JPS60202122A - Novel fluorine-containing polyether, its production and use - Google Patents

Abstract

PURPOSE:To obtain a fluorine-containing polyether excellent in heat and chemical resistances and suitable as a heating medium, lubricating oil or vacuum pump oil, by fluorinating a specified polyether by heating or by irradiation with ultraviolet rays. CONSTITUTION:A fluorine-containing polyether having repeating units of formula I (wherein n is 2-200), obtained by polymerizing 2,2,3,3,-tetrafluorooxetane, or the like by ring opening in the presence of 0.001-30mol% polymerization initiator (e.g., CsF) [e.g., a compound of formula II (wherein A is F, Br, or I)] is fluorinated by blowing fluorine gas into the reaction solution or passing it through the vapor phase while heating the system to 160-300 deg.C or irradiating it with ultraviolet rays at 0-120 deg.C. Thus, a fluorine-containing polyether having repeating units of formula III (wherein p, q, and r are each 0 or an integer satisfying the relationships: 2<=p+q+r<=200 and q+r>=1) can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel fluorine-containing polyether and its production method and uses.

The novel halogen-containing polyether of the present invention has the formula: % formula %) (1) [wherein p, q and r are each 0 or a positive integer, 2≦p + q + r≦200 and q+
This is a number that satisfies r≧1. ] It is a compound having a repeating unit shown as follows.

The halogen-containing polyether of the present invention is, for example, -(CH
2CF2CF20)n-(II) [wherein n represents a number from 2 to 200. ] It can be easily produced by fluorinating a fluorine-containing polyether having a repeating unit represented by the following formula.

Fluorination is applied to polyether (II) from 160 to 300
This can be carried out by reacting fluorine gas at a temperature of 180 to 250°C. A more preferred fluorination method is to fluorinate polyether (I) under ultraviolet irradiation.
This is a method of reacting I) with fluorine gas, and fluorination can be carried out more efficiently. In the latter reaction, hydrogen fluoride is inevitably produced, so it is resistant to fluorine and hydrogen fluoride under the reaction conditions,
It is necessary to protect the ultraviolet light source with a material that can transmit a required amount of light having a wavelength of 0 nm to 400 nm.

Therefore, glasses such as quartz glass windows, which are often used in ordinary photoreactions, cannot be used in this reaction because they are corroded by hydrogen fluoride.

The light transmitting materials preferably used in the present invention include ``single crystal sapphire, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/perfluoropropyl vinyl ether copolymer,
Examples include transparent, melt-moldable fluororesins such as tetrafluoroethylene/ethylene copolymer, chlorotrifluoroethylene polymer, and vinylidene heptafluoride polymer.

From an industrial standpoint, single crystal sapphire is expensive and it is difficult to secure a large area, so fluororesin is preferred.

When irradiating the inside of the reactor with ultraviolet rays, the surface of a transparent glass material such as quartz glass can be coated with the above-mentioned resin, and when irradiating from the outside of the reactor, a film of the above-mentioned resin can be coated. It may be used as a light transmission window. Of course, it is also possible to use these films by laminating them on, for example, a quartz plate in order to impart pressure resistance to the window.

The light may be irradiated directly into the reaction solution, or may be irradiated through the gas phase.

The wavelength of light that can be used is 200 nm-40 Onun, preferably 250 ron-35 On+n.

In the fluorination reaction using ultraviolet rays, the reaction temperature is not a very important reaction condition, and it is sufficient to select a temperature that allows stirring of the reaction solution necessary for the reaction to proceed smoothly. The reaction temperature is mainly determined by the molecular weight of the raw material polyether (II). Generally, as the fluorination reaction progresses, the pour point and viscosity of the product decrease, so the reaction temperature can be lowered accordingly. Practically 0-12
A reaction temperature of 0°C, preferably room temperature to 100°C is employed.

In any of the fluorination methods, fluorine gas may be blown into the reaction solution or may be passed through the gas phase.

In addition, the 7 nitrogen gas may be diluted with an appropriate inert gas (for example, carbon dioxide, nitrogen, etc.) before use.

As the reaction mode, both the flow type and the nozu, nochi type may be adopted.

Polyether (n) is also a new compound and has 2,2゜3.
It is produced by ring-opening polymerization of 3-tetrafluorooxetane. The manufacturing method will be explained below.

When carrying out the ring-opening polymerization, a polymerization initiator is generally used. As the polymerization initiator, it is preferable to use an initiator that generates an active halogen anion in an abrotic solvent, such as an alkali metal decadenate, or a compound that exhibits strong Lewis acidity.

The amount of initiator used is not particularly limited, but is usually 2.
, 001 to 30 mo1%, preferably 0.01 to l), relative to the amount of 2,3.3-tetrafluorooxetane
O+no1% may be adopted.

The alkali metal 210genide as the polymerization initiator is
Although not particularly limited, for example, potassium 7-chloride, cesium fluoride, potassium iodide, potassium bromide, etc. are preferably used. When an alkali metal hadenide is used as an initiator, the product generally has the formula: %Formula % (1) [wherein A is F, Br or ■, 11 is 0-200
represents an integer of ]. The acid fluoride terminal group of this compound can be easily converted into a corresponding acid, alkali salt, ester, or amide by well-known reaction methods such as hydrolysis and esterification.

For example, if an acyl fluoride compound represented by the formula: RfCOF or Rf'0(CFCF20)t CFCOF is used simultaneously with the alkali metal fluoride as the polymerization initiator, the above (1)
A in the formula is the formula: RfCF20- or F3 Rf'0(CFCF20)t, respectively.

(However, Rf is a perfluoroalkyl group having 1 to 10 carbon atoms, Rf' is a perfluoroalkyl group having 1 to 10 carbon atoms, or a compound having a repeating unit represented by the formula CH2CF2CF20- is synthesized. be able to.

Furthermore, when an acyl fluoride called FCH2CF2COF obtained by ring-opening of 2,2,3,3-tetrafluorooxetane is used simultaneously with cesium fluoride, the polymerization is the same as when an alkali metal fluoride is used alone. A polymer with a structure is obtained. This method is effective when trying to obtain a low molecular weight oligomer while controlling the molecular weight distribution.

In addition, as can be seen from the above explanation, the relatively volatile low molecular weight products contained in the polymerization product are recovered by distillation after the polymerization reaction is completed, and then used again at the same time as the alkali metal fluoride. can be reused as a polymerization initiator.

Furthermore, as described above, instead of using an acyl fluoride compound from the beginning, for example, a fluorine-containing epoxide that reacts with an alkali metal fluoride to form an acyl fluoride is used, and this is - Can be removed by reacting with tetrafluorooxetane. For example, by reacting hexafluoropropylene oxide with cesium chloride in an aprotic solvent, a compound with the formula: It is also possible to introduce 2,2,3°3-tetrafluorooxetane into the system, resulting in the synthesis of a compound similar to that obtained when the above-mentioned acyl fluoride is used alone.

On the other hand, in a system in which 2,2,3,3-tetrafluorooxetane has been subjected to ring-opening polymerization using an alkali metal halide initiator or a co-initiator of an alkali metal fluoride and an acyl 7-fluoride, for example, By charging hexafluoropropylene oxide [where A is the same as in formula (1), x is an integer from 2 to 200,
y represents an integer from 0 to 50. ] It is also possible to synthesize a compound.

As can be understood from the above explanation, theoretically 2.2
, 3.3-tetrafluorooxetane and an epoxy compound capable of ring-opening polymerization in the same initiator system, such as hexafluoropropylene oxide, can be alternately or randomly given to give a block copolymer, and e.g. When a bifunctional acyl fluoride such as oxalic acid fluoride (FOC-COF) is used as a polymerization initiator for 2,2,3,3-tetrafluorooxetane at the same time as an alkali metal fluoride, FOCCF2C112 ( OCF2CF2C11□)ZO
CF2CF20 (C112CF2CF20) Ill-C
112CF2CO'F' (3) [In the formula, Z and W each represent an integer from () to 200] A bifunctional polymer having each terminal end being an acyl fluoride is obtained.

Generally, on interaction with an alkali metal fluoride in an abrotic solvent, -COF+MF, t-CF20- M+, (4) where M is an alkali metal species. All acyl fluoride compounds that form an equilibrium amount of fluoroalkoxy anions as shown in formula 1(4) are ring-opening of 2,2,3,3-tetrafluorooxetane in the coexistence of an alkali metal heptafluoride. It can be said that it can act as a polymerization initiator and form the terminal end of a ring-opened polymer in the form of an alkoxy group of ~CF20-.

As a Lewis acidic initiator, antimony pentafufluoride (SbF
5) is preferably used.

The ring-opening reaction of 2.2,3.3-tetrafluorooxetane is usually carried out in the liquid phase, and the reaction ? In addition to the Lewis acid initiator, as the 8 medium, abrotic solvents such as polyethylene glycol dimethyl ethers such as diglyme, triglyme or tetraglyme are preferably used. Acetonitrile or Cl-1,0CH2CH20
When CH, (glyme) is used as a solvent, the reaction is slow or does not occur at all, but the reaction can be carried out smoothly by using a small amount of a macrocyclic polyether compound such as 18-crown ether-6. Acetonitrile and glyme have a low boiling point, so they are advantageous in that they can be easily distilled and separated from the target product at the end of the reaction.

In the case of a Lewis acid initiator, a dimer or trimer of hexafluoropropylene can be used as a solvent, although no particular solvent is required.

Although the reaction temperature may vary depending on the type of initiator and solvent, a temperature of -80 to 100°C is usually used, preferably -30°C.
Reaction temperatures of ˜50° C. may be employed.

The reaction product can be recovered by conventional methods. For example, solid products can be washed with water to remove solvent and initiator residues and then filtered, and volatile products can be recovered by rectification.

The reaction product is A (CI-12CF 2
-CF20)nCH2CF2COF As is well known, the terminal acyl fluoride has high reaction activity and is chemically valuable in itself, but depending on the application, it is required to be inert. . For example, the above acyl fluoride compound is antimony pentafluoride (S
By using a catalytic amount of IIF5) and heating it above room temperature in a dimer or trimer of hexafluoropropylene, it can be converted into a compound represented by the formula: %Formula %. Polyethers whose terminal ends have been chemically inert can meet the above-mentioned requirements.

During fluorination with fluorine gas in the presence of ultraviolet rays, the terminal becomes 10CH2CF2COF or -oCl-12-C
When using polyether (11) which is F2COOI-1, at the stage where most of the hydrogen is replaced with fluorine,
There are products whose terminal ends are -0CF2CF2COF and -〇〇F2CF3. When the introduction of fluorine and nitrogen is stopped, the inside of the reaction system is replaced with nitrogen and phosphorus gas, and the ultraviolet irradiation is continued, all of the terminals of 10CF2-CF2COF are converted to 10CF2CF.

Therefore, in the fluorination reaction in the presence of light, when trying to obtain a chemically stable terminal product, it is necessary to use a terminal-stabilized polyether (terminal-stabilized polyether without ribs). Polyether (I) can be obtained.

In addition, completely fluorinated polyether can be obtained by carrying out a thorough fluorination reaction, but if the fluorination reaction is stopped before then, the product will naturally be completely 7. The result is a mixture of the hydrogenated polyether and the fluorine-containing hepta-containing polyether that partially contains hydrogen.

It is difficult to separate and purify completely 7-N-substituted polyether from such a mixture using ordinary distillation methods. However, by using a polar solvent such as acetone, it is possible to easily separate the two. That is, when the above mixed product is mixed with a polar solvent, the fully fluorinated polyether is separated into a lower layer, and liquid-liquid separation can be easily performed.

The main chain of the new fluorine-containing polyether (1) of the present invention is very stable both thermally and chemically, and is expected to be used in the same way as conventional perfluoropolyethers. It can be applied to various purposes. For example, compounds with terminal acyl fluoride groups are used as intermediates for synthesizing fluorine-containing compounds, those converted to terminal carboxyl groups are used as fluorine-containing surfactants, etc., and terminal-stabilized polyethers are used as heat-resistant As a chemical-resistant oil, it can be used as a solvent, heat medium, lubricating oil, vacuum pump oil, various modifiers, etc.

In particular, when fully fluorinated polyether is used as a vacuum pump oil during plasma etching of silicon with tetrafluoromethane, its viscosity remains unchanged even after continuous use for one month, and stability is required. It can be a suitable material for this field.

Next, the present invention will be specifically explained with reference to Reference Examples and Examples.

Reference Example 1 50 ml of well-dried diglyme and 0.1 cesium fluoride were placed in a 200 ml glass tube with a rotor flow valve.
5 g and 50 g of 2,2,3.3-tetrafluorooxetane were charged and kept under stirring at room temperature for 15 hours. The reaction mixture was poured into 10,100 O of water, and the precipitated solid substance was separated with a glass filter, washed with methanol, and then vacuum dried to obtain 45 g of white powder. Melting point near 8℃
. Decomposition temperature: 316°C0 Elemental analysis: CHF Measured value (%) 27.6 1,51 58.0 Calculated value (
%) 27.7 1.55 58.4N M R: δ
(ppm) = 4.62 (CH2) (internal standard: TMS)
.

δ (ppm) = -7,2 (-CF20-).

-41,4 (CH2CF2) (external standard: TEA) (the lower magnetic field side than the standard is defined as 10).

An IR chart of this compound is shown in FIG.

From these results, it was confirmed that the product was a polymer having a -CH2CF2CF20- skeleton. Average molecular weight is 1.5X10 by GPC
It turned out to be 4.

Reference Example 2 Eleven flasks connected to a dry ice condenser and a dropping funnel were sufficiently purged with dry nitrogen gas, and 200+ nl of dry diglyme and 4.2 g of cesium fluoride were charged, and while stirring in a water bath, perfluoro-2-propoxy 166 g of propionic acid fluoride was added and held for 30 minutes. 2.2,3゜3-tetrafluorooxetane 6
50 g was added dropwise over 5 hours. After the addition was completed, the water bath was changed to a 25°C water bath and maintained for 15 hours. The homogeneous liquid was distilled under reduced pressure to obtain 725g of liquid (60~20 +
11° C./11 Hg) was obtained.

This applies to GC/MS, NMR and IR analysis! As a result, CsF 70CF CF 20 (CH2CF 2CF
20) It turned out to be a mixture of acI12cF 2COF1 CF3 (a is an integer from 1 to 10).

Reference Example 3 A 300ml flask connected to a dry ice condenser and a dropping funnel was sufficiently replaced with dry nitrogen gas,
50ml of dry diglyme and 0.2g of cesium fluoride
While stirring in a water bath, 26° of 2°2.3-)lifluoropropionic acid fluoride was added and maintained for 30 minutes. 130g of 2,2,3.3-tetrafluorooxetane
was added dropwise over 3 hours. After the dropping was completed, the water bath was replaced with a water bath and kept for 12 hours. After dropping 30 g of methanol and keeping it for 30 minutes, the reaction mixture was poured into water 21, thoroughly stirred, and the lower layer was separated using a separating funnel (yield: 150 g).
).

As a result of analysis, this is F(CH2CF20F20)bCH2CF2coocI
-I31 (b is an integer from O to 9).

Reference Example 4 Hexafluorinated propylene guimer [(CF3)2CFCF=
330 parts by weight of CFCF and (CF3)2C=CFCF2(
: Mixture with 370 parts by weight of F] IS Og and 0.3 g of antimony pentafluoride were charged, and while stirring, 2.2,3
．． 65 g of 3-tetrafluorooxetane was slowly added dropwise and kept at -50 to 0°C for 5 hours. The low boiling fraction was removed under reduced pressure to obtain 50 g of a waxy product. Melting point: 52°C.

As a result of analysis, this was found to have a structure of -CH2CF2CF20-.

Reference Example 5 Well-dried diglyme 100+111 and 1.0 g of potassium fluoride were placed in a 500 ml glass flask, and 130 g of 2,2,3,3-tetrafluorooxetane was slowly added dropwise in a water bath while stirring, and kept for 15 hours. Ta. Polymer 1 was obtained by performing the same post-treatment as in Reference Example 1.
20g was obtained.

As a result of analysis, this was found to have a structure of -CH2CF2CF20-. The average molecular weight is 1 from Gpc
．． It was 0xlO'.

Reference Example 6 50 ml of dry diglyme and 15 g of potassium iodide were charged, and 32.5 g of 2,2,3.3-tetrafluorooxetane was slowly added dropwise while stirring, and the mixture was kept for 24 hours.

10 g of methanol was added dropwise, kept for 30 minutes, and then thoroughly washed with water to obtain 30 g of an oily product.

As a result of analysis, this is I(CH2CF20F20)ccH2cF2cOOcH
3 (C is an integer from 0 to 5).

Reference Example 7 A 100 m 17 flask connected to a dry ice condenser and a dropping funnel was charged with 3°+nl of dry diglyme and 1.2 g of cesium fluoride, and stirred in a bath cooled to -30'C. Next, 10 g of perfluoropropionic acid fluoride was charged in the form of a glass.
After keeping it for a minute, raise the bath temperature to 0℃ and
．． 50 g of 3-tetrafluorooxetane was added dropwise over 20 hours. After the completion of the dropwise addition, the bath temperature was gradually raised to 20° C., stirring was continued for an additional 5 hours, the mixture was poured into 50 g of methanol, stirred, and further washed with a large amount of water to obtain an oily product 474.

As a result of analysis by NMR, IR and GC-MS, the product is CF3CF2CF20(C112CF2CF20)dC
It was found to be a mixture of H2CF2COOC113 (d is an integer from 1 to 8).

Reference Example 8 Dry diglyme 1011+1. 1.2 g of cesium fluoride and 2.0 g of 2,2,3-trifluoropropionic acid fluoride were added, and the mixture was stirred in a water bath for 1 hour. Then, 10.08 g of 2,2,3,3-tetrafluorooxetane was added dropwise over 3 hours while stirring. After the dropwise addition was completed, stirring was continued for an additional 15 hours. Then,
The water bath was replaced with a water bath, hexafluoropropylene oxide was blown into the system at a flow rate of 10 ml/min for 2 hours, and the reaction was continued for an additional 5 hours. The reaction solution was treated with methanol and washed with water to form an oily substance18. OI? I got it.

Analysis shows that the product is CF3CF31F(C112CF2CF20)e(CHCF20)fc
FcOOcl13 (e is an integer of 2 to 9, f is 0 to 3
was found to be a mixture of (an integer of )

Reference Example 9 The same procedure as Reference Example 8 was repeated except that 10 g of perfluoroacetone was used instead of perfluoropropionic acid fluoride and reacted with 50 g of 2,2,3.3-tetrafluorooxetane, and an oil was produced. 53 g of material was obtained.

As a result of analysis, the product is (CF,)2CFO(Cl12CF2CF20)gcI
It was found to be a mixture of I2cF2COOCII3 (g is an integer from 1 to day).

Reference Example 10 C3F obtained in Reference Example 2, 0CFCF20(Cl12CF2CF20)a
cH2cF2cOFCF3 50, og, hexafluoropropylene dimer 1
0ml and 1.2g of antimony pentafluoride, and heated at 50°C for 1 hour. During the reaction, when the gas phase was subjected to infrared analysis, a large amount of -carbon oxide was detected. When the reaction solution was analyzed by IR, 189, which is a specific absorption of -COF, was found.
It was confirmed that the absorption of 0c+n-' was completely eliminated. After washing with hydrochloric acid, alkaline washing and water washing, it was dried and distilled under reduced pressure to obtain 43.8 g of a liquid material.

Boiling point 100-200°b This is the result of analysis, C3F70CFCF 20 (CH2CF2CF 20)
aclI2cF 3CF3 (a is 1-xoLf) v number. ) It became clear that 'I'l+.

Example 1 A white powder of polyfluoro-fluorine-containing polyether having the formula: oo8, heated in fluorine oil with stirring and gradually raised the temperature from 140°C to 200°C, and heated with 100+n of fluorine/nitrogen (20/80) mixed gas for 3 hours.
The flow rate was 1/min. After cooling while purging with nitrogen, 2.05 g of a viscous liquid reaction product was taken out. From the results of IR, NMR and elemental analysis, the reaction product was determined to be (C11□CF2CF20)l)-(CIIFCF2C
It was found to be a mixture of compounds containing repeating units represented by F20)'Q (p:q=7:3).

Example 2 5.20 g of fluorine-containing polyether represented by the formula: % formula % was placed in a steel reactor with a capacity of 100 m1, and the temperature was gradually raised from 140°C to 200°C with stirring.
．． A fluorine/nitrogen (20/80) mixed gas was passed through the reactor at a rate of 10 Jml/min for 5 hours. 2.48 g of a liquid reaction product was taken out while purging with nitrogen.

From the results of IRSNMR and elemental analysis, the reaction product was determined to be (CF2CF2CF20)Q-(Cl1CF2CF20
)r(q:r=5:1) It was found that it was a mixture of compounds containing repeating units represented by the following formula.

Example 3 A polymerization reaction product of 2,2,3,3-tetrafluorooxetane [F( CH2CF2CF20)n
CH2CF2COOH (average of n=24) 14.90g
was heated to 100°C in an oil bath in a nitrogen stream.

Next, while stirring with a magnetic cooler, 50 il
Fluorine/nitrogen mixed gas (mixture ratio 20/, 8
0) from the top of the reactor using a high-pressure mercury lamp (Next Summer H400PL, 312.5-577 nm).
Ultraviolet irradiation was performed (distance 1.Oc+n).

The flow of the fluorine/nitrogen mixed gas was stopped after 15 hours, and without irradiation with light, nitrogen was added for another 12 hours.
It circulated at 11/min. After the reaction was completed, the light irradiation was stopped and the mixture was cooled to obtain 5.90 g of an oily substance. Pour point knee 55°C.

Elemental analysis HF Measured value (%) 21.7 0.01 68.7 Calculated value (
%) 21.5 0 69.1 Figures 2 and 3 show changes over time in infrared spectroscopy. FIG. 2 is a chart 2 hours after the start of the photofluorination reaction, and FIG. 3 is a chart at the end of the reaction.

From the above analysis, it was found that the oily substance was a mixed composition of F(CF2CF2CF20)nCF2CF3 (average of 11 = 23on number was determined from the integral value of NMR).

Example 4 In the same reactor as Example 3, C.F.

C3F, 0CFCF20 (C112CF2CF20) ■
Cl12CF.

(Average of ++ = 7) Add 6.9 g of the mixed composition represented by the following and apply Magnetic?
Fluorine/nitrogen mixed gas (mixing ratio 20/80) was passed through the reactor at a flow rate of 50 m1/min while stirring with a cooler, and a low-pressure mercury lamp (UL2-IQ manufactured by Ushio Electric Co., Ltd.) was introduced from the top of the reactor.
, LOW, 184.9-546° lnm) as a light source and irradiated with ultraviolet rays (distance: 5 cm).

After 19 hours, the reaction was stopped and replaced with nitrogen.

7.0 g of product was obtained.

Analysis result CF3 ■ C3F 70CFCF 20 (C1l 2CF 2CF
20 )n (CHFCF 2CF 20 )+nC
IIFCF 3 (+n+++ average = 7, m: n
= 1:4).

Example 5 Into the same reactor as in Example 3, 2.6 g of a mixed composition represented by the formula % was placed, and while stirring, 50
Fluorine/nitrogen mixed gas (mixing ratio 20
/80) was irradiated from the top of the reactor with ultraviolet rays using a high-pressure mercury lamp as a light source.

After 11 hours, the reaction was stopped and the liquid was replaced with nitrogen.
I got g.

Analysis results CF3 C1F, 0CFCF20 (CF2CF2CF20) II
It was found that the average of CF2CF3(1)=7).

Example 6 A SUS condenser was connected, and chlorotrifluoroethylene polymer (PCTFE) was placed in the 30φ upper window.
Photoreaction device with film attached (inner volume 100m1)
In the formula 2F(CH2CF2CF20)2-CF2CF2
After charging the liquid io, og expressed by COF and cooling it in a water bath, while flowing a fluorine/nitrogen mixed gas (20/80) at a flow rate of 50 ml/min under stirring in a nitrogen stream,
(Light source: high pressure mercury lamp). The condenser was cooled with dry ice. After flowing for 15 hours, the product was fractionated on nitrogen substitution to obtain F(CF2CF2CF20)2C.
39.8 g of F2CF was obtained.

Example 7 A similar experiment was conducted using the same equipment as in Example 5, using a film made of ethylene/tetrafluoroethylene copolymer (ETFE) instead of PCTFE as a window film. 0)2CF2CF was obtained in 80% yield.

Example 8 A similar experiment was conducted using the same equipment as in Example 6, using a polyvinylidene fluoride film instead of PCTFE as a window film, and F(CF, -CF2CF20)
CF2CF3 was obtained in 28% yield.

Example 9 In a reactor with a window plate of single crystal sapphire on the side, 2,
Polymerization composition of 2,3.3-tetrafluorooxetane [
F(CH2CF2CF20)nCH2CF2-COF,
Average of n=22] 130.0 g was added, and a heating medium of 80° C. was circulated through the jacket in a nitrogen stream to liquefy the polymer.

Next, while stirring with a magnetic cooler, add 200+
Fluorine/nitrogen mixture (mixing ratio 1/1/2
1) was passed through the single-crystal sapphire window plate from the side of the reactor, and a high-pressure mercury lamp (next summer H10'OPL,
312.5-577 nm) and irradiated with ultraviolet rays (distance between lamp and window plate: 5 cm).

Further, during the reaction, the temperature of the heating medium was controlled so that the internal temperature range was 00°C to 120°C.

After 50 hours, stop the fluorine gas and add 100ml of nitrogen only.
The mixture was allowed to flow under light irradiation for an additional 24 hours at a flow rate of /min.

After completion, 158 g of oily product were obtained at room temperature.

As a result of analysis, the product is F(CF2CF2CF20) summerlCF2CF3(n
The average of 22) was confirmed.

Example 10 1.5 kg of polymer composition F (CH2CF2CF20) nCH2CF2cOF (n
average = 25) and heated to 100°C in an oil bath in a nitrogen stream.

Next, while stirring with a magnetic cooler,
1/min and nitrogen at 11/min were thoroughly mixed and introduced into the system, and ultraviolet rays were irradiated from the top using a high-pressure mercury lamp (Natsuya H400, PL). During the reaction, the temperature of the oil bath was controlled to prevent the temperature inside the reactor from rising above 120°C. 10 (The removal of fluorine was stopped for 11 hours, and only nitrogen was passed through at a flow rate of 21/min for 50 hours, and then cooled to room temperature. After the reaction was completed, F(CF2CF2CF20)nCF2CF.

(Average of n=25) 1.8 kg of an oily composition was obtained. This is 0.05T.

rr under reduced pressure, and fraction 1 at 180-220°C
．． Obtained 2Kg. When the kinematic viscosity at 40°C was measured, it was 65.
It was csL.

Example 11 After directly connecting the oil rotary pump, the oil rotary pump was thoroughly cleaned with a solvent, and then the oil obtained in Example 10 was added, and a test plasma generator using a mixed gas of 70 N14 and water and oxygen was operated. Ta. No abnormality was observed in the motor current value even after 30 days of operation.

As a result of extracting the oil and examining it, the viscosity was 65 at 40℃.
cst, and no significant change was observed compared to the oil before injection, which was 65 cst. In addition, the IR of the oil after use,
All NMR analysis results showed no change compared to before use.

[Brief explanation of the drawing]

FIG. 1 is an IR chart of the polymer obtained in Reference Example 1, and FIGS. 2 and 3 are IR charts showing changes over time in infrared spectroscopy during fluorination in Example 3. Patent Applicant Daikin Industries, Ltd. Agent Patent Attorney Aoyama Aoyama and 2 others (2 others volunteered to write the amendments) November 9, 1981 Patent Application No. 058877 2 Name of Invention New fluorine-containing polyether and Its manufacturing method, usage 3, and relationship with the case of the person making the amendment Patent applicant address: 12-39 Kin IJH-chome, Osaka City, Osaka Prefecture Name of Shin Hankyu Building (285) Daikin Industries, Ltd. Representative Yama 1) Minoru 4 representative Date of amendment order by Person 5: Own The following sections of the detailed description of the invention, drawing 7, content of amendment A, and the description will be amended. ■As per the appendix in the claims section. ■1 Column for detailed description of the invention (1), page 4, lines 12-14, [More preferred...
"Also, fluorination is possible even at temperatures lower than the above temperature range, but in such a low temperature range polyether (II) is reacted with fluorine under ultraviolet irradiation. If so,” he corrected. (2) On page 27, lines 12-13, the words ``r#2'' and ``Figure 3'' were corrected to ``Figures 2-4''. (3) On page 27, line 15, insert "Figure 4 is a chart after the decarboxylation reaction" before "is." ■ 1 Brief description of drawings column (1) Page 34, line 3, replace the text "It is." with "" Figure 4 is an IR chart of the polymer obtained in Example 3 after decarbonylation It is corrected. B. Add Figure 4 as shown in the attached sheet. Above (Attachment) Claim (1) Formula: % Formula %) [In the formula, p, q and r are each O or a positive integer, and 2≦p + q + r≦200 and q
+ is a number that satisfies r≧1. ] A fluorine-containing polyether having a repeating unit represented by the following. (2) The fluorine-containing polyether according to claim 1, wherein p=q=0. (3) Formula: % Formula %) [In the formula, n represents a number from 2 to 200. ] A fluorine-containing polyether having a repeating unit represented by the following formula is fluorinated to obtain the formula: % formula %) [where p, q and r are each O or a positive integer, and 2≦p 10q + r ≦200 and q+r
The number satisfies ≧1. ] A method for producing a fluorine-containing polyether, characterized by obtaining a compound having a repeating unit represented by the following. (4) The manufacturing method according to claim 3, wherein the fluorination is carried out using fluorine gas. (5L) Formula: %Formula%) where p, q and r are each 0 or a positive integer, 2≦p+q+r≦200 and q+r≧
This is a number that satisfies 1. ] Vacuum pump oil consisting of a fluorine-containing polyether having repeating units. <6) The vacuum pump oil according to claim 9, comprising a fluorine-containing polyether in which p=q=o.

Claims (10)

[Claims] (1) Formula: %Formula%) [In the formula, p, q and r are each O or a positive integer, and 2≦11 +q + r≦200 and q
It is a number that satisfies 10r≧1. ] A fluorine-containing polyether having a repeating unit represented by the following. (2) The fluorine-containing polyether according to claim 1, wherein p=q=0. (3) Formula: % Formula %) [In the formula, 1] represents a number from 2 to 200. ] by fluorinating a fluorine-containing polyether having a repeating unit represented by
CF 2CF 20)Q −(CF 2CF 2CF
20) In the r-E formula, p, q and r are each 0
or a positive integer, 2≦1) + q 10r≦2
00 and q+r≧1. ] A method for producing a fluorine-containing polyether, characterized by obtaining a compound having a repeating unit represented by the following. (4) The manufacturing method according to claim 3, wherein the fluorination is carried out using fluorine gas. (5) The manufacturing method according to claim 3, wherein the fluorination is carried out at a temperature of 160 to 300°C. (6) The manufacturing method according to claim 4, wherein the fluorination is performed under irradiation with light having a wavelength of 200 to 400 nm. (7) The manufacturing method according to claim 6, wherein light is introduced into the reaction system through single crystal sapphire or fluorine-based molten resin. (8) As the fluorine-based molten resin, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, tetrafluoroethylene/perfluorovinyl ether copolymer, polychlorofluoroethylene, poritzized vinylidene, or The manufacturing method according to claim 7, which uses a vinylidene oxide/hexafluorobutylene copolymer. (9) Formula: %Formula%) [In the formula, p, q and r are each 0 or a positive integer, and 2≦p 10q + r≦200 and q+r
The number satisfies ≧1. ] Vacuum pump oil consisting of a fluorine-containing polyether having repeating units. (10) The vacuum pump oil according to claim 9, comprising a fluorine-containing polyether in which p=q=o.