JP2854795B2 - Hexafluoropropylene oxide polymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heterobifunctional hexafluoropropylene oxide polymer having a vinyl group at one end of a molecular chain and a --COF group at the other end, and a method for producing the same.

[0002]

2. Description of the Related Art Hexafluoropropylene oxide (H
The polymer of FPO) can have various groups at its terminals by selecting the type of polymerization initiator used for polymerization. For example, CF ₃ −, CF
₃ (CF ₂ ) ₄ −, (CF ₃ ) ₂ CF−, (CF ₃ ) ₂ CF−CF (C
F ₃ ) −, FSO ₂ −, CH ₃ S −, CH ₃ OCO −, ICF ₂ −
HFPO polymers having such groups are known. HFPO polymers having these groups are described in Angew.
A review is provided in hem. Int. Ed. Engl., 24 , 161 (1985).

[0003] More specifically, as the above-mentioned initiator,
Carbonyl fluoride (US Pat. No. 3,114,778), perfluoropentanoic acid fluoride (DOS 2,614,333),
Hexafluoroacetone (US Pat. No. 3,274,239),
Perfluoromethyl isopropyl ketone (U.S. Pat.
274,239). HFPO polymer obtained by polymerization of using these initiators, the following formula: Rf '-O - (Y) p -CF (CF 3) -COF ( wherein, Rf' is a perfluoroalkyl group Yes, Y
_{Is, -CF (CF 3) -CF 2} O - an HFPO unit represented by, p is 0 or a positive integer. ), And one end of the molecular chain (the end opposite to the side to which the -COF group is bonded) is a perfluoroalkyl group, that is, a non-functional group.

There is also known an HFPO polymer in which a functional group is introduced into one end of a molecular chain by using a specific acid fluoride as an initiator. For example, UK Patent Application No. 2,053,902 discloses the use of FSO ₂ CF ₂ CF ₂ CF ₂ COF as an initiator, in which case the following formula: FSO ₂ CF ₂ CF ₂ CF ₂ CF ₂ O − (Y) _p −CF (CF ₃ ) −CO
An HFPO polymer represented by F (wherein Y and p are the same as described above) is obtained. This functional group at one end of the molecular chain (-FSO ₂ groups) it is understood that the heterologous bifunctional polymer introduced. Various initiators other than those described above are known as an initiator from which such a heterobifunctional polymer can be obtained. For example, CH ₃ S— (CF ₂ ) ₃ —COF (UK Patent Application No. 2,051,831), CH ₃ OOC − (CF ₂ ) ₄ −CO
F (DOS 2,708,677), I-CF ₂ -COF (U.S. Pat. No. 3,311,658) and the like are known.

[0005]

However, an HFPO polymer having a vinyl group introduced at one end of a molecular chain as a functional group at a molecular terminal has not yet been reported. Since the functional group at the molecular end of the above-mentioned conventionally known HFPO polymer is not a vinyl group, it cannot be bonded to a silicon compound by a hydrosilylation reaction, and its use in the field of silicon chemistry is limited.

On the other hand, as a compound having a vinyl group, the following formula: CH ₂ CH—CH ₂ O—CF ₂ — (Z) —COF (where Z is —CF (CF ₃ ) —OCF ₂ CF ₂ O -CF (CF ₃₎ -. a a) compounds represented by is known. This compound has a molecular structure similar to that of an HFPO polymer having a vinyl group introduced at one end of a molecular chain, but has the following formula: FOC- (Z) -COF (where Z is as defined above) 2) represented by
It is produced by reacting a compound having two -COF groups with allyl bromide in the presence of cesium fluoride. This reaction has problems such as poor selectivity of the product and formation of a diallyl compound as a by-product.

Accordingly, an object of the present invention is to provide a polymer of HFPO having a vinyl group at a terminal and a method for producing the same.

[0008]

According to the present invention, there is provided a compound represented by the following general formula:
(1):

Embedded image

(Wherein R ¹ is a single bond or a group having 1 to 1 carbon atoms)
10 alkylene groups or groups in which part or all of the hydrogen atoms of the alkylene group are substituted with fluorine atoms, and Rf is a fluorine atom or a perfluoroalkyl group or a perfluoroalkyl ether group having 1 to 10 carbon atoms. Yes,
n is an integer of 0 or more. The present invention provides a hexafluoropropylene oxide polymer represented by the formula:

Further, the present invention relates to a method for preparing hexafluoropropylene oxide, which is represented by the following general formula (2):

Embedded image

(Wherein, R ¹ is a single bond or a group having 1 to 1 carbon atoms)
10 alkylene groups or groups in which part or all of the hydrogen atoms of the alkylene group are substituted with fluorine atoms, and Rf is a fluorine atom or a perfluoroalkyl group or a perfluoroalkyl ether group having 1 to 10 carbon atoms. is there. A method for producing a hexafluoropropylene oxide polymer represented by the general formula (1), characterized by reacting a vinyl-containing compound represented by the formula (1).

Novel HFPO Polymer The HFPO polymer of the present invention has a vinyl group at one end and a -COF group at the other end.
It is a compound represented by these.

In the above general formula (1), R ¹ is a single bond or an alkylene group having 1 to 10 carbon atoms or a group in which part or all of the hydrogen atoms of the alkylene group are substituted with fluorine atoms. Specifically, the following _{formula: -, - CH 2 -,} - CF
₂ −, − (CF ₂ ) ₂ −, − (CF ₂ ) ₃ −, − (CF ₂ ) ₅
And a group represented by-or the like.

In the general formula (1), Rf is a fluorine atom or a perfluoroalkyl group or a perfluoroalkyl ether group having 1 to 10 carbon atoms. Specifically, the following _{formula: -F, -CF 3, -CF 2} CF 3, -CF (CF 3) -O-CF
₂ CF ₂ CF ₃ , -CF (CF ₃ ) -O-CF ₂ -CF (CF ₃ ) -O-CF ₂ CF ₂ CF
Examples include groups represented by _{3 and the} like. Further, the above general formula (1)
In the formula, n is an integer of 0 or more, particularly an integer of 0 to 100.

Production Method The polymer of HFPO of the present invention has the following general formula (2) as a polymerization initiator:

Embedded image (Wherein, R ¹ and Rf are as described above).

Specific examples of the polymerization initiator represented by the above general formula (2) include the following formulas: CH ₂ CHCHCF ₂ COF, CH ₂ CHCH (CF ₂ ) ₂ COF, CH ₂ CHCH ( _{CF 2) 3 COF, CH 2} = CH (CF 2) 5 COF, CH 2 = CHCOF, CH 2 = CHCH 2 COF, CH 2 = CHCF 2 COCF 2 CF 3, CH 2 = CHCOCF 3, CH 2 = CHCH 2 COCF ₃ , CH ₂ = CHCH ₂ COCF ₂ CF ₃ , CH ₂ = CHCF ₂ COCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ , CH ₂ = CHCF ₂ COCF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ C
F ₃ , CH ₂ = CHCH ₂ COCF (CF ₃ ) OCF ₂ CF ₂ CF _{3 and the} like.

The reaction between the above vinyl-containing compound and HFPO is carried out, for example, by mixing HFPO with stirring in a solution in which the vinyl-containing compound is dissolved or dispersed in a suitable solvent together with a catalyst.
(A gas in a normal state).

Examples of the catalyst used here include alkali fluorides such as sodium fluoride, potassium fluoride and cesium fluoride, and quaternary ammonium fluorides such as tetrabutylammonium fluoride and tetramethylammonium fluoride. Among them, potassium fluoride and cesium fluoride are particularly preferable. The amount of the catalyst to be used is generally 0.01 to 1 mol per mol of the vinyl-containing compound.
The range is preferably 1.2 mol, but when the reaction rate is low, it can be appropriately adjusted according to the charged amount of HFPO.

As the solvent, an aprotic polar organic solvent is preferable, and for example, glymes such as diglyme, triglyme and tetraglyme, and nitriles such as acetonitrile, propionitrile and adiponitrile are preferably used. Is done. Generally, such solvents are:
It is used in an amount of 1 to 100 parts by weight per 1 part by weight of the vinyl-containing compound.

It is generally preferable to supply HFPO at a rate of 0.02 to 3 mol / hour with respect to 1 mol of the vinyl-containing compound, but the whole amount can be added at once by using a pressure-resistant vessel as the reaction vessel. . The supply amount of HFPO is set according to the molecular weight of the target polymer.

The reaction temperature is -30 to 70 ° C, especially -30 to 30 ° C.
It is preferable to set it in the range. When the reaction temperature is lower than −30 ° C., the reaction does not proceed effectively. When the reaction temperature is higher than 70 ° C., side reactions and the like occur, and it becomes difficult to obtain a target polymer.

In general, after completion of the HFPO supply, the reaction is carried out with stirring for about 1 to 5 hours, and then the reaction mixture is recovered to separate the desired polymer. This separation is
The separation can be performed by a means known per se, such as separation, extraction, or distillation.

In the present invention, instead of the vinyl-containing compound represented by the general formula (2), the following general formula (3):

Embedded image

(Wherein R ¹ and Rf are as described above, and M is a cesium or potassium atom). The vinyl-containing compound represented by the general formula (3) is
In a mixture of the vinyl-containing compound represented by (2) and an aprotic polar organic solvent, 1 mol or more of cesium fluoride or potassium fluoride is added to 1 mol of the vinyl-containing compound,
Preferably, the mixture is stirred in an amount of 1.0 to 1.3 mol, and the resulting precipitate is separated to obtain a homogeneous solution.
Therefore, the desired polymer can be obtained by supplying HFPO into this solution under the same conditions as described above and causing the reaction to proceed.

Utility The novel HFPO polymer of the present invention has a vinyl group at one end and a -COF group at the other end. Can be expected. That is, the vinyl group can introduce various functional silicon residues by a hydrosilylation reaction,
It is possible to carry out an addition polymerization reaction. Also, -COF
The group can be linked to various organic groups via an ester or amide bond. Further, the HFPO polymer of the present invention can be dimerized by light irradiation or converted to perfluorovinyl ether by thermal decomposition. Therefore, the novel HFPO polymer of the present invention can be used as an important intermediate material by, for example, producing a novel functional silicon compound containing a HFPO polymerized unit by combining the conversion reactions at both ends as described above. There is expected. Further, according to the present invention, the above-mentioned novel HFPO polymer can be easily produced.

[0026]

EXAMPLE 1 After replacing the inside of a 500 ml three-necked flask equipped with a magnetic stirrer and a thermometer with nitrogen, 65.1 g of dried cesium fluoride and dried tetraglyme were added to the flask.
447g was charged. Next, 45.7 g of 2,2-difluoro-3-butenoic acid fluoride was charged into the flask and stirred at room temperature (about 25 ° C.) for 8 hours. After completion of the stirring, was allowed to precipitate the excess cesium fluoride on standing flask, ¹⁹ F-NM removed by aspiration the supernatant in the flask
Analysis by R confirmed that the supernatant was a tetraglyme solution containing 16% by weight of the following formula: CH ₂ = CHCF ₂ CF ₂ OCs.

Next, after replacing a 1-liter flask equipped with a magnetic stirrer, a thermometer, a gas inlet tube and a cryogenic condenser with nitrogen, 500 g of the above prepared tetraglyme solution was charged. Subsequently, while maintaining the temperature in the flask at 2 ° C., HFPO 1 was introduced from the gas inlet tube.
14 g were fed in portions over 24 hours. After the completion of the HFPO charging, the reaction mixture in the flask was further stirred for 2 hours. After completion of the stirring, the reaction mixture was distilled under reduced pressure to 2 mm.
Under Hg pressure, a fraction (551 g) having a boiling point of 140 ° C. or less was recovered. Since the fraction was separated into two layers, the lower layer liquid was separated and collected. When the weight of the liquid in the lower layer was measured, 140
g. Further, the lower layer is distilled to have a boiling point of 86.0 to 86.5.
GC-MS, ¹ H-N
As a result of analysis by MR, ¹⁹ F-NMR and IR, the following formula was obtained.
(Four) :

[0028]

Embedded image It was confirmed that it was a compound represented by these. The above analysis results are as shown below.

GC-MS 271 (MF) ^{+ 1} H-NMR (based on TMS) 5.9 ppm (m, 3H) ¹⁹ F-NMR (based on CF ₃ COOH) -53.6 ppm (d, 1F,- _{OC F (CF 3) -)} -40.8ppm (s, 2F, = CH-C F 2 -) -10.3ppm (m, 2F, -C F 2 -O-) - 5.7ppm (m, 3F, -C _{F 3) 102.1ppm (s, 1F} , -CO F) · IR: spectrum (see Figure ^{1) 1885cm -1 (C = O} ) 1660cm -1 (C = C)

As a result of analyzing the lower layer, the lower layer was found to be 2,2-difluoro-3-butenoic acid fluoride,
(Five) :

[0031]

Embedded image (Wherein s is an integer of 0 to 4), and a HFPO polymer having a vinyl group at a terminal represented by the following formula (6):

[0032]

Embedded image (In the formula, t is an integer of 1 to 3.)
It was found to be a mixture containing the O polymer. Table 1 shows the results of GC analysis of the abundance ratios of these components.

[0033]

[Table 1]

Example 2 After replacing the inside of a 50 ml three-necked flask equipped with a magnetic stirrer, a thermometer and a gas inlet tube with nitrogen gas, 0.12 g of dried potassium fluoride and 4.2 g of dried tetraglyme were added to the flask. I charged. Next, 5.0 g of 2,2-difluoro-3-butenoic acid fluoride was charged into the flask and mixed. Cool the flask with ice water and adjust the internal temperature to 2 ℃
6.6 g of HFPO was supplied little by little over a period of 13 hours from the gas introduction tube while maintaining the temperature at. After the supply of HFPO was completed, the mixture in the flask was further stirred for 1 hour. After completion of the stirring, the reaction mixture was allowed to cool to room temperature and stood still, and 10.3 g of a liquid separated into a lower layer was recovered. As a result of analyzing the components of the lower layer, the lower layer was found to be 2,2-difluoro-3 as in Example 1.
-Butenoic acid fluoride, an HFPO polymer having a vinyl group at the terminal represented by the above formula (5) (where s is an integer of 1 to 10), and a compound represented by the above formula (6) H
It was found to be a mixture containing an FPO polymer (where t is an integer of 1 to 8). Table 2 shows the results of GC analysis of the abundance ratios of these components.

[0035]

[Table 2]

Example 3 After replacing the inside of a 100 ml three-necked flask equipped with a magnetic stirrer and a thermometer with nitrogen, 9.1 g of dried cesium fluoride and dried tetraglyme were added to the flask.
55.5g was charged. Next, 8.4 g of 2,2-difluoro-3-butenoic acid fluoride was charged into the flask, and the mixture was cooled to room temperature (25%).
(About ° C) for 10 hours. After completion of the stirring, the flask was allowed to stand still to precipitate excess cesium fluoride, and the supernatant in the flask was taken out by suction and subjected to ¹⁹ F-NMR.
As a result, it was confirmed that the supernatant was a tetraglyme solution containing 23% by weight of the following formula: CH ₂ CHCHCF ₂ CF ₂ OCs.

Next, after replacing a 100 ml flask equipped with a magnetic stirrer, a thermometer, a gas inlet tube and a cryogenic condenser with nitrogen, 22.1 g of the tetraglyme solution prepared above was charged. Subsequently, while maintaining the temperature in the flask at −28 ° C., HFPO11.9
g was fed in portions over 21 hours. After the completion of the HFPO charging, the reaction mixture in the flask was further stirred for 2 hours.
After stirring, 32.4 g of the reaction mixture was distilled under reduced pressure to obtain 2
Under a mmHg pressure, a fraction (28.0 g) having a boiling point of 200 ° C. or less was recovered. Since the fraction was separated into two layers, the liquid in the lower layer was separated and collected. The weight of the solution in the lower layer was measured to be 12.1 g. Analysis of the components of the lower layer revealed the following. The average value of the HFPO polymer represented by the above formula (5)
3.6) 90% HFPO polymer represented by the above formula (6) (the average value of t is
4.9) 10%

Example 4 After replacing the inside of a 300 ml three-necked flask equipped with a magnetic stirrer and a thermometer with nitrogen, 14.4 g of dried cesium fluoride and dried tetraglyme were added to the flask.
187g was charged. Next, formula (7):

[0039]

Embedded image

Was charged and stirred at room temperature (about 25 ° C.) for 4 hours. After completion of the stirring, was allowed to precipitate the excess cesium fluoride on standing flask, ¹⁹ F-NM removed by aspiration the supernatant in the flask
When analyzed by R, the supernatant was obtained by the following formula (8):

[0041]

Embedded image Was confirmed to be a tetraglyme solution containing 17% by weight.

Next, after replacing a 300 ml flask equipped with a magnetic stirrer, a thermometer, a gas inlet tube and a cryogenic condenser with nitrogen, 209 g of the above prepared tetraglyme solution was charged. Subsequently, while maintaining the temperature in the flask at 2 ° C, 4.7 g of HFPO
Was fed in portions over 20 hours. After the completion of the HFPO charging, the reaction mixture in the flask was further stirred for 2 hours. After completion of the stirring, the reaction mixture was distilled under reduced pressure to recover a fraction (53.6 g) having a boiling point of 130 ° C. or less under a pressure of 2 mmHg.
Since the fraction was separated into two layers, the liquid in the lower layer was separated and collected. When the weight of the lower layer solution was measured, it was 43.1 g.
Met. Further, the lower layer was distilled under a reduced pressure of 120 mmHg, and the fraction having a boiling point of 103 to 107 ° C was subjected to GC-MS, ¹ H-N
As a result of analysis by MR, ¹⁹ F-NMR and IR, the following formula was obtained.
(9):

[0043]

Embedded image

It was confirmed that the compound was represented by the following formula: The above analysis results are as shown below.

GC-MS 537 (MF) ^{+ 1} H-NMR (based on TMS) 6.0 ppm (m, 3H) ¹⁹ F-NMR (based on CF ₃ COOH) -59.6 ppm (m, 2F,- O-C F -C F -O-) -52.3ppm (s, 1F, -O-C F -C (= O) -) -51.8ppm (s, 2F, CF 3 -C F 2 -) -31.9 ppm (m, 2F, = CH -C F 2 -) - 3.0ppm (m, 11F, C F 3 -, -C F 2 -O-) 103.6ppm (s, 1F, -CO F) · IR: spectrum (See Fig. 2) 1880cm ^-1 (C = O) 1660cm ^-1 (C = C)

Further, as a result of analyzing the lower layer, the lower layer was formed of a compound represented by the above formula (7), the following formula (10):

[0047]

Embedded image

(Wherein, u is an integer of 0 to 5) and a HFPO polymer having a vinyl group at the terminal, and the above formula (6) (where t is an integer of 1 to 5) Was found to be a mixture containing the HFPO polymer represented by Table 3 shows the results of GC analysis of the abundance ratios of these components.

[0049]

[Table 3]

[0050]

Since the novel HFPO polymer of the present invention has a vinyl group at one end and a -COF group at the other end, for example, a novel functional silicon compound containing a HFPO polymerized unit can be produced. As important intermediate raw materials,
Its usefulness is expected. Further, according to the present invention, the above-mentioned novel HFPO polymer can be easily produced.

[Brief description of the drawings]

FIG. 1 is a chart of an infrared absorption spectrum of a hexafluoropropylene polymer of the present invention obtained in Example 1.

FIG. 2 is a chart of an infrared absorption spectrum of a hexafluoropropylene polymer of the present invention obtained in Example 4.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Toshio Takaai 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronics Materials Research Laboratory (58) Field surveyed (Int.Cl. ⁶ , DB name) C07C 59/60 B01J 27/12 C07C 51/367 C08G 65/32 C07B 61/00 300 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] [Claim 1] The following general formula (1): (Wherein, R ¹ is a single bond or an alkylene group having 1 to 10 carbon atoms or a group in which part or all of the hydrogen atoms of the alkylene group are substituted with fluorine atoms, and Rf is a fluorine atom or a carbon atom number. A hexafluoropropylene oxide polymer represented by 1 to 10 perfluoroalkyl groups or perfluoroalkyl ether groups, and n is an integer of 0 or more. 2. Hexafluoropropylene oxide,
The following general formula (2): (Wherein, R ¹ is a single bond or an alkylene group having 1 to 10 carbon atoms or a group in which part or all of the hydrogen atoms of the alkylene group are substituted with fluorine atoms, and Rf is a fluorine atom or a carbon atom number. The method for producing a hexafluoropropylene oxide polymer according to claim 1, wherein a vinyl-containing compound represented by 1 to 10 perfluoroalkyl groups or perfluoroalkyl ether groups is reacted. 3. The method according to claim 2, wherein the reaction is performed in the presence of a catalyst selected from the group consisting of alkali fluoride and quaternary ammonium fluoride. 4. The method according to claim 3, wherein potassium fluoride or cesium fluoride is used as the catalyst. 5. The method according to claim 1, wherein the vinyl-containing compound represented by the general formula (2) is replaced with a compound represented by the following general formula (3): (Wherein, R ¹ and Rf are the are as, M is a cesium or potassium atom.) The method according to claim 2 using containing vinyl compound represented by the.