JP3075588B2 - Fluorine-containing compound 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 novel fluorine-containing compound and a method for producing the same.

[0002]

2. Description of the Related Art The fluorine-containing compound of the present invention is a novel fluorine-containing dioxole compound not described in any literature.

[0003] Fluorine-containing dioxole compounds include U
Compounds represented by the following formula (3) or (4) according to SP 3,865,845, USP 4,429,143, etc.
It has been known. However, in the formulas (3) and (4) , R ¹ and R ² are each independently a perhaloalkyl group having 1 to 3 carbon atoms, and Y ¹ , Y ² and Y ³ are each independently a fluorine atom or
A chlorine atom, and R ^f Is a perfluoroalkyl group having 1 to 4 carbon atoms .

[0004]

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Further, the fluorine-containing dioxole compounds, homopolymers or it is known that non-crystalline fluoropolymer by copolymerizing a fluoroolefin such as can be obtained. However, highly fluorinated,
Dioxol compounds having a spiro ring containing O are not known.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a fluorine-containing compound represented by the following formula (1) which has not been known before.
It is intended to be newly provided. However, in equation (1)
X and Y independently represent a fluorine atom, a hydrogen atom or a salt
And n is 2 or 3.

[0007]

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[0008]

Means for Solving the Problems The present invention provides the following formula (1)
And a fluorine-containing compound represented by the formula: Also, the following equation
The fluorine-containing compound represented by (2) and a dehalogenating agent
Characterized by reacting, represented by the following formula (1)
Provided is a method for producing a fluorine-containing compound. However, equation (1)
And in the formula ( 2 ), X and Y independently represent a fluorine atom,
A hydrogen atom or a chlorine atom, and n is 2 or 3.

[0009]

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The novel fluorine-containing compound of the present invention is effective as a monomer for homopolymerization or as a comonomer for synthesizing a fluorine-containing polymer. Further, a polymer obtained by polymerizing the novel fluorine-containing compound of the present invention,
In order to dissolve in a specific solvent, cast molding, coating and the like are possible in addition to molding methods such as melt molding. Further, the novel fluorine-containing compound of the present invention has an advantage that potting polymerization is possible.

The novel fluorine-containing compound of the present invention is cut at manufacturing by a method shown below.

[0012]

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That is, perfluoro (2-methyl-3-oxacyclohexanone) [where n = 3 in the formula (A)]
] To adding ethylene oxide and passes the after photochlorination, partially fluorinated, it is possible to obtain a fluorine-containing compound by dechlorination.

The raw material perfluoro (2-methyl-3-o)
Xacyclohexanone) IsCan be obtained in various ways
It is not particularly limited. For example, JP-A-54-112
No. 869, molecular sieve 4A
Is a fixed bed, and 250 ° C. to 400 ° C., preferably 300 ° C.
Perfluoro at ℃ ~ 350 ℃B (2-methyl-3-oxa
HeptaNggioIl)DifluoLido [FCOCF (CF
_Three ) O (CF _Two ) _Three COF]By thermal decomposition
It can be easily obtained.

In addition, perfluoro (2-methyl-3-oxacyclopentanone) [ where n = 2 in the formula (A)]
Of] is obtained by the F CO CF ₂ COOCH ₃ was synthesized in USP4,608,206 manner by adding hexafluoropropylene <br/> Oki shea de, pyrolysis.

[0016] (A) → addition reaction of ethylene oxide and pass the (B) are, for example, by the method described USP3,324,144, and potassium iodide, water and catalyst 100 ° C. to 150 DEG
C, preferably at 120C to 130C.

The photochlorination reaction (B) → (C) is carried out, for example, by a method described in US Pat.
It can be carried out at 0 ° C, preferably at 50 ° C to 80 ° C.
Furthermore, by where by controlling the chlorine supply amount, it is possible to obtain different compounds degree of chlorination.

[0018] (C) → fluorination reaction of (D) is, SbF _3, for example, USP3,865,845 described methods, Sb
Cl _5, using a suitable solvent (e.g., perfluoro (2-butyl tetrahydrofuran)) in, or in no solvent, 50 ° C. to 200 DEG ° C., preferably from 100 ° C. to 150 DEG
C. can be performed. In the case of producing a compound of the present invention in which neither X nor Y is a fluorine atom , this fluorination reaction is omitted.

The dechlorination reaction (D) → (E) is carried out, for example, by the method described in US Pat.
Using l ₂ and I ₂ , tetrahydrofuran (THF)
Medium, it can be performed at 50 ° C to 70 ° C.

In the compound of the present invention, X and Y are both
A compound which is a chlorine atom can be obtained by omitting the fluorination reaction from (C) to (D) in the above reaction step. In addition, the dechlorination reaction is performed using Zn, ZnCl ₂
Can be used in propanol.

Compounds wherein X is a chlorine atom and Y is a hydrogen atom
及 beauty X, compound Y are both hydrogen atoms, (B) →
In the photochlorination reaction (C), the compound represented by the formula (5) or (6) is synthesized by controlling the supply amount of chlorine, and then dechlorination is performed in propanol using Zn and ZnCl _2. It can be synthesized by performing a chemical reaction.

[0022] X is fluorine atom, Y is compound <br/> compound 及 beauty X is a chlorine atom is hydrogen atom, compound Y is a fluorine atom,
In the fluorination reaction of (C) → (D), a compound represented by the formula (7) is synthesized by controlling fluorination,
Next, it can be synthesized by performing a dechlorination reaction in propanol using Zn and ZnCl ₂ .

[0023]

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[0024]

The novel fluorine-containing compound of the present invention is polymerized singly regardless of the type of isomer due to the presence of optically active carbon,
Alternatively, by copolymerizing with another comonomer, an amorphous transparent fluoropolymer having a cyclic structure in the main chain can be provided. These monomers have high boiling points, are possible potting polymerization, their homopolymers and copolymers of both, special solvents, for example soluble in perfluoro (2-butyl tetrahydrofuran).

[0025]

EXAMPLES Reference Example 1 0.75 g of potassium iodide was placed in a 200 ml autoclave.
(4.52 mmol), 0.2 g of water (11.1 mmol)
l) is charged and vacuum degassed. 128.5 g of perfluoro (2-methyl-3-oxacyclohexanone) (437
mmol), ethylene oxide and pass 25g (567mmo
1) is introduced and kept at 120 to 130 ° C. using an oil bath. The pressure gradually decreases with the progress together with the reaction. About 1
Two hours later, the reaction was terminated when no pressure drop was observed. Vacuum distillation was performed, and a fraction of 50.8 ° C./12 mmHg was collected. The isolation yield was 76%.

Reference Example 2 In a 500 ml flask equipped with a stirrer, a reflux condenser, a chlorine gas injection tube, and a thermocouple thermometer, 2, 2, 3, 3
-Tetrahydro-perfluoro (6-methyl-1,4,4)
7-Trioxa-spiro [4 . 5] Decane)
Chlorine gas introduction was started at 0 ° C., and the temperature was gradually raised and kept constant at 80 ° C. The reaction was terminated when the chlorine was no longer consumed. Yield 98%. The following reaction was performed without purification.

Reference Example 3 Antimony trifluoride 195.3 was placed in a 1-liter three-necked flask equipped with a stirrer, a reflux condenser and a thermocouple thermometer.
0 g (1.09 mol), antimony pentachloride 50.0 g
(0.167 mol) and 100 ml of perfluoro ( 2-butyltetrahydrofuran ) ,
3,3 tetrachloro - perfluoro B (6-methyl -
1,4,7-Trioxa-spiro [4 . 5] Decane) 4
84 g (1.01 mol) was added, and reflux was continued for 32 hours. In these conditions the objective 2,3-dichloro - Per <br/> fluoride B (6-methyl-1,4,7-trioxa - spiro [. 4 5] decane) only was selectively obtained. After cooling to room temperature, the supernatant was collected by decantation, and a fraction at 62 ° C. at 18 mmHg was collected by vacuum distillation. The isolation yield was 87.4%.

EXAMPLE 13.4 g (551 mmol) of magnesium powder and 2.3 g of iodine were placed in a 1-liter four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermocouple thermometer.
(9.1 mmol), 0.6 g of mercuric chloride (2.21)
mmol) and 350 ml of tetrahydrofuran, and heated using a mantle heater. Refluxing stopped heating Once begun, 2,3-dichloro - perfluoro B (6-methyl-1,4,7-trioxa - spiro [. 4 5] decane) was slowly added dropwise. If necessary, cool the reaction vessel due to vigorous heat generation. After completion of the dropwise addition, the pressure in the reaction vessel is reduced, and tetrahydrofuran and a product are collected by a liquid nitrogen trap.

The collected matter was poured into cold water, and the lower fluorocarbon layer was separated.
A 9.5 ° C. fraction was collected. Perf <br/> Luo B having a purity of 98% - give (6-methyl-1,4,7-trioxa-spiro [4 5.] Dec-2-ene) and. 9.2% isolation yield
Met.

[0030]

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[0031] _{^{19 F-NMR (CDCl 3,}} δppm) F a: -157.77 (d, J (F a -F b) = 52.9Hz) F b: -158.34 (d, J (F a ^{-F b) = 52.9Hz) F c} : -79.78 (s) F d: -133.92~-134.03 (m) F e: -91.49~-92.02 (m) F ^{f: -77.97~-78.57 (m)} F g: -141.32~-142.16 (m) F h: -126.50~-127.38 (m) F i: -136. ^{70~-137.58 (m) F j} : -124.17~-125.08 (m)

[0032] Polymerization Example perfluoro - (6-methyl-1,4,7-trioxa - spiro [. 4 5] dec-2-ene) 3.7 g, perfluoro (2-butyl tetrahydrofuran) 7 g and the polymerization initiator 0.16 g of a 5% solution of (C ₃ F ₇ COO) ₂ in trichlorotrifluoroethane was placed in a pressure-resistant glass ampoule having an internal volume of 50 ml. After the system was frozen and degassed three times, it was shaken in a water bath at 30 ° C. for 18 hours. The obtained solution was diluted with trichlorotrifluoroethane, poured into acetone, and the precipitate was dried under vacuum at 100 ° C. for 20 hours. As a result, 1.4 g of a polymer was obtained.

From the measurement by thermogravimetric analysis, the starting temperature for weight loss of this polymer was 338 ° C., and the temperature for 10% weight loss was 4%.
38 ° C. After dissolving in perfluoro (2-butyltetrahydrofuran) to prepare a solution, the film obtained by casting on a glass plate was measured for refractive index using an Abbe refractometer and found to be 1.33. Further, the glass transition temperature was observed at 300 ° C. by viscoelasticity measurement. The intrinsic viscosity was 1.42 dl / g in perfluoro (2-butyltetrahydrofuran) at 30 ° C.

[0034]

The novel fluorine-containing compound of the present invention is easily homopolymerized or copolymerized with tetrafluoroethylene, and has the effect of obtaining a polymer having a high glass transition temperature and a low refractive index.

Claims (4)

(57) [Claims] 1. A fluorine-containing compound represented by the following formula (1) .
However, in the formula (1), X and Y are each independently a fluorine atom.
A hydrogen atom or a chlorine atom, and n is 2 or 3.
You. Embedded image Wherein where X and Y are both fluorine atoms, the fluorine-containing compound of claim 1 wherein n is 3. 3. A method comprising reacting a fluorine-containing compound represented by the following formula (2) with a dehalogenating agent:
A method for producing a fluorine-containing compound represented by the formula (1). However,
In the formulas (1) and ( 2 ) , X and Y are independently
A nitrogen atom, a hydrogen atom or a chlorine atom, and n is 2 or
3. Embedded image Wherein where X and Y are both fluorine atoms, method according to claim 3 wherein n is 3.