JPH04217936A - New fluorovinyl ether - 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]

0001

FIELD OF THE INVENTION This invention relates to new fluorovinyl ethers. More particularly, the present invention relates to novel fluorovinyl ethers useful for modifying polymers containing ethylenically unsaturated compounds.

0002

[Prior Art] By copolymerizing fluoroolefins with other fluoroolefins or fluorine-free olefins, various forms ranging from resinous to elastomeric can be obtained, depending on the type and proportion of the fluoroolefins and other monomers in the copolymer. A copolymer is obtained. This copolymer can be formed into mechanical parts such as O-rings, flange seals, gasket stock, pump diaphragms and liners and is particularly useful where special resistance to heat and corrosive fluids is required.

[0003] When obtaining an elastomeric polymer material, the crosslinking method is an important factor. Fluoroolefin copolymers are thermally and chemically stable, so
Very difficult to crosslink. As a method for crosslinking this copolymer, a method has been proposed in which a monomer that provides a crosslinking site is introduced. As monomers that provide such crosslinking sites, compounds having a perfluorophenoxy group (Japanese Patent Publication No. 11823/1982) and compounds having a nitrile group (Japanese Patent Publication No. 26303/1989, Japanese Patent Application Laid-open No. 61119/1987) are used. , compounds containing bromine (Japanese Patent Publication No. 53-4115, Japanese Patent Publication No. 54-1585) have been proposed, but the vulcanization reaction requires a long time,
The physical properties of the obtained vulcanizate are also not satisfactory.

Among fluoroolefin resins, polytetrafluoroethylene (hereinafter referred to as PTFE) with a high molecular weight of 1 million or more is usually used as a raw material for molding, but it has a melt viscosity of 380°C. 1x108Pa
s and is difficult to process in the molten state. In order to obtain copolymers with low melt viscosity, some copolymers made by copolymerizing tetrafluoroethylene with other fluorine-containing monomers are commercially available. 2 mol% based on the total copolymer
PTFE copolymerized with other fluorine-containing monomers in an amount that does not exceed ), it can be processed using the same molding method as PTFE. Comonomers used as modifiers include, for example,
CF3CF=CF2, C3F7OCF=CF2, ClC
F=CF2, C4F9CH=CH2, etc. alone or in mixtures are common. Modification may develop physical properties and moldability that are not found in pure PTFE, but modified PTFE that has further improved physical properties and moldability is desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the above-mentioned drawbacks and to provide new monomers which provide hardening sites. More particularly, it is an object of the present invention to provide new fluorovinyl ethers which provide crosslinking sites to polymers of ethylenically unsaturated compounds, especially fluorine-containing ethylenically unsaturated compounds. When the fluorovinyl ether of the present invention is used, (1) an elastic polymer comprising an ethylenically unsaturated compound that can be crosslinked in a short time; (2) physical properties such as tensile strength, elongation, and heat resistance. (3) Elastic polymer with improved low-temperature properties; (4) Excellent creep resistance after firing. Modified PT in the form of a granular powder that can be compression molded and ram extruded to obtain articles with
FE, and (5) a fine powder-like modified PTFE that can be shaped by paste extrusion so as to obtain an article with improved mechanical strength before firing.

[0006]

[Means for Solving the Problems] The gist of the present invention is that the formula:
XCH2CF2CF2(OCH2CF2CF2)m(
OCFYCF2)nOCF=CF2
(I) [wherein, X is hydrogen or halogen, Y is fluorine or trifluoromethyl group, m is an integer of 0 to 5, and n
represents an integer from 0 to 2. ] It exists in fluorovinyl ether shown by

[0007] Fluorovinyl ether (I) is disclosed in JP-A-60-137928 or JP-A-60-136536.
can be derived from the corresponding acid fluoride prepared by the method described in No. When Y in compound (I) is a trifluoromethyl group, fluorovinyl ether can generally be produced from the corresponding acid fluoride in the following manner.

First, the formula: XCH2CF2CF2(OCH2CF2CF2)m
(OC(CF3)FCF2)nOC(CF3)F-CO
F [wherein, X, m and n have the same meanings as above. ]
The acyl fluoride represented by is reacted with a lower alcohol such as methanol to form the formula: XCH2CF2CF2(OCH2CF2CF2)m
-(OC(CF3)FCF2)nOC(CF3)FC
OOCH3 [wherein X, m and n have the same meanings as above. ]
The ester shown is obtained. The resulting ester is then reacted with an alkali hydroxide (MOH) such as sodium hydroxide to form the formula: XCH2CF2CF2(OCH2CF2CF2)m(
OC(CF3)FCF2)nOC(CF3)F-COO
M [wherein X, m and n have the same meanings as above. ]
The fluorovinyl ether (I) is obtained by heating the salt at 150 to 250° C. under reduced pressure or under an inert gas atmosphere such as nitrogen.

By using the fluorovinyl ether (I) of the present invention, a copolymer comprising the fluorovinyl ether (I) and at least one ethylenically unsaturated compound can be obtained. The ethylenically unsaturated compound copolymerized with the fluorovinyl ether (I) may be any known monomer. Ethylenically unsaturated compounds include the fluorine-free ethylenically unsaturated compounds ethylene, propylene, butylene, carboxylic acid vinyl esters (e.g. vinyl acetate), vinyl ethers (e.g. methyl vinyl ether, ethyl vinyl ether), vinyl chloride, vinylidene. chloride, acrylic acid and methacrylic acid, fluorine-containing ethylenically unsaturated compounds such as tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, hexafluoropropylene, pentafluoropropylene, hexafluoroisobutene, Perfluorocyclobutene, perfluoro(methylcyclopropylene), perfluoroarene, α,β,β-trifluorostyrene, perfluorostyrene, perfluoroalkyl vinyl ethers (e.g., perfluoro(methyl vinyl ether), perfluoro(propyl) Examples include vinyl ether)), perfluoro(alkyl vinyl polyether), polyfluoroacrylic acid, polyfluorovinyl acetic acid, polyfluorovinyl ether sulfonic acid, and polyfluorodienes.

Fluorovinyl ether (I) in the copolymer
) may vary depending on the type of copolymer produced. Generally, the amount of fluorovinyl ether (I) is from 0.01 to 60 mol% relative to the total number of moles of other monomers. The amount of fluorovinyl ether (I) is 0.01 to 5 mol%, preferably 0.1 to 5 mol%, based on the total number of moles of other monomers, in order to provide crosslinking sites to the elastic copolymer. 5 to 60 mol%, preferably 10 to 5 mol%, to improve the low temperature properties of the elastic copolymer.
0 mol%, and in order to modify resin polymers such as PTFE, it is 0.01 to 2 mol%, preferably 0.03 to 2 mol%.
It is 1 mol%.

According to a first preferred embodiment, the copolymer has the formula: CF2=CAB

(II) [Wherein A and B each represent fluorine or chlorine. ] 50 to 95 mol% of repeating units derived from fluoroolefins, formula: CF2=CFO(CF2CFYO)pRf

(III) [In the formula, Y has the same meaning as above, and Rf has 1 carbon number
-6 perfluoroalkyl group, p represents an integer of 0-5. 50 to 5 mol% of repeating units derived from perfluorovinyl ether represented by ], and 0.1 to 5 mol% of fluorovinyl ether based on the total number of moles of the fluoroolefin (II) and perfluorovinyl ether (III). It consists of repeating units derived from (I). The terpolymer of this embodiment may include repeat units derived from at least one other ethylenically unsaturated compound as described above. The amounts of other ethylenically unsaturated compounds include compounds (I), (II) and (I).
It is preferably 0.1 to 20 mol % based on the total number of moles of II).

According to a second preferred embodiment, the copolymer comprises 20 to 90 mol % of repeating units derived from vinylidene fluoride and at least one other ethylenically unsaturated compound copolymerizable with vinylidene fluoride. 10 to 80 mol% of repeating units derived from compounds and 0.01 to 3 mol% of repeating units derived from fluorovinylether (I), based on the total number of moles of vinylidene fluoride and other ethylenically unsaturated compounds. Consists of units. Preferably, the other ethylenically unsaturated compound is a mixture of 10-45 mol% hexafluoropropylene and 0-35 mol% tetrafluoroethylene.

According to a third preferred embodiment, the copolymer comprises 20 to 100 mol % of repeating units derived from vinylidene fluoride and at least one other ethylenically unsaturated compound copolymerizable with vinylidene fluoride. from 80 to 0 mol% of repeating units derived from compounds and from 5 to 60 mol% of repeating units derived from fluorovinylether (I), based on the total number of moles of vinylidene fluoride and other ethylenically unsaturated compounds. Become. The amount of fluorovinyl ether (I) is preferably 10 to 50 mol%.

According to a fourth preferred embodiment, the copolymer has repeating units derived from tetrafluoroethylene and 0.0000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000 0.000.
It consists of repeating units derived from 01 to 2 mol % of fluorovinyl ether (I). The amount of fluorovinyl ether (I) is preferably 0.03 to 1 mol%.

[0015] Polymerization can be carried out in bulk, suspension or solution polymerization, as well as emulsion polymerization using a water-soluble or oil-soluble peroxide in the presence of a perfluoro emulsifier. Solvents used for solution polymerization include dichlorodifluoromethane, trichlorofluoromethane, chlorodifluoromethane, 1,1,2-trichloro-1,2,
2-trifluoroethane, 1,2-dichloro-1,1,
Highly fluorinated solvents such as 2,2-tetrafluoroethane, 1,1,2,2-tetrachloro-1,2-difluoroethane, perfluorocyclobutane, and perfluorodimethylcyclobutane are preferably used.

[0016] In bulk, suspension, and solution polymerization forms, organic initiators can generally be used. Among these, the most preferred initiators are highly fluorinated peroxides (
Particularly preferred are diacyl peroxides represented by Rf-COO)2 (where Rf is a perfluoroalkyl group, an ω-hydroperfluoroalkyl group or a perchlorofluoroalkyl group).

Molecular weight can be easily adjusted by adding a chain transfer agent. As chain transfer agents, hydrocarbons having 4 to 6 carbon atoms, alcohols, ethers, organic halides (for example, CCl4, CBrCl3, CF
2BrCFBrCF3, CF2I2) and the like can be advantageously used. Fluorocarbon iodides (e.g. CF2I2, I(CF2)4I, CF2=CFCF
When using 2CF2I) as a chain transfer agent, the presence of polyfunctional unsaturated compounds such as triallyl isocyanurate and triallyl cyanurate is important because iodine is still radically active after being bonded to the end of the molecule. Another advantage is that peroxide vulcanization using peroxide as a radical source is possible.

The polymerization temperature is determined by the decomposition temperature of the initiator, but is preferably 0 to 130°C. The polymerization pressure is usually preferably 5 to 50 kg/cm2G.

The copolymers of the present invention can be cured in the presence of various sources of crosslinking. As the crosslinking source, high-energy electromagnetic waves such as radiation (α rays, β rays, γ rays, electron beams, X rays, etc.) and ultraviolet rays can also be used, but organic peroxide compounds are preferably used. The amount of the organic peroxide compound used is 0.05 to 10 parts by weight, preferably 1.0 to 5 parts by weight, based on 100 parts by weight of the copolymer. Generally speaking, organic peroxide compounds that easily generate peroxy radicals in the presence of heat or a redox system are preferred, such as 1,1-bis(t-butylperoxy)-3,5,5-trimethyl. Cyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide α
, α'-bis(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(t-
butylperoxy)hexane, 2,5-dimethyl-2,
5-di(t-butylperoxy)-hexyne-3, benzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxymalein acid, t-
Examples include butylperoxyisopropyl carbonate. Among these, preferred are those of the dialkyl type. Generally, the type and amount of peroxide to be used are selected in consideration of the amount of active -O-O-, decomposition temperature, etc.

Furthermore, when an organic peroxide compound is used, significant curing can be observed by appropriately using a crosslinking aid or a co-crosslinking agent. This crosslinking aid or co-crosslinking agent is effective in principle as long as it has reactive activity toward peroxy radicals and polymer radicals, and the type thereof is not particularly limited. Preferably,
Triallyl cyanurate, triallyl isocyanurate, triallyl formal, triallyl trimellitate, N,N'-m-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalamide, triallyl phosphate, etc. Can be mentioned. The amount used is preferably 0.1 to 10 parts by weight, more preferably 0.5 parts by weight based on 100 parts by weight of the copolymer.
~5 parts by weight. Examples of materials that can be co-crosslinked include silicone oil, silicone rubber, ethylene/vinyl acetate copolymer, 1,2-polybutadiene, fluorosilicone oil, fluorosilicone rubber, fluorophosphazene rubber, and hexafluoropropylene/ethylene copolymer. Polymers, tetrafluoroethylene/propylene copolymers, and even other radically reactive polymers are used. There are no particular limitations on the amount of these used, but the amount should not be so large as to essentially impair the properties of the copolymer of the present invention.

Furthermore, a pigment for coloring the copolymer,
Fillers, reinforcing agents, etc. may be used. Commonly used fillers or reinforcing agents include inorganic materials such as carbon black, TiO2, SiO2, clay, and talc, and organic materials such as polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, Examples include fluorine-containing polymers such as tetrafluoroethylene/ethylene copolymer and tetrafluoroethylene/vinylidene fluoride copolymer.

[0022] As a means for mixing these hardening components, an appropriate method is adopted depending on the viscoelasticity and form of the material, and in the case of a solid material, an ordinary open roll or powder mixer is used. In the case of liquid, a conventional mixer can be used as appropriate. Of course, it is also possible to dissolve or disperse solid components in a solvent and perform dispersion mixing.

The vulcanization temperature and time depend on the type of peroxide used, but usually press vulcanization is performed at 120
5 to 30 minutes at a temperature of ~200℃, and oven vulcanization for 1
It is carried out for 1 to 24 hours at a temperature of 50 to 250°C.

[0024] The copolymer can be used as general molding materials, sealants,
Used as adhesives, paints, etc. with heat resistance, oil resistance, chemical resistance,
Effectively used where solvent resistance is required. Resin copolymers, especially modified PTFE, can be produced by a method of starting from a suspension polymerization method and pulverizing it (granular resin), or a method of coagulating and drying the polymer from a latex obtained by an aqueous dispersion polymerization method (emulsion polymerization method) ( fine powder). The polymerization method is to use PTFE or conventional modified P
The method may be similar to the method for manufacturing TFE. Regarding the polymerization operation, for suspension polymerization, the method described in Japanese Patent Publication No. 52-25398 and No. 59-31524 can be applied, and for aqueous dispersion polymerization, the method described in U.S. Pat.
, No. 965,595, etc., a general method is introduced in detail and can be similarly applied. Typically, the modified PTF of the present invention
E can be manufactured as follows.

Deionized and deoxidized water is placed in a polymerization tank equipped with a stirrer and whose temperature can be adjusted, various additives are added, and the polymerization tank is purged several times with N2 gas.
After pressurizing with FE), a modifier and an initiator are charged to start the reaction. Usually, the pressure inside the polymerization tank is maintained at 4 to 30 kg/cm2 by continuous supply of TFE, and the reaction temperature is 1.
The reaction is carried out at a constant or varying temperature of 0 to 120°C. In the suspension polymerization method, stirring is performed vigorously with enough power to disperse the powder, but in the aqueous dispersion polymerization method, stirring is performed slowly to maintain the stability of the latex. In order to improve the stability of the latex during the reaction, it is common in aqueous dispersion polymerization to add an inert, liquid hydrocarbon having 12 or more carbon atoms to the polymerization reaction.

Various additives include buffering agents, molecular weight regulators, initiation aids, anti-adhesion agents, and fluorine-containing dispersants (surfactants), but the biggest difference between suspension polymerization and aqueous dispersion polymerization is In the former method, no dispersant is used or in a very small amount, whereas in the latter method, a sufficient amount (approximately 100 to 10,000 ppm) to stably disperse the latex particles is added to carry out the reaction.

The modified PTFE using the fluorovinyl ether (I) of the present invention as a modifier has the following characteristics compared to unmodified PTFE. Granular type powders can be subjected to general compression molding or ram extrusion molding, and the baked product has particularly excellent creep resistance. Further, fine powder has a characteristic that the strength of the unfired extrudate after paste extrusion is extremely high.

The fluorovinyl ether (I) of the present invention can be copolymerized with other fluoroolefins to produce a copolymer in which the end of the side chain of the copolymer is extremely reactive. It is also easy to copolymerize with fluoroethylene and then convert the end of the side chain into a hydrophilic group such as a hydroxyl group, carboxyl group, or sulfonic acid group through a polymer reaction. Copolymers with such hydrophilic groups can be used as ion exchange membranes with excellent heat and chemical resistance, and can also be used more generally as hydrophilic diaphragms, filtration membranes, and separation membranes. It is. Furthermore, it is useful as a biocompatible material.

[0029]

PREFERRED EMBODIMENTS OF THE INVENTION The present invention will be specifically explained below by showing Reference Examples, Examples, Application Examples, and Comparative Application Examples. Reference example 1 2,2,3-trifluoropropionyl fluoride (
Production of carbon tetrachloride (FCH2CF2COF) in a 5 liter flask equipped with a stirrer, condenser and dropping funnel.
0 ml and 108 g of aluminum chloride were added thereto, and the internal temperature was set at 30 to 35°C. 2, 2, 3, 3 while stirring
-1800 g of tetrafluorooxetane was added dropwise from the dropping funnel over 2 hours. Thereafter, in order to complete the reaction, 90 g of aluminum chloride was added in three portions at 30 g portions every 1.5 hours. After keeping the temperature in the system at 27-29℃ and stirring for 4 hours, the title compound 2 was obtained by distillation.
,2,3-trifluoropropionyl fluoride 1
130g was obtained. Boiling point 23-23.5°C.

Reference Example 2 2,2,5,5,6,6,7-heptafluoro-4-oxa-heptanoyl fluoride (FCH2CF2C
Production of F2OCH2CF2COF) Into a 5-liter flask equipped with a stirrer, a condenser, and a dropping funnel, 1059 g of 2,2,3-trifluoropropionyl fluoride obtained in Reference Example 1, 5 g of crown ether, 40 g of cesium fluoride, and 1000 ml of monoglyme were added. was added, and 1515 g of 2,2,3,3-tetrafluorooxetane was slowly added dropwise at 15° C. to 20° C. over 3 hours and 30 minutes while stirring. After completion of the dropwise addition, stirring was continued for 5 hours while maintaining the internal temperature at 15°C to 20°C. The reaction solution was then distilled under reduced pressure.
Title compound 2,2,5,5,6,6,7-heptafluoro-4-oxa-heptanoyl fluoride 300g
I got it. Boiling point: 62-64°C (80mmHg).

Reference Example 3 2,2,5,5,6,6,9,9,10,10-decafluoro-4,8-dioxa-undecanoyl fluoride (FCH2CF2CF2OCH2CF2CF2OCH
Production of 2CF2COF) 2,2,5,5,6,6,9,9,10,10-
264 g of decafluoro-4,8-dioxa-undecanoyl fluoride was obtained. Boiling point: 23℃ (5mmHg
).

Reference Example 4 Production of 2,2-difluoro-3-iodopropionyl fluoride (ICH2CF2COF) 1500 ml of dry tetraglyme was placed in a 3 liter four-necked flask and 825 g of sodium iodide was added while stirring at room temperature.
completely dissolved. Next, while passing water through a cooler, the reaction temperature was slowly increased to 30°C to 40°C.
Add 650 g of 3-tetrafluorooxetane dropwise,
The dropwise addition of 2,2,3,3-tetrafluorooxetane was completed within minutes. The title compound 2,2-difluoro-
1050 g of 3-iodopropionyl fluoride was recovered. Boiling point: 95-96°C.

Example 1 Perfluoro(6,6-dihydro-3-oxa-1-
Hexene) (FCH2CF2CF2OCF=CF2) Reference Example 1
1055 g of 2,2,3-trifluoropropionyl fluoride obtained in step 1 was added. Hexafluoropropylene oxide was added from a bomb at a rate of reflux using a dry ice cooler while stirring and maintaining the temperature inside the flask at -10 to -15°C. 52 hours after the start of the reaction, the addition of hexafluoropropylene oxide was stopped, 1324 ml of methanol was added while cooling with ice water, washed with water several times, and FCH2CF2CF2OC (CF3
) FCOOCH3 was separated. Yield: 804g, boiling point:
138℃.

[0034] Subsequently, the produced methyl ester was placed in a 2-liter flask, and a saponification reaction was carried out at 60 to 70°C with a 10% by weight NaOH/methanol solution using phenolphthalein as a pH indicator. Methanol was distilled off under reduced pressure from a viscous solution colored slightly pink.
Vacuum drying was carried out at °C until a constant weight was reached, yielding 810 g of solid material. Next, this solid material was crushed well and placed in a 3-liter flask connected to a trap sufficiently cooled with dry ice, and the flask was sufficiently purged with nitrogen gas. 1 over 5 hours
When heating was continued from 50°C to 250°C, 542g of liquid accumulated in the trap. This was distilled to obtain 324 g of the title compound perfluoro(6,6-dihydro-3-oxa-1-hexene). Boiling point: 61-6
2℃.

Example 2 Perfluoro(6,6,10,10-tetrahydro-
3,7-dioxa-1-decene) (FCH2CF2CF
Production of 2OCH2CF2CF2OCF=CF2) 2,2,5,5 obtained in Reference Example 2 by the same method as in Example 1
, 65 g of the title compound perfluoro(6,6,10,10-tetrahydro-3,7-dioxa-1-decene) was obtained from 204 g of 6,6,7-heptafluoro-4-oxa-heptanoyl fluoride. . Boiling point: 44-4
5°C (13mmHg).

Example 3 Perfluoro (6,6,10,10,14,14-hexahydro-3,7,11-trioxa-1-tetradecene) (FCH2CF2CF2OCH2CF2CF
Production of 2OCH2CF2CF2OCF=CF2) 2,2,5 produced in Reference Example 3 by the same method as in Example 1
,5,6,6,9,9,10,10-decafluoro-4
,8-dioxa-undecanoyl fluoride 321
g to the title compound perfluoro (6,6,10,10
, 14,14-hexahydro-3,7,11-trioxa-1-tetradecene) 54 g was obtained. Boiling point: 88
~89°C (13mmHg).

Example 4 Perfluoro(6,6 dihydro-6-iodo-3-oxa-1-hexene) (ICH2CF2CF2OCF=
CF2) 43 g of cesium fluoride, 6 ml of tetraglyme, and 400 g of 2,2-difluoro-3-iodopropionyl fluoride obtained in Reference Example 4 were placed in a 2-liter four-necked flask, and the internal temperature was brought to 10° C. while stirring. Subsequently, hexafluoropropylene oxide was introduced from the cylinder at a rate of reflux using a dry ice cooler for 21 hours, and then 300 ml of methanol was added while cooling with ice water. After washing the reaction product several times with water, ICH was obtained by distillation.
2CF2CF2OC(CF3)FCOOCH3 was separated. Yield: 205g, boiling point: 114-115℃ (100
mmHg).

Subsequently, the obtained methyl ester was transferred to a 1 liter flask and heated to 60 to 70°C, and then mixed with 10% by weight NaOH/phenolphthalein as a pH indicator.
A saponification reaction was carried out using a methanol solution, excess methanol was distilled off under reduced pressure, and drying under reduced pressure was continued at 100° C. until a constant weight was reached. A white solid with a slightly pink color was obtained. Yield: 202g. Next, this solid material was thoroughly crushed and placed in a 1-liter flask connected to a trap sufficiently cooled with dry ice, and the flask was sufficiently purged with nitrogen gas. 2
from 150°C to 250°C over 3 hours under a reduced pressure of 5mmHg.
When heating continued until the temperature reached ℃, 148g was found in the trap.
of purple liquid has accumulated. Distill this to obtain the title compound
81 g of perfluoro(6,6 dihydro-6-iodo-3-oxa-1-hexene) was obtained. Boiling point: 71-7
2°C (100mmHg).

Example 5 Perfluoro(9,9-dihydro-9-iodo-5-
Trifluoromethyl-3,6-dioxa-1-nonene (
ICH2CF2CF2OC(CF3)FCF2OCF=
Production of CF2) 60 g of cesium fluoride, 10 ml of tetraglyme, and 600 g of 2,2-difluoro-3-iodopropionyl fluoride obtained in Reference Example 4 were placed in a four-necked 2-liter flask, and the internal temperature was adjusted to 10°C while stirring.
And so. Subsequently, hexafluoropropylene oxide was flowed into the dry ice cooler from the cylinder at a rate of reflux for 30 hours. Thereafter, the flow of hexafluoropropylene oxide was stopped, and 500 ml of methanol was added while cooling with ice water. The reaction product was washed several times with water and distilled into ICH2CF2C.
F2OC(CF3)FCF2OC(CF3)FC-OO
CH3 was separated. Yield: 116g, boiling point 91-92℃
(6mmHg). The obtained methyl ester was treated in the same manner as in Example 4, saponified and thermally decomposed to obtain a purple colored liquid, and this liquid was distilled to obtain 63.5 g of the title compound. Boiling point 87-87.5℃ (45
mmHg).

Application Example 1 Put 1660 ml of pure water into a glass-lined autoclave with an internal volume of 3 liters, cool it to 5°C, and add C.
3F7(OCF(CF3)CF2)2OCF=CF2(
Hereinafter, it will be referred to as "φ2VE". ) 300g, fluorovinyl ether ICH2CF2CF2OCF=CF27.6
g, C7F15COO-NH415g, 1 of 1,3,5-trichloroperfluorohexanoyl peroxide
, 9.6 ml of 1,2-trichloro-1,2,2-trifluorotoethane solution (concentration 0.44 g/ml) was added, and the substitution was quickly repeated with tetrafluoroethylene. 2.2k
The pressure was increased to g/cm2 (gauge pressure).

The pressure decreases as the polymerization reaction progresses, so when it decreases to 2.0 kg/cm2 (gauge pressure),
The pressure was re-pressurized to 2.2 kg/cm2 (gauge pressure) with tetrafluoroethylene, and polymerization was carried out for 28 hours and 40 minutes while repeatedly lowering and increasing the pressure. After the reaction was completed, unreacted tetrafluoroethylene was released and the product was recovered, washed with water, and dried to obtain 182 g of a copolymer. This copolymer contains 28 mol% of φ2VE units, and as a result of iodine analysis, the copolymer contains 0.69 mol% of ICH2CF2CF2OCF.
= It was found that it contained CF2.

Application Examples 2 to 5 and Comparative Application Example 1 Polymerization pressure, polymerization time, 1,1,2-trichloro-1 of 1,3,5-trichloroperfluorohexanoyl peroxide
,2,2-trifluoroethane solution (concentration 0.44g
/ml) (DLP) and fluorovinyl ether (
In application examples 2 to 4, ICH2CF2CF2OCF=CF2
, In application example 5, ICH2CF2CF2OCF (CF3)
A copolymer was obtained by repeating the same procedure as in Application Example 1 except that the amount of CF2OCF=CF2) was as shown in Table 1. Its yield and fluorovinyl ether and φ2VE
The content is shown in Table 1.

[0043]

[Table 1]

[0044] The components shown in Table 2 were blended with the copolymers obtained in Application Examples 1 to 5 and Comparative Application Example 1 to prepare a vulcanized composition. Vulcanizability was measured at 160°C. Further, the composition was vulcanized under the conditions of press vulcanization at 160° C. for 10 minutes and oven vulcanization at 180° C. for 4 hours, and the physical properties of the vulcanized product were measured. The results are shown in the same table. In addition, "parts" in the table means "parts by weight."

[0045]

[Table 2]

Application Example 6 A polymerization tank having an internal volume of 3 liters was charged with 1 liter of pure water and 42 g of C7F15COONH as an emulsifier, and after the system was sufficiently purged with nitrogen gas, 22.5 g of fluorovinyl ether ICH2CF2CF2OCF=CF was introduced under pressure. Subsequently, a monomer mixture of vinylidene fluoride (hereinafter referred to as VdF), hexafluoropropylene (hereinafter referred to as HFP) and tetrafluoroethylene (hereinafter referred to as TFE) (molar ratio 18/ 71/11) with an internal pressure of 16 kg/cm
It was press-fitted so that the pressure was 2 (gauge pressure). Next, a solution of 3.3 g of ammonium persulfate in 80 ml of pure water was pressurized together with nitrogen gas to start the reaction.

As the pressure decreases as the polymerization reaction progresses, when the pressure decreases to 14 kg/cm2 (gauge pressure), the monomer mixture of VdF/HFP/TFE (mole ratio 5
0/30/20), repressurize to 16 kg/cm2G,
While repeating pressure reduction and pressure increase, 1.7, 3.
After 6 and 7.1 hours, 2.5 g of the above fluorovinyl ether was injected under pressure to continue polymerization, and after 8 hours and 45 minutes from the start of polymerization, the polymerization tank was cooled and unreacted monomers were discharged to reduce the solid content to 25. A .7% by weight aqueous emulsion was obtained. A 5% by weight aqueous solution of potassium alum was added to this aqueous emulsion to cause coagulation, and the coagulated product was washed with water and dried to obtain 347 g of a rubbery polymer. Mooney viscosity (100°C) was 32. Iodine analysis revealed that this copolymer contained 0.76 mol% of ICH2CF2CF2OCF=CF2.

Application Example 7 A polymerization tank with an internal volume of 3 liters was charged with 1 liter of pure water and 42 g of C7F15COONH as an emulsifier, and after the system was sufficiently replaced with nitrogen gas, VdF/H was added at 80°C.
FP/TFE monomer mixture (molar ratio 18/71/1
1) was press-fitted so that the internal pressure was 16 kg/cm2G. Then, a 0.2% by weight aqueous solution of ammonium persulfate 1
The reaction was started by injecting 0 ml. As the polymerization reaction progresses, the pressure decreases, so when the pressure decreases to 15 kg/cm2G, 1.2 g of I(CF2)4I, a molecular weight regulator, is added.
was injected, and when the pressure further decreased to 14 kg/cm2G, the pressure was re-pressurized to 16 kg/cm2G with a monomer mixture of VdF/HFP/TFE (molar ratio 50/30/20), and the pressure was repeatedly lowered and increased for 3 hours. Each time, 10 ml of the ammonium persulfate aqueous solution was pressurized with nitrogen gas to continue the reaction.

The total pressure drop from the start of the polymerization reaction is 5k.
g/cm2G (after 5 hours), the fluorovinyl ether ICH2CF2CF2OCF=CF21.
8 g was press-fitted. Similarly, the total pressure drop is 43kg/c.
When the temperature reached m2G (after 19 hours), the polymerization tank was cooled,
Unreacted monomers were released to obtain an aqueous emulsion with a solids content of 26.7% by weight. A 5% by weight aqueous potassium alum solution was added to this aqueous emulsion to cause coagulation, and the coagulated product was washed with water and dried to obtain 394 g of a rubbery polymer. Mooney viscosity (100℃) is 83
The intrinsic viscosity [η] (dl/g, solvent: tetrahydrofuran, 35°C) was 0.53. As a result of iodine analysis, this copolymer contained 0.12 mol% ICH2CF.
It was found that 2CF2OCF=CF2 was included.

Application example 8 Fluorovinyl ether ICH2CF2CF2O-CF
The same operation as in Application Example 7 was repeated except that 5.4 g of =CF2 was used and the reaction time was 31 hours, to obtain 401 g of a rubbery copolymer. Mooney viscosity = 48. [η]=0.
34. Fluorovinyl ether content = 0.39 mol%.

Application example 9 Fluorovinyl ether ICH2CF2CF2O-CF
= Rubbery copolymer 3 was obtained by repeating the same procedure as in Application Example 7 except that 9 g of CF2 was used and the reaction time was 34 hours.
98g was obtained. Mooney viscosity = 43. [η]=0.31
. Fluorovinyl ether content = 0.63 mol%.

Application example 10 ICH2CF2CF2- as fluorovinyl ether
OCF=ICH2CF2CF2OCF instead of CF2
(CF3)CF2OCF=383 g of a rubbery copolymer was obtained by repeating the procedure of Application Example 7 except that 214.9 g of CF was used and the reaction time was changed to 9 hours and 30 minutes. Mooney viscosity = 47. Fluorovinyl ether content = 0.74 mol%
.

Application Example 11 The initial monomer mixture had a molar ratio of 65/35/0, the additional monomer mixture had a molar ratio of 78/22/0, 7.2 g of fluorovinyl ether was used, and the reaction time was 25 hours. The same procedure as in Application Example 7 was repeated except that 345 g of a rubbery copolymer was obtained. Mooney viscosity = 20. Fluorovinyl ether content = 0.52 mol%.

Comparative Application Example 2 The same procedure as Application Example 6 was repeated except that the reaction was carried out for 5 hours without using fluorovinyl ether.
I got g. Mooney viscosity 87.

Comparative Application Example 3 A copolymer was obtained by repeating the same procedure as Application Example 6, except that fluorovinyl ether was not used, 10 g of ammonium persulfate was used as an initiator, and the reaction time was 4.1 hours. Mooney viscosity 43.

[0056] The components shown in Table 3 were blended with the copolymer obtained in the application example or comparative application example, and the components were uniformly blended using a rubber roll in a conventional manner to prepare a vulcanized composition. Vulcanizability was measured at 160° C. using JSRII type). In addition, press vulcanization at 160°C x 10 minutes and 18
Vulcanize the composition under oven vulcanization conditions of 0°C x 4 hours,
The physical properties of the vulcanizate were measured. In addition, the physical properties of the vulcanizate are JI
Measured according to SK 6301. The results are shown in the same table. In addition, "parts" in the table means "parts by weight."

[0057]

[Table 3]

Application Example 12 FCH2CF2CF2OCF=CF2 6.9 g, 1,
10 ml of 1,2-trichloro-1,2,2-trifluoroethane (hereinafter abbreviated as R-113) and an R-113 solution of 2,4,5-trichloroperfluorohexanoyl peroxide (concentration 0. 7g/ml)
After charging 0.5 ml and cooling with dry ice/methanol solution, the inside of the system was purged with nitrogen. Then VdF6.8
g was prepared and allowed to react at 20±1°C for 20 minutes with shaking. Along with the reaction, the gauge pressure in the system decreased to 6.3 kg/kg before the reaction.
The weight decreased from cm2 to 5.5 kg/cm2. Unreacted monomers were released, the contents were dissolved in acetone and taken out, and then released into pure water for precipitation to separate the copolymer. Vacuum drying was performed until a constant weight was obtained, and 2.2 g of a copolymer was obtained. From 1H-NMR analysis, the composition ratio of this copolymer was found to be VdF:(FCH2CF2CF2OCF=CF2)=7
The molar ratio was 1.8:28.2. The glass transition temperature of the copolymer was measured using a scanning calorimeter (DSC) and was found to be -30°C, indicating good low-temperature properties.

Application example 13 F(CH2CF2CF2O)2CF=CF2 10.8 in a 100 ml pressure-resistant glass ampoule equipped with a bulb.
g, R-113 10ml and R-1 of 2,4,5-trichloroperfluorohexanoyl peroxide
Prepare 0.5 ml of solution 13 (0.44 g/ml),
After cooling with dry ice/methanol solution, the inside of the system was purged with nitrogen gas. Next, 5.7 g of VdF was charged, and 2
The reaction was allowed to proceed at 0±1° C. for 35 minutes with shaking. As the reaction progressed, the gauge pressure within the system decreased from 9.8 kg/cm2 before the reaction to 6.8 kg/cm2. Unreacted monomers were discharged, and the contents were dissolved in acetone and taken out, and then discharged into water for precipitation to separate the copolymer. The weight of the copolymer after vacuum drying was 10.2 g. The composition ratio of this copolymer was determined by 1H-NHR analysis to be VdF:
[F(CH2CF2CF2O)2CF=CF2]=72
．． The molar ratio was 8:27.2, and the glass transition temperature of the copolymer was -30.5%.

Application example 14 Instead of FCH2CF2CF2OCF=CF2, F(CH
2CF2CF2O)3CF=CF214.7g was used and the reaction was carried out in the same manner as in Application Example 12, except that the reaction time was 23 minutes, and the system gauge pressure was 9.8kg/c.
m2 to 8.0 kg/cm2. The amount of copolymer after vacuum drying was 16.2 g. The composition molar ratio of the copolymer is VdF:[F(CH2CF2CF2O)3C
F=CF2]=73.9:26.1, and the glass transition temperature was -42.0°C.

Application Example 15 When the reaction was carried out in the same manner as in Application Example 12 except that 3.5 g of TFE was charged in place of VdF and the reaction time was changed to 1 hour, the gauge pressure in the system changed from 2.2 kg/cm2 to 1.5 kg/cm2. 8kg/
It changed to cm2. The weight of the copolymer after vacuum drying is 0.
．． It was 7g. The copolymer was elastic and no melting point was observed. The glass transition temperature was 8.5°C.

Application Examples 16 to 20 Application Example 12 except that the amounts of VdF and FCH2CF2CF2OCF=CF2 were changed and TFE was added.
The reaction was carried out in the same manner. Table 4 shows the amount charged, the weight, composition ratio, and glass transition temperature of the obtained copolymer in each case. The composition molar ratio of the copolymer was determined by 1H-NMR and 19F-NMR analysis. In the table, “FM” and “DLP” are respectively “F-CH2CF2CF2OC
F=CF2" and "R-113 solution of 2,4,5-trichloroperfluorohexanoyl peroxide (concentration 0.7 g/ml)".

[0063]

[Table 4]

Application Example 21 A reaction was carried out in the same manner as in Application Example 12, except that 0.8 g of ethylene was added in place of VdF and the reaction time was changed to 20 minutes. Gauge pressure in the system ranges from 7.2 kg/cm2 to 6.
It changed to 7kg/cm2. The weight of the copolymer after vacuum drying is 0.8 g, and the composition ratio of this copolymer is ethylene: (FCH2CF2CF2OCF=CF2)=56
．． The molar ratio was 3:43.7. Moreover, the glass transition temperature was -11°C.

Application example 22 3 equipped with a temperature control jacket, stirrer and baffle plate
A liter stainless steel autoclave was charged with 1.45 liters of deionized and deoxygenated water, 3 mg of ammonium triphosphate, and 9 mg of ammonium perfluorooctanoate. Next, the reactor was degassed, nitrogen gas was charged, and the reactor was degassed again. After repeating the degassing and charging operations three times in total, the same operation was repeated twice with TFE. After the final degassing, FCH2CF2CF2OCF=CF
1.2g of 2 was charged. Then start the stirrer and
rpm, and the temperature of the charge was raised to 70°C. Next, TFE was charged until the internal pressure reached 7.5 kg/cm2 (gauge pressure), and 4.5 kg/cm2 of ammonium persulfate was added.
A solution of 0 mg/50 ml of water was injected using TFE, and the internal pressure was adjusted to 8.
The pressure was set at 0 kg/cm2 (gauge pressure). After a few minutes, the pressure began to decrease, confirming that the reaction had started, but from this point on, TFE was continuously fed to maintain it at 8.0 kg/cm2 (gauge pressure), and the amount of feed (=polymer solid content) is 25
When the temperature reached 0 g, TFE was expelled, stirring was stopped, and the reaction was completed.

[0066] Take out the powder and put it in an industrial mixer,
Add water and run for 1 minute to grind the powder. The mixture was ground for an additional 5 minutes while the water was replaced and washed. The resulting fine powder was dried in an air circulating dryer at 150° C. for 14 hours. The dried fine powder was formed into a film and the infrared absorption spectrum was found to be 956 cm-1, 1003 cm-1.
A characteristic absorption peak not seen in FE was present. 956
From the ratio of the absorbance at cm-1 and the absorbance at 2360 cm-1 (corresponding to the film thickness), the content of FCH2CF2CF2OCF=CF2 in the polymer was estimated to be 0.1 mol% based on a separately determined calibration curve. Ta.

[0067] Also, the creep of the molded product of this powder is 24°C.
It was 3.5%. Creep measurement was performed using the following procedure. 190 g of powder was put into a cylindrical mold with a diameter of 50 mm, compression molded at 300 kg/cm 2 (holding time 5 minutes), and then taken out from the mold. Thereafter, the temperature was raised to 365°C at a heating rate of 50°C/hour in an air firing furnace, and the temperature was increased to 365°C.
The temperature was kept at 5°C for 5 hours, and the temperature was lowered to room temperature at a rate of 50°C/hour. This fired product was cut into a cylindrical shape with a diameter of 11.3 mm and a height of 10 mm so that the direction of compression coincided with the height direction of the cylinder. A load of 140 kg/cm2 was applied to a cylindrical sample in a constant temperature room at 24°C, and 10
The height of the cylinder was measured after seconds and 24 hours. Creep was calculated using the following formula. Creep (%) = (Height after 10 seconds - Height after 24 hours) ÷ (Height before loading) x 100

Comparative Application Example 4 The reaction was carried out in the same manner as in Application Example 22 except that FCH2CF2CF2OCF=CF2 was not charged. The creep of the molded article was 8.6% at 24°C.

Application Example 23 In a 3 liter autoclave similar to Application Example 22,
1.45 liters of deionized and deoxygenated water, 100 ml of reagent first-class liquid paraffin, and 1.5 g of ammonium perfluorooctanoate were charged, and the degassing and charging of nitrogen gas and TFE were repeated in the same manner as in Application Example 22. After the last degassing FCH2CF2CF2O-CF=CF2
Charge 1.00g with TFE and set the stirrer speed to 250rpm.
m and the content temperature was raised to 70°C. Next, the internal pressure was increased to 7.5 kg/cm2 (gauge pressure) using TFE, and 50 m of water containing 11.3 mg of ammonium persulfate was added.
1 solution was pressurized with TFE, and the internal pressure was set to 8.0 kg/cm2 (
gauge pressure). TF to maintain the pressure during the reaction.
E was supplied and the reaction temperature was maintained at 70°C. When the consumed TFE reached 730 g, TFE was expelled, stirring was stopped, and the reaction was terminated.

The resulting dispersion was diluted with water, ammonium carbonate was added, and the mixture was powdered by mechanical stirring. This powder was dried at 130°C for 14 hours. The fluorovinyl ether content by infrared analysis was 0.04 mol%. About the obtained fine powder
Paste extrusion molding was carried out under the conditions described in No. 34, and after removing the extrusion aid by drying the extrudate in the steady state in the latter half of extrusion, three rods for tensile testing of about 10 cm were cut out. 20cm/about these rods
The tensile test was conducted at a tensile speed of 100 min. The strength at break was measured for three samples and the average value was calculated. Extrusion pressure is 153kg/cm2, tensile strength at break is 45kg
/cm2.

Comparative Application Example 5 The operation of Application Example 23 was carried out except that FCH2CF2CF2OCF=CF2 was not added. The extrusion pressure of the obtained powder was 110 kg/cm2, and the tensile strength was 24 kg.
/cm2.

Claims (2)

[Claims] [Claim 1] Formula: XCH2CF2CF2(OCH2CF2CF2)m
(OCFYCF2)nOCF=CF2
(I) [wherein, X is hydrogen or halogen, Y is fluorine or trifluoromethyl group, m is an integer of 0 to 5, and n
represents an integer from 0 to 2. ] Fluorovinyl ether. 2. The fluorovinylether of claim 1, wherein X is a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine.