JPS5885832A - 7,7-dihydro-7-hydroxy-perfluoro(3-oxa-heptene-1) - Google Patents

Abstract

NEW MATERIAL:7,7-Dihydro-7-hydroxy-perfluoro(3-oxa-heptene-1) of formulaI. USE:Useful as a comonomer capable of giving a reactive hydroxyl group to a polymer containing fluorine, copolymerizable easily with various fluoroolefins without the deterioration in the polymerization rate, contributing to the improvement in the thermal and chemical stability of the copolymeric backbone, and further giving the flexibility, heat, chemical, solvent and oil resistance thereto. PROCESS:The double bond in the methyl ester or a perfluoro(3-oxa-1-heptenoic acid) expressed by formula II is protected by blowing chlorine gas thereinto, and the resultant compound is then reduced with sodium boron hydride to afford 1,2-dichloro-7,7-dihydroperfluoro(3-oxa-heptanol) expressed by formula III, which is then dechlorinated with a metal, e.g. zinc, to give the compound of formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 7-hydro-7-hydroxy-perfluoro(3-oxahebutene-1).

7.7-Difluoro 7-hydroxyperfluoro(3
-oxa-hebuty-1) (CF, =CFO(CFz
)s CHwOH] (hereinafter abbreviated as HFvE) is a new substance that has not been described in any literature.

The compound HFVm of the present invention is extremely useful as a comonomer that provides a reactive hydroxyl group to a fluorine-containing polymer.

Comonomers that provide hydroxyl groups to the polymer include hydroxyalkyl (meth)acrylate 1 such as hydroxyethyl (meth)acrylate such as hydroxybutyl vinyl ether.

Hydroxyl group-containing unsaturated compounds are known, and examples of fluorine-containing compounds include compounds such as 4-hydroxy-4,4-bistrifluoromethyl-butene-11[C, =CH-CH2-C(CF3)OH]. It has been known. 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 co-merged with other fluoroolefins and does not significantly reduce the polymerization rate = (2) Because it is incorporated into the copolymer main chain as a perfluorovinyl group, the thermal stability of the main chain is improved. and contributes to improved chemical stability: (3) Since the side chain is a perfluoroether group, the copolymer is given flexibility, as well as heat resistance and chemical resistance.

It has various advantages such as good solvent resistance and oil resistance.

The compound of the present invention can be applied to various polymers other than fluorine-containing polymers as a comonomer providing a reactive site, but its application to fluorine-containing polymers is limited to the above-mentioned various types. This is preferable because it brings out the advantages of For this purpose, the compound of the present invention can be preferably applied to a fluorine-containing polymer such as a tetrafluoroethylene-propylene copolymer.

Hynyritene fluoride-hexafluoropropene.

Copolymer, vinylidene fluoride-perfluorovinylether copolymer, tetrafluoroethylene-perfluorovinylether copolymer, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylizofluoride/, ethylene-tetrafluoroethylene copolymer , ethylenenochloro0) refluoroethylene copolymer.

Examples include tetrafluoroethylene-hexafluoropropene copolymers, which are preferably used to form 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, 0.05
A copolymer having a reactive site is formed by copolymerizing about 20 mol, preferably about 0.1 to 10 mol. The copolymer thus obtained is melamine resin and isocyanate.

1. It easily reacts with various reactive compounds such as base resin, anhydride or silanol at room temperature or under heating to give a crosslinked product. Useful for binding rubber, thermosetting resins, paints, sealants, adhesives, etc.

The compound of the present invention can be produced by reducing a carboxyl group-containing fluorovinyl ether after prosocating its double bond. For example, after protecting the double bond of perfluoro(3-oxa-1-hebutenoic acid) methyl ester (cy2=cFo(cy2)3CUOCH5) in trichlorotrioleoethane by bubbling chlorine gas, , 1. by reduction with sodium borohydride (NaBH4).
2-cycloloaf, 7-cyhydroperpolyfluoro(3-
oxahbutyl/-ol) [cF, CICFCIO(C
F,)3CH,OH) is obtained. If this is dechlorinated with a metal such as zinc, the desired HFVFi can be obtained.

The compound of the present invention is a colorless and transparent liquid with a boiling point of 54° C./30 sm Hg and can be identified based on the following spectroscopic data. That is, in the infrared absorption spectrum, a broad characteristic absorption based on the -OH group is observed at 3200 to 3400 cM&-1, and a characteristic absorption based on the CF, =CF-〇- group is observed at 1835cM&-1.

Further, the data of the 1'' F-NMR spectrum is as follows.

■ -115da ■) -124tdd (g) -137taa ■　　　　　-86m ■ -137m ■ -128tt d: Doublet t Nitriplet m: multi bullet Next, the present invention will be explained in more detail with reference to Examples.

Example Hl; Production of VE In a 500 mg three-neck flask equipped with a gas blowing tube and a thermometer, methyl ester of perfluoro(3-oxa-1-hebutenoic acid) [CF, =CFO(CF2
)3COOCH3) 204 g and 1.1.2 of the solvent
-) dichloro-1,2,2,-)lifluoroethane 2
00 yxl was charged, and chlorine gas diluted with nitrogen was blown into the liquid phase while cooling with water (5 to 10°C).

Since the yellow coloration based on the chlorine dissolved in the liquid was no longer observed in about 1 hour after the start of blowing, the blowing gas was changed to nitrogen to remove unreacted chlorine.

The common medium was distilled off to give 2 (1 g of perfluoro(l, 2-dichloro-3-oxahebutanoate)methyl) (CF, ClC
FCIO(CF,)3COOCB,) (CIJ*,)
was isolated.

Internal volume 50 with reflux condenser, thermometer and stirring bar installed
．． Sodium borohydride 12 in Oxe three-loaf flask
．． 0.9 and 25011 g of ethanol were added and stirred well. Next is 〇1m obtained above.

240.11 was added dropwise with stirring at such a rate that the ethyl was slowly refluxed. 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 ethanol flow temperature for 1.5 hours. The reaction mixture was diluted with 800% IN hydrochloric acid. After standing still, the organic layer was separated, washed with water, and dried to obtain 140 g of 1,2-cycloloaf, 7-cyhydroperfluoro(3-oxa-heptatool) as a fraction of ~7 mm Rg. (CF2'C
ICFCIO(CF2)3CH20H)(ClAl)
I got it. 0, ClAl obtained above 1,201 + zinc powder 45
, 0 J, zinc chloride 04.5 g and ethanol 15
0m1. The internal volume with the reflux condenser, thermometer and i push rod is 3'0011tI! The mixture was charged into a three-hole flask and stirred under reflux for 8 hours. Pass the reaction mixture once and remove excess
After separating the zinc, the desired H
A FVK of 60.2/I was obtained. Note that th]= was based on the spectroscopic data described above.

Reference Example: Application as four comonomers providing vulcanization sites for a fluoroelastic copolymer.Ion-exchanged water was placed in a stainless steel reactor with an internal volume of 200 mA'.
6.2. lit, t-butanol 10'p, ammonium perfluorononanoate i, og, sodium hydrogen phosphate decahydrate 2g 15% aqueous sodium hydroxide solution 283. Ammonium persulfate 0.50 g, and ethylenediaminetetraacetic acid [8 sodium salt trihydrate 0.0
An aqueous solution of 189 + 0.015 g of ferrous sulfate and 0.08 fi of Rongalit dissolved in 59 water is charged.

HFVB 1.4.9 is then added, the reactor is closed, and assimilative degassing is carried out twice with liquid nitrogen. After that, a mixed gas of propylene and tetrafluoroethylene (molar ratio 15/
, 85) is introduced, the reactor is attached to a 25° C. shaker type constant temperature water bath, and the reaction is started. At 2 o'clock N, the pressure drops from the initial value of 25 to 10. Unreacted monomers are purged, the recovered latex is frozen and solidified, and the polymer is precipitated, followed by washing and drying.

Polymer yield was 12.09.

This polymer exhibits an intrinsic viscosity of 070 at 30°C in tetrahydrofuran and an infrared spectrum of 3200-34
A characteristic absorption of -OH was shown at 00 mm-1. This polymer 10.9 is phenol-blocked isophorone diisocyanate 0,21/, MT carbon 3.5p
, 0.02 g of tetraphenyltin were blended in an open roll, and then heated and heated at 170° C. for 20 minutes. The resulting sheet was a tetrahydrofuran-insoluble vulcanized rubber exhibiting elastic recovery. ″

Claims (1)

[Claims] (]) 7,7-sihydro 7-hydro, oxy-perfluoro(3-oxahebutene-1)