JPS6212734A - Novel fluorovinyl ether and copolymer containing same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is H or halogen; Y is F or CF3; m is 0-5, n is 0-2). EXAMPLE:Perfluoro(6,6-dihydro-6-iodo-3-oxa-1-hexene). USE:Monomer for copolymer. Useful for the modification of a polymer containing ethylenic unsaturated compound. It can be used effectively as a general molding material, sealant, adhesive, paint, etc., which is to be applied to a part necessitating heat-resistance, oil-resistance, chemical resistance, solvent resistance, etc. PREPARATION:The compound of formula I wherein Y is CF3 can be produced by reacting the acyl fluoride of formula II with a lower alcohol such as methanol, reacting the resultant ester of formula III with an alkali metal hydroxide of formula MOH (e.g. NaOH) to obtain the salt of formula IV and heating the salt at 150-250 deg.C under reduced pressure or in an inert gas atmosphere such as N2.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel fluorovinyl ether and a copolymer containing the same. More particularly, the present invention relates to novel fluorovinylethers useful for modifying polymers containing ethylenically unsaturated compounds, and copolymers containing at least one ethylenically unsaturated compound and novel fluorovinylethers.

[Prior Art] By copolymerizing fluoroolefins with other fluoroolefins or non-fluoroolefins, various copolymers ranging from resinous to elastomeric can be produced, depending on the type and proportion of the fluoroolefins and other monomers in the copolymer. A polymer 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.

When obtaining an elastomeric polymer material, the crosslinking method is an important factor. Copolymers of fluoroolefins are thermally and chemically stable and are therefore 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 a monomer providing such a crosslinking site, a compound having a perfluorophenoxy group (Japanese Patent Publication No. 47-118
No. 23), compounds with nitrile groups (Japanese Patent Publication No. 45
-26303 Publication, Japanese Patent Application Laid-open No. 49-61119)
, 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 and the physical properties of the obtained vulcanized product must not be satisfactory. It's not a kimono.

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 its melt viscosity is as high as 1x108 Pas at 380°C. , 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. For those copolymerized with other fluorine-containing monomers in an amount not exceeding 2 mol% based on the total copolymer, modified P
Sometimes called TFE (PTF whose molecular type has been adjusted with methane or methanol in addition to a small amount of copolymerization)
E is also sometimes called modified PTFE. ), P.T.
It can be processed using the same molding method as F'E. Comonomers used as modifiers include, for example, CF3CF
=CF2, C3P.

0CF-CF3, CσCF=CF2, C, F9CH=C
H, etc. alone or in mixtures are common. Modification may develop physical properties and moldability that are not found in pure PTPE, but modified PTFE that has further improved physical properties and moldability is desired.

[Object of the Invention] An object of the present invention is to eliminate the above-mentioned drawbacks and provide a new monomer that provides a curing site and a polymer that has excellent physical properties and moldability. More specifically, the object of the present invention is to provide (I) novel fluorovinyl ethers that provide crosslinking sites to polymers of ethylenically unsaturated compounds, especially fluorine-containing ethylenically unsaturated compounds; (2) ethylene that can be crosslinked in a short period of time; (3) an elastomeric polymer comprising an ethylenically unsaturated compound, which provides a crosslinked product with excellent physical properties such as tensile strength, elongation, heat resistance, and compression set; (4) an elastic polymer with improved low temperature properties; and (5) an article with excellent creep resistance after firing.
Granular powder modified PTFE that can be compression molded and ram extruded, and (6) fine powder modified PTFE that can be molded by paste extrusion so as to yield articles with improved mechanical strength before firing. There is a particular thing.

[Structure of the Invention One gist of the present invention is the formula: %Formula%] [In the formula, X is hydrogen or halogen, Y is fluorine or trifluoromethyl group, m is an integer from 0 to 5, """° ”°
〜°°2″l−1t°].

The fluorovinyl ether shown in

Another aspect of the invention consists in a copolymer consisting of fluorovinyl ether (I) and at least one ethylenically unsaturated compound.

Fluorovinyl ether (I) is disclosed in JP-A-60-137
928 or the corresponding acid fluoride prepared by the method described in JP-A-60-136536. Compound (I)? , :Hey, Yka(
, IJ 7 / lz o. , <f/LJi-A61
In this case, fluorovinyl ether can generally be produced from the corresponding acid fluoride as follows:

] First, the formula: %Formula% [In the formula, XSn+ and n have the same meanings as above. ] is reacted with a lower alcohol such as methanol to form the formula: XCH2CF2CF2(OCHzCF,CF,)m-(
OC(CF 3)F CF 2)+100 (CF 3
) F -CO0 (jb [wherein, X, m and n have the same meanings as above] is obtained. Then,
The obtained ester is reacted with an alkali hydroxide (MOH) such as sodium hydroxide to produce a salt represented by the formula: This is then heated to 150 to 250° C. under reduced pressure or under an inert gas atmosphere such as nitrogen to obtain fluorovinyl ether (I).

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,
Hexafluoroisobutyne, perfluorocyclobutene, perfluoro(medylcyclopropylene), perfluoroarene, α, β, β-trifluorostyrene, perfluorostyrene, perfluoroalkyl vinyl ethers (e.g., perfluoro(methyl vinyl ether) ), perfluoro(propyl vinyl ether)), perfluoro(alkyl vinyl polyethers), polyfluoroacrylic acid, polyfluorovinyl acetic acid, polyfluorovinyl ether sulfonic acid, and polyfluorodienes.

The amount of fluorovinyl ether (I) in the copolymer may vary depending on the type of copolymer being 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 0.01 to 5 mol%, based on the total number of moles of other monomers, in order to provide crosslinking sites to the elastic copolymer. In order to improve the low temperature properties of elastic copolymers, it is 5 to 60 mol%, preferably 10 to 50 mol%, and in order to modify resin polymers such as PTFB, it is 0.
．． 0.01 to 2 mol%, preferably 0.03 to 1 mol%.

According to a first preferred embodiment of the invention, the copolymer has the formula: % Formula % () where A and B each represent fluorine or chlorine. 50 to 95 mol% of repeating units derived from fluoroolefins represented by the formula: %Formula% ([[) [wherein, Y has the same meaning as above, and Rf has 1 to 6 carbon atoms]
is a perfluoroalkyl group, p represents an integer of 0 to 5.

]
Derived from perfluorovinyl ether indicated by i! 50 to 5 mol % of repeating units, and 0.0 to 5 mol % based on the total number of moles of the fluoroolefin (II) and perfluorovinyl ether (II[). It consists of repeating units derived from 11 to 5 mol % of fluorovinyl ether (I). The terpolymer of this embodiment may include repeating units derived from at least one other ethylenically unsaturated compound as described above. The amount of other ethylenically unsaturated compounds is compound (I), (II) and (III)
The amount is preferably 0.1 to 20 mol% based on the total number of moles.

According to a second preferred embodiment of the invention, the copolymer comprises 2 repeating units derived from vinylidene fluoride.
0 to 90 mol%, 10 to 80 mol% of repeating units derived from at least one other ethylenically unsaturated compound copolymerizable with vinylidene fluoride, and 10 to 80 mol% of repeating units derived from at least one other ethylenically unsaturated compound copolymerizable with vinylidene fluoride. 0.01 to 3 mol% of fluorovinyl ether (I) based on the total number of moles
Consists of repeating units derived from. Other ethylenically unsaturated compounds include hexafluoropropylene 10-45
Preferably, it is a mixture of 0 to 35 mol% of tetrafluoroethylene.

According to a third preferred embodiment of the invention, the copolymer comprises 2 repeating units derived from vinylidene fluoride.
0 to 100 mol%, 80 to 0 mol% of repeating units derived from at least one other ethylenically unsaturated compound copolymerizable with vinylidene fluoride, and 80 to 0 mol% of repeating units derived from at least one other ethylenically unsaturated compound copolymerizable with vinylidene fluoride. It consists of 5 to 60 mol %, based on the total number of moles, of repeating units derived from fluorovinyl ether (I). The amount of fluorovinyl ether (D is preferably 10 to 50 mol%).

According to a fourth preferred embodiment of the invention, the copolymer comprises repeating units derived from tetrafluoroethylene and 0.01 based on the number of moles of tetrafluoroethylene.
Consisting of ~2 mol % repeating units derived from fluorovinyl ether (I). Fluorovinyl ether (
The amount of I) is preferably 0.03 to 1 mol%.

Polymerization can be carried out in bulk, suspension, and solution polymerization, as well as in 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-1,1,2, 2-tetrafluoroethane, 1,1,2.2-tetrachloro-1
, 2-fluoroethane, perfluorocyclobutane,
Highly fluorinated solvents such as perfluorodimethylcyclobutane are preferably used.

In bulk, suspension, and solution polymerization forms, organic initiators can generally be used. Among these, the most preferred initiators are highly fluorinated peroxides (Rr-COO
)2 (Here, Rf is a perfluoroalkyl group, an ω-hydroperfluoroalkyl group, or a perchlorofluoroalkyl group.

) is particularly preferred.

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, CCa, , CBrC(Js, CFtBrCFB
rCFs, CF, 12) etc. can be used advantageously. Fluorocarbon iodides (e.g. CF x
I t, I (CF t) + I, CF t = CFC
When P, CF, or Ri is used as a chain transfer agent, iodine is still radically active after being bonded to the end of the molecule. There is an advantage that peroxide vulcanization using peroxide as a radical source is possible in the presence of the compound.

The polymerization temperature is determined by the decomposition temperature of the initiator, but
~130°C is desirable.

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. Crosslinking sources include radiation (α rays, β
Although high-energy electromagnetic waves such as UV rays, gamma rays, electron beams, X-rays, etc.) and ultraviolet rays can also be used, organic peroxide compounds are preferably used.

The amount of organic peroxide compound used is 100% of the copolymer.
0.05 to 10 parts by weight, preferably 1.
It is 0 to 5 parts by weight.

The organic peroxide compound is generally one that easily generates peroxy radicals in the presence of heat or a redox system, such as 1,1-bis(t-butylperoxy)-3,5,5-). Limethylcyclohexane, 2.5
-dimethylhexane-2,5-dihydroberoxide, di-t-butylperca 5.1-2 a/L/y
= tbt<-o+-r-5, 1 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~dibruperoxy)-hexyne-3, benzoyl peroxide, t-butylperoxybenzene, 2゜5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl Examples include peroxymaleic acid and 1-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 activity -〇-〇-, decomposition temperature, etc.

Further, 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.

In principle, the crosslinking agent or co-crosslinking agent is effective as long as it has reactive activity toward peroxy radicals and polymer radicals, and the type thereof is not particularly limited. Preferred examples include triallyl cyanurate, triallyl isocyanurate, triallyl formal, triallyl trimellitate, and N.

Examples include N'-m~phenylene bismaleimide, dibrobagyl terephthalate, diallyl phthalate, tetraallyl terephthalamide, triallyl phosphate, and the like. The amount used is 0.1 per 100 parts by weight of the copolymer.
The proportion is preferably 10 to 10 parts by weight, more preferably 0.5 to 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, pigments, fillers, reinforcing agents, and the like are used to color the copolymer. Commonly used fillers or reinforcing agents include carbon black, Tie,
, 5iOz, clay, talc, etc., and organic substances such as polytetrafluoroethylene, polyvinylidene fluoride,
Examples include fluorine-containing polymers such as polyvinyl fluoride, polychlorotrifluoroethylene, tetrafluoroethylene/ethylene copolymer, and tetrafluoroethylene/vinylidene fluoride copolymer.

As a means for mixing these hardening components, an appropriate method is adopted depending on the viscoelasticity and form of the materials, and in the case of solid materials, ordinary open rolls or powder mixers are 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.

Vulcanization temperature and time depend on the type of peroxide used, but press vulcanization is usually carried out at a temperature of 120 to 200 °C for 5 to 30 minutes, and oven vulcanization is carried out at a temperature of 150 to 250 °C.
℃ temperature for 1 to 24 hours. Used effectively.

The resin copolymer of the present invention, especially modified PTFE, can be produced by a method of starting from a suspension polymerization method and pulverizing it (granular resin).
Alternatively, the polymer is coagulated from latex obtained by aqueous dispersion polymerization method (emulsion polymerization method) and dried.
Obtained by drying method (fine powder).

The polymerization method may be similar to methods for producing PTFE or conventional modified PTFE. The polymerization operation is “1!61
．． Knee+cr’” #8BiH52-253984t
For aqueous dispersion polymerization, methods such as those described in 1.
1 is a general method such as U.S. Patent No. 2,965,595.
: The method is introduced in detail and can be applied in the same way.
) 2I o, oe,. . Yu, 1. . 9, sea urchin. 6 o, ・1 t can be manufactured.
:・Pour deionized and deoxygenated water into a polymerization tank equipped with a stirrer and whose temperature can be adjusted, add various additives, replace the polymerization tank with N and gas several times, and pressurize with tetrafluoroethylene (TFE). , a denaturant and an initiator are charged to start the reaction. Usually, the pressure inside the polymerization tank is maintained at 4-30 to 9/cry'' by continuous supply of TFE, and the reaction is carried out while the reaction temperature is kept constant or changing at 10-120°C. In the aqueous dispersion polymerization method, rotation is performed vigorously with sufficient power to disperse the polymer, but in aqueous dispersion polymerization, rotation is performed slowly to maintain the stability of the latex.In order to increase the stability of the latex during the reaction, it is inert to the polymerization reaction and takes on a liquid state. Addition of a hydrocarbon having 12 or more carbon atoms is also common in aqueous dispersion polymerization methods.

Various additives include buffers, molecular weight regulators, initiation aids,
There are anti-adhesion agents, fluorine-containing dispersants (surfactants), etc., but the biggest difference between suspension polymerization and aqueous dispersion polymerization is that the former does not use a dispersant or uses a very small amount of it. , the latter in an amount sufficient to stably disperse the latex particles (
(approximately 100 to 10,000 ppm) to carry out the reaction.

The modified PTF'E using fluorovinyl ether (I) of the present invention as a modifier has the following characteristics compared to unmodified PTPE. Granular type powders can be subjected to general compression molding or ram extrusion molding, and have particularly excellent creep resistance among the properties of the fired product. 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. After copolymerization, the end of the side chain is converted into a hydroxyl group and a carboxyl group through a polymer reaction.

It is also easy to convert into a hydrophilic group such as a sulfonic acid group. In addition, copolymers into which hydrophilic groups have been introduced can be used as ion exchange membranes with excellent heat and chemical resistance, and
More generally, it can be applied as a hydrophilic diaphragm, filtration membrane, or separation membrane. Furthermore, it is useful as a biocompatible material.

[Preferred Embodiments of the Invention] The present invention will be specifically explained below by showing Reference Examples, Examples, and Comparative Examples.

Reference example! 2.2.3-Trifluoropropionyl fluoride (
Preparation of FCH, CP, C0F) Carbon tetrachloride 360x (l and aluminum chloride 10
8g was added and the internal temperature was set at 30-35°C.

While stirring 2. '2.3.3-Tetrafluorooxecune 18009 was added dropwise from the dropping funnel over a period of 2 hours. Thereafter, in order to complete the reaction, aluminum chloride 909 was added in three portions at 1.5 hour intervals. After stirring was continued for 4 hours while maintaining the temperature in the system at 27 to 29° C., 1130 g of the title compound 2,2.3-trifluoropropionyl fluoride was obtained by distillation. boiling point 2
3-23.5°C.

Reference Example 2 2.2,5,5,6,6.7-hebutafluoro-4-oxa-heptanoyl fluoride (FCH, -CFIC
Preparation of F20CI-1, CF2C0F') 2,2,3-trifluoro obtained in Reference Example 1 was placed in a 5a flask equipped with a stirrer, a condenser, and a dropping funnel. , Oni/, 7 ) b Owi F105991. Wow
) Acre 2, 52, Yau, 71. Oh, Ido,
. 9.1 □ Grime looOm (Add 2 and stir at 15℃~20℃ 2.2, 3.3-*h57) LtO. Oyaya, a115
15 g was slowly added dropwise over 3 hours and 30 minutes.

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 to obtain the title compound 2,2,5,5,6,6.7-hebutafluoro-4.
-Oxaheptanoyl fluoride 3009 was obtained.

Boiling point: 62-64°C (80mmHLi).

Reference example 3 2.2,5,5,6,6,9,9,10.10-decafluoro-4,8-dioxa undecanoyl fluoride (F CHt CF t CF * OCH! CF
Production of 2.2.5°5,
6,6.9,9,10.10-decafluoro-4°8-
Dioxa-undecanoyl fluoride 2649 was obtained. Boiling point = 23°C (5mmH!?).

Reference Example 4 Production of 2.2-difluoro-3-iodopropionyl fluoride (I CH* CF 2 COP) 1500x dry tetraglyme was placed in a 3Q four-necked flask and 825 g of sodium iodide was added while stirring at room temperature.
completely dissolved. Next, while passing water through the cooler, the reaction temperature was slowly maintained at 30°C to 40°C.
．． Add 650 g of 3-tetrafluorooxetane dropwise,
The dropwise addition of 2.2°3.3-tetrafluorooxetane was completed in 5 minutes. Under reduced pressure of 30mmH9, 38-40℃
The title compound 2,2-difluoro-3-iodopropionyl fluoride 10509 was recovered by distillation. Boiling point: 95-96°C.

Example 1 Perfluoro(6,6-dihydro-3-oxa-■-
Hexene XPCI-1. CF20F20CF=CF,)
Production of cesium fluoride 88g and tetraglyme 34g
2,2,3-trifluoropropionyl fluoride 10551? obtained in Reference Example 1 was added to a 3Q four-bottle flask containing 10551? of 2,2,3-trifluoropropionyl fluoride containing 10551? of 2,2,3-trifluoropropionyl fluoride. Hexafluoropropylene oxide was added from a cylinder at a rate of reflux using a dry ice cooler. 52 hours after the start of the reaction, the addition of hexafluoropropylene oxide was stopped, and while cooling with ice water, 1324 mQ of methanol was added, and the mixture was washed with water several times. and distilled to obtain F CHtCF tc F 20 C (
CF3)F-COOCH3 was separated. Yield: 80
49. Boiling point: 38°C.

Next, the produced methyl ester was placed in a 2Q flask and heated at 60 to 70°C using phenolphthalein as a pH indicator.
A saponification reaction was carried out using a 0% by weight NaOH/methanol solution. Methanol was distilled off under reduced pressure from the slightly pink-colored viscous solution, and vacuum drying was performed at 100° C. until a constant weight was reached to obtain 810 g of a solid.

Next, this solid material was crushed well and placed in a 3ρ flask connected to a trap sufficiently cooled with dry ice, and the flask was sufficiently purged with nitrogen gas. 150℃ to 250℃ over 5 hours
When heating was continued until reaching , 5429 liquid was collected in the trap. This was distilled to produce the title compound perfluoro(6,6-dihydro-3-oxa-■-hexene).
324g was obtained. Boiling point: 61-62°C.

Example 2 Perfluoro(6,6,10,10-tetrahydro-
3,7-thioxal-1-decene X FCHtCFt-C
F t OCH2CF 2 CF t OC−F =
Production of CF t ) The title compound was obtained from 204 g of 2,2,5,5,6,6.7-hebutafluoro-4-oxa-heptanoyl fluoride obtained in Reference Example 2 by the same method as in Example 1. 65 g of perfluoro(6,6,10,10-tetrahydro-3,7-thioxal-1-decene) was obtained. Boiling point = 44-45°C (I3mmH9).

Example 3 Perfluoro(6,6,10,10,14,14-hexahydro-3,7,11-trioxa-1-tetradecene) (FCHzCF2CFtOCHzCFt-CF
t OCHt CF 2 CF t OCF=CF 2,2,5,5,6,6,9,9,10.10-decafluoro- produced in Reference Example 3 by the same method as in Example 1 From 4,8-dioxa-undecanoyl fluoride 3219 to the title compound perfluoro(6,6,1
0,10,14,14-hexahydro-3,7,11
54 g of oxa-1-tetradecene) were obtained. Boiling point: 88-89°C (I3mmHg).

Example 4 Perfluoro(6,6 dihydro 6-iodo 3-oxa-1-hexene XI CH, CF, CF, -0CF
= CFt) 43 g of cesium fluoride and 6 m of tetraglyme (I, 400 g of 2,2-difluoro-3-iodopropionyl fluoride obtained in Reference Example 4) were placed in a 2Q four-bottle flask, and the internal temperature was set to 10°C while stirring. .

Next, hexafluoropropylene oxide was flowed from the cylinder at a rate of reflux in a dry ice cooler for 21 hours, and then 300 mQ of methanol was added while cooling with ice water.
added. After washing the reaction product several times with water, I
CHtCFtcFtO-C (CF J F COOC
H3 was separated. Yield: 2059, boiling point: 114-11
5°C (lOOmmH9).

Subsequently, the obtained methyl ester was transferred to a 112 flask and heated to 60 to 70°C, and then phenolphthalein was
A saponification reaction was performed using a 10% by weight NaOH/methanol solution as an indicator, and excess methanol was distilled off under reduced pressure.
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: 2029
Next, this solid material was crushed well and placed in a lQ flask connected to a trap sufficiently cooled with dry ice, and the flask was sufficiently purged with nitrogen gas. When heating was continued from 150° C. to 250° C. over 3 hours under a reduced pressure of about 25 mmH, 1489 purple liquid was collected in the trap.

This was distilled to obtain the title compound perfluoro(6,6 dihydro-6-iodo-3-oxa-1-hexene)st4.
I got it. Boiling point near 1-72°C (I00mmH9).

Example 5 Perfluoro(9,9-sibidro9-iodo-5-
Trifluoromethyl-3,6-thioxal-1-nonene (
I C82CF, CF, 0C (CF3) F-CF, 0C
Production of P=CF 60 g of cesium fluoride in a 4-necked 212 flask,
Tetraglyme 10xσ and 2,2- obtained in Reference Example 4
Difluoro-3-iodopropionyl fluoride 60
0g was added, and the internal temperature was set to 10°C while stirring. Subsequently, hexafluoropropylene oxide was flowed into the dry ice cooler from the cylinder at a rate of reflux for 30 hours. After that, the inflow of hexafluoropropylene oxide was stopped, and while cooling with ice water, 500 J of methanol was added! 12 was added.

The reaction product was washed with water several times and distilled into ICHz-CFz.
CFtOC(CFs)FCFtOC(CF3)FC-0
0CH, was separated. Yield 1:1169, boiling point 91-92
°C (6mmH9).

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 the title compound 63.59.
I got it. Boiling point 87-87.5'C (45mmH1?).

Example 6 Pure water 1660zC was placed in a glass-lined autoclave with an internal volume of 3g, cooled to 5°C, and C3Ft was added to the autoclave.
(OCF(CFa)CFt)tOcF=CFt (hereinafter,
[φ, called VEJ. ) 30 og, fluorovinyl ether I CH* CF z CF ! OCF =
CF t7.

6g1CtF15COO-NH415g-1,3,5-
1.1.2-) Lichloro 1.2.2-) Lifluorotoethane solution (concentration 0.44 g/distillate) of trichloroperfluorohexanoyl peroxide (concentration 0.44 g/distillate) 9, 6 x Q was added, and the substitution was quickly repeated with tetrafluoroethylene.
2 with tetrafluoroethylene at 5°C under stirring.
, 2 kg/cm' (gauge pressure).

As the pressure decreases as the polymerization reaction progresses, the pressure decreases to 2.0k.
g/cm" (gauge pressure), tetrafluoroethylene drops to 2.2 kg/cm" (gauge pressure).
Pressure was re-pressurized to
Polymerization was carried out for 0 minutes.

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% φ and VE units, and as a result of iodine analysis, 0.69 mol%
ICHzCFzCFt-OCF=CF.

Example 7~! 0 Polymerization pressure, polymerization time, 1.1° 2-trichloro-1,2,2-trifluoroethane solution of 1,3.5-)lichloroperfluorohexanoyl peroxide (illll
lffio, 44 g/ml) (DLP) and fluorovinyl ether (ICH!-CF in Examples 7-9)
t CP t OCF = CF t, in Example 10 ICH2CP*CFtOCP(CFs)CFtOCF=
Example 6 except that the amount of CF*) was as shown in Table 1.
A copolymer was obtained by repeating the same procedure. The yield and the content of fluorovinyl ether and φ, VE are determined as follows.
Shown in the table.

Example 6~! The components shown in Table 2 were added to the copolymer obtained in step 0 to prepare a vulcanized composition, and the vulcanizability was measured at 160°C using a curelastometer (JSRn type). . In addition, press vulcanization at 160°C for 10 minutes and 180°C
The composition was vulcanized under oven vulcanization conditions of 4 hours at °C, 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."

Example 11 A polymerization tank with an internal volume of 3Q was charged with 112 g of pure water and 42 g of CvP+sCOONH as an emulsifier, and after the system was sufficiently replaced with nitrogen gas, fluorovinyl ether ICHz
CF2CFtOCF=2.5 g of CFt was press-fitted. 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) was pressurized so that the internal pressure was 16 kg/am'' (gauge pressure). Next, a solution of 3.3 g of ammonium persulfate in 80% pure water was pressurized together with nitrogen gas to start the reaction.

As the pressure decreases as the polymerization reaction progresses, 14 k
g/cm” (gauge pressure), VdF/
Monomer mixture of HFP/TFE (molar ratio 50/30/
20), and while repeating pressure reduction and pressure increase, 1.7.3.6 and 7.
．． After 1 hour, 2.5 g of the above fluorovinyl ether was injected under pressure to continue polymerization. After 8 hours and 45 minutes from the start of polymerization, the polymerization tank was cooled and unreacted monomers were discharged, resulting in a solid content of 25.7% by weight. An 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 (I00℃) is 32
Met. As a result of iodine analysis, this copolymer has an iodine content of 0.76
Mol% of I CH! CF t −CF, 0CR=CF
, was found to contain.

Example 12 Pure water IQ and C as an emulsifier were added to a polymerization tank with an internal volume of 3Q.
After charging 42g of tF and 5COONH and thoroughly replacing the inside of the system with nitrogen gas, VdF/HFP/TFE was heated at 80°C.
A monomer mixture (molar ratio 1B/71/II) was injected so that the internal pressure was 16 kg/cm"G. Then,
The reaction was started by increasing the pressure of a 0.2% by weight aqueous solution of ammonium persulfate by 10 ml.

As the pressure decreases as the polymerization reaction progresses, 15 k
g/cm"G, the molecular weight regulator I
(For CF, 1.2g of I was press-fitted, and the pressure was further increased to 14
When it drops to kg/c+n”G, VdF/HFP/
Repressurize to 16 kg/c+a'G with a monomer mixture of TFE (molar ratio 50/30/20), repeat pressure reduction and pressure increase, and react by pressurizing the above ammonium persulfate aqueous solution 10xQ with nitrogen gas every 3 hours. continued.

The total pressure drop from the start of the polymerization reaction is 5 kg/cm”
At the time when it becomes G (after 5 hours), fluorovinyl ether I CHt CF t CF t OCF = CF
t 1 , 8 g was press-fitted. Similarly, when the total pressure drop reaches 43 kg/cm"G (after 9 hours), the polymerization tank is cooled and unreacted monomers are discharged to reduce the solid content to 2.
A 6.7% by weight aqueous emulsion was obtained.

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 (I00℃) is 83
and the limiting viscosity [η] (di/g.

Solvent: Tetrahydrofuran. 35°C) was 0.53. Iodine analysis showed that this copolymer contained 0.12 mol% of I C'HzCF2CFzOCP=CF2.

Example I3 Fluorovinylether I CHlCFtCFzO-C
The same operation as in Example 12 was repeated except that 5.4 g of F = CF t 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%.

Example 14 Fluorovinylether I CHtCF tc F t
The same procedure as in Example 12 was repeated except that 9 g of o -CF=CF* was used and the reaction time was 34 hours to obtain 398 g of a rubbery copolymer.

Mooney viscosity = 43° [η Koni 0.31. Fluorovinyl ether content = 0.63 mol%.

Example 15 ICHtCFffiC as fluorovinyl ether,
.

F * - OCF = I CH instead of C'F t
, CFICF.

0-CF(CFs)CP, 0CF=CFtl 4.9g
383 g of a rubbery copolymer was obtained by repeating the procedure of Example 12 except that the reaction time was changed to 9 hours and 30 minutes.

Mooney viscosity = 47° Fluorovinyl ether content = 0
．． 74 mol%.

Example 16 The composition of the initial monomer mixture was 65/3510 molar ratio, the composition of the additional monomer mixture was 7 g/2210 molar ratio, 7°2 g of fluorovinyl ether was used, and the reaction time was 25 hours 45 minutes. The same procedure as in Example 12 was repeated to obtain 345 g of a rubbery copolymer.

Mooney viscosity = 20° Fluorovinyl ether content = 0
．． 52 mol%.

Comparative Example 2 Copolymer 37 was prepared by repeating the same procedure as in Example 11 except that the reaction was carried out for 5 hours without using fluorovinyl ether.
5g was obtained. Mooney viscosity: 87° Comparative Example 3 A copolymer was obtained by repeating the same procedure as in Example 2, except that fluorovinyl ether was not used, IOg of ammonium persulfate was used as an initiator, and the reaction time was 4.1 hours.

Mooney viscosity: 43° The components shown in Table 3 were blended with the copolymer obtained in the Examples or Comparative Examples, and the vulcanized composition was prepared by uniformly blending with a rubber roll in a conventional manner. The vulcanizability was measured at 160° C. (JSRn type). In addition, press vulcanization at 160°C
The composition was vulcanized under oven vulcanization conditions of 80° C. for 4 hours, and the physical properties of the vulcanized product were measured.

The physical properties of the vulcanizate were measured according to JIS K 6301.

The results are shown in the same table. In addition, "parts" in the table means "parts by weight."

Example 17 FCH, CF, CF, 0CF=CF, 6.9 g, 1.
1.2-) Rechloro 1.2.2-) Refluoroethane (hereinafter abbreviated as R-113) IOa (2 and 2
．． 4.5-) R-113 solution of dichlorobarfluorohexanoyl peroxide (a degree 0°79/x(I)
0,5z(l) was charged, and after cooling with dry ice/methanol solution, the inside of the system was purged with nitrogen.

Next, 6.8 g of VdF was charged and reacted at 20±1'C for 20 minutes with shaking. As the reaction progresses, the gauge pressure within the system decreases from 6.3 kg/crtt" before the reaction to 5.5 k
g/cm'. 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, yielding a copolymer body 2.29. This copolymer composition ratio was determined from 'H-NMR analysis by VdF:(FCHt
CF”, CFtOCF=CF2)=71.8:2B, 2
(molar ratio). 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.

Example 18 F(CH2CF, CF, 0) 20F=CF, 10°8 in a 100x12 pressure glass ampoule equipped with a bulb
g, R-11310mQ and R-113 of 2,4.5-trichloroperfluorohexanoyl peroxide
Prepare 0.5m12 of solution (0,449/x12),
After cooling with dry ice/methanol solution, the inside of the system was purged with nitrogen gas. Next, VdF5.79 was charged and 20
The reaction was allowed to proceed at ±I'C for 35 minutes with shaking. As the reaction progresses, the gauge pressure in the system decreases to 9.8 kg/c from before the reaction.
112 to 6.8 kg/cr1". Unreacted monomers were released, the contents were dissolved in acetone and taken out, and then released into water to precipitate and separate the copolymer. After vacuum drying, the copolymer was separated. The weight of the polymer was 10.29.The composition ratio of this copolymer was determined from 'H-NHR analysis by VdF
:[F(CH, CFtCF2-0)2CF = CF
The copolymer had a glass transition temperature of -30.5%.

Example 19 F(CH
, CF', CF, 0)scF=cF214.7g was used, and the reaction was carried out in the same manner as in Example 17 except that the reaction time was 23 minutes, and the gauge pressure in the system was 9.8 to 9/c.
m' to 8.0 kg/cm''. The amount of copolymer after vacuum drying was 16.29.

The composition molar ratio of the copolymer is VdF:[F(CHt-CF
2 CF t O) 3 CF = CF t co=7
3,9:26.1, and the glass transition temperature was -42.0°C.

Example 20 When the reaction was carried out in the same manner as in Example 17 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/cll'' to 1.5 g/cll''.
The weight of the copolymer after vacuum drying was 0.79.The copolymer was an elastic body and no melting point was observed.The glass transition temperature was 8.5. It was ℃.

Examples 21-25 VdF and F CHt CF t CF t OCF
= CF The reaction was carried out in the same manner as in Example 17, except that the amount of charged t was changed and TPE was further added. Table 4 shows the amount charged, the weight, composition ratio, and glass transition temperature of the copolymer obtained in each case. The compositional molar ratio of the copolymer was determined by 'H-NMR and 'P-NMR analysis.

In the table, rFMJ and rDLPJ are rF-C
H = CF2CF20CF = CF tJ and r2,4.5 = R-113 solution of trichloroperfluorohexanoyl peroxide (concentration 0.79/village)
” represents.

Table 4 Example 26 0.18g of ethylene was added in place of VdF and the reaction time was 2.
The reaction was carried out in the same manner as in Example 17 except that the reaction time was 0 minutes. Gauge pressure in the system is 7.2 kg/Q shoulder 2 to 6
The weight of the copolymer after vacuum drying was 0.89, and the composition ratio of this copolymer was ethylene:(FCH,CF,CF,0CR=CF,)-
The molar ratio was 56.3:43.7.

Further, the glass transition temperature was -11°C.

Example 27 3 equipped with temperature control jacket, stirrer and baffle plate
Q volume of deionized and deoxygenated water in a stainless steel autoclave 1.4512. Tertiary ammonium phosphate tertiary 9, and ammonium perfluorooctanoate 9 part 9
I prepared it. 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, FCHICFtCFtOCF=CF2 is 1.2
9 prepared. The stirrer was then started and rotated at 400 rpm to raise the temperature of the charge to 70°C.

Next, TFE was charged until the internal pressure reached 7.5 kg/cm2 (gauge pressure), and 4.0 kg/cm2 of ammonium persulfate was added.
1119/water 50iQ solution was injected with TFE, and the internal pressure was increased to 8
, 0 kg/cm" (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 supplied to maintain the pressure at 8.0 to 9/am'' (gauge pressure), and when the supply amount (=polymer solid content) reached 2509, TFE was expelled, stirring was stopped, and the reaction was stopped. finished.

Take out the powder, put it in an industrial mixer, add water and mix 1
The powder was ground by running for a minute. 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.

When the dried fine powder was formed into a film and an infrared absorption spectrum was taken, there were characteristic absorption peaks at 956 cm-' and 1003 ci-' that were not observed in poly-TFE.

From the ratio of the absorbance of 956ca+-' and the absorbance of 2360CI-' (corresponding to the film thickness), F
The content of F=CP in the polymer was estimated to be 0.
It was 1 mol%.

The creep of molded articles made from this powder was 3.5% at 24.degree.

Creep measurement was performed using the following procedure. Put 190g of powder into a cylindrical cylinder mold with a diameter of 50mm, and
kg/ax'' (holding time 5 minutes) and then removed from the mold.Then, the heating rate was 50% in an air firing furnace.
Raise the temperature to 365℃ at a rate of ℃/hour, keep it at 365℃ for 5 hours,
The temperature was lowered to room temperature at a rate of 50°C/hour. This fired product was heated to a diameter of 11.3 mm so that the compression direction and the height direction of the cylinder matched.
+, cut into a cylindrical shape with a height of 10 mm. A load of I40 9/cx'' was applied to a cylindrical sample in a constant temperature room at 24°C, and the height of the cylinder was measured 10 seconds and 24 hours after the start of loading. Creep was calculated using the following calculation. It was calculated from the formula.

] Comparative example 4 F CHx CF * CF 20 CF = CF
Don't prepare tL1ptp+c"1"i'"I'""L+
*L: KE, le iiiol・191 items have 2 creep
It was 8.6% at 4°C.
1 Example 28
'In a 3Q volume autoclave similar to Example 27, 1.45Q of deionized and deoxygenated water.
, reagent grade (liquid paraffin 10
0me and ammonium perfluorooctanoate 1.
59 and nitrogen gas and TF in the same manner as in Example 27.
Deaeration and preparation of E, I Q,! L? , :. 5゜Work 9. . □t CF t CF t. −(CF=CF2
1.009 was charged with TFE and the stirrer speed was set to 25 Or
pm and the content temperature was raised to 70°C. Then TF the internal pressure to 7.5 kg/cm” (gauge pressure).
Pressurize with E and add 11.3 rxg of ammonium persulfate to 5 ml of water.
011ρ solution was injected with TFE, and the internal pressure was set to 8,0 kg.
/cm" (gauge pressure). During the reaction, TFE was supplied to maintain that pressure, and the reaction temperature was maintained at 70°C. When the consumed TFE reached 7309, TFE was expelled.
Stirring was stopped to complete the reaction.

The resulting dispersion was diluted with water, ammonium carbonate was added, and the mixture was pulverized by mechanical stirring. 130% of this powder
It was dried at ℃ for 14 hours.

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 LO cm were cut out. 20ci/ for 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 153 kg/cN'', tensile strength at break is 45 kg
7cm".

Comparative Example 5 The operation of Example 28 was performed except that FCH2CF, CF, and 0CF=CF were not added. For the powder obtained, the extrusion pressure was 110 kg/cm” and the tensile strength was 24 K.
g/cm'.

Patent applicant: Daikin Industries, Ltd. Agent: Patent attorney: Aobai Ao and two others Procedural amendment (
(Voluntary) May 30, 1986

Claims (1)

[Claims] 1. Formula: XCH_2CF_2CF_2(OCH_2CF_2CF
_2)m-(OCFYCF_2)nOCF=CF_2(
I) [wherein, X is hydrogen or halogen, Y is fluorine or a trifluoromethyl group, m is an integer of 0 to 5, and n is an integer of 0 to 2. ] Fluorovinyl ether represented by. 2. The fluorovinylether of claim 1, wherein X is a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine. 3. Formula: XCH_2CF_2CF_2(OCH_2CF_2CF
_2)m-(OCFYCF_2)nOCF=CF_2(
I) [wherein, X is hydrogen or halogen, Y is fluorine or a trifluoromethyl group, m is an integer of 0 to 5, and n is an integer of 0 to 2. ] A copolymer comprising a repeating unit derived from a fluorovinyl ether represented by the following and a repeating unit derived from at least one ethylenically unsaturated compound. 4. Ethylenically unsaturated compounds include ethylene, propylene, butylene, carboxylic acid vinyl ester, vinyl ether, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, vinyl fluoride , vinylidene fluoride, hexafluoropropylene, pentafluoropropylene, hexafluoroisobutene, perfluorocyclobutene, perfluoro(methylcyclopropylene), perfluoroarene, α,β,β-trifluorostyrene, perfluorostyrene, perfluoro Claim 3 is a compound selected from the group consisting of alkyl vinyl ethers, perfluoro(alkyl vinyl polyethers), polyfluoroacrylic acid, polyfluorovinyl acetic acid, polyfluorovinyl ether sulfonic acid, and polyfluorodienes. Copolymer described in section. 5. Formula: CF_2=CAB(II) [In the formula, A and B each represent fluorine or chlorine. ] 50 to 95 mol% of repeating units derived from a fluoroolefin represented by the formula: CF_2=CFO(CF_2CFYO)pRf(III)
[In the formula, Y has the same meaning as above, and Rf has 1 to 6 carbon atoms.
is a perfluoroalkyl group, p represents an integer of 0 to 5. ] 50 to 5 mol% of repeating units derived from perfluorovinyl ether represented by fluoroolefin (II) and perfluorovinyl ether (III
4. The copolymer according to claim 3, comprising repeating units derived from fluorovinyl ether (I) in an amount of 0.1 to 5 mol % based on the total number of moles of fluorovinyl ether (I). 6. 0.1 to 20 mol% of repeating units derived from at least one other ethylenically unsaturated compound based on the total number of moles of the three compounds (I), (II) and (III). The copolymer according to claim 5, which also contains the copolymer of claim 5. 7. 20 to 90 mol% of repeating units derived from vinylidene fluoride, 10 to 80 mol% of repeating units derived from at least one other ethylenically unsaturated compound copolymerizable with vinylidene fluoride, and vinylidene. A copolymer according to claim 3 consisting of repeating units derived from fluorovinyl ether (I) in an amount of 0.01 to 3 mol % based on the total number of moles of fluoride and other ethylenically unsaturated compounds. . 8. The copolymer according to claim 7, wherein the other ethylenically unsaturated compound is a mixture consisting of 10 to 45 mol% of hexafluoropropylene and 0 to 35 mol% of tetrafluoroethylene. 9. 20 to 100 mol% of repeating units derived from vinylidene fluoride, 80 to 0 mol% of repeating units derived from at least one other ethylenically unsaturated compound copolymerizable with vinylidene fluoride, and vinylidene. 4. A copolymer according to claim 3, comprising from 5 to 60 mol % of repeating units derived from fluorovinyl ether (I), based on the total number of moles of fluoride and other ethylenically unsaturated compounds. 10, a repeating unit derived from tetrafluoroethylene, and 0.01 to 2 mol% fluorovinyl ether (I) based on the number of moles of tetrafluoroethylene
A copolymer according to claim 3, comprising repeating units derived from.