JPS632418B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides 7,7-dihydro-7-hydroxy-
It concerns perfluoro(3-oxaheptene-1). 7,7-dihydro-7-hydroxyperfluoro(3-oxaheptene-1) [ _CF2 =CFO
(CF ₂ ) ₃ CH ₂ OH] (hereinafter sometimes abbreviated as HFVE) is a new substance that has not been described in any literature. The compound HFVE of the present invention is extremely useful as a comonomer that provides a reactive hydroxyl group to a fluorine-containing polymer. As comonomers that provide hydroxyl groups to polymers, hydroxyl group-containing unsaturated compounds such as hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether or hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate are known. , for fluorine-based ones, 4-hydroxy-4,4-bistrifluoromethyl-butene-1 Compounds such as: however
A hydroxyl group-containing unsaturated compound such as HFVE in which a perfluorovinyl group at an unsaturated site is bonded to a perfluoroalkylene group via an ether bond is new. The compound of the present invention, as a comonomer that provides a reactive hydroxyl group to a fluorine-containing polymer, has (1) monomer reactivity as a perfluorovinyl ether compared to known hydroxyl group-containing unsaturated compounds;
Easily copolymerized with various fluoroolefins and does not significantly reduce the polymerization rate: (2) Since perfluorovinyl groups are incorporated into the copolymer main chain, the thermal stability and chemical properties of the main chain are Contributes to improved physical stability: (3) Since the side chain is a perfluoroether group, it not only gives the copolymer flexibility but also heat resistance, chemical resistance, solvent resistance, and oil resistance. It has various advantages such as: The compound of the present invention can be applied to various polymers other than fluorine-containing polymers as a comonomer that provides a reactive site, but application to fluorine-containing polymers is
This is preferable from the standpoint that the various advantages described above are exhibited. Examples of fluorine-containing polymers to which the compound of the present invention can be suitably applied for such purposes include tetrafluoroethylene-propylene copolymer, vinylidene fluoride-hexafluoropropene copolymer, and vinylidene fluoride-perfluorovinylether copolymer. Polymer, tetrafluoroethylene-perfluorovinylether copolymer, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, ethylene-chlorofluoroethylene copolymer, tetrafluoroethylene -Hexafluoropropene copolymers are exemplified, and are preferably applied to forming vulcanization sites in elastic polymers, but can also be applied to resinous polymers. When the compounds of the present invention are used for such purposes, they usually contain 0.05 to 20
A copolymer having a reactive site is formed by copolymerizing the mole %, preferably about 0.1 to 10 mole %. The copolymer obtained in this way easily reacts with various reactive compounds such as melamine resin, isocyanate, urea resin, acid anhydride, or silanol at room temperature or under heating to give a crosslinked product, so it can be used as a rubber, thermosetting material, etc. Useful as resins, paints, sealants, adhesives, etc. The compound of the present invention can be produced by blocking the double bond of a carboxyl group-containing fluorovinyl ether and then reducing it. For example, methyl ester of perfluoro(3-oxa-1-heptenoic acid) [CF ₂ = CFO
(CF ₂ ) ₃ COOCH ₅ ] in trichlorotrifluoroethane by bubbling chlorine gas to protect the double bond, and then reducing it with sodium borohydride (NaBH ₄ ). 2
-dichloro-7,7-dihydroperfluoro(3
-oxaheptanol) [CF ₂ ClCFClO
(CF ₂ ) ₃ CH ₂ OH]. If this is dechlorinated with a metal such as zinc, the desired HFVE can be obtained. The compound of the present invention is a colorless and transparent liquid with a boiling point of 54° C./30 mmHg, and can be identified based on the following spectroscopic data. That is, in the infrared absorption spectrum, there is a broad characteristic absorption based on -OH groups at 3200 to 3400 cm ^-1 , and a characteristic absorption based on CF ₂ at 1835 cm ^-1 .
Characteristic absorption based on the =CF-O- group is observed. Moreover, the data of the ¹⁹ F-NMR spectrum is as follows.

[Table] Next, the present invention will be explained in more detail with reference to Examples. Example Manufacture of HEVE Perfluoro (3-oxa-1
methyl ester [CF ₂ =
CFO (CF ₂ ) ₃ COOCH ₃ ] 204g and solvent 1, 1, 2
200 ml of -trichloro-1,2,2,-trifluoroethane was charged, and chlorine gas diluted with nitrogen was blown into the liquid phase under ice cooling (5 to 10°C). Since the yellow coloration based on the chlorine dissolved in the liquid ceased to be observed approximately 1 hour after the start of blowing, the blowing gas was changed to nitrogen to remove unreacted chlorine. The solvent was distilled off and 241 g of perfluoro(1,2-dichloro-3
-oxaheptanoate) methyl [CF ₂ ClCFClO
( _CF2 ) _{3COOCH3 ]} (ClEs) was isolated. 12.0 g of sodium borohydride and 250 ml of ethanol were charged into a 500 ml three-necked flask equipped with a reflux condenser, thermometer, and stirring rod, and stirred well. Next, 240 g of ClEs obtained above was added dropwise under stirring at a rate that caused the ethanol to slowly reflux. After 2 hours, 9.1 g of sodium borohydride was added, and the mixture was stirred at room temperature for 3 hours, and then further stirred at the reflux temperature of ethanol for 1.5 hours. The reaction mixture was mixed with 800 ml of IN hydrochloric acid, and after standing still, the organic layer was separated, washed with water, dried, and fractionated to reduce the boiling point to 63.
-64℃/6-7mmHg fraction of 140g 1,2
-dichloro-7,7-dihydroperfluoro(3
-oxaheptanol) [CF ₂ ClCFClO
(CF ₂ ) ₃ CH ₂ OH] (ClAl) was obtained. 120 g of ClAl obtained above, 45.0 g of zinc powder, 0.45 g of subchloride and 150 ml of ethanol were mixed into a 300 ml inner volume equipped with a reflux condenser, thermometer and stirring rod.
The mixture was charged into a three-necked flask and stirred under reflux for 8 hours. After filtering the reaction mixture to separate excess zinc, the desired HFVE is obtained by distillation.
Obtained 60.2g. The identification was based on the spectroscopic data mentioned above. Reference example Application of fluorine-containing elastic copolymer as a comonomer providing vulcanization sites Ion-exchanged water was placed in a stainless steel reactor with an internal volume of 200 ml.
96.2 g, t-butanol 10 g, ammonium perfluorononanoate 1.0 g, disodium hydrogen phosphate dodecahydrate 2 g, 5% aqueous sodium hydroxide solution 2.8
g, ammonium persulfate 0.50 g, and ethylenediaminetetraacetic acid disodium salt dihydrate 0.018 g,
An aqueous solution of 0.015 g of ferrous sulfate and 0.08 g of Rongarit dissolved in 5 g of water is charged. after that
After adding 1.4 g of HFVE, the reactor is closed and solidified and degassed twice with liquid nitrogen. After that, a mixed gas of propylene and tetrafluoroethylene (molar ratio
15/85) 20g was introduced, the reactor was placed in a shaking type constant temperature water bath at 25°C, and the reaction was started. The pressure drops from the initial value of 25 Kg/cm ² to 10 Kg/cm ² in 2 hours.
Unreacted monomers are purged, the recovered latex is frozen and solidified, and the polymer is precipitated, followed by washing and drying. Polymer yield was 12.0g. This polymer exhibits an intrinsic viscosity of 0.70 at 30°C in tetrahydrofuran and an infrared spectrum of 3200
It showed a characteristic absorption of -OH at ~3400 cm ^-1 . 10g of this polymer, 0.2g of isophorone diisocyanate blocked with phenol, 3.5g of MT carbon,
After blending 0.02 g of tetraphenyltin with an oven roll, the mixture was heated and vulcanized at 170°C for 20 minutes. The resulting sheet was a tetrahydrofuran-insoluble vulcanized rubber exhibiting elastic recovery.

Claims (1)

[Claims] 1 7,7-dihydro-7-hydroxy-perfluoro(3-oxaheptene-1)