JP3171826B2 - Fluorine-containing elastomer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluorine-containing elastomer. More specifically, it relates to a fluorine-containing elastomer having a cyano group as a crosslinkable group.

[0002]

2. Description of the Related Art JP-A-59-109546 discloses tetrafluoroethylene, perfluoro (methyl vinyl ether).
And a terpolymer of a perfluorounsaturated nitrile compound represented by the general formula CF ₂ = CF [OCF ₂ CF (CF ₃ )] nO (CF ₂ ) mCN n: 1 to 2, m: 1 to 4 General formula (Where A is an alkylidene group having 1 to 6 carbon atoms, 1 to 1 carbon atoms)
A perfluoroalkylidene group, a SO ₂ group, an O group, a CO group or a carbon-carbon bond directly bonding two benzene rings, and X and Y are a hydroxyl group or an amino group. A fluorinated elastomer composition containing a (phenyl) compound as a curing agent is described.

However, the perfluorounsaturated nitrile compound copolymerized as a crosslinking site monomer of the above terpolymer is synthesized through many steps as described in US Pat. No. 4,138,426. Therefore, it cannot be said that it is an industrially advantageous raw material. Further, compression set at high temperature is not satisfactory.

On the other hand, US Pat. No. 3,933,767 discloses that tetrafluoroethylene and perfluoro (methyl vinyl ether) have the general formula CF ₂ CFCF [OCF ₂ CF (CF ₃ )] nC
A terpolymer obtained by copolymerizing a perfluorounsaturated nitrile compound represented by N (n: 1 to 5) as a crosslinking site monomer is described, and the crosslinking is performed using tetraphenyltin. It is also described.

The above-mentioned perfluorounsaturated nitrile compound used as a comonomer component of the terpolymer is excellent from the corresponding CN [CF (CF ₃ ) CF ₂ O] nCF (CF ₃ ) COF. Although it can be easily synthesized with a high selectivity, since the obtained terpolymer is crosslinked by highly toxic tetraphenyltin, there is a problem in industrial use in terms of safety. Not only that, there is also a problem that the crosslinking speed is slow. Further, the obtained crosslinked product has a disadvantage that it is inferior in water resistance and amine resistance at high temperatures.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a copolymer obtained by copolymerizing a cyano group-containing crosslinking site monomer which can be easily synthesized with a good selectivity. It is an object of the present invention to provide a fluorine-containing elastomer which is commercially available and can provide a vulcanized rubber having good vulcanization properties and compression set by using a cross-linking agent having no problem in terms of safety.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
45-75 mol% of tetrafluoroethylene, 50-25 mol% of perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy lower alkyl vinyl ether) and the general formula CF ₂ ＝ CFO (CF ₂ ) nOCF (CF ₃ ) CN (here Where n is 3-5
Having a copolymer composition of 0.1 to 5 mol% of a perfluorounsaturated nitrile compound represented by
Achieved by a fluorine-containing elastomer in the range of 0.05 to 4 dl / g.

The terpolymer of tetrafluoroethylene, perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy lower alkyl vinyl ether) and a perfluorounsaturated nitrile compound according to the present invention has a tetrafluoroethylene content of about 45 to 75%. Mole% and about 50 perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy lower alkyl vinyl ether)
Approximately 0.1 to 5 mol% of a perfluorounsaturated nitrile compound is copolymerized as a crosslinking site monomer with 〜25 mol%. If the proportion of tetrafluoroethylene is higher than this, the obtained terpolymer will not be in the form of an elastomer, while if it is lower than this, not only the copolymerization reaction will not proceed smoothly but also the heat resistance and the vulcanizate properties will decrease. In addition, the cost is increased due to the increase in perfluorovinyl ether. Further, even if the crosslinking site monomer is used at a higher ratio, the vulcanization properties are not particularly improved, and the heat resistance is rather lowered.

The perfluoro (lower alkyl vinyl ether) of the copolymer component includes perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether),
Perfluoro (propyl vinyl ether) or the like is used, but perfluoro (methyl vinyl ether) is preferably used. As perfluoro (lower alkoxy lower alkyl vinyl ether), for example, the following are used: CF ₂ CFCFOCF ₂ CF (CF ₃ ) OC _n F _{2n + 1} (n: 1 to 5) CF ₂ CF CFO (CF ₂ ) ₃ OC _n F _{2n + 1} (n: 1 to 5) CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ O) _m C _n F _{2n + 1} (n: 1 to 5, m _{: 1~3) CF 2 = CFO (} CF 2) 2 OC n F 2n + 1 (n: 1~5) among them, preferred by particular C _n F _{2n + 1} group is a CF ₃ group Used.

The perfluorounsaturated nitrile compound represented by the above general formula can be synthesized by, for example, the following three reaction routes.

Synthesis method (A) Perfluorounsaturated carboxylic acid represented by the general formula CF ₂ 2CFO (CF ₂ ) nOCF (CF ₃ ) COOR (R: alkyl group having 1 to 10 carbon atoms, n: 3 to 5 ) The acid ester is subjected to an addition reaction of chlorine or bromine to the vinyl group, and CF ₂ XCFXO (CF ₂ ) nOCF (CF ₃ ) COOR (X: chlorine or bromine) ammonia is added to the obtained halogenated perfluorounsaturated carboxylic acid ester. Reaction converts the ester group to an acid amide group, CF ₂ XCFXO (CF ₂ ) nOCF (CF ₃ ) CONH _{2 and} then a dehalogenation reaction to form a vinyl group, CF ₂ CCFO (CF ₂ ) nOCF ( CF ₃ ) CONH _{2 Then} , a dehydration reaction is carried out to obtain the desired product.

The above perfluorounsaturated carboxylic acid ester as a starting material for this reaction has the general formula FOC (CF ₂ ) _n-2 COF
By reacting hexafluoropropene oxide with dicarboxylic acid fluoride represented by (Angew. Chem. Int. Ed.
Vol. 24, pp. 161-179, 1985), the general formula _{FOCCF (CF 3) O (CF} 2) nOCF (CF 3) to give the dicarboxylic acid difluoride represented by COF, alcohol only one of the dicarboxylic acid fluoride group FOCCF (CF ₃ ) O (CF ₂ ) nOCF (CF ₃ ) COOR (R: alkyl group having 1 to 10 carbon atoms) and then FCOF reaction of the other carboxylic acid fluoride group Is obtained by

In the halogen addition of the perfluorounsaturated carboxylic acid ester thus obtained, chlorine or bromine is used, and bromine is preferably used in view of handleability and easy control of the reaction. . The halogen addition reaction can be carried out without a solvent, but is preferably carried out in the presence of a solvent. As the solvent, any solvent can be used as long as it can dissolve the raw material and is inert to halogen, but preferably 1,1,2-trichloro-1,2,2-
Fluorine-containing solvents such as trifluoroethane (F-113), perfluoro (2-butyltetrahydrofuran), and perfluorohexane are used. In order to activate this reaction, the reaction can be carried out under irradiation with light such as sunlight or ultraviolet lamp light.

The reaction between the halogenated perfluorosaturated carboxylic acid ester and ammonia can be carried out without a solvent, but is preferably carried out in the presence of a solvent as used in the halogenation reaction. This reaction can be carried out under normal pressure or under pressure.

The vinyl group is formed by a dehalogenation reaction of the obtained halogenated perfluorosaturated carboxylic acid amide using a protic polar solvent such as methanol or ethanol or an aprotic polar solvent such as dioxane or tetrahydrofuran. , Zn / ZnCl ₂ , Zn / ZnBr ₂ , Zn / Cu and the like, in the presence of a dehalogenating agent. In this case, Zn may be used after activating the surface with dilute hydrochloric acid or the like.

The final dehydration of the carboxylic acid amide group is as follows:
In the absence of solvent, using various dehydrating agents such as phosphorus pentoxide,
The reaction is performed at a reaction temperature of about 100 to 300 ° C.

Synthesis method (B) The perfluorounsaturated carboxylic acid ester as a starting material is directly reacted with ammonia, and the obtained perfluorounsaturated carboxylic acid amide is subjected to a dehydration reaction to obtain a desired product.

The reaction of ammonia with the perfluorounsaturated carboxylic acid ester can be carried out in the same manner as the reaction of ammonia in the above-mentioned synthesis method (A). However, in this case, since the perfluorovinyl group (CF ₂ CFCF—) is not protected, a side reaction such as formation of an NC—CHF— group may occur. Must be controlled to be equimolar to the starting ester.

The dehydration reaction of the obtained perfluorounsaturated carboxylic acid amide is carried out in the same manner as in the above synthesis method (A).

Synthesis method (C) In the above-mentioned synthesis method (A), a step of halogenating a perfluorounsaturated carboxylic acid ester and then reacting with ammonia is sequentially performed, and then the obtained halogenated perfluorosaturated carboxylic acid amide is obtained. After dehydration of the acid amide group of the above, CF ₂ XCFXO (CF ₂ ) nOCF (CF ₃ ) CN (X: chlorine or bromine) is subjected to a dehalogenation reaction to obtain the desired product.

These dehydration and dehalogenation reactions are carried out in the same manner as in the synthesis method (A).

In the terpolymer having the above components as essential components together with tetrafluoroethylene, a fluorinated compound having a fluorinated amount of about 20 mol% or less that does not inhibit the copolymerization reaction and does not impair the vulcanization properties. Olefin and various vinyl compounds can be copolymerized. Examples of the fluorinated olefin include vinylidene fluoride, monofluoroethylene,
Trifluoroethylene, trifluoropropylene, pentafluoropropylene, hexafluoropropylene, hexafluoroisobutylene, chlorotrifluoroethylene, dichlorodifluoroethylene and the like are used, and as the vinyl compound, for example, ethylene, propylene, 1-
Butene, isobutylene, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl propionate,
Vinyl chloride, vinylidene chloride, trifluorostyrene and the like are used.

The copolymerization reaction can be carried out by any polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, etc., but the emulsion polymerization method is preferred from the viewpoint of economy. The emulsion polymerization reaction is generally performed at a pressure of about 5 to 50 kgf / c using a water-soluble inorganic peroxide or a redox system thereof as a catalyst and a surfactant such as ammonium perfluorooctanoate.
m ² G, is carried out under conditions of a temperature of about 40 to 85 ° C., there intrinsic viscosity (3M Company product Fluorinert FC-77,1 wt% solution, 35 ° C.) of about 0.05~4dl / g, preferably about 0.2 A fluoroelastomer in the range of ~ 1.5 dl / g is formed.

The terpolymer is represented by the general formula (Where A is an alkylidene group having 1 to 6 carbon atoms or carbon number
1 to 10 perfluoroalkylidene groups, X and Y
Is a hydroxyl group or an amino group), and is cross-linked by using a bis (aminophenyl) compound represented by a cross-linking agent. As the bis (aminophenyl) compound, for example, the following compounds are used in a ratio of about 0.1 to 5 parts by weight, preferably about 0.5 to 2 parts by weight, per 100 parts by weight of the terpolymer.

In the fluorine-containing elastomer composition containing such a bis (aminophenyl) compound as a crosslinking agent component, an inorganic filler such as carbon black and silica, an oxide of a divalent metal, a hydroxide, a stearate, Acid acceptors such as litharge,
Other necessary compounding agents are appropriately compounded. The composition is prepared by kneading using a roll, kneader, Banbury mixer, etc., the crosslinking of which is about 100-250.
It is performed by heating at about 1 to about 120 minutes. When performing the secondary vulcanization, it is preferable to perform the secondary vulcanization in an inert atmosphere such as a nitrogen gas atmosphere at about 150 to 280 ° C. within about 30 hours.

[0026]

SUMMARY OF] The Applicant has instead of the cyano group-containing said Sho 59-109546 JP (perfluoro vinyl ether), the general formula _{CF 2 = CFO (CF 2)} nCN: with (n 2 to 12) The perfluoro (ω-cyanoalkyl vinyl ether) represented as a crosslinking site monomer is copolymerized with tetrafluoroethylene and perfluoro (lower alkyl vinyl ether), and as a crosslinking agent of the copolymer, represented by the above general formula It has been proposed to use a bis (aminophenyl) compound (JP-A-6-263952).

The nitrile group of this copolymer is a primary nitrile group. In contrast, the secondary nitrile group of the copolymer of the present invention has an o-aminophenol compound and an oxazole ring due to steric hindrance. Was difficult to form and was considered impractical (Journal of Flourine Chemistry, Vol. 8, No. 2,
95-304, 1976).

However, the secondary nitrile group of the copolymer of the present invention has higher selectivity for the oxazole ring formation reaction than the primary nitrile group, and the vulcanizate has improved compression set resistance. .

Further, the secondary nitrile group of the monomer is less susceptible to chain transfer than the primary nitrile group, and a high molecular weight polymer is obtained. Therefore, physical properties such as compression set of the vulcanized product are large. Be improved.

[0030]

According to the present invention, a copolymer obtained by copolymerizing a cross-linking site monomer which can be easily synthesized with a good selectivity, is generally commercially available, and has a problem in terms of safety. The present invention provides a fluoroelastomer which can provide a vulcanized rubber having good vulcanization properties and compression set by using a crosslinking agent having no vulcanizate.

[0031]

Next, the present invention will be described by way of examples.

Reference Example 1 (1) Capacity 1 equipped with a stirrer, a dropping funnel and a cooling pipe
L into a three-neck glass flask, methyl-perfluoro (2-
_{Methyl-3,7-dioxa-8-Nonenoeto) CF 2 = CFO (CF 2} ) 3 OCF (CF 3) COOCH 3 was charged with 422g and F-113 300 g, under UV irradiation, maintaining the reactor in 40 ° C. While adding 160g of bromine from the dropping funnel
It was dropped over time. After completion of the dropwise addition, the reaction mixture was sequentially washed with a 5% aqueous sodium bisulfite solution and water. The organic layer was dried over magnesium sulfate, filtered, and distilled to obtain methyl-perfluoro (2-methyl-3,7-dioxa-8,9-dibromo-8-nonanoate) 582 g (yield 100). %)
Obtained. Boiling point: 87 to 88 ° C. (5 Torr), d ₄ ²⁰ : 1.8801, n _D ²⁰ : 1.3510 ¹⁹ F-NMR (based on CFCl ₃ ): a = -60.7 ppm b = -68.5 c = -83.5 d = -126.7 e = -76.1, -79.8 f = -128.9 g = -80.1 (2) Capacity equipped with a stirrer, gas inlet tube and dry ice cooling tube In a 1 L glass three-necked flask, add the methyl
-Perfluoro (2-methyl-3,7-dioxa-8,9-dibromo-8
(Nonanoate) 582 g and F-113 400 g are charged, and while the temperature inside the reactor is kept at 30 ° C. or lower, 20 g of ammonia gas is slowly introduced from the gas introduction tube with stirring. After the exotherm in the reactor has ended, the mixture is stirred for an additional 8 hours. Thereafter, the solvent, ammonia and produced methanol were distilled off from the system under reduced pressure, and the residue was further distilled under reduced pressure to have a melting point of 70 to
540 g (95% yield) of perfluoro (2-methyl-3,7-dioxa-8,9-dibromo-8-nonanamide) at 75 ° C was obtained as white crystals. (3) Perfluoro (2-methyl-3,7-dioxa-8,9-dibromo
540 g of -8-nonanamide) and 250 g of phosphorus pentoxide were mixed, powdered, and charged in a 2 L glass flask. 160-170
After heating at 10 ° C. for 10 hours, the mixture was distilled under reduced pressure, and the obtained crude product was distilled under reduced pressure while a small amount of phosphorus pentoxide was present,
Perfluoro (2-methyl-3,7-dioxa-8,9-dibromo-8-
Nonanitrile) was obtained in an amount of 459 g (yield 87%). Boiling point: 72 ℃ (25Torr), d 4 20: 1.9281, n D 20: 1.3382 19 F-NMR (CFCl 3 reference): a = -60.8 ppm b = -68.9 c = -79.4, -81.6 d = -126.6 e = -79.4, -83.8 f = -112.0 g = -81.6 (4) Use a stirrer, thermometer, dropping funnel and cooling tube. A 2-liter glass four-necked flask equipped with was charged with 65 g of zinc powder, 1 g of zinc bromide, and 1 L of dioxane, heated to reflux temperature with vigorous stirring, and then mixed with perfluoro (2-methyl-3,7-dioxa). -8,9-dibromo-8-nonanitrile) 459 g
Was added dropwise over 2 hours. After completion of the dropwise addition, the solvent and the product are distilled off from the system. The evaporated mixture is washed four times with water, and the organic layer is dried over magnesium sulfate and filtered. The filtrate was distilled to obtain 280 g (89% yield) of perfluoro (2-methyl-3,7-dioxa-8-nonenonitrile). Boiling ^{_{point: 103~104 ℃, d 4 20:}} 1.5951, n D 20: 1.2870 19 F-NMR (CFCl 3 reference): a = -115.6ppm (dd, Jac = 67Hz, Jab = 87Hz) b = -123.2 (dd, Jab = 87Hz, Jbc = 113Hz) c = -137.0 (dd, Jac = 67Hz, Jbc = 113Hz) d = -86.0 (S) e = -129.5 (s) f = -82.5, -85.1 (AB, J = 145Hz) g = -115.0 (m) h = -85.0 (s)

Reference Example 2 (1) Capacity 500 equipped with a stirrer, a dropping funnel and a cooling pipe
33 g of zinc powder and 200 ml of dioxane were charged into a four-neck glass flask and heated to the reflux temperature with vigorous stirring. Then, the perfluoro obtained in Reference Example 1 and (2) was used.
(2-methyl-3,7-dioxa-8,9-dibromo-8-nonanamide) 1
41 g was added dropwise. After completion of the dropwise addition, dioxane was distilled off, 200 ml of toluene was added to the residue, and the mixture was heated to the reflux temperature and filtered while hot. Toluene was distilled off from the filtrate to obtain 61 g of crude perfluoro (2-methyl-3,7-dioxa-8-nonenamide). (2) Using 61 g of crude perfluoro (2-methyl-3,7-dioxa-8-nonenamide) and 21 g of phosphorus pentoxide, the reaction was carried out under the conditions of Reference Example 2 and (2) to obtain perfluoro (2- Methyl-3,7-dioxa
-8-nonenonenitrile) (50 g, 52% overall yield).

Example 1 The inside of an autoclave having a capacity of 1 L was replaced with argon, and after degassing, 440 g of distilled water, 1.1 g of ammonium persulfate,
4.6 g of potassium dihydrogen phosphate, ammonium perfluorooctanoate-ammonium perfluorodecanoate (weight ratio
60:40) 4.4 g of the mixture and 0.3 g of sodium sulfite were charged. Then, 17.8 g of perfluoro (2-methyl-3,7-dioxa-8-nonenonitrile) obtained in Reference Example 1 [FCV-82; n = 3 in the above general formula], perfluoro (methyl vinyl ether) [FMVE] ] 136.7g and tetrafluoroethylene [T
FE] 63.5 g of the monomer mixture (molar ratio 3:54:43) was charged until the pressure in the autoclave reached 6 to 7 kgf / cm ² G. Heat the autoclave to 60 ° C and further add the monomer mixture
It was charged until the pressure reached 11 kgf / cm ² G.

The dispensing of the monomer mixture was continued while maintaining the polymerization temperature at 60 ° C. and the polymerization pressure at 10-11 kgf / cm ² G. Thereafter, when the reaction was continued at this polymerization temperature for 23 hours, the pressure dropped from 11 kgf / cm ² G to 3.6 kgf / cm ² G. At this time, the unreacted monomer mixture was discharged from the autoclave, and the reaction mixture was frozen and coagulated to precipitate a copolymer. The precipitated copolymer was washed with hot water and ethanol, and dried at 60 ° C. under reduced pressure to obtain 169.8 g of a white terpolymer A (intrinsic viscosity ηsp / c = 0.75). Infrared absorption spectrum: FIG. 1 ¹⁹ F-NMR (based on CFCl ₃ ): -51.8 ppm (-OCF ₃ ) -120 to 110 ppm (-CF _2- ) -136 to 130 ppm (-CF-)

Example 2 In Example 1, the amount of the mixture of ammonium perfluorooctanoate-ammonium perfluorodecanoate was 6.6 g.
And FCV-82 23.9g, FMVE 122.4g, TFE 7
3.7 g of a monomer mixture (molar ratio of 4:48:48) was used and charged in an autoclave at a time to conduct a polymerization reaction at 60 ° C. The reaction was carried out for 18 hours. When the pressure became 4 kg / cm ² , the reaction was terminated, and 176.0 g of a white terpolymer B was obtained.
(Intrinsic viscosity ηsp / c = 0.76) was obtained.

Example 3 In Example 1, the amount of the mixture of ammonium perfluorooctanoate-ammonium perfluorodecanoate was 6.6 g.
And FCV-82 is 12.39g, FMVE is 129.56g, TFE is
Using a monomer mixture of 78.05 g (molar ratio 2:49:49),
The batch was charged in an autoclave and a polymerization reaction was carried out at 60 ° C. The reaction was carried out for 18 hours. When the pressure became 4 kg / cm ² , the reaction was terminated, and 180.0 g of a white terpolymer C (intrinsic viscosity ηsp / c = 0.77) was obtained.

Each of the three elements obtained in each of the above embodiments is used.
The polymer composition of the polymer (mol%), ¹⁹According to the result of F-NMR
It is as follows.

Comparative Example 1 In Example 1, the same amount of perfluoro (7-oxa-8-nonenonitrile) CF ₂ CCFO (CF ₂ ) ₅ CN was used in place of FCV-82.
[5CNVE] was used to obtain 165.0 g of a white terpolymer D (intrinsic viscosity ηsp / c = 0.46). Its polymer composition by ¹⁹ F-NMR was as follows. 5CNVE 2.9 mol% FMVE 49.4 mol% TFE 47.7 mol%

The 3 obtained in each of the above Examples and Comparative Examples
100 parts by weight of the original copolymers A to D, MT carbon black 20
Parts by weight and 1 part by weight of bis (aminophenol) AF were added and kneaded with a roll mill. 160 ° C, 3
Primary (press) vulcanization for 0 minutes and secondary at 250 ° C for 22 hours
(Oven) Vulcanization was performed, and the physical properties of the vulcanized product and the permanent compression set were measured. The results obtained are shown in the following table. Tercopolymer A B C D [Physical properties in normal state] 100% modulus (kg / cm ² ) 76 150 Tensile strength (kg / cm ² ) 179 86 76 167 Elongation (%) 153 90 140 114 [Permanent compression set] 275 ° C, 70 hours (%) 15 (destruction)

Comparative Example 2 In Example 1, instead of FCV-82, the same amount of CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₂ CN [FCV-80] was used, and 196.3 g of FCV-82 was used. White terpolymer E (intrinsic viscosity ηs
p / c = 0.44). Its polymer composition by ¹⁹ F-NMR was as follows. FCV-80 3.1 mol% FMVE 39.6 mol% TFE 57.3 mol%

MT was added to 100 parts by weight of the obtained terpolymer E.
15 parts by weight of carbon black and bis (aminophenol
G) 1 part by weight of AF was added and kneaded with a roll mill. Kneaded material
About 180 ° C, 30 minutes primary (press) vulcanization and 250 minutes
Perform secondary (oven) vulcanization for 24 hours at
The normal physical properties and compression set were measured. [Normal physical properties] 100% modulus 34kg / cm^Two  Tensile strength 114kg / cm^Two  Elongation 230% [compression set] 275 ℃, 70 hours 60%

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a terpolymer obtained in Example 1.

────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Harumi 3-8-4 Benten-cho, Hitachi, Ibaraki (72) Inventor Volkova Margarita Alexei Ehna 194017 Ulica Morisatreza Dom 94 Corpus 2 St. Petersburg, Russia Kubartila 46 (72) Inventor Rondalev Dmitri Stefanovich 198096 St. Petersburg, Russia St. Petersburg, Russia 198096 Ulica Stroitte Lay Dom 7a Kubartila 1 (72) Inventor Sokolov Sergey Vasilievich, 198217 Prospect Suslobade, St. Petersburg, Russia 1 Corpus 1 Kubartila 222 (72) Inventor Greenblatt Marc Peisachovich Rossi St. Petersburg, Russia 196 128 Procydi Che Runichevskoba Dom 9 Kubartheira 135 (72) Inventor Senyusov Lev Nikolaevich St. Petersburg, Russia 198142 Urica Lensobeta Dom 10 Kubartila 241 (56) References JP 58-89909 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 214/26 C08F 216/14-216/20 C08L 27/18

Claims (1)

(57) [Claims] (1) 45-75 mol% of tetrafluoroethylene,
Perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy lower alkyl vinyl ether)
50 to 25 mol% and the general formula CF ₂ = CFO (CF ₂ ) nOCF (CF ₃ ) CN
(Where n is an integer of 3 to 5 ) having a copolymer composition of 0.1 to 5 mol% of a perfluorounsaturated nitrile compound having an intrinsic viscosity in the range of 0.05 to 4 dl / g. Fluorine elastomer.