorocarbon products, whereas acid fluorides give perfluorocarbon products with a new ether linkage in the first or second center: Examples are: hexafluoroacetone, chloropentafluoroacetone, 1,3-dichlorotetrafluoroacetone, 1.1-
Difluoroethyl-2-oxypentafluoropropane sulfonate, dimethyltetrafluoroacetone-1,
3-dicarboxylate, 1,3-bis(2-heptafluoropropoxy)tetrafluoropropanone, octafluoroptanone, 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-butanedione is produced by the reaction of initially formed perfluoroalkoxide with both perfluoroallylfluorosulfate and another molar equivalent of hexafluoro-2,3-butanedione to form two types of heterocyclic compounds. This is a special case (Reference Example 12) in which it is generated.

Examples of useful polyfluorinated acid fluorides are: carbonyl fluoride, trifluoroacetyl fluoride, pentafluoropropionyl fluoride, heptafluorobutyroyl fluoride, nonafluoropentanoyl fluoride, niphfluoride. Tetrafluorodiglycolyl, undecafluorohexanoyl fluoride, tridecafluoroheptanoyl fluoride, pentadecafluorooctanoyl fluoride, heptadecafluorononanoyl fluoride, nonadecafluorodecanoyl fluoride, difluoro difluoride malonyl, tetrafluorosuccinyl difluoride, hexafluoropropane difluoride-1゜3-dioyl, hexafluoroglutaryl fluoride), octafluorobutane difluoride-1,4-
di-oil (octafluoroadipoyl difluoride), decafluoropentane-1,5-di-oil difluoride (decafluoropimelyl difluoride), dodecafluorohexane-1,6-di-oil difluoride (difluoride) dodecafluorosperyl), fluorosulfonyl difluoroacetyl fluoride, 2-(fluorosulfonyl)-tetrafluoropropionyl fluoride, 2-(1-heptafluoropropoxy)-tetrafluoropropionyl fluoride, 4-fluoride
[2-(1-heptafluoropropoxy)hexafluoropropoxy]tetrafluoropropionyl, and fluorinated 2-(2-[2-(1-heptafluoropropoxy)hexafluoropropoxy]hexafluoropropoxy)tetra Fluoropropionyl, carbomethoxydifluoroacetyl fluoride.

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

Many of the starting materials are commercially available, e.g. PC
R., Gainsville, Florida, is a supplier of fluorinated ketones and fluorinated carboxylic acids.

Examples 2.3, 4.5, 7, 9.10, 11.12.1
3. 16 and 19 are some of the compounds and methods that are not commercially available. Generally, perfluoroketones can be prepared from perfluoroalkane carboxylic acids and from the reaction of carbonyl fluoride with perfluoroalkanes (W).

A., Sheppard and C. M. Sharts, “
Organi, Fluorine Chemistry
”, p. 365-368.

W. A. Benjamin, New York, 196
9, 7th. P.

Braindlin and E. T. McBee, Adb.
ances in Fluorine Chemistry
, 3, 1 (1963)).

Fluorinated perfluoroalkanecarboxylic acid and difluorinated perfluoroalkane-α,ω-dicarboxylic acid are
By adding the carbonyl fluoride to the perfluoroalkane by treating the corresponding acid with sulfur tetrafluoride (F, S, Fawcett, C, W, Tulloa
k and D. D. Coffman, J., Amer, Ch.
em, Soc, 8442?5, 4285 (1962))
Then, by electrolysis of an alkanecarboxylic acid in a small amount of fluoridated water (M. Rudlicky “Chemistry of F.
"Luorine Compounds", p, 86.
Mac-Ajiran Co. New York, 19
62), manufactured. Perfluoroalkanedicarboxylic acids are produced by oxidation of fluorinated α,ω-dialkenes or fluorinated cycloalkenes (Hudlicd. lo
c, cit, p, 150-152). Perfluoroalkyl polyethers with terminal acid fluoride groups are R,A
, Darby U.S. Pat. No. 3.450.684 (1969
) and P, Tarrant, C, G, Alt1son.
.

K. P. Barthold and E. C. Stump;
Jr.

Fluorine Chem RevA, 88 (1971
) can be prepared from hexafluoropropene oxide and its fluoride ion-induced oligomers.

In terms of stoichiometry, substitution of polyfluoroallyl chloride or polyfluoroallyl fluorosulfate requires one molar equivalent of the above proposal for each reactive center in the polyfluoroalkoxide anion.

However, with difunctional polyfluoroalkoxides, it is possible to shield the stoichiometry to form mono- or di-substituted products, i.e., the formation of polyfluoroalkogides and subsequent polyfluoroallyl chloride or The reaction with polyfluoroallyl fluorosulfate can be carried out sequentially in a glass apparatus at atmospheric pressure, with precautions taken to exclude moisture, without separation of the intermediates. The use of a cold feed and a cryogenic condenser (eg, packed with a mixture of dry ice and acetone) moderates the reaction and promotes retention of volatile reactants and products. The direct reaction progresses with the salt MY(5
) due to the appearance of a precipitate, air-concentration chromatography (g
lpc) and by fluorine nuclear magnetic resonance spectroscopy (19F NMR). The substitution reaction can be carried out at -20°C to +80°C, preferably 0 to 30°C. Typically, the reaction mixture is externally cooled to 0<0>C to 15<0>C during the addition of polyfluoroallylalkyl chloride or polyfluoroallyl fluorosulfate and then left at 25<0>C to 30<0>C for the remainder of the reaction time.

The time required to complete the substitution reaction varies from 1 to 24 hours, preferably from 2 to 4 hours. typically 1:1
, the reaction mixture is heated between 5 and 4 during the addition of polyfluoroallyl chloride or polyfluoroallyl fluorosulfate.
Cool externally for 5 minutes, then stir at room temperature for 2-3 hours.

The products of the reaction are isolated by standard procedures. In some cases, the reaction product is the high-boiling solvent used (d
iglyme (boiling point 162°C, DMF boiling point 153°C), in a trap cooled to -80°C by heating the reaction vessel to 30-50°C under a vacuum of 1-200 HO. It can be distilled to Alternatively, the reaction mixture can be poured into 5-10 times its volume of water; the insoluble lower layer of the fluorinated product is separated, washed with additional water to remove the solvent, dried, phosphorous pentoxide or Fractionally distilled from sulfuric acid.

The polyfluoroallyloxy 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, such as the need for expensive monomers and high pressure operation, it is preferred to form these monomers into copolymers with cheaper ethylenically unsaturated monomers. Examples of such ethylenically unsaturated monomers are:
Olefins such as ethylene or propylene; halogenated olefins such as tetrafluoroethylene, trifluoroethylene, hexafluoropropylene, vinylidene fluoride, vinylidene chloride,
Trifluoromethyl trifluorovinyl ether and chlorotrifluoroethylene; and acrylic or methacrylic acid. Preference is given to halogenated olefins, especially tetrafluoroethylene, chlorotrifluoroethylene, trifluoromethyltrifluorovinyl ether, hexafluoropropylene and vinylidene fluoride. Such copolymers include poly(tetrafluoroethylene)
, poly(trifluoroethylene), poly(vinylidene fluoride), poly(chlorotrifluoroethylene) or polyethylene have completely novel or ever-desirable properties. Copolymerization is defined as any method of incorporating two or more monomers as integral parts of a high 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.

A copolymer containing about 5 to 55 weight percent (about 1 to 25 mole percent) polyfluoroallyloxy comonomer has a lower melting point than the corresponding polyfluoroolefin;
After all, they can be easily molded and shaped into useful objects.

A copolymer containing about 0.1 to 10% by weight, preferably about 1 to 10% by weight (about 0.3 to 5 mol%) of a linear polyfluoroallyloxy comonomer of SO2F or COF is partially hydrolyzed. It can be a copolymer with so, ott or CO, Ii groups that have an affinity for cationic dye molecules. That is, fluorocarbon polymers can be dyed in various colors. This is not possible with comonomer-free polyfluoroolefins of this type.

About 5 to 35 weight percent (about 1.0 to 10
copolymers containing (mol%) may also be partially or substantially completely hydrolyzed to form new aqueous groups SO, OH and CO2H.
It can be a copolymer with 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. -SO2OH or-
CO, H or their ionized steels, such as -
A second important characteristic of copolymers containing about 1.0 to 10 mole percent polyfluoroallyloxy comonomers with SO2O-NA+ or CO2-NA+ is their ion exchange capacity. A special use of such polymers is 1
German patent application 2,2 published on April 26, 1973
No. 51,660 and Dutch Patent Application No. 7217598 published June 29, 1973. In this tank an ion exchange polymer in the form of a film membrane or diaphragm is used to separate the anode and cathode parts of the tank, in which chlorine and hydroxide are removed respectively from the plines flowing in the anode part of the tank. Produces sodium.

The properties of each copolymer depend on the distribution of monomer units along the polymer chain. This is because a copolymer is not 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 become incorporated into polymer chains does not correspond closely to their relative rates of polymerization... "and totally independent of chain length and composition", C. lol
alling, “Free Radicais In s
solution”.

Pages 99-100, John Wiley & Sou
s.

Inc., 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 reactive components and initiator in a non-aqueous or aqueous medium in a closed vessel with a stirrer. . This type of reaction is well known to those skilled in the art; copolymerization is initiated with free radical initiators. The initiator generally accounts for 0.001-5% by weight of the reaction mixture, preferably 0.01% by weight of the reaction mixture.
Present at a concentration of ~1.0% by weight. Such free radical initiator systems can preferably be used at temperatures below 25°C, examples of which include, but are not limited to: pentafluoropropionyl peroxide (C,P
, COO), dinitrogen difluoride (N2F2), azobisisobutyronitrile, ultraviolet light and ammonium or potassium persulfate: iron sulfate (11) and hydrogen peroxide, ammonium persulfate, potassium persulfate, cumene hydroperoxide. , a mixture with t-butyl hydroperoxide; a mixture of silver nitrate with ammonium persulfate or potassium persulfite; a mixture with trifluoroic acid M, pentafluoropropionic acid, heptafluorosulfuric acid or pentadecafluorooctanoic acid with 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 in the copolymerization, the system is a sodium or potassium salt of a saturating membrane acid having about 14 to 20 carbon atoms or a sodium salt of a perfluoroalkanoic acid and perfluoroalkanesulfonic acid having about 6 to 20 carbon atoms. It contains emulsifiers in the form of salts or potassium salts, such as potassium stearate or potassium pentadecafluorooctanoate. These emulsifiers contain 0 of the reaction mixture.
, 1 to 10.0% by weight, preferably 0.5 to 5% by weight.

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

The following three copolymerization systems are preferred for the preparation of the preferred copolymers of the invention: l) 1,1,2-trichloro-1,2°2-trifluoroethane containing pentafluoropropionyl peroxide ( Preon@113) A solution of a binary or more comonomer in a solvent is shaken in an autoclave at about 25° C. for about 20 hours.

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

2) An aqueous emulsion of two or more comonomers containing an emulsifier such as potassium perfluorooctane sulfonate and an initiator such as ammonium persulfate is heated in an autoclave at about 70°C and 20-200 psi (1,4
Shake at an internal pressure of ~14.1 kg/cm) gauge for 0.75 to 8 hours. The polymer is isolated by filtration and centrifugation.

3) When attempting to incorporate a large proportion (up to 25 mol %) of polyfluoroallyloxy components into the polymer in method 1), the polyfluoroallyloxy comonomer is
, 1,2-trichloro-1,2,2-trifluoroethane can be used as a solvent.

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 analyses, the nuclear magnetic resonance chemical shifts of fluorine are in ppm from internal fluorotrichloromethane and the nuclear magnetic resonance chemical shifts of proton are in ppm from internal tetramethylsilane. Infrared and nuclear magnetic resonance spectra were recorded on undiluted liquid materials unless otherwise noted.

Reference example 1 1-(heptafluoro-2-propoxy)-1,1,3
,3,-tetrafluoro-2-chloro-2-propanehexafluoroacetone (16.6g, 0.10mol)
is distilled to produce potassium fluoride (5, go?.

0,10 mol) and 1-(2-methoxyethoxy)-2-
Methoxyethane (hereinafter referred to as diglyms) (100
ml) to form a homogeneous solution. This mixture was kept at 25-30°C, and 1.2
-dichloro1.1,3.3-tetrafluoropropene (18.3 g, 0.10 mol, H. Goldwhite
and D. G. Rowell. J. Org. Cham,
32, 1542 (1967)). Let this mixture cool for 1 night, then add water (5 liters)
00q/). The lower layer was washed with water (250 ml), dried 12 and distilled to give 1-(heptafluoro-2-
propoxy)-1,1.3.3-tetrafluoro-2-
Chloropropene (13,Of, 0.039 mol, 39 ml), boiling point 82-83°C, was obtained and its composition was confirmed by the following data: (CC1=CF,) and 7.5-10 um (CF ,C
-O);”FNME, -64,9(m)2F, -OCP
', C=(1'1-76.0(2nd order m)2F, C=CP
, :-81,2 (tJ=5.7#g, each member dJ=2.2
F1g)6F.

CF, i and −146,7 ppm (tJ=22.9H
g each member 7J=z211s) IF, CPU.

Calculation order for analysis c, ctp, 1o: c, 2t, a'r; cl, to, es actual measurement 1!
6: C121,43HCj, 10.89 Reference Example 2 1-(1,1,1,2,3,3-hexafluoro-3-
Chloro-2-propoxy)-pentafluoro-2-propene A) Pentafluoro-2-propenyl fluorosulfate (perfluoroallyl fluorosulfate) Commercially available liquid sulfur trioxide (10 ml) and hexafluoropropene (45f, 0 The mixture with .30 mol was sealed in a Carius tube under an atmosphere of liquid nitrogen, mixed well at 25°C, left at 25°C for 4 days, and finally heated in a steam bath for 6 mol.
heated for an hour. From two such tubes, by distillation,
3-(trifluoromethyl)-3,4,4-trifluoro-1-oxa-2-thiacyclobutane 2,2-dioxide (2-hydroxy-1-trifluoromethyl-1,
2,2-trifluoroethanesulfonic acid sultone, D.
C. England, M. A. Dietrich and R. V., Lindsey, Jr.J., Awter, Che.
rn, Soc. , 82, 6181 (1960)) (25
F, 22%), boiling point 44°C, and pentafluoro-2
- Propenyl fluorosulfate (hereinafter referred to as perfluoroallyl fluorosulfate) (73g, 63%
), a boiling point of 58-60°C is obtained.

Perfluoroallyl fluorosulfate is characterized by: B. 1-(1,1,1,2,3,3-hexafluoro-
3-chloro-2-propoxy)-pentafluoro-2-
Propene potassium fluoride (5,80g, 010mol) and digl
yme (100 ml) in a cooling bath at 20°C.
While stirring, chloropentafluoroacetone (103t, o, tomol) was distilled in at the same time. . After the potassium fluoride had dissolved, perfluoroallyl fluorosulfate (23,0g, 0.10 mol) was added rapidly while cooling the reaction mixture, and the resulting sanding reaction was accompanied by precipitation of the cylinders. The mixture was stirred at 25°C for 1 hour, then the volatile components were transferred to a trap cooled to -80°C by heating the reaction mixture to 42°C (5 mmHg). When distilled from phosphorus pentoxide, the volatile product is 1-(1,1,1,2,3,3-hexafluoro-
3-chloro-2-propoxy)-pentafluoro-2-
Propene (1qer, o, o59 mole, 59%) boiling point 8
The properties were as follows: Reference Example 3 2-(1-pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl fluoride (
2-Perfluoroallyloxypropane 1-1 sulfonyl fluoride) A) 2-oxopentafluoropropane sulfonic acid (1) Sulfur trioxide (1z, sr, 0.16 mol)
-Ethoxy-1,1,3,3,3-pentafluoropropene (D.W. Willy and E,E.

Simmons, J. Org, Chem, 29, 187
6 (1964)) (29.0 g, 0.165 mol), an exothermic reaction occurred. Distilling the black reaction mixture recovered 2-ethoxy-1,1,33,3-
Pentafluoropropene (6,3f, 0.036 mol,
22%, fixed by infrared analysis) and ethyl 2-oxopentafluoropropanesulfonate (20.2 g, 0.07
8 mol, 49% conversion and 63% yield), boiling point 4
7-4B"C (12mfig) was obtained, and the characteristic values of the ester were as follows: (11) Sulfur trioxide (88F, .L%y+,) and 2-
The above reaction was repeated using ethoxy-1,1,3,3,3-pentafluoropropene (176y, t, o mol) at 0-5<0>C. A colorless reaction mixture is obtained,
When this is left undisturbed overnight, it becomes a dark color, and when distilled,
Recovered 2-ethoxy-1,1,3,3,3-pentafluoropropene (28.6 g, 0.16 mol, 16%
), boiling point 46-48°C, ethyl 2-oxopentafluoropropanesulfonate (145.1 g, 0.57 mol,
57% conversion and 68% yield), boiling point 48-52
C. (12 gm#g) and a high boiling fraction consisting mainly of 2-oxopentafluoroprononesulfonic acid was obtained. Redistilling the crude acid at 81-82°C (6,2 nmHg) gives 35.6f (0.16 mol, 16% turnover and 19% yield) of pure acid: (ii) Ethyl 2-oxopentafluoropropanesulfonate (25.6 g, ola mol) was stirred at 25°C and trifluoroacetic acid (17.1 g.

015 mol). This mixture was allowed to stand overnight and then placed on a spinning band still.
The mixture was heated to reflux (60°C) in hand still.

This mixture was fractionally distilled at a pot temperature below 100°C, resulting in 2-oxopentafluoropropanesulfonic acid (1
8.4 g, 0.081 mol, 81%), boiling point 73°C (2
6 UG) was obtained.

B. 2-oxopentafluoropropanesulfonic acid 1,
1-difluoroethyl 2-oxopentafluoropropanesulfonic acid (23,
gf, 0.10 mol) was cooled to below -40°C and vinylidene fluoride (1,1-difluoroethane) (13 g, o, 2 a mol) was added. The mixture was shaken and warmed to 25°C where it was maintained for 4 hours. When the liquid product is distilled, 2(1,4f(0,0
7 mol, 70 ml) of 2-oxopentafluoropropanesulfonic acid, 1-difluoroethyl, boiling point 62-63
A similar experiment on the 08 molar scale gave an 86% yield of product, boiling point 60°C (50 mmHg). This material was stored in polytetrafluoroethylene bottles to prevent decomposition.

C,2(1-pentafluoro-2-propenyloxy)
Hexafluoropropane-1-sulfonyl fluoride 2,5,8,11-tetraoxadodecane (trigl
dry potassium fluoride (5,
80 f, 0.10 mol) was stirred and cooled to 0° C. and at the same time 2-oxopentafluoropropanesulfonic acid 1,1- prepared as in Reference Example 3B.
Difluoroethyl (29.2g, 0.10mol) was added. When almost all of the potassium fluoride was dissolved, 0% of the perfluoroallyl fluorosulfate (23.0 g, 0.10 mol) prepared by the method in Reference Example 2A was dissolved.
C. and the resulting mixture was stirred at 20-26.degree. C. for 3 hours. The volatile components were removed at a flask temperature of 25 °C and 1
It was removed by distillation at a pressure of mHg. The distillate was washed with cold dilute ammonium hydroxide, dried, and diluted to give 2-(1
-pentafluoro-2-propenyloxy)hexafluoropropane-l-sulfonyl fluoride (13,O
f, 0.034 mol, 34%), boiling point 47-48°C (6
0 mmHg) was obtained, and its structure was confirmed by the following data: In a reaction similar to Reference Example 3C, the gas generated is mainly composed of acetyl fluoride and small amounts of hexafluoropropene and sulfuryl fluoride. This was shown by infrared analysis.

Reference example 4 1-{1,3-bis(2-heptafluoropropoxy)
-2-pentafluoropropoxy}-pentafluoro-
2-propene A, 1,3-bis(2-heptafluoropropoxy)tetrafluoropropanone dry potassium fluoride (21,, Ot, 0.3 emol),
Dry N,N-dimethylformamide (DMF) (150
ml), hexafluoroacetone (5989,0,36
mol) and 1,3-dichlorotetrafluoroacetone (35.8 g, 0.18 mol) was heated under reflux for 3 days. When distilled into a trap cooled to -80°C,
Recovered hexafluoroacetone (16.5 m/, 4
6%) and 63 g of liquid, boiling point 30-145°C. Redistilling high-boiling substances from sulfuric acid yields l,3-
bis(2-heptafluoropropoxy)tetrafluoropropanone (18.7 g, 0.037 mol, 21% conversion, 39% yield based on hexafluoroacetone),
Boiling point 117-118°C: B. 1-{1,3-bis(2-heptafluoropropoxy)-2-pentafluoropropoxy}-pentafluoro-2-propene 1,3-bis(2-heptafluoropropoxy)tetrafluoropropanone (20,0r , 0.04 mol), d
iglyrne (100ml) and potassium fluoride (
2.32 g, 0.04 mol), stirred a mixture of 55
Warmed to ℃. The two liquid phases and the solid initially present became homogeneous and remained that way upon cooling. Perfluoroallyl fluorosulfate (10, or, 0.043 mol) prepared as in Reference Example 2A was added rapidly at 10°C and the mixture was allowed to warm. The somewhat exothermic reaction was accompanied by the precipitation of a solid and the appearance of a second liquid phase.

Stir the mixture for 2 hours, then add water (350 ml)
injected into. The lower layer was washed with water (75 ml), dried over phosphorous pentoxide, and distilled to give 1-1t, a-bis(2-heptafluoropropoxy)-2-pentafluoropropoxy}-pentafluoro-2-propene ( 16.1g,
0.024 mol, 62%), boiling point 64-67°C (25 m
mHg) was obtained, the structure of which was confirmed by the following data: Reference Example 5 3-(1-pentafluoro-2-propenyloxy)tetrafluoropropionyl fluoride A. Difluoromethyl difluoride 3-methoxytetrafluoropropionyl fluoride (F.S. Fawcett, C.W., Tullock and D.D. Coffman, J., Amer, Chgm.
, Sac, 84.4275 (1962)) (81g, 0
．． 45 mol) was slowly added to sulfur trioxide (80 g, 1.0 mol) at 40°C, and the product difluoromalonylsofluoride, boiling point -9°C, was continuously removed by distillation from a low-temperature distillation kettle. , 58 g (0.40 mol, 90%) were obtained. The structure of this product was confirmed from the following data: dry potassium fluoride (7.5 g, 0.13 mol) and di
Stir the mixture with glyme (100-) at 10°C and add difluoromalonyl difluoride (18-) from Part A.
, 5f, 0.13 mol) was distilled into the solution. 20 minute shun,
Almost all of the potassium fluoride is bathed, and reference example 2
Perfluoroallyl fluorosulfate (29, or, o, xa mol) prepared as in A was added to 10
It was added dropwise at ~15°C. The mixture was stirred for 3 hours and then the volatile components were removed at a bottom temperature of 32° C. and a pressure of 48 Hg. When the distillate is fractionally distilled, 3-
(1-pentafluoro-2-propenyloxy)tetrafluoropropionyl fluoride (14.9 g, 0.
051 mol, 39 t), boiling point 70-71°C, and a small amount of higher boiling material was obtained. The structure of the product was confirmed by the following data: Reference Example 6 Perfluoro-3,6-dioxanone-8-enoyl fluoride A. Tetrafluorodiglycoyl chloride 307,6
N (1,46 mol) dichlorotetrafluorodihydrofuran, 157.8 IC3,9 mol) ■αOH, 31
2,11,97 mol) of potassium manganate and 1
The 500 ml water mixture was refluxed for 17 hours. for a short time (
water vapor) when distilled.

10.6.9 (3%) of recovered dihydrofuran was used. Filter this reaction mixture and remove the filter cake with 2X40
Triturated with 0 ml of water. The combined aqueous solution was evaporated to 1500 ml, treated cold with 300 liters of pure SO4, and evaporated continuously with ether for 1 day. The extract was evaporated until no more ether evolved at 25°C (05 mmHg).

Crude solid diacid, 279 g (~93% yield).

5 g (0.06 mol) of pyridine and 416.5 g (a5
mol) of thionyl chloride was added. Although a small amount of gas was generated at this stage, a considerable amount of gas was generated as the mixing nozzle was stirred and heated to over 40°C. The generated gas is reduced to 0.
After 4 hours at about 40°C, gas evolution slowed and the contents of the trap (10d) were returned to the pot. The mixture was then refluxed, occasionally returning the contents of the cold trap to the reaction, until the head temperature reached 81 DEG C. and no gas was evolved. By fractional distillation, 61% from 215.21 dihydrofuran
) tetrafluorodiglycoyl chloride, boiling point 94
~97°C was obtained. The structure is I"F-77,0 ppm (71, -CFlo-) ng by NMR.

Tetrafluorodiglycoyl chloride, boiling point 96.5
°C was previously produced by different routes (R, E, 1
lanka, E.D., Barring, B.A.

Dodd, and Malign, J., CAgm, S.
oo.

(C), 1706 (1969)).

B. Conversion of tetrafluorodiglycoyl fluoride diacid chloride to the corresponding fluoride, boiling point 32-33° C., was achieved on a large scale (R, E, Ban
ks, E. D., Burltng, B.

Dodd, A., and Malign, J. Chtr.
m, Soo.

(C), 1706 (1969)). 21511 (0,8
85 mol) of tetrafluorodiglycoyl dichloride, 140.5 II (135 mol) of NaF.

and 1200 mg of anhydrous acetonitrile.
Stirring overnight and then distillation yielded a fraction that settled at 35-79°C. This distillate was treated with 20 g of NaF and distilled to yield 105 g of tetrafluorodicricolyl difluoride, 32-33°C. Another 100g
(2.38 mol) of NaF was added to the reaction mixture and slow distillation yielded another fraction, boiling point 35-81°C.

When treated with ION's NaF and fractionated, other 37,0
．． A difluoride product of 9, boiling point 32-83°C was obtained, giving a total of 142&(76%).

C. A mixture of perfluoro-3,6-dioxanone-8-enoyl fluoride (0,6'7 mol), tetrafluorodicricolyl difluoride, and 500 ml of dry diglymn was stirred at 5°C for 30 minutes, during which time Almost all of the KF was dissolved. Then 1s4.1.9(0,67
5 moles) of perfluoroallyl fluorosulfate
The mixture was stirred at 0-5°C for 3 hours, 25°C for 2 hours, and left overnight. inducing an injector and di
glym- was refluxed at 38° C. (3 concentrations of Hg). 20g
Distillation of the inducer from NaF of
25.1' (52%) of monoacid fluoride, almost all of which had a boiling point of 93-94°C, was obtained. The structure was confirmed by:

Reference Example 7 Potassium fluoride (5
Stir a suspension of 8g% (0.10mol).

While cooling, fluorosulfonyl difluoroacetyl fluoride (11 (1,0,10 mol) (D, C, E
ngland, M, A, I) igtrich and R,
V., Lindamy, Jr., J., Aynsr., Chg.
m.

Soc. 82, 6181 (1960)) was rapidly added. This mixture was stirred for 15 minutes at 20-30°C, during which time the potassium fluoride dissolved, and it was then combined with perfluoroallylfluorosulfate (0.11 mol in 25.0) prepared as in Reference Example 2A. 20-25
℃ for 5 minutes. The mixture was stirred for 2 hours during which solids precipitated and the temperature rose to 28°C and fell again. By heating the solution to 38°C (5 mHIJ) and refluxing, the F-emitting component was reduced to 80°C.
Transferred to a cooled trap. The distillate was dissolved in concentrated sulfuric acid (10 m
l) to remove digLynm5 and then distilled to give 2-(1-pentafluoro-2-propenyloxy)
Tetrafluoroethanesulfonyl fluoride (19,
9g, 0.06 mol, 60%).

A boiling point of 55-56°C (150 mRg) was obtained. The structure of the product was confirmed by the following Reference Example 8 2-(1-pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluoride The method of Reference Example 7 was repeated using acetonitrile instead of diglymm as the solvent. repeated. The acetonitrile was not rigorously purified and the yield of 2-(l-pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluoride, node 54-55°C (150 mmHg) was 40-50 g.

Reference Example 9 1-[1-(pentafluoro-2-propenyloxy)
] Hexafluoropropane-2-sulfonyl fluoride potassium fluoride (5.80 g, 010 mol) and digl
yme (100we) was stirred at 10°C while 12-fluorosulfonyltetrafluoropropionyl fluoride (23.0g, 0.10mol) (D,
C, England, M, A, Digtriah and R, V, Lindaery, Jr, J, ksr, Ch.
mm.

5otJ, 6181 (1960)) was added.

The resulting solution was treated at 10° C. with perfluoroallyl fluorosulfate prepared as in Reference Example 2AK, and after the addition was complete the mixture was stirred at 25° C. for 3 hours and then poured into water (500 ml). I put it in.

The lower layer was washed with water (100 y+t), dried, and distilled to give pure 1-[1-(pentafluoro-2-propenyloxy)]hexafluoropropane-2-sulfonyl by gas-liquid chromatography (ylpc). Fluoride (25.7g, 0.068mol, 68%), boiling point 5
0°C (60mmHg) was obtained. The structure of the product was confirmed by Reference Example 10 2-[1-(1,2,3,4,4-pentafluoro-2
-cyclobutenyloxy)]tetrafluoroethanesulfonyl fluoride in diglymg (100 ml) of potassium fluoride (5
, 80 g, 0.10 mol).

The temperature was maintained at 15° C. by external cooling and at the same time fluorosulfonyl difluoroacetyl fluoride (1 & Og, 0.
10 mol) was added rapidly. This mixture was heated to 10-15℃.
1-(1,2,3,4゜4-pentafluoro-
2-cyclobutenyl) fluorosulfate (24,2
,9,0,1omol) (B.

(1976)), then stirred at 25'C for 3 hours and poured into water (500ml). Water the lower layer (10
0 ml), dried and distilled to give 2-(1-(1
, 2,3,4,4-pentafluoro-2-cyclobutenyloxy)]tetrafluoroethanesulfonyl fluoride (24,0g, 0.07 mol, 70%), boiling point 62
°C (100 pm H1) was obtained. The structure of this main organism is
Example 11 2-(1-pentafluoro-2-propenyloxy)-
3,6-bis(trifluoromethyl)-2,3,5,5
,6-pentafluoro-1,4-dioxane potassium fluoride (5,8 g, 0,10 mol) and digl
yms (100ktff,) at 25°C.
．． fl-tetrafluoro-1,4-dioxan-2-one (S, Snrman, U.S. Pat. No. 3,321°517)
(31.0 g, 0.10 mol).

The mixture was stirred for 1 hour and then treated portionwise with perfluoroallyl fluorosulfate (200β, 0.10 mol) prepared as in Reference Example 2A.

The exothermic reaction was maintained at 35-40°C with external ice melting. The mixture was stirred at 25° C. overnight, during which time no gas evolution was detected and a yellow-orange color developed. This mixture was poured into water (500 m6) and the lower layer was roughened and dried with water (100 m6).

Distilled at 73-74°C (180-140 mmHg).

When the distillate is treated with a small amount of phosphorus pentoxide and re-divided, 2-
(1-pentafluoro-2-propenyloxy)-3,
6-bis(trifluoromethyl)-2,3,5,5,6
-Pentafluoro-1,4-dioxane was obtained as a mixture of isomers, boiling point 55-57°C (60 mmHg).

The structure of this product was confirmed by the following Reference Example 12 2-[1-(pentafluoro-2-propenyloxy)
]-2,3,5,6-tetrakis(trifluoromethyl)-5-fluoro-1,4,7-trioxabicyclo[
2+2tt]heptane and 2-[1-(pentafluoro-2-propenyloxy)tetrafluoromethyl]-
4-[1-(pentafluoro-2-propenyloxy)
]-2,4,5-tris(trifluoromethyl)-5-
A suspension of anhydrous potassium fluoride (5.80 g, 0.10 mol) in fluoro-1,3-dioxolane dtglyma (100 ml) was stirred at 10°C, while hexafluoro-2,3-butanedione (hexafluorone Acetyl, L, 0°1dan, 2472
(1965)) was distilled into the solution.

This mixture was stirred until almost all of the potassium fluoride was dissolved, and then added with perfluoroallyl fluorosulfate prepared as in Reference Example 2A.
Processed rapidly at 5°C.

The temperature rose to 3°C due to a somewhat exothermic reaction.

The pale yellow mixture was stirred overnight at 25°C and then distilled. The two-phase distillate, boiling at 49-54°C (10 mH1), was combined with concentrated sulfuric acid (8 ml), treated with anhydrous calcium sulfate, and divided into two bands in a still. 2-C1-Cpentafluoro-2-propenyloxy))-2゜3.5. b-tetrakis(trifluoromethyl)-5-fluoro-1,4,7-trioxabicyclo(2121t)heptane (301%0.00
55 mol, 11%) boiling point 50-51°C (15mmHg)
contained one major component by gas-liquid chromatography. An analytical sample of this product was obtained by partial air-liquid chromatography, and the structure of the second fraction was confirmed as follows: 2-(:1-(pentafluoro-2-propenyloxy)tetrafluoroethyl) -4-(l-(pentafluoro-2-propenyloxy))-2,4,5
-tris(trifluoromethyl)-5-fluoro-1,
3-dioxolane (7.2 g, 0101 mol, 21%)
It is a mixture of

It contained only a small amount of impurity as determined by gas-liquid chromatography. The structure of this product was confirmed by the following Reference Example 13 Perfluoro-1,5-bis(2-propenyloxy)
potassium hexane fluoride 11.62@, 0.20 mol), dig
A mixture of lyme (200ml) and octafluoroaziboyl difluoride (PCR28.2g, 0.096mol) was stirred at 5°C for 1.5 hours. The mixture was kept at 5-10°C and at the same time perfluoroallyl fluorotorfaate prepared as in Reference Example 2A (
46.11 g, 0.20 mol) was added dropwise. When the addition was complete, the mixture was stirred at 5°C for 30 minutes, then it was allowed to warm to 25°C, and stirring was continued for an additional 3 hours. - After storing at night, pour this mixture into water (1)
Pour into water, wash the lower layer with water (150aj), dry,
Distillation gave two products.

The fraction with a lower boiling point is perfluoro-1,6-bis(2
-propenyloxy)hexane (21.1 g, 0.03
55 mol, 37%), boiling point 84-86°C (20 degrees H9)
and its structure was confirmed by 16), boiling point 10
9 to 110℃ (5mmHg), which is the former GLYM
e produced by hydrolysis of perfluoro-6-(2-propenyloxy)hexanoyl fluoride in an aqueous wash solution. The structure of this complex was confirmed by Reference Example 14 Methyl perfluoro-3,6-dioxanone-8-enoate 42 g (1,0 mol) of N in 100 ml of methanol
The suspension of aF was stirred at 5°C, and 114 g (0,
317 mol) of acid fluoride were 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, IO2,
0186) methyl perfluoro-3.

6-dioxanone-8-enoate, boiling point 60-61°C
(20+uHg) was obtained, which contained small ring impurities. Redistillation gave a somewhat pure ester (1-2 impurities as determined by gas chromatography), boiling point 61-62°C (20 maHg). The structure was confirmed by the following; Reference Example 15 Dimethylperfluoro-3-aloxyglutarate A. Bis(2-methoxytetrafluoroethyl)ketone Synthesis of bis(2-methoxytetrafluoroethyl)ketone from dimethyl carbonate, tetrafluoroethylene and sodium methoxide was described in D,W.

U.S. Patent No. 2,988.537/1961 to W.E.Y.
It is described in. Extending this reaction gave 1,3,3,5-tetramethoxyoctafluoropentane in a one-pot reaction.

27.0 g (0.50 mol) sodium methoxide,
5aQ10.62 mol) of carbon dimethyl, and 100
- A mixture of dry tetrahydrofuran was stirred under 1-3 atmospheres of tetrafluoroethylene in a 350 ml tube. Tetrafluoroethylene was pumped in as it was consumed, for a total of 1109 (1.1 mol) added.

A mildly exothermic reaction maintained the temperature around 35°C. After the addition, the reaction mixture was heated to 40° C. for 1 hour. The viscous solution from this reaction was directly treated with 75.6 g (0.60 mol) of dimethyl sulfate at 40° C. for 15 hours. When filtered and distilled, the result is 87.17 (52) 1°3.3.
5-tetramethoxyoctafluoropentane, boiling point 54
°C (0,3awH9), nL'1.3605 was obtained,
Its structure was confirmed by B. 50 ml of dimethyltetrafluoroacetone-3,3-dicarboxylate #H,SO2 was added dropwise to 33.6ii (0.10 mol) of the above tetraether. After the mild exothermic reaction has stopped, the mixture is heated to 70°C (50rtunHQ).
to remove volatiles, and then heated to about 50°C (1 mHj
7). The crude distillate is then fractionated, 16.
99 (69%) dimethyltetrafluoroacetone-1
, 3-dicarboxylate, boiling point 58°C (for 2 minutes), n”
1.3713 was obtained. The structure was confirmed by: When the same reaction was carried out on a 0.56 molar scale, the diester yield was 82 molar.

c. Dimethyl perfluoro-3-aloxyglutarate 27.39 (0.18 mol) of dry C8F in 100 ml of old gJyme to 43.59 (0.18 mol) of 0=
C(CF2C00CHs)2 was added at 5-10°C and stirred for 1 hour. 41.4q (0.18 mol) of C
F2=CFCF'20SOtF was added at 5-10<0>C and the mixture was stirred vigorously for 3 hours. This reaction mixture was poured into 1 liter of 11.0, and the lower layer was separated.
I washed it twice. After treatment in 20 ml (DH, So4TeO'C) and extraction with Freon 11.3, the extract was distilled in a molecular distiller to yield 4.54
g (yield of 7.2 g) of product, boiling point 51-53 °C (0
, 1 order) were obtained. The structure was confirmed by: Reference Example 16 Perfluoro-3-(2-propoxy-2-methylethoxy)propene potassium fluoride (fi, 917.0, 12 mol), rl
iglyme (150 ml) and 2-(1-% butafluoropropoxy)tetrafludecaropropioni refluoride (dimer of hexafluoropropene obtained by treatment with fluoride ions) (29,49,0,089
1, a mixture of perfluoroallyl fluorosulfate (27,fi9, (1,12 mol) prepared as in Reference Example 2A) was stirred at 5°C for 1 hour. The mixture was then stirred at 5°C for 3 hours and at 25°C overnight.

The reaction mixture was poured into water (1t), the lower layer was separated and the volatile components were removed at 25°C (o, 5mmHg).

Distilling volatile components from concentrated sulfuric acid produces perfluoro-3-
(2-propoxy-2-methylethoxy)propene (2
5,29,0,052 mol, 59 parts), boiling point 62-63
°C (100aHE) and its structure was confirmed by the following: Reference Example 17 Perfluoro-1,3-bis(2-propenyloxy)
Potassium propane fluoride (15G 9.0.26 mol), dig
lyme (200d) and difluoromalonyl difluoride (17) prepared as in Reference Example 5A.
, 39, 0, 12 mol) was stirred at 5°C for 15 minutes. Perfluoroallyl fluorosulfate (5
7,59,0,25 mol) at 5-10°C for 45 minutes, the mixture was stirred for a further 1 hour at 5°C and then for 2 hours at 25°C. The reaction mixture was poured into water (11), the lower layer was washed with water (100 ml),
When dried and distilled, perfluoro-1,3-bis(2
-propenyloxy)propane (12.0 g, 0.02
7 mol, 23 mol), boiling point 88-90°C (200 mt (9
) was obtained, and its structure was confirmed by the following: Reference Example 1
8 Perfluoro-3-(butoxy)propene dry potassium fluoride (7.50 g, 0.13 mol), rljglym
e (100m) and heptafluorobutyroyl fluoride (prepared from treatment of acid with sulfur tetrafluoride) (
A mixture of 28, 1, 9, 0, 13 mol) was stirred at 5°C for 30 minutes. Perfluoroallyl fluorosulfate was lowered at 5°C and the mixture was heated at this temperature for 1 hour for 2 hours.
Stir at 5°C for 3 hours. Volatile components are removed by distillation
℃ (8BH9), washed with water (100d) and distilled from a small amount of concentrated sulfuric acid to give perfluoro-3-(butoxy)propene (30.3g, 0.083mol, 641),
A boiling point of 80-84°C was obtained, and its structure was confirmed by: Reference Example 19 Perfluoro-3-(octyloxy)propene potassium fluoride (5,8OL 0.10 mol), rNglyme
(150d) and pentadecafluorooctanoyl fluoride (prepared by treatment of perfluorooctanoic acid of cloth board with sulfur tetrafluoride) (25,0El, 0
．． The mixture was stirred at 5° C. for 1 hour. Perfluoroallyl fluorosulfate (23, Og, 0
．． 10 mol) was added dropwise and the mixture was stirred at 5°C for 4 hours and then at 25°C for a further 3 hours. The mixture was poured into water (1 t), separated, and the lower layer was distilled from concentrated sulfuric acid to give perfluoro-3-(octyloxy)propene (27.1 g, 0.048 mol, 80 m), b.p.
70° C. (20 awHg) was obtained, and its structure was confirmed by: Reference Example 20 2-Trifluoromethoxypentafluoropropene (perfluoro(allyl methyl ether) carbonyl fluoride (ts, og, 0.27 mol) , cesium fluoride (38
, OJ7.0.25 mol) and dry diglyme (
The mixture of perfluoroallyl fluorosulfate (46,0 p
, 0.20 mol) was added. This mixture was heated to -10℃ for 2 hours.
The mixture was stirred at 0°C for 2 hours and then at 25°C overnight.

This mixture was heated under slightly reduced pressure, and volatile, distillate (−
2-trifluoromethoxypropene (3.2 g, 2.0 ml, 0.01
4 mol, 7 parts) and a boiling point of 11-12°C were obtained. Its structure was established by spectroscopy: Reference Example 21 Perfluoro-6-(2-propenyloxy)hexanoic acid and its methyl ester potassium fluoride (11,7Ii, 0.20 mol), '+
glyme (2!'lOml) and octafluoroaziboyl difluoride (PCR58,8g, 0.20
mol) mixture was stirred for 30 minutes at 0-5°C.

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 stirred at 0-5°C for 2 hours, then allowed to warm to 25°C and stirring continued for an additional 4 hours. The reaction mixture was evacuated to 35°C (3wHJiJ) and 45-
liquid was removed. The high boiling residue was poured into water (1 t), the lower layer (10 Mj) was combined with the volatile fraction from above, water (1, nOm/) and diglyme (20 ml)
) After the resulting exothermic reaction, the mixture is allowed to cool, the lower layer is separated and distilled to give perfluoro-1
, 6-bis'(2-propenyloxy)hexane (Example 13, 13.6, 9.0.023 mol, 23 parts),
2:1 complex of perfluoro-6-(2-propenyloxy)hexanoic acid and digIyme (Reference Example 13.5
2.8g, 0.109mol, 54.5g), boiling point 82~
84°C (0.8gH?) was obtained.

The old glyme complex of the high boiling point fraction was dissolved in concentrated sulfuric acid (401/
) to give perfluoro-6-(2-propenyloquine)hexanoic acid containing its methyl ester. This ester is the digly present in the complex.
arises from the action of sulfuric acid on me. These products were identified by infrared and NMR analysis: the spectra were also consistent with these structures.

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

The crude reaction mixture was poured into water (750 at) and the lower layer was washed with water (IQO++l). By distillation of the lower phase layer,
The same two products as in Example 21 were obtained. When diglyme was removed from the fraction, boiling point 45-53°C (6wHIi7) by water washing, crude perfluoro-1,6-bis(2-propenyloxy)hexane (9.5g, 0,0
16 mol, 16 mol) remained.

The complex of high boiling point perfluoro-6-(2-propenyloxy)hexanoic acid and djglyme is 1.1.2-
Trichloro-1,2,2-trifluoroethylene (sn
az) and sequentially extracted with 50ml and 25j+7 concentrated sulfuric acid. Treatment of the organic phase with calcium sulfate, filtration and distillation yields pure perfluoro-6-(2-7'robenyloquine)hexanoic acid C42,29,0,0988
mol, 49 mm) and a boiling point of 75° C. (1.0 msHg). This material was identified by IR and NMR analysis: The following example illustrates the preparation of useful copolymers from the polyfluoroallyloxy comonomers of this invention.

Example A Solution Polymerization of Tetrafluoroethylene and 2-[:1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride Into a stainless steel lined 80 d tube, 1.1.2-trichloro- 1,
2,2-1 Lifluoroethane (Freon 113) (
10m), 1.1.2-trichloro-1゜2 of 8th pentafluoropropionyl peroxide (3P initiator)
．． 2-trifluoroethane solution (1-), and 2-[
1-(pentafluoro-2-flopenyloxy)]-tetrafluoroethanesulfonyl fluoride (Reference Example 7
．． 17.5 g, 0.1153 mol) of a cold mixture (-45
℃) was added. The tube was closed, cooled to -40°C, evacuated and tetrafluoroethylene (20g, 0.20mol)
I put it in. The tube was warmed to 25°C and shaken at this temperature for 20 hours.

The volatiles were evaporated and the product polymer was heated to 0.5 mHg.
was exhausted. The product is then converted into 1.1.2-1lichloro-
Extraction with 1,2,2-1 refluoroethane and vacuum drying yielded a white solid copolymer (16.9 g, 851): λ
max (KBr) 6.79 (So, F) and +2. a
μm (broad) as well as the infrared band of normal polytetrafluoroethylene were obtained. Gravimetric sulfur analysis is 0.481
and 0.20 parts of S, which corresponded to an average of 0.34 parts of S or 3.5 weight (1.1 parts by moles) of polyfluoroallyloxy comonomer, corresponding to an equivalent weight of 9400. Equivalent weight is the molecular weight of the polymer per functional group (-8o, F here). Differential scanning passion analysis (11SC)
showed a reduction in endothermic peak (mp) by a factor of 12 compared to polytetrafluoroethylene.

Example B Tetrafluoroethylene and 1[1-(pentafluoro-
2-propenyloxy)]hexafluoropropane-2
- Solution polymerization of sulfonyl fluoride 1.1.2-trichloro-1,2,2-trifluoroethane (10 l), 1,1,2-trichloro-1.2.
A solution of 8 liters of pentafluoropropionyl peroxide in 2-trifluoroethane (2.0 liters), 1-(1-
(Pentafluoro-2-propenyloxy)]hexafluoropropane-2-sulfonyl fluoride Reference Example 9
, i7.4p, 0.046 mol) and tetrafluoroethylene (209.0.20 mol), 16.7 g (79%) of the copolymer was obtained. X-ray fluorescence analysis showed the presence of S at modulus 0.49. This corresponds to 5.8% by weight (over 1.6 moles) of polyfluoroallyloxy comonomer, which corresponds to 6540.2 This sample was found by DSC to have an mp of 11°C compared to polytetrafluoroethylene. There was a decrease in

Example C Solution polymerization of tetrafluoroethylene and 3-[1-(pentafluoro-2-propenyloxy)tetrafluoropropionyl fluoride] 2-C1,-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride 3-(1-(pentafluoro-2-propenyloxy)]]tetrafluoropropionyl fluoride instead of lide Reference example 5.13.3g, Q, 04
17.81 using the procedure of Example A with
86%) copolymer: λIT, ax(KBr)5. fi
2 (CO,H, weak) and 9.7 am bands were obtained; m
The reduction in p (DSC) was 14° C. compared to polytetrafluoroethylene; gravimetric analysis showed 3.7 parts by weight of polyfluoroallyloxy comonomer, corresponding to an equivalent weight of 7900.

A sample of this polymer was stirred for 2 days with a solution of sodium hydroxide in Part 33 ethanol, filtered and washed with water until the extract was no longer basic. The resulting polymer was easily wetted with water and dried under vacuum. Atomic absorption spectroscopy showed 0.29% Na, which is 3.
This corresponded to 7% by weight (1.3 mol%) of the original comonomer.

Example D Tetrafluoroethylene and 1-(1,1,2,3,,3
Solution polymerization of -hexafluoro-3-chloro-2-propoxy)pentafluoro-2-propene instead of 2-[1-(pentafluoro-2-propenyloxy)]-tetrafluoroethanesulfonyl fluoride ，
1,1,2,3゜3-hexafluoro-3-chloro2
-Fropoxy)pentafluoro-2-propane 1-11
Example 2.14, 18.3 g (87%) of the copolymer following the procedure to the example using: 17.0.043 mol):
Reduction in mp compared to polytetrafluoroethylene (D
SC) 14°C, was obtained; 1F quantitative analysis resembled 0.61 and 0.61 01, which corresponded to a polyfluoroallyloxy comonomer of 5.7 and 5800. : Very accurate analysis by X-ray fluorescence is 0.
It shows a CI of 53%, which is 5.0 weight + #% (1,56
It corresponded to the polyfluoroallyloxy comonomer (molar ratio). A reduction in mp of 14°C compared to polytetrafluoroethylene corresponds to a reduction of 1°C per mole of polyfluoroallyloxy comonomer present/)
. In contrast to this result, the smaller branch in hexafluoropropene exhibits a decrease in mp equivalent to about 1° C. per 0.3 mol % comonomer in its copolymer with tetrafluoroethylene. This means that copolymers prepared from polyfluoroallyloxy comonomers have better molding properties than copolymers thus prepared from hexafluoropropene comonomers when incorporated with comonomers of the same molar ratio. .

Example E Tetrafluoroethylene and 2-(1-pentafluoro-
2-propenyloxy)hexafluoropropane-1-
Solution polymerization of sulfonyl fluoride 2-(1-pentafluoro-2-propenyloxy)hexafluoropropane-1- instead of 2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride Sulfonyl fluoride (Reference examples 3, 16
Following Example A using 1p, (1,042 mol):
Copolymer of 18.5188'l): A mp reduction (DSC) of 8°C compared to polytetrafluoroethylene was obtained; This corresponded to 1 part by weight of polyfluoroallyloxy comonomer and 7460 equivalents.

Example F Vinylidene fluoride and 2-[1-(pentafluoro-2-
Propenyloxy)] Solution polymerization of tetrafluoroethanesulfonyl fluoride (vinylidene fluoride (20, lit, 0.32 mol), 2
-[1-(pentafluoro-2-propenyloxy)]
-Tetrafluoroethanesulfonyl fluoride reference example 7.16.5g, 0.05mol), 1.1.2-trichloro-1,2,2-trifluoroethane (10ml),
and 8% of pentafluoropropionyl peroxide
1.1. The procedure of Example A was followed using 2-trichloro-1,2,2-trifluoroethane solution (5Ml).

This mixture was shaken with I cloth and the highest temperature recorded was 31
It was warm at ℃. The solid copolymer produced (21,5q.

60%) contained 46 wounds (14.2 moles) of polyfluoroallyloxy comonomer with an equivalent weight of 71.9. DS
C showed no thermal events between 25°C and 400°C.

Analysis (CEil=Crt)a, ns(CF!=CFCF
Calculation for 2QCF20F25o,F): tT, 28
．． fi2; H, 1,70; Actual value: (2,28,4 H
F1.1.71;S, 4.46 Example () Solution polymerization of vinylidene fluoride and 1-(heptafluoro-2-propoxy)-1,1,3,:3-tetrafluoro-2-propene 2- [1-(pentafluoro-2-propenyloxy)
] 1-(heptafluoro-2-propoxy)-1,1 instead of tetrafluoroethanesulfonyl fluoride
, : U, 3-tetrafluoro-2-propene (Reference Example 1
．． The solid copolymer (20,6q, 73 g
) was obtained. This material has an equivalent weight of 878 and 36% by weight (
9.8 mol %) of polyfluoroallyloxy comonomer.

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

Example H Solution polymerization of tetrafluoroethylene and perfluoro-3-(butoxy)propene According to the procedure of Example A, perfluoro-3-(butoxy)propene (Reference Example 18.19.ng, 0.052 mol), tetrafluoroethylene ( 209.0.2 nmol)
, 1,1.2-trichloro-1,2,2-trifluoroethane (10 ml) and 1.1.2-trichloro-1
．． 2.8 pentafluoropropionyl peroxide (2 ml) in 2-trifluoroethane gives 1
．． 89 g of solid copolymer were obtained. Cutting this crude material in a blender with more solvent, rinsing and drying yielded 16.5 g of copolymer with an mp of 309°C, indicating that it was a true copolymer. showed that.

Example I Solvent Polymerization of Tetrafluoroethylene and Perfluoro-1,6-bis(2-propenyloxy)hexane Following the procedure of Example H, perfluoro-1,6-bis(
2-propenyloxy)hexane (Reference example 13.20g
, 0.20 mol) was used as the polyfluoroallyloxy comonomer. This resulted in a 16.3V dry powder offshore body: Amax"-55μm (CF=CF
't); the remainder of the infrared spectrum was similar to that of poly(tetrafluoroethylene). DSCVi noticeable fever T
, 315<0>C, and an endotherm ~: (3:1<0>C and 339<0>C (first heating)); the second heating showed no exotherm and a broad endotherm Tp ~326<0>C. Infrared spectra showed that a thermal decomposition reaction of the pentafluoroallyloxy side group occurred on the first heating: the normally sharp broad DSc endotherm around the MP of poly(tetrafluoroethylene) indicated that cross-linking had occurred. shows.

Examples, J Vinylidene fluoride and perfluoro-1,3-bis(2-
Solution polymerization of propenyloxy)propane perfluoro-propane
1,3-bis(2-propenyloxy)propane (Reference example 17.5.7 g, o, nt 3 mol), 1,1,2-trichloro-1,2,2-trifluoroethane (25 sl
), and 1,1.

8qb pentafluoropropionyl peroxide (5m
/) in a stainless steel lined shaker tube.
The temperature was maintained at 0°C, while vinylidene fluoride (20 so, 0.
32 mol) was condensed into the tube. 1 of this mixture
The mixture was roasted overnight at room temperature and the product was isolated as described above. The crude polymer was dried in vacuo, triturated with 95% ethanol in a blender, filtered, and dried to yield 24.0@ solid copolymer. DSC showed an endotherm T of 174°C and was stable up to at least 300°C, indicating that a true octapolymer was produced since the poly(vinylidene fluoride) Hmp was 171°C.

This product is insoluble in acetone and CF=CF2
The absence of infrared absorption bands for side groups indicates that cross-linking has occurred.

Example K Tetrafluoroethylene and methyl perfluoro-3,6
- copolymer of dioxanone-8-enoate Q with 45 g of methyl perfluoro-3,6-dioxanone-8-enoate, 04 g of perfluoropropionyl peroxide, tQpsi (0,7 Kf/side 2)
4 at 50°C under pressure of tetrafluoroethylene.
Time reaction. Upon filtration, a solid was obtained, which was
Dry in a vacuum filter at 0.71 g. The amount of tetrafluoroethylene added was 4q. The equivalent weight by titration was 1176, thus accounting for 28 qb of ester incorporated into the polymerization λ, and the yield based on tetrafluoroethylene was determined to be 20 q6.

A transparent film was obtained by heating to 220° C. in a Carvcr press.

Example L Dyeable Fluorocarbon Polymer Samples of the polymers of Examples B and E were treated with aqueous alcoholic ammonia solution for 1 day at 25°C, filtered, washed with ethanol and water, and dried in vacuo.

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

The above-mentioned partially hydrolyzed polymer is made into Sevron Red GL (Sevrnn"), which has remarkable diameter hardness and sharp dust, and is suitable for dyeing KOrlon"' and other acrylic fibers. A series of cationic dyes - TauFontProductsBook.

January 1975, p. 34) for 1-3 hours at 25 DEG C. and then extracted until the extract no longer contains dye. All three dyes stained well orange-red.

Example M Wettable Fluorocarbon Polymer A sample of the polymer of Example C was treated with aqueous alcoholic sodium hydroxide as described in the Examples. The resulting fluorocarbon polymer contained carbonyl groups and was water-lubricable.

Example N Emulsion polymerization of tetrafluoroethylene and 2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride Water (140 genus 1), 1,1,2-trichloro-1°2,
2-trifluoroethane (10n/), 2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride (Example 7.6.0g
), potassium perfluorooctane sulfonate (0,1
61i1), ammonium carbonate (0,50!?) and ammonium persulfate (0,509) were placed in a stainless steel shaker tube. This mixture was brought to 200 psi (14,114/ryn2) gauge with tetrafluoroethylene;
Heated to 70°C. The pressure of tetrafluoroethylene is 2
00psi (14,1Ky/lyn”) gauge at 70℃
The polymerized raw hV product thus obtained, which was kept for 45 minutes, was filtered, washed and dried to yield 43.2 g of white fixation. It had a total polyfluoroallyloxy comonomer content of approximately 1.4% by weight (Fl, 43 molar cycles) according to infrared analysis. Differential thermal analysis (DTA) showed a crystalline transition of 10°C, a recycle freezing temperature of 293°C and a recycle melting point of 1311°C. From these, the polyfluoroallyloxy comonomer content was calculated at 351°C by weight% (1
, 09 molar width).

Example O Emulsion polymerization of tetrafluoroethylene and 2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride Following the procedure of Example N, 8.09 of 2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethane sulfonyl fluoride -2-propenyloxy)] tetrafluoroethanesulfonyl fluoride, 0.20 g potassium perfluorooctane sulfonate and 30 psi (2,
Tetrafluoroethylene at a pressure of 1 Ky/ryn2) was used at 70° C. for a reaction time of 8 hours. No other ingredients were provided. This yielded 45 g of a solid polymer whose infrared spectrum showed strong So and F absorptions.

Differential thermal analysis showed a crystal transition of 5 °C, a recycle freezing temperature of 282 °C, and a recycle melting point of 300 °C.
．． This corresponds to a polyfluoroallyloxy comonomer content of 9% by weight (1,86 molar width).

Example P Emulsion polymerization of tetrafluoroethylene and 2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride Following the procedure of Example N, 10.7 g of 2-[:1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride was Fluoro-2-propenyloxy)) tetrafluorosulfonyl fluoride, 0.20 J7 ammonium persulfate, and 5Qpsr (3,5 Kf/cm2)
Gauge tetrafluoroethylene was used at 70° C. for a reaction time of 5 hours. No other ingredients are supplied. This gave 28.6 g of a white polymer whose infrared spectrum showed the presence of So, F groups corresponding to a 3.5-fold (1.08 mole) polyfluoroallyloxy comonomer. Differential thermal analysis showed two melting peaks at 290 DEG C. and 17 DEG C., and the comonomer content was estimated to be 5.5 weight percent (1.73 mole percent).

Example Q Copolymerization of tetrafluoroethylene and 2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride and production of conductive film from this copolymer product 2-[1 -(pentafluoro-2-propenyloxy)
] Tetrafluoroethanesulfonyl fluoride (Reference example 7.52.8g) and pentafluoropropionyl peroxide initiator 6nt,t,2-trichloro-1,2
, 2-trifluoroethane solution (0,19,!?) was placed in a steel pipe. The mixture was heated to 40°C and charged with tetrafluoroethylene (TFE) at 10 psi (0.7 Kg/m
The pressure of tetrafluoroethylene was adjusted to 10 psi (0.7 Kg/nn) gauge at 40°C.
It was maintained for 6 hours. The polymer product thus obtained was filtered, washed and dried as a white solid (9,829).
obtained: λmax'(Kl(r)8.65μ(soti
r") and 8-10 am (wide) and the TR band of regular polytetrafluoroethylene. The reduction in melting point of DSC was 91 °C compared to polytetrafluoroethylene. Sulfur analysis by X-ray fluorescence 28.0% by weight (8,5%
mole qb) of polyfluoroallyloxy comonomer to 4
I got it.

The product was pressed into a clear 4-5 mil (o, tn~0.13 silk) film at 220-240°C. Four 4-inch diameter (10°2ay+) film samples were reacted with a 3-15% potassium hydroxide solution at 90° C. for 1 hour, dried and mixed with tetrafluoroethylene and CF, = CFCF, 0CFtCF.

A copolymer with So and K was produced. The IR spectrum is
It was shown that the -802F' functionality was virtually completely converted to the sulfonate.

It has a diameter of 4 inches (10,2 m) and a thickness of 4 to 5 mils (0.
, 10~0.13m+) film, 2. This was done as an ion exchanger in a chloralkali electrolyzer operated at 0 amperes per square inch (0.3 amperes per square inch). It was measured.

The following results were obtained for the 15 day test: Example R Copolymerization of tetrafluoroethylene and perfluoro-6-oxanone-8-enoic acid and conductive film from the copolymer product. Preparation of perfluoro-6-oxanon-8-enoic acid (47,51,
t, 8% pentafluoropropionyl peroxide in 1,2-trichloro-1,2,2-trifluoroethane (0,05 J?), and 10 psi (0,7 Kf/c
m2) gauge tetrafluoroethylene at 40°C to obtain a solid white copolymer of 2.41f: D
The melting point reduction of SC was 157°C compared to polytetrafluoroethylene. Analysis of the carboxyl groups by titration showed 6.8% by weight (9.3 mol%) of polyfluoroallyloxy comonomer corresponding to 1070.

This copolymer was pressed to 4-5 mils (0.10-0.
13 mm) and hydrolyzed as described in Example Q. The IR spectra show that the -COF' functional group has been virtually completely converted to carboxylate, indicating that tetrafluoroethylene and CF,=CF'CFgO(Cr
t)<C()a- indicates a copolymer with +.

4 inches (10.2 cm) in diameter, 4-5 mils (0.2 cm) thick.
A sample of the film (10-0.13 mm) was placed in a chloralkali bath operated at 2.0 Amps/in2 (0.3 Amps/cm') as an ion exchanger;
The following results were obtained during the 76 day study:

Claims (1)

[Claims] 1. Formula (wherein X is -Cl or -F, W and Z are independently -F, and taken together -CF, -, D is , independently -F, or -R2J, where -R<7 can be interrupted with 1 to 4 oxygen atoms for every second or lower carbon atom, -SO,F, -CUF. -Co, H, -CO, Rs, -Cl, -OCF2CF=
0~ selected from CF2 and -OCF2CO, R3
A linear or branched perfluoroalkyl having 1 to 10 carbon atoms and having two functional groups, R3 is -CB or -C2,H, and E is independently -F, - CF3, -CF2C1, -CF2CO,R
” or -R2FOCF(G)2, R3 is as defined above, and D and E taken together form a 5-membered ring or a 6-membered ring in which the ring member is -RF-
0 to 2 substituents -CF3-, forming a membered ring (where RF is interrupted by l or 2 oxygen atoms).
a 4- or 5-membered perfluoroalkylene chain having 1 ), or , and G is -F or -CF, and at least one ethylenically unsaturated monomer. Copolymer with. 2. The copolymer according to claim 1, wherein the ethylenically unsaturated monomer is selected from the group consisting of olefin, halogenated olefin, trifluoromethyl trifluorovinyl ether, acrylic ester, and methacrylic ester. 3. The polyfluoroallyloxy compound has the formula (wherein X is -Cl or -F, D is -CF2R4 or, R4 is -F, -SO, F, -COF, -CO2H, or - (t'F, IR', x is 1 to 6, R'
is -CF3, -0CP2CF=CF2, -COF, -C
O2CB, or -502F, E is -F, -CF3 or -CF2Cl, G is -F, and W and Z are independent and -F). A copolymer according to scope 1. 4. The copolymer of claim 2, wherein the polyfluoroallyloxy compound content is about 01 to 55% by weight of the copolymer. 5. The copolymer according to claim 3, wherein the polyfluoroallyloxy compound content is about 0.1 to 55% by weight of the copolymer. 6. The copolymer according to claim 4, wherein the ethylenically unsaturated monomer is selected from the group consisting of vinylidene fluoride, chlorotrifluoroethylene, trifluoromethyltrifluorovinyl ether, tetrafluoroethylene, and hexafluoropropylene. . 7. The copolymer according to claim 6, wherein the ethylenically unsaturated monomer is selected from the group consisting of vinylidene fluoride, chlorotrifluoroethylene and tetrafluoroethylene. 8. The copolymer of claim 5, wherein the polyfluoroallyloxy compound content is about 1 to 10% by weight of the copolymer.