Fluorine-containing diene compound, fluorine-containing polymer, and methods for producing same

Abstract

The present invention relates to a fluorine-containing diene compound represented by the following formula I, and to a polymer thereof. In the formula, each of R.sup.1 to R.sup.7 is independently a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having a carbon number of 1 to 5 which may be substituted by a fluorine atom, k is 0 or 1, and at least one of R.sup.1 to R.sup.7 is a hydrogen atom. ##STR00001##

Claims

1. A fluorine-containing diene compound represented by the following formula I: ##STR00028## wherein in the formula, each of R.sup.1 to R.sup.3, R.sup.6, and R.sup.7 is independently a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having a carbon number of 1 to 5 which may be substituted by a fluorine atom, each of R.sup.4 and R.sup.5 is independently a hydrogen atom, a chloride atom, or an alkyl group having a carbon number of 1 to 5 which may be substituted by a fluorine atom, k is 0 or 1, and at least one of R.sup.1 to R.sup.7 is a hydrogen atom.

2. The fluorine-containing diene compound according to claim 1, wherein in the formula I, each of R.sup.1 and R.sup.2 is independently a hydrogen atom or a fluorine atom, R.sup.3 is a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and each of R.sup.4 and R.sup.5 is independently a hydrogen atom, a methyl group, or a trifluoromethyl group.

3. A method for producing a fluorine-containing diene compound represented by the following formula I, the method comprising reacting a compound represented by the following formula a with a compound represented by the following formula b in the presence of a base: ##STR00029## wherein in the formulae, each of R.sup.1 to R.sup.7 is independently a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having a carbon number of 1 to 5 which may be substituted by a fluorine atom, k is 0 or 1, and at least one of R.sup.1 to R.sup.7 is a hydrogen atom.

4. The method for producing a fluorine-containing diene compound according to claim 3, wherein the reaction is performed in the presence of a solvent.

5. The method for producing a fluorine-containing diene compound according to claim 3, wherein the base is an aliphatic tertiary amine.

6. The method for producing a fluorine-containing diene compound according to claim 4, wherein the solvent contains at least one of glyme and nitrile.

7. A fluorine-containing polymer obtained by polymerizing a fluorine-containing compound represented by the following formula I′ as a raw material monomer: ##STR00030## wherein in the formula, each of R.sup.11 to R.sup.13, R.sup.16, and R.sup.17 is independently a hydrogen atom, a chlorine atom, a fluorine atom, or a monovalent organic group which may have a heteroatom, each of R.sup.14 and E.sup.15 is independently a hydrogen atom, a chlorine atom, or a monovalent organic group which may have a heteroatom, k is 0 or 1, at least one of R.sup.11 to R.sup.17 is a hydrogen atom, R.sup.11 or R.sup.12 may combine with any one of R.sup.13 to R.sup.17 to form a ring, and R.sup.13 may combine with any one of R.sup.11, R.sup.12 and R.sup.14 to R.sup.17 to form a ring.

8. The fluorine-containing polymer according to claim 7, wherein the fluorine-containing compound represented by the formula I′ is a fluorine-containing diene compound represented by the following formula I: ##STR00031## wherein in the formula, each of R.sup.1 to R.sup.3, R.sup.6, and R.sup.7 is independently a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having a carbon number of 1 to 5 which may be substituted by a fluorine atom, each of R.sup.4 and R.sup.5 is independently a hydrogen atom, a chlorine atom, or an alkyl group having a carbon number of 1 to 5 which may be substituted by a fluorine atom, k is 0 or 1, and at least one of R.sup.1 to R.sup.7 is a hydrogen atom.

9. The fluorine-containing polymer according to claim 8, wherein in formula I, each of R.sup.1 and R.sup.2 is independently a hydrogen atom or a fluorine atom, R.sup.3 is a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and each of R.sup.4 and R.sup.5 is independently a hydrogen atom, a methyl group, or a trifluoromethyl group.

10. A method for producing a fluorine-containing polymer, the method comprising polymerizing a raw material monomer containing a fluorine-containing compound represented by the following formula I′: ##STR00032## wherein in the formula, each of R.sup.11 to R.sup.13, R.sup.16, and R.sup.17 is independently a hydrogen atom, a chlorine atom, a fluorine atom, or a monovalent organic group which may have a heteroatom, each of R.sup.14 and R.sup.12 is independently a hydrogen atom, a chloride atom, or a monovalent organic group which may have a heteroatom, k is 0 or 1, at least one of R.sup.11 to R.sup.17 is a hydrogen atom, R.sup.11 or R.sup.12 may combine with any one of R.sup.13 to R.sup.17 to form a ring, and R.sup.13 may combine with any one of R.sup.11, R.sup.12 and R.sup.14 to R.sup.17 to form a ring.

11. The method for producing a fluorine-containing polymer according to claim 10, wherein the fluorine-containing compound represented by formula I′ is a fluorine-containing diene compound represented by the following formula I: ##STR00033## wherein in the formula, each of R.sup.1 to R.sup.3, R.sup.6, and R.sup.7 is independently a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having a carbon number of 1 to 5 which may be substituted by a fluorine atom, each of R.sup.4 and R.sup.5 is independently a hydrogen atom, a chlorine atom, or an alkyl group having a carbon number of 1 to 5 which may be substituted by a fluorine atom, k is 0 or 1, and at least one of R.sup.1 to R.sup.7 is a hydrogen atom.

12. The method for producing a fluorine-containing polymer according to claim 11, wherein in formula I, each of R.sup.1 and R.sup.2 is independently a hydrogen atom or a fluorine atom, R.sup.3 is a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and each of R.sup.4 and R.sup.5 is independently a hydrogen atom, a methyl group, or a trifluoromethyl group.

Description

EXAMPLES

(1) The present invention is described specifically below by referring to Examples, but the present invention is not limited thereto.

(2) <Evaluation Method>

(3) In this Example, various properties of the synthesized fluorine-containing diene compound and fluorine-containing polymer were measured by the following methods.

(4) <Structural Analysis>

(5) The structures of the obtained compound and polymer were identified by performing .sup.1H-NMR, .sup.13C-NMR and .sup.19F-NMR measurements with a nuclear magnetic resonance apparatus (JNM-AL300 or ECA600) manufactured by JEOL Ltd. or conducting an analysis using two-dimensional NMR of these measurements. The reference materials of .sup.1H-NMR and .sup.19F-NMR chemical shifts are tetramethylsilane and CFCl.sub.3, respectively.

(6) (Weight Average Molecular Weight)

(7) As for the weight average molecular weight of the polymer, the weight average molecular weight in terms of PMMA was determined using a gel permeation chromatography (GPC) measuring apparatus (manufactured by Tosoh Corporation, HLC-8320GPC). As the solvent, ASAHIKLIN AK-225 SEC Grade -1 produced by AGC Inc. was used. As the column, two PLgel 5 μm MIXED-C columns (produced by Polymer Laboratories Ltd.) were used by connecting them in series. The measurement temperature was set to 40° C. As the detector, an evaporative light scattering detector was used.

(8) (Thermal Decomposition Temperature Td)

(9) Using Thermogravimetry/Differential Thermal Analyzer STA7200 (Hitachi High-Tech Science Corporation) by raising the temperature at 10° C./min in dry air or in nitrogen, a 3% weight loss temperature Td (3%) was determined.

(10) (Glass Transition Temperature Tg)

(11) In the measurement of Tg, a DSC apparatus (unit name: Q100, manufactured by TA Instruments, or unit name: DSC 204 F1 Phoenix, manufactured by NETZSCH) was used. The polymer was put in an aluminum-made container for a differential scanning calorimeter (DSC) and after raising the temperature to a temperature higher by at least 30° C. than the measured Tg, cooled to −50° C. at 10° C./min. Subsequently, the polymer was heated to a temperature higher by at least 30° C. than the transition end temperature by raising the temperature at 10° C./min, and a DSC curve was drawn to determine Tg (midpoint glass transition temperature).

(12) The glass transition temperature of the polymers produced in Examples 2-1 to 2-14 and 2-16 was measured using the apparatus manufactured by TA Instruments, and the glass transition temperature of the polymers produced in Examples 2-15 and 2-17 to 2-21 was measured using the apparatus manufactured by NETZSCH.

(13) Abbreviations of the compounds used in Examples are as follows.

(14) (Reagent)

(15) PFAS: perfluoroallyl fluorosulfate (CF.sub.2═CFCF.sub.2OSO.sub.2F)

(16) (Monomer)

(17) FHDAE: CH.sub.2═CHCH.sub.2OCF.sub.2CF═CF.sub.2

(18) 1M-FHDAE: CH.sub.3—CH═CHCH.sub.2OCF.sub.2CF═CF.sub.2

(19) 2M-FHDAE: CH.sub.2═C(CH.sub.3)CH.sub.2OCF.sub.2CF═CF.sub.2

(20) 3M-FHDAE: CH.sub.2═CHCH(CH.sub.3)OCF.sub.2CF═CF.sub.2

(21) 33DFM-FHDAE: CH.sub.2═CHC(CF.sub.3).sub.2OCF.sub.2CF═CF.sub.2

(22) FHBAE: CH.sub.2═CHCH.sub.2CH.sub.2OCF.sub.2CF═CF.sub.2

(23) 44DFM-FHBAE: CH.sub.2═CHCH.sub.2C(CF.sub.3).sub.2OCF.sub.2CF═CF.sub.2

(24) C6FMA: CH.sub.2═C(CH.sub.3)COO(CH.sub.2).sub.2(CF.sub.2).sub.6F

(25) (Radical Initiator)

(26) IPP: diisopropyl peroxydicarbonate

(27) PFBPO: perfluorobenzoyl peroxide (compound represented by the following formula)

(28) ##STR00018##
(Solvent)

(29) HCFC-225cb: CClF.sub.2CF.sub.2CHClF

Example 1-1

Synthesis 1 of FHDAE

(30) Diglyme (13.5 g) dehydrated with molecular sieve 4A, sodium carbonate (1.09 g, 10.3 mmol) and allyl alcohol (9.00 g, 155 mmol) were charged in a nitrogen atmosphere into a 50 mL four-neck round bottom flask equipped with a reflux condenser, a dropping funnel and a thermometer and cooled in ice water while stirring with a stir bar until the internal temperature became 5° C. or lower. While keeping the internal temperature at 15° C. or lower, PFAS (4.50 g, 19.6 mmol) was added dropwise over 15 minutes. The internal temperature at the end of dropwise addition was 2° C. After ice was removed from the ice water bath and the solution was stirred for 5 hours, the internal temperature was 12° C. The reaction yield of FHDAE was determined from the gas chromatograph (GC) analysis of the reaction solution and found to be 65%.

(31) The area ratio of FHDAE to diallyl ether (CH.sub.2═CHCH.sub.2OCH.sub.2CH═CH.sub.2) produced as a by-product was 26:1. The reaction yield was calculated utilizing the sensitivity ratio of gas chromatography peaks determined using FHDAE obtained afterward by distillation purification and using diglyme. The conversion of PFAS was 100%. The same reaction was performed, and the reaction solution was washed with water three times, dried by molecular sieve 4A and after adding 4,4′-bipyridyl, distilled to obtain FHDAE having a boiling point of 45.8° C./26.6 kPa and a GC purity of 99% or more.

(32) .sup.1H-NMR (CDCl.sub.3): δ (ppm) 4.48 (2H), 5.28 (1H), 5.38 (1H), 5.92 (1H).

(33) .sup.19F-NMR (CDCl.sub.3): δ (ppm) −73.7 (2F), −95.3 (1F), −107.4 (1F), −189.4 (1F)

Example 1-2

Synthesis 2 of FHDAE

(34) Tetraglyme (60.8 g) dehydrated with molecular sieve 4A, triethylamine (10.7 g, 106 mmol) and allyl alcohol (6.13 g, 106 mmol) were charged in a nitrogen atmosphere into a 200 mL four-neck round bottom flask equipped with a reflux condenser, a dropping funnel and a thermometer and cooled in ice water while stirring with a stir bar until the internal temperature became 5° C. or lower. While keeping the internal temperature at 10° C. or lower, PFAS (20.3 g, 88.0 mmol) was added dropwise over 30 minutes. The internal temperature at the end of dropwise addition was 7° C. After ice was removed from the ice water bath and the solution was stirred for 5 hours, the internal temperature was 18° C. As a result of GC analysis of the reaction solution, the conversion of PFAS was 100%, and the reaction yield of FHDAE was 71%. Diallyl ether was not produced. The reaction yield was calculated utilizing the sensitivity ratio of gas chromatography peaks determined using FHDAE obtained by distillation purification and using tetraglyme.

Example 1-3

Synthesis 3 of FHDAE

(35) Tetraglyme (60.8 g) dehydrated with molecular sieve 4A, tripropylamine (15.1 g, 106 mmol) and allyl alcohol (6.13 g, 106 mmol) were charged in a nitrogen atmosphere into a 200 mL four-neck round bottom flask equipped with a reflux condenser, a dropping funnel and a thermometer and cooled in ice water while stirring with a stir bar until the internal temperature became 5° C. or lower. While keeping the internal temperature at 10° C. or lower, PFAS (20.3 g, 88.0 mmol) was added dropwise over 25 minutes. The internal temperature at the end of dropwise addition was 8° C. After ice was removed from the ice water bath and the solution was stirred for 1 hour, the internal temperature was 15° C. Subsequently, the reaction was allowed to proceed at room temperature overnight.

(36) The dropping funnel and the reflux condenser were removed, a water bath at room temperature was set to the four-neck flask and the flask was connected to a vacuum pump via a cooling trap cooled with dry ice-ethanol and a cooling trap cooled with liquid nitrogen, and low-boiling-point components were distilled into the cooling trap while stirring. As a result, 13.7 g of FHDAE containing a small amount of tripropylamine was obtained in the cooling trap cooled with dry ice-ethanol. Diallyl ether was not contained. This crude product was treated with 1 N HCl and then washed with water, and FHDAE not containing tripropylamine was thereby obtained with a GC purity of 99.5%. The yield of the target product was 12.2 g, and the isolation yield was 74%.

Example 1-4

Synthesis of 2M-FHDAE

(37) Tetraglyme (182 g) dehydrated with molecular sieve 4A, tripropylamine (45.4 g, 317 mmol) and β-methallyl alcohol (22.8 g, 317 mmol) were charged in a nitrogen atmosphere into a 1 L four-neck round bottom flask equipped with a reflux condenser, a dropping funnel and a thermometer and cooled in ice water while stirring with a stir bar until the internal temperature became 5° C. or lower. While keeping the internal temperature at 10° C. or lower, PFAS (60.8 g, 264 mmol) was added dropwise over 40 minutes. The internal temperature at the end of dropwise addition was 9° C. After ice was removed from the ice water bath and the solution was stirred for 1 hour, the internal temperature was 16° C. Subsequently, the reaction was allowed to proceed at room temperature overnight. As a result of GC analysis of the reaction solution, the conversion of PFAS was 100%, and the reaction yield of 2M-FHDAE was 81%. The reaction yield was calculated utilizing the sensitivity ratio of gas chromatography peaks determined using 2M-FHDAE obtained by distillation purification and using tetraglyme. After the reaction, the reaction solution was washed with water, treated with 1 N HCl, again washed with water, and distilled. As a result, 2M-FHDAE having a boiling point of 52.4° C./16 kPa and a GC purity of 99.5% or more was obtained.

(38) .sup.1H-NMR (CDCl.sub.3): δ (ppm) 1.79 (3H), 4.39 (2H), 4.98 (1H), 5.05 (1H)

(39) .sup.19F-NMR (CDCl.sub.3): δ (ppm) −73.7 (2F), −95.2 (1F), −107.4 (1F), −189.4 (1F)

Example 1-5

Synthesis of 1M-FHDAE

(40) Tetraglyme (60.8 g) dehydrated with molecular sieve 4A, tripropylamine (15.1 g, 106 mmol) and crotyl alcohol (7.62 g, 106 mmol) were charged in a nitrogen atmosphere into a 200 mL four-neck round bottom flask equipped with a reflux condenser, a dropping funnel and a thermometer and cooled in ice water while stirring with a stir bar until the internal temperature became 5° C. or lower. While keeping the internal temperature at 10° C. or lower, PFAS (20.3 g, 88.0 mmol) was added dropwise over 40 minutes. The internal temperature at the end of dropwise addition was 9.8° C. After ice was removed from the ice water bath and the solution was stirred for 1 hour, the internal temperature was 16° C. Subsequently, the reaction was allowed to proceed at room temperature overnight. After the reaction, the reaction solution was washed with water, treated with 1 N HCl, and again washed with water. As a result, 1M-FHDAE having a GC purity of 89% was obtained in a yield of 67%.

(41) .sup.1H-NMR (CDCl.sub.3): δ (ppm) 1.75 (3H), 4.41 (2H), 5.58 (1H), 5.87 (1H)

(42) .sup.19F-NMR (CDCl.sub.3): δ (ppm) −73.5 (2F), −95.5 (1F), −107.5 (1F), −189.2 (1F)

Example 1-6

Synthesis of 3M-FHDAE

(43) Tetraglyme (91.1 g) dehydrated with molecular sieve 4A, triethylamine (16.0 g, 158 mmol) and 1-buten-3-ol (8.57 g, 119 mmol) were charged in a nitrogen atmosphere into a 300 mL four-neck round bottom flask equipped with a reflux condenser, a dropping funnel and a thermometer and cooled in ice water while stirring with a stir bar until the internal temperature became 10° C. or lower. While keeping the internal temperature at 10° C. or lower, PFAS (30.4 g, 6,132 mmol) was added dropwise over 45 minutes. The internal temperature at the end of dropwise addition was 7° C. After ice was removed from the ice water bath 30 minutes after the completion of dropwise addition and the solution was stirred for 30 minutes, the internal temperature was 7° C. Subsequently, the reaction was allowed to proceed at room temperature overnight. When 0.9 g (4 mmol) of PFAS was added and the solution was stirred at room temperature for one day, the conversion of PFAS was 100%.

(44) The dropping funnel and the reflux condenser were removed, a water bath at room temperature was set to the four-neck flask and the flask was connected to a vacuum pump via a cooling trap cooled with dry ice-ethanol and a cooling trap cooled with liquid nitrogen, and low-boiling-point components were distilled into the cooling trap while stirring. After the water bath temperature was kept at room temperature (about 20° C.) for 1 hour, the water bath temperature was raised sequentially to 30° C., 40° C. and 50° C. and kept at each temperature for 30 minutes and at 60° C. for 2 hours. As a result, 21.4 g of 3M-FHDAE containing a small amount of triethylamine was obtained in the dry ice-ethanol cooling trap. This crude product was treated with 1 N HCl and then washed with water, and 3M-FHDAE not containing triethylamine was thereby obtained with a GC purity of 96.9%. The yield of the target product was 15.6 g, and the isolation yield was 65%.

(45) .sup.1H-NMR (CDCl.sub.3): δ (ppm) 1.39 (3H), 4.92 (1H), 5.17 (1H), 5.27 (1H), 5.88 (1H)

(46) .sup.19F-NMR (CDCl.sub.3): δ (ppm) −73.0 (2F), −95.8 (1F), −107.5 (1F), −188.9 (1F)

Example 1-7

Synthesis of 33DFM-FHDAE

(47) Tetraglyme (45.6 g) dehydrated with molecular sieve 4A, tripropylamine (11.4 g, 79.2 mmol) and CH.sub.2═CHC(CF.sub.3).sub.2OH (produced by SYNQUEST LABORATORIES) (15.4 g, 79.2 mmol) were charged in a nitrogen atmosphere into a 200 mL four-neck round bottom flask equipped with a reflux condenser, a dropping funnel and a thermometer and cooled in ice water while stirring with a stir bar until the internal temperature became 5° C. or lower. While keeping the internal temperature at 10° C. or lower, PFAS (15.2 g, 66.0 mmol) was added dropwise over 20 minutes. The internal temperature at the end of dropwise addition was 8° C. The internal temperature lowered to 4° C. after 15 minutes. After ice was removed from the ice water bath and the solution was stirred for 1 hour, the internal temperature was 6° C. Subsequently, the reaction was allowed to proceed at room temperature overnight.

(48) The dropping funnel and the reflux condenser were removed, a water bath at room temperature was set to the four-neck flask and the flask was connected to a vacuum pump via a cooling trap cooled with dry ice-ethanol and a cooling trap cooled with liquid nitrogen, and low-boiling-point components were distilled into the cooling trap while stirring. This crude product was treated with 1 N HCl and then washed with water, and 33DFM-FHDAE (boiling point: 52° C./13.3 kPa) not containing tripropylamine was thereby obtained with a GC purity of 98.6%. The yield of the target product was 13.9 g, and the isolation yield was 65%.

(49) .sup.1H-NMR (CDCl.sub.3): δ (ppm) 5.88, 5.92, 5.95, 6.01 (total 2H), 6.09 to 6.23 (1H)

(50) .sup.19F-NMR (CDCl.sub.3): δ (ppm) −65.3 (2F), −74.3 (6F), −93.2 (1F), −105.8 (1F), −189.5 (1F)

Example 1-8

Synthesis of FHBAE

(51) Tetraglyme (45.6 g) dehydrated with molecular sieve 4A, triethylamine (8.02 g, 79.2 mmol) and 3-buten-1-ol (4.28 g, 59.4 mmol) were charged in a nitrogen atmosphere into a 200 mL four-neck round bottom flask equipped with a reflux condenser, a dropping funnel and a thermometer and cooled in ice water while stirring with a stir bar until the internal temperature became 5° C. or lower. While keeping the internal temperature at 10° C. or lower, PFAS (15.2 g, 66.0 mmol) was added dropwise over 30 minutes. The internal temperature at the end of dropwise addition was 6° C. After ice was removed from the ice water bath 15 minutes after the completion of dropwise addition and the solution was stirred for 45 minutes, the internal temperature was 9° C. Subsequently, the reaction was allowed to proceed at room temperature overnight. As a result of GC analysis of the reaction solution, the conversion of PFAS was 100%.

(52) The dropping funnel and the reflux condenser were removed, a water bath at room temperature was set to the four-neck flask and the flask was connected to a vacuum pump via a cooling trap cooled with dry ice-ethanol and a cooling trap cooled with liquid nitrogen, and low-boiling-point components were distilled into the cooling trap while stirring. After the water bath temperature was kept at room temperature (about 20° C.) for 1 hour, the water bath temperature was raised sequentially to 30° C., 40° C. and 50° C. and kept at each temperature for 30 minutes and at 60° C. for 2 hours. As a result, 10.9 g of FHBAE containing a small amount of triethylamine was obtained in the dry ice-ethanol cooling trap. This crude product was treated with 1 N HCl and then washed with water, and FHBAE not containing triethylamine was thereby obtained with a GC purity of 99.0%. The yield of the target product was 7.6 g, and the isolation yield was 64%.

(53) .sup.1H-NMR (CDCl.sub.3): δ (ppm) 2.44 (2H), 4.02 (2H), 5.13 (2H), 5.79 (1H)

(54) .sup.19F-NMR (CDCl.sub.3): δ (ppm) −73.9 (2F), −95.4 (2F), −107.4 (1F), −189.4 (1F)

Example 1-9

Synthesis of 44DFM-FHBAE

(55) Tetraglyme (136.7 g) dehydrated with molecular sieve 4A, triethylamine (24.1 g, 238 mmol) and 1,1-bis(trifluoromethyl)-3-buten-1-ol (37.1 g, 178 mmol) were charged in a nitrogen atmosphere into a 500 mL four-neck round bottom flask equipped with a reflux condenser, a dropping funnel and a thermometer and cooled in ice water while stirring with a stir bar until the internal temperature became 5° C. or lower. While keeping the internal temperature at 10° C. or lower, PFAS (45.6 g, 198 mmol) was added dropwise over 1 hour. Ice was removed from the ice water bath 30 minutes after the completion of dropwise addition, and the solution was continuously stirred at room temperature overnight. As a result of GC analysis of the reaction solution, the conversion of PFAS was 100%.

(56) The dropping funnel and the reflux condenser were removed, a water bath at room temperature was set to the four-neck flask and the flask was connected to a vacuum pump via a cooling trap cooled with dry ice-ethanol and a cooling trap cooled with liquid nitrogen, and low-boiling-point components were distilled into the cooling trap while stirring. The water bath temperature was kept at room temperature for 2 hours, then raised to 40° C., and kept for 2 hours. As a result, 60.1 g of 44DFM-FHBAE containing a small amount of triethylamine was obtained in the dry ice-ethanol cooling trap. This crude product was treated with 1 N HCl and then washed with 3.0 N brine. The lower layer was separated and collected, and 44DFM-FHBAE not containing triethylamine was thereby obtained with a GC purity of 97.9%. The yield of the target product was 53.7 g, and the isolation yield was 90%.

(57) After distillation under reduced pressure, a target product having a purity of 99.5% or more was obtained in a distillation yield of 68%. The boiling point was 59° C./6.7 kPa.

(58) .sup.1H-NMR (CDCl.sub.3): δ (ppm) 3.11 (2H), 5.30 (2H), 5.83 (1H)

(59) .sup.19F-NMR (CDCl.sub.3): δ (ppm) −66.3 (2F), −73.8 (6F), −93.2 (1F), −105.5 (1F), −189.6 (1F)

Example 2-1

Synthesis of 2M-FHDAE Polymer

(60) 2M-FHDAE (6.00 g) was charged into a hastelloy-made autoclave having an internal volume of 120 mL. Isopropyl alcohol (0.93 g) that had been 10-fold diluted with HCFC-225cb was added, a solution obtained by 200-fold diluting IPP (48 mg) with HCFC-225cb was then added, and finally, HCFC-225cb was added to make the total amount of HCFC-225cb charged 53.02 g.

(61) After repeating freeze-pump-thaw degassing twice using liquid nitrogen, the temperature was returned to about 0° C., and a nitrogen gas was introduced until reaching 0.3 MPaG (G indicates gauge pressure). The autoclave was set in a water bath and after stirring for 6 hours while keeping the internal temperature at 40° C., the autoclave was immersed in ice water and cooled to 20° C. or lower.

(62) The reaction solution was moved from the autoclave to a beaker and combined with a washing solution using HCFC-225cb to make the total amount of contents 104 g and after stirring for 30 minutes, 126 g of n-hexane was added, followed by further stirring for 30 minutes. After filtration under reduced pressure, ethyl acetate was added to the obtained solid matter to make a total amount of 58 g. After stirring for 30 minutes, the polymer was coagulated by the addition of 126 g of n-hexane and filtered under reduced pressure. The same operation using ethyl acetate and n-hexane was repeated once more.

(63) The resulting polymer was vacuum-dried overnight at 60° C. to obtain 4.72 g of a white polymer. The weight average molecular weight was 40,100, Td (3%) in air was 316° C., Td (3%) in nitrogen was 415° C., and Tg was 176° C.

(64) From the analyses using .sup.1H-,.sup.13C- and .sup.19F-NMRs and their two-dimensional NMRs, the obtained polymer was confirmed to be a homopolymer composed of a repeating unit shown below.

(65) ##STR00019##

Examples 2-2 to 2-10

Syntheses 2 to 10 of 2M-FHDAE Polymer

(66) Polymerization of 2M-FHDAE polymer was performed in the same manner as in Example 2-1 except that the preparation conditions in Example 2-1 were changed to the conditions shown in Table 1. The polymer yield, weight average molecular weight, thermal decomposition initiation temperature and glass transition temperature obtained are also shown in Table 1.

(67) The polymer of Example 2-6 dissolved in all of tetrahydrofuran, ethyl acetate, acetone, dichloromethane and perfluorobenzene at a polymer concentration of 3 mass %.

(68) TABLE-US-00001 TABLE 1 Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 Internal volume of reactor/cm.sup.3 120 120 120 120 120 120 120 120 34 34 2M-FHDAE/g 6 6 6 6 6 6 6 6 5 5 IPP/mg 48 24 24 24 24 24 24 24 60 20 Molecular Isopropyl alcohol/g 0.93 0.93 0.47 0.23 — — — — — — weight Methanol/g — — — — — 0.93 — — 0.093 0.31 adjusting n-Hexane/g — — — — — — 0.93 — — — agent Monoglyme/g — — — — — — — 0.93 — — HCFC-225cb/g 53.02 53.04 53.51 53.74 53.98 53.04 53.04 53.04 14.85 14.67 Reaction temperature/° C. 40 40 40 40 40 40 40 40 45 40 Reaction time/hrs 6 6 6 6 6 6 6 6 6 3 Polymer yield/g 4.72 3.27 4.41 5.05 5.6 5.05 3.86 4.64 4.69 3.49 Weight average molecular 40,100 81,000 130,900 208,300 456,900 290,500 275,300 259,900 205,700 485,200 weight Td(3%), in air/° C. 316 316 315 298 283 322 313 297 304 307 Td(3%), in nitrogen/° C. 415 420 425 420 404 403 425 410 414 not measured Tg/° C. 176 186 186 187 163 184 187 169 183 182
(Measurement of Absorption Spectrum)

(69) The polymer of Example 2-6 was dissolved at a concentration of 10 mass % in a mixed solvent of ethyl acetate and propylene glycol monomethyl ether acetate (in this order, mass ratio: 4:1). The solution was cast at room temperature using a PFA petri dish, left standing overnight, dried at 60° C. for 2 hours, then annealed at 220° C. for 30 minutes, and further hot-pressed at 220° C. to obtain a colorless transparent film with a smooth surface having a thickness of about 100 μm. The absorption spectrum of 200 to 1,700 nm was measured using UV-3100 manufactured by Shimadzu Corporation, as a result, absorption was not observed at 400 to 1,700 nm.

(70) (Measurement of Refractive Index)

(71) With respect to the above film of Example 2-6, the refractive indices of the film for light having a wavelength of 473 nm, 594 nm and 658 nm were measured using a refractometer (manufactured by U.S. Metricon, prism coupler: 2010/M), and the refractive index for light having a wavelength of 589 nm was calculated using Metricon Fit attached to the device. As a result, the refractive index was 1.41 (589 nm).

(72) (Measurement of Abbe's Number)

(73) With respect to the above film of Example 2-6, the refractive indices at a wavelength of 486 nm, 589 nm and 656 nm were calculated using Metricon Fit attached to the device, and the Abbe's number was calculated according to the following formula (I). As a result, the Abbe's number was 57.26.
ν.sub.D=(n.sub.D−1)/(n.sub.F-n.sub.C)  (I)
ν.sub.D is the Abbe's number, n.sub.D is the refractive index for light having a wavelength of 589 nm, n.sub.F is the refractive index for light having a wavelength of 486 nm, and n.sub.C is the refractive index for light having a wavelength of 656 nm.

Example 2-11

Synthesis (1) of Low-Molecular-Weight 2M-FHDAE Polymer

(74) 2M-FHDAE (3.00 g) was charged into a hastelloy-made autoclave having an internal volume of 120 mL. Isopropyl alcohol (3.73 g) was added, a solution obtained by 20-fold diluting 1PP (38 mg) with HCFC-225cb was then added, and finally, HCFC-225cb was added to make the total amount of HCFC-225cb charged 52.89 g. Thereafter, polymerization and post-treatment were performed in the same manner as in Example 2-1 to obtain 1.44 g of a white polymer. The weight average molecular weight was 7,400, Td (3%) in air was 307° C., and Tg was 154° C.

Example 2-12

Synthesis of Low-Molecular-Weight 2M-FHDAE Polymer and End Stabilization (2)

(75) 2M-FHDAE (3.00 g) was charged into a hastelloy-made autoclave having an internal volume of 120 mL. CF.sub.3(CF.sub.2).sub.3-I (6.44 g) was added, a solution obtained by 200-fold diluting IPP (38 mg) with HCFC-225cb was then added, and finally, HCFC-225cb was added to make the total amount of HCFC-225cb charged 50.52 g. Thereafter, polymerization and post-treatment were performed in the same manner as in Example 2-1 to obtain 2.15 g of a white polymer. The weight average molecular weight was 12,200, Td (3%) in air was 296° C., and Tg was 157° C.

(76) Next, the end group was stabilized as follows in accordance with the method described in International Publication WO2017/086465.

(77) 1.35 g of the obtained polymer was dissolved in HCFC-225cb (40.00 g) and charged into a hastelloy-made autoclave having an internal volume of 120 mL. Subsequently, a mixed solution of IPP (38 mg), HCFC-225cb (5.50 g) and n-hexane (0.675 g) was added, and HCFC-225cb was further added to make the total amount of the solution charged 67.50 g.

(78) After repeating freeze-pump-thaw degassing twice using liquid nitrogen, the temperature was returned to about 0° C., and a nitrogen gas was introduced until reaching 0.3 MPaG. The autoclave was set in a water bath and after stirring for 7 hours while keeping the internal temperature at 70° C., the autoclave was allowed to cool.

(79) The contents were moved to an eggplant flask together with a washing solution using HCFC225cb and concentrated on an evaporator until the weight of contents became 27.0 g. After coagulation by n-hexane and filtration, HCFC225cb was added to the obtained solid matter to make a total amount of 27 g, and the solid matter was dissolved with stirring. This operation of coagulation, filtration and dissolution was repeated and thereafter, the polymer was coagulated by n-hexane and vacuum-dried at 60° C. for 18 hours. The weight of the obtained white polymer was 1.22 g. When .sup.19F-NMR was measured by dissolving the polymer in perfluorobenzene, peaks based on —CF2-I at −40 to −50 ppm of the polymer ends, which were observed before the treatment with IPP/n-hexane, disappeared.

Example 2-13

Synthesis of 2M-FHDAE Polymer

(80) 2M-FHDAE (6.00 g) was charged into a hastelloy-made autoclave having an internal volume of 120 mL. A solution obtained by 400-fold diluting IPP (24 mg) with ethyl acetate was then added, and finally, ethyl acetate was added to make the total amount of ethyl acetate charged 53.98 g.

(81) After repeating freeze-pump-thaw degassing twice using liquid nitrogen, the temperature was returned to about 0° C., and a nitrogen gas was introduced until reaching 0.3 MPaG. The autoclave was set in a water bath and after stirring for 6 hours while keeping the internal temperature at 40° C., the autoclave was immersed in ice water and cooled to 20° C. or lower.

(82) The reaction solution was moved from the autoclave to a beaker and combined with a washing solution of ethyl acetate to make the total amount of contents 70 g. After stirring for 30 minutes, 153 g of n-hexane was added, followed by further stirring for 30 minutes. After filtration under reduced pressure, ethyl acetate was added to the obtained solid matter to make a total amount of 70 g. After stirring for 30 minutes, the polymer was coagulated by the addition of 153 g of n-hexane and filtered under reduced pressure. The same operation using ethyl acetate and n-hexane was repeated once more.

(83) The resulting polymer was vacuum-dried overnight at 60° C. to obtain 5.05 g of a white polymer. The weight average molecular weight was 62,200, Td (3%) in air was 304° C., Td (3%) in nitrogen was 386° C., and Tg was 188° C.

Example 2-14

Synthesis of FHDAE Polymer

(84) FHDAE (3.00 g) was added to a 50 ml three-neck flask containing a stir bar, isopropyl alcohol (0.47 g) that had been 10-fold diluted with HCFC-225cb was added, a solution obtained by 100-fold diluting IPP (96 mg) with HCFC-225cb was then added, and finally, HCFC-225cb was added to make the total amount of HCFC-225cb charged 26.44 g.

(85) After attaching a Dimroth condenser and repeating freeze-pump-thaw degassing twice using liquid nitrogen, the temperature was returned to about 0° C., and a nitrogen gas was introduced into the system. The contents were stirred for 6 hours by heating the system at 40° C. in a nitrogen-sealed state and after cooling in ice water, moved to a beaker. The total amount of the contents combined with a washing solution of HCFC-225cb was 52 g.

(86) After stirring for 30 minutes, 63 g of n-hexane was added, and the contents were further stirred for 30 minutes. After filtration under reduced pressure, ethyl acetate was then added to make a total amount of 41 g followed by stirring for 30 minutes. 88 g of n-hexane was added, and stirring for 30 minutes and then filtration under reduced pressure were performed. The same operation using ethyl acetate and n-hexane was repeated once more.

(87) The resulting polymer was vacuum-dried overnight at 60° C. to obtain 2.21 g of a white polymer. The thermal decomposition temperature Td (3%) in air of the obtained polymer was 301° C. This polymer dissolved in acetone at a concentration of 0.5 mass %.

(88) The obtained polymer contains a repeating unit shown below.

(89) ##STR00020##

Example 2-15

Synthesis of 3M-FHDAE Polymer

(90) 3M-FHDAE (6.00 g) was charged into a hastelloy-made autoclave having an internal volume of 120 mL. A solution obtained by 100-fold diluting IPP (120 mg) with HCFC-225cb was added, and finally, HCFC-225cb was added to make the total amount of HCFC-225cb charged 53.88 g. Thereafter, polymerization was performed in the same manner as in Example 2-1 except that the polymerization temperature was changed to 45° C. The contents were moved to a beaker, and a washing solution of HCFC-225cb was added thereto. The total amount was 115 g. After stirring for 30 minutes, the polymer was coagulated by the addition of 172 g of methanol, stirred for 30 minutes, and filtered. The obtained polymer was dissolved in 93 g of HCFC-225cb, and the polymer was coagulated by 142 g of methanol and filtered. The same operation was repeated once more, and the polymer was vacuum-dried for 16 hours at 60° C. to obtain 5.17 g of a white polymer. The weight average molecular weight was 54,800, Td (3%) in air was 352° C., Td (3%) in nitrogen was 405° C., and Tg was 103° C.

(91) The obtained polymer contains a repeating unit shown below.

(92) ##STR00021##

Example 2-16

Synthesis of 33DFM-FHDAE Polymer

(93) 33DFM-FHDAE (3.00 g) was charged into a hastelloy-made autoclave having an internal volume of 30 mL. A solution obtained by 40-fold diluting PFBPO (75 mg) with HCFC-225cb was added, and finally, HCFC-225cb was added to make the total amount of HCFC-225cb charged 11.93 g.

(94) After repeating freeze-pump-thaw degassing twice using liquid nitrogen, the temperature was returned to about 0° C., and a nitrogen gas was introduced until reaching 0.3 MPaG. The autoclave was set in an oil bath and after stirring for 6 hours while keeping the internal temperature at 80° C., the autoclave was immersed in ice water and cooled to 20° C. or lower. The obtained reaction solution was a colorless transparent liquid.

(95) The reaction solution was moved from the autoclave to a beaker, and 17.5 g of n-hexane was added while stirring, followed by further stirring for 30 minutes. After filtration under reduced pressure, HCFC-225cb was added to the obtained solid matter to make a total amount of 29 g. After stirring for 30 minutes, the polymer was coagulated by the addition of 38 g of n-hexane and filtered under reduced pressure. The same operation using HCFC-225cb and n-hexane was repeated once more.

(96) The polymer was vacuum-dried for 32 hours at 60° C. to obtain 2.78 g of a white polymer. The weight average molecular weight was 20,300, Td (3%) in air was 389° C., and Tg was 119° C.

(97) The obtained polymer contains a repeating unit shown below.

(98) ##STR00022##

Example 2-17

Synthesis of FHBAE Polymer

(99) FHBAE (6.00 g) was charged into a hastelloy-made autoclave having an internal volume of 120 mL. A solution obtained by 100-fold diluting IPP (120 mg) with HCFC-225cb was added, and finally, HCFC-225cb was added to make the total amount of HCFC-225cb charged 53.88 g. Thereafter, polymerization and post-treatment were performed in the same manner as in Example 2-1 except that the polymerization temperature was changed to 45° C. As a result, 2.4 g of a white polymer was obtained. The weight average molecular weight was 10,300, Td (3%) in air was 323° C., Td (3%) in nitrogen was 372° C., and Tg was 124° C. The obtained polymer dissolved in HCFC-225cb and acetone.

(100) The obtained polymer contains a repeating unit shown below.

(101) ##STR00023##

Example 2-18

Synthesis of 44DFM-FHBAE Polymer

(102) 44DFM-FHBAE (6.00 g) was charged into a hastelloy-made autoclave having an internal volume of 120 mL. A solution obtained by 400-fold diluting IPP (24 mg) with HCFC-225cb was added, and finally, HCFC-225cb was added to make the total amount of HCFC-225cb charged 53.98 g. Thereafter, polymerization and post-treatment were performed in the same manner as in Example 2-1 to obtain 5.01 g of a white polymer. The weight average molecular weight was 318,200, Td (3%) in air was 369° C., Td (3%) in nitrogen was 433° C., and Tg was 145.5° C. The obtained polymer dissolved in acetone, tetrahydrofuran and HCFC-225cb.

(103) The obtained polymer contains a repeating unit shown below.

(104) ##STR00024##

Example 2-19

Synthesis of Copolymer of FHDAE and 2M-FHDAE

(105) 2.30 g (12.2 mmol) of FHDAE and 3.70 g (18.3 mmol) of 2M-FHDAE were charged into a hastelloy-made autoclave having an internal volume of 120 mL. Isopropyl alcohol (0.466 g) that had been 20-fold diluted with HCFC-225cb was added, a solution obtained by 100-fold diluting IPP (24 mg) with HCFC-225cb was added, and finally, HCFC-225cb was added to make the total amount of HCFC-225cb charged 53.51 g. Thereafter, polymerization was performed in the same manner as in Example 2-1. The contents were moved to a beaker, and a washing solution of HCFC-225cb was added thereto. The total amount was 95 g. 20 g of ethyl acetate as a good solvent was added thereto, and the contents were stirred for 30 minutes. The polymer was coagulated by the addition of 139 g of n-hexane, stirred for 30 minutes, and filtered. After that, the obtained solid matter was dissolved in 39 g of ethyl acetate while stirring, and the polymer was coagulated by 86 g of n-hexane and filtered. The operation of dissolving in ethyl acetate and coagulating by n-hexane was repeated once more and after filtration, the polymer was vacuum-dried for 16 hours at 60° C. to obtain 3.38 g of a white polymer. The weight average molecular weight was 95,300, Td (3%) in air was 303° C., Td (3%) in nitrogen was 423° C., and Tg was 166° C.

(106) The obtained polymer contains repeating units shown below.

(107) ##STR00025##

Example 2-20

Synthesis of Copolymer of 2M-FHDAE and C6FMA

(108) 4.85 g (24.0 mmol) of 2M-FHDAE and 1.15 g (2.67 mmol) of C6FMA were charged into a hastelloy-made autoclave having an internal volume of 120 mL. A solution obtained by 100-fold diluting IPP (120 mg) with HCFC-225cb was added, and finally, HCFC-225cb was added to make the total amount of HCFC-225cb charged 53.88 g. Thereafter, polymerization was performed in the same manner as in Example 2-1. The contents were moved to a beaker, and a washing solution of HCFC-225cb was added thereto. The total amount was 108 g. After stirring for 30 minutes, the polymer was coagulated by the addition of 166 g of methanol, stirred for 30 minutes, and filtered. The obtained polymer was dissolved in 43 g of HCFC-225cb, and the polymer was coagulated by 66 g of methanol and filtered. The same operation was repeated once more, and the polymer was then vacuum-dried for 16 hours at room temperature to obtain 0.78 g of a white polymer. The weight average molecular weight was 21,200, Td (3%) in air was 267° C., Td (3%) in nitrogen was 292° C., and Tg was 66° C. .sup.19F-NMR was measured by dissolving the polymer in perfluorobenzene. As a result, the ratio of 2M-FHDAE and C6FMA repeating units was 57:43.

(109) The obtained polymer contains repeating units shown below.

(110) ##STR00026##

Example 2-21

Synthesis of Copolymer of 2M-FHDAE and (Perfluorohexyl)ethylene

(111) 2.21 g (10.9 mmol) of 2M-FHDAE and 3.79 g (10.9 mmol) of (perfluorohexyl)ethylene were charged into a hastelloy-made autoclave having an internal volume of 120 mL. A solution obtained by 100-fold diluting IPP (120 mg) with HCFC-225cb was added, and finally, HCFC-225cb was added to make the total amount of HCFC-225cb charged 53.88 g. Thereafter, polymerization was performed in the same manner as in Example 2-1 except that the polymerization temperature was changed to 45° C. The contents were moved to a beaker, and a washing solution of HCFC-225cb was added thereto. The total amount was 108 g. After stirring for 30 minutes, the polymer was coagulated by the addition of 134 g of n-hexane, stirred for 30 minutes, and filtered. The obtained polymer was dissolved in 68 g of HCFC-225cb, and the polymer was coagulated by 88 g of n-hexane and filtered. The same operation was repeated once more, and the polymer was then vacuum-dried for 24 hours at 60° C. to obtain 1.84 g of a white polymer. Td (3%) in air was 289° C., Td (3%) in nitrogen was 387° C., and Tg was 142° C. .sup.19F-NMR was measured by dissolving the polymer in perfluorobenzene. As a result, the ratio of 2M-FHDAE and (perfluorohexyl)ethylene repeating units was 84:16.

(112) The obtained polymer contains repeating units shown below.

(113) ##STR00027##

(114) While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. This application is based on a Japanese patent application filed on Dec. 26, 2017 (Application No. 2017-249732), the contents of which are incorporated herein by reference.

INDUSTRIAL APPLICABILITY

(115) In the present invention, a novel fluorine-containing diene compound is provided, and a novel fluorine-containing polymer obtained from a fluorine-containing compound such as the fluorine-containing diene compound as a raw material monomer is expected to be utilized in a wide variety of fields such as optical material, electronic material, etc.