JP5036198B2 - Phthalimides containing fluorene skeleton and diamines derived therefrom - Google Patents

Description

  The present invention relates to fluorene skeleton-containing phthalimides that are useful as raw materials for fluorene skeleton-containing diamines that are useful as raw materials for polyamides and polyimides, and diamines derived therefrom.

  A polymer compound derived from a monomer having a fluorene skeleton has a cardo skeleton that increases the free volume, and since it exhibits unique properties such as gas permeability and gas selective separation, it has recently been developed. Is energetically advanced. For example, in polyamides and polyimides, those derived from diamines having a fluorene skeleton have been proposed, but there are not so many kinds of diamines used for such purposes because of manufacturing limitations. As such a diamine, for example, 9,9-bis (aminophenyl) fluorenes having two aminophenyl groups are known (Patent Document 1). As a diamine having an aliphatic amino group at the 9,9-position, 9,9-bis (aminopropyl) fluorene represented by the following formula (5) is known (Patent Document 2, Non-Patent Document 1). .

９，９−位に脂肪族アミノ基を有するジアミンとしては他に、ポリイミドの製造において、下記一般式（６）

In addition to the diamine having an aliphatic amino group at the 9,9-position, in the production of polyimide, the following general formula (6)

で示されるジメチル化された９，９−ビス（アミノメチル）フルオレンを使用したという例が示されているが（特許文献３）、このジアミンの製法や物性については全く明らかにされていない。

Although the example of using the dimethylated 9,9-bis (aminomethyl) fluorene shown by this is shown (patent document 3), the manufacturing method and physical property of this diamine are not clarified at all.

Japanese Patent Laid-Open No. 5-31341 US Patent No. 2320029 US Pat. No. 6,531,569 Journal of Applied Polymer Science Vol. 9, 3949 (1965)

  It is an object of the present invention to produce polyamides and polyimides having a fluorene having an aliphatic amino group at the 9,9-position with the smallest number of carbon atoms in the aliphatic amino group and thus being more rigid and excellent in heat resistance. Another object of the present invention is to provide a diamine and its production method, as well as its raw material and its production method.

で表されるフルオレン骨格含有フタルイミド類（式中、Ａは、水素、ハロゲン又は炭素数１〜３のアルコキシ基であり、Ｂは、水素、アルキル基、アリール基又はアルコキシ基である）が提供される。 That is, according to the present invention, the following general formula (1)

(Wherein A is hydrogen, halogen or an alkoxy group having 1 to 3 carbon atoms, and B is hydrogen, an alkyl group, an aryl group or an alkoxy group). The

で表されるフルオレン骨格含有ジアミン類（式中、Ａは、水素、ハロゲン又は炭素数１〜３のアルコキシ基である）が提供される。 According to the present invention, the following general formula (2)

A fluorene skeleton-containing diamine represented by the formula (wherein A is hydrogen, halogen, or an alkoxy group having 1 to 3 carbon atoms) is provided.

で表されるフルオレン骨格含有ビスメチル化合物類（式中、Ａは、水素、ハロゲン又は炭素数１〜３のアルコキシ基であり、Ｘは脱離基のメシルオキシ基である）と下記一般式（４） Furthermore, according to the present invention, the following general formula (3)

A fluorene skeleton-containing bismethyl compound represented by the formula (wherein A is hydrogen, halogen or an alkoxy group having 1 to 3 carbon atoms, and X is a mesyloxy group of a leaving group) and the following general formula (4)

で表されるフタルイミド塩（式中、Ｂは水素、アルキル基、アリール基又はアルコキシ基であり、Ｙはアルカリ金属又は１，８−ジアゾビシクロ［５，４，０］ウンデ−セン−７である）を反応させることを特徴とする上記一般式（１）で表されるフルオレン骨格含有フタルイミド類の製造方法が提供される。

(Wherein B is hydrogen, an alkyl group, an aryl group or an alkoxy group, and Y is an alkali metal or 1,8-diazobicyclo [5,4,0] undecene-7) ) Is reacted, and a method for producing a fluorene skeleton-containing phthalimide represented by the general formula (1) is provided.

  According to the present invention, the fluorene skeleton-containing diamine represented by the general formula (2) is characterized by reacting the fluorene skeleton-containing phthalimides represented by the general formula (1) with hydrazines. A manufacturing method is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the fluorene frame | skeleton containing diamine useful as a raw material of polyamide and a polyimide, and its economical manufacturing method can be provided. The present invention can also provide a raw material useful for the production of the fluorene skeleton-containing diamine and an economical production method thereof.

  The fluorene skeleton-containing phthalimide represented by the general formula (1) is useful as a raw material for producing the fluorene skeleton-containing diamine represented by the general formula (2), which is useful as a raw material for polyamide and polyimide. In the general formula (1), A represents hydrogen; halogen, for example, fluorine, chlorine, bromine, iodine, etc .; or an alkoxy group having 1 to 3 carbon atoms, for example, methoxy group, ethoxy group, propoxy group, etc. Two A's may be the same or different. B represents hydrogen; an alkyl group such as a methyl group, an ethyl group, or an isopropyl group; an aryl group such as a phenyl group or a tolyl group; or an alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group. Two Bs may be the same or different. In view of easy availability of raw materials and low cost production, it is preferable that both B are hydrogen.

The fluorene skeleton-containing phthalimides represented by the general formula (1) are reacted with the fluorene skeleton-containing bismethyl compounds represented by the general formula (3) and the phthalimide salt represented by the general formula (4). Obtainable. In general formula (3), A is the same as A in general formula (1). The leaving group X in the general formula (3), mesyloxy _{(CH 3} SO 2 O-), tosyloxy _{(p- (CH 3) C 6} H 4 SO 2 O-), triflate oxy _(CF 3 _SO 2 O- ), chloromethane sulfonate oxy _{(ClCH 2} SO ₂ O-), and the like smell element. Of these, mesyloxy, tosyloxy, triflateoxy, or chloromethanesulfonateoxy is preferable, and mesyloxy is preferable because it can be synthesized at low cost. These fluorene skeleton-containing bismethyl compounds are, for example, mesyl chloride, tosyl chloride, chlorine gas, oxy-oxygen in the presence of a base such as triethylamine or pyridine in a dichloromethane solvent and having a hydroxymethyl group at the 9,9-position. It can be produced by reacting phosphorus chloride or the like. Examples of the phthalimide salt represented by the general formula (4) include sodium, potassium, 1,8-diazobicyclo [5,4,0] undecene-7, and phthalimide salts. Preferred phthalimide salts are potassium phthalimide and sodium phthalimide, particularly preferred is potassium phthalimide.

  In the reaction of the fluorene skeleton-containing bismethyl compounds and the phthalimide salt, the latter is preferably used in an amount of about 2 to 10 mol with respect to 1 mol of the former. The reaction is preferably carried out in the presence of a solvent and a catalyst. Examples of the solvent include aprotic polar solvents such as N, N-dimethylformamide, or aromatic solvents such as toluene and xylene. It is particularly preferable to use an aprotic polar solvent. A solvent is used about 1-30 mass times of fluorene skeleton containing bismethyl compounds, for example. As the catalyst, a phase transfer catalyst can be used. Specific examples of the phase transfer catalyst include phosphonium compounds, quaternary ammonium compounds, pyridinium compounds, crown ethers, and the like, preferably phosphonium compounds that can be used at high temperatures. The usage-amount of a catalyst is a ratio of 0.001-0.5 mol with respect to 1 mol of fluorene skeleton containing bismethyl compounds, for example.

  The above reaction is generally performed in the range of 50 to 200 ° C. The reaction time is in the range of 0.1 to 100 hours, although it varies depending on the type of raw material and reaction temperature. After completion of the reaction, the fluorene skeleton-containing phthalimide represented by the general formula (1) can be isolated by removing by-products generated by the elimination reaction, such as potassium methanesulfonate, and washing as necessary. Furthermore, if necessary, crude fluorene skeleton-containing phthalimides can be purified by recrystallization or chromatography.

  In the fluorene skeleton-containing diamines represented by the general formula (2), those in which both A are hydrogen are used as raw materials for producing polyamides and polyimides having excellent heat resistance, gas permeability, gas selective separation, and mechanical strength. Useful. In general formula (2), the diamine in which at least one of A is a halogen or an alkoxy group is itself a polyamide or polyimide excellent in heat resistance, gas permeability, gas selective separation, mechanical strength, solubility, etc. In addition to being expected as a production raw material, it can be used as a raw material by which a new diamine can be produced by changing the reactivity of A to other substituents.

  The fluorene skeleton-containing diamines are a method of heating the fluorene skeleton-containing phthalimides represented by the general formula (1) with an acid, a method of alkali hydrolysis, a treatment with an acid, a method of reacting with hydrazines, After the treatment with sodium borohydride, it can be produced by a method of heating with acetic acid. Of these, the method of reacting with hydrazines is most preferable. Examples of hydrazines that can be used for the reaction with fluorene skeleton-containing phthalimides include hydrazine, hydrazine hydrate, and methyl hydrazine. The amount of hydrazine used is 2 to 20 mol, preferably 2.5 to 15 mol, per mol of fluorene skeleton-containing phthalimide. It is preferable to use a solvent in this reaction. Suitable solvents include, for example, alcohols such as ethanol, ethers such as tetrahydrofuran and dimethoxyethane, or a mixed solvent of these organic solvents and water. A solvent is 1-50 mass times normally with respect to fluorene frame | skeleton containing phthalimides, Preferably it is used in the ratio of 2-30 mass times.

  The reaction of the fluorene skeleton-containing phthalimides and hydrazines is usually performed at a temperature of 40 to 150 ° C, preferably 60 to 120 ° C. The reaction time is about 0.1 to 30 hours. After completion of the reaction, crude fluorene skeleton-containing diamines can be obtained by removing phthalic hydrazides by-produced from the reaction mixture, and then washing as necessary. If necessary, the crude fluorene skeleton-containing diamines can be purified by recrystallization, distillation, chromatography, or recrystallization by forming a salt with an acid, followed by treatment with a base to release the diamine.

Hereinafter, the present invention will be described in more detail with reference to examples. The analysis in Reference Example and Example 1 was performed by high performance liquid chromatography under the following conditions.
Measurement conditions Column: Inertsil ODS-2 150 mm length, 4.6 mm inner diameter
Column temperature: 40 ° C
Eluent: acetonitrile / water = 65/35
Detector: UV (254 nm)

[Reference Example] Synthesis of 9,9-bis (mesyloxymethyl) fluorene In a 50 ml three-necked flask equipped with a calcium chloride tube, 0.98 g (4.33) of 9,9-bis (hydroxymethyl) fluorene (manufactured by Aldrich). Mmol), 20 ml dichloromethane and 1.35 g (13.34 mmol) triethylamine in 2 ml dichloromethane. To this solution, a solution of 1.3 g (11.35 mmol) of methanesulfonyl chloride in 2 ml of dichloromethane was added dropwise over 20 minutes with cooling. The temperature change during this period was −2.8 ° C. to −0.8 ° C. After dropping, the mixture was stirred for 8.75 hours. The obtained reaction liquid was filtered and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (dichloromethane). The obtained yellow powder was washed with methanol to obtain white 9,9-bis (mesyloxymethyl) fluorene powder (yield 82%). The purity (area percentage) determined by high performance liquid chromatography was 99.84%. The ¹ H-NMR spectrum of this product is shown in FIG.
¹ H-NMR (CDCl ₃ ): δ (ppm) 3.00 (s, 6H, CH ₃ ), 4.45 (s, 4H, CH ₂ ), 7.34-7.80 (m, 8H, ArH )
It was confirmed that a methyl group (3.00 ppm), a methylene group (4.45 ppm), and an aromatic ring (7.34-7.80 ppm) were present.

Example 1 Synthesis of 9,9-bis (phthalimidomethyl) fluorene In a 100 ml three-necked flask under nitrogen atmosphere, 1.38 g (3.61 mmol) of 9,9-bis (mesyloxymethyl) fluorene and N, N -13 ml of dimethylformamide was added. To this solution, 1.70 g (9.18 mmol) of phthalimide potassium salt was charged, and the resulting suspension was heated and stirred for 21 hours. During the heating and stirring, the temperature was raised to 139.4 ° C. Further, 6 ml of N, N-dimethylformamide, 1.21 g (6.53 mmol) of phthalimide potassium salt and 0.37 g (0.73 mmol) of tributylhexadecylphosphonium bromide were added during heating and stirring. After the reaction, the reaction solution was cooled to room temperature, and 40 ml of toluene was added and stirred. Subsequently, the powder obtained by filtering this was washed 3 times with 10 ml of toluene. Dichloromethane was added to the remaining white powder, stirred, and filtered. By distilling off the solvent of the filtrate, 1.03 g (yield 57.1%) of white powdery 9,9-bis (phthalimidomethyl) fluorene having a melting point of 296 ° C. was obtained. The purity (area percentage) determined by high performance liquid chromatography was 99.76%. The ¹ H-NMR spectrum of this product is shown in FIG. 2, and the ¹³ C-NMR spectrum is shown in FIG.

¹ H-NMR spectrum (CDCl ₃ ): δ (ppm) 4.36 (s, 4H, CH ₂ ), 7.26-7.70 (m, 16H, ArH)
It was confirmed that a methylene group (4.36 ppm) and an aromatic ring (7.26-7.70 ppm) were present.
¹³ C-NMR spectrum (CDCl ₃ ): δ (ppm) 43.5, 56.3, 119.3, 123.0, 125.8, 126.3, 128.0, 131.3, 133.5, 140.4, 143.8, 167.4
Carbon bonded to the nitrogen atom of the imide group (43.5 ppm), quaternary carbon at the 9-position (56.3 ppm), carbon bonded to a hydrogen atom of the fluorene ring (119.3 ppm, 125.8-128.0 ppm), Carbon to which hydrogen atoms of the benzene ring of phthalimide are bonded (123.0 ppm, 133.5 ppm), carbon to which a carbonyl group of the benzene ring of phthalimide is bonded (131.3 ppm), carbon forming a five-membered ring of fluorene ring (140 .4 ppm, 143.8 ppm), the presence of imide carbon (167.4 ppm) was confirmed.

Identification by LC / MS was performed under the following conditions.
Apparatus: LCMS-2010 manufactured by Shimadzu Corporation
Column: Inertsil ODS-80A (length 150 mm, inner diameter 2.1 mm)
Acetonitrile: water = 75: 25, flow rate: 0.2 ml / min, column temperature: 40 ° C., ionization method ESI
MS: 485 (M + H) ⁺ , 507 (M + Na) ⁺ , 548 (M + CH ₃ CN + Na) ⁺

Example 2 Synthesis of 9,9-bis (aminomethyl) fluorene In a 100 ml three-necked flask, 3.02 g (6.23 mmol) of 9,9-bis (phthalimidomethyl) fluorene and 10 ml of ethanol were placed under a nitrogen atmosphere. At reflux. To this suspension was added dropwise a solution of 0.90 g (18.0 mmol) of hydrazine monohydrate in 5 ml of ethanol over 7 minutes, and then refluxing was continued for 3 hours. During the reflux, 25 ml of ethanol and 2.91 g (58.1 mmol) of hydrazine monohydrate were added. Under cooling, 40 ml of 4.5% hydrochloric acid was added to adjust the pH to 1.35. The temperature change during addition of 4.5% hydrochloric acid was −1.5 to + 1.5 ° C. This suspension was heated to reflux for 30 minutes. The reaction solution was filtered to remove white powder, and the filtrate was concentrated and dried at 40 ° C. under reduced pressure to obtain a white yellow powder. To this was added 10 ml of ethanol and heated, and the ethanol layer was separated by decantation. Further, ethanol (5 ml × 5) was added, and decantation was repeated in the same manner. Crystals precipitated from the obtained ethanol layer were removed by filtration. The filtrate was concentrated under reduced pressure, and ethanol was distilled off to obtain a white yellow powder. 25 ml of water was added and dissolved therein, and insoluble components were removed by filtration. To the filtrate, a 23% aqueous potassium hydroxide solution was added under cooling to pH 10.3, and 15 ml of toluene was added. This was extracted once with 20 ml of chloroform and 5 times with 10 ml. Insoluble components of the extract were removed by filtration. After the filtrate was dehydrated with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. Chloroform 15 ml was added to a part of the residue, insoluble components were separated by filtration, and purified by column chromatography (chloroform / methanol / 25% aqueous ammonia = 90/9/2) to obtain 9,9- 0.276 g of bis (aminomethyl) fluorene was obtained. The purity (area percentage) determined by high performance liquid chromatography was 99.34%.

The analysis in Example 2 was performed by high performance liquid chromatography under the following conditions.
Measurement conditions Column: Inertsil ODS-2 150 mm length, 4.6 mm inner diameter
Eluent: 0.1-15 minutes 0.1% phosphoric acid water / methanol = 50/50
15-30 minutes 0.1% phosphoric acid water / methanol = 10/90
Detector: UV (254 nm)
The identification by GC / MS was performed under the following conditions.
GC device: GC-17A + QP-5000 manufactured by Shimadzu Corporation
Column: CBP-1 inner diameter 0.2mm, length 50m
Column temperature: 200 ° C. to 300 ° C. Temperature increase rate: 10 ° C./min MS 224 (M +), 208, 195, 178, 165, 151

The ¹ H-NMR spectrum of this product is shown in FIG. 4, the ¹³ C-NMR spectrum is shown in FIG. 5, and the IR spectrum is shown in FIG.
¹ H-NMR spectrum (CDCl ₃ ): δ (ppm) 0.69 (s, 4H, NH ₂ ), 3.19 (s, 4H, CH ₂ ), 7.27-7.75 (m, 8H, ArH)
It was confirmed that an amino group (0.69 ppm), a methylene group (3.19 ppm), and an aromatic ring (7.27-7.75 ppm) were present.

¹³ C-NMR spectrum (CDCl ₃ ): δ (ppm) 48.3, 61.0, 120.0, 122.9, 127.4, 127.7, 142.1, 146.5
Presence of carbon to which an amino group was bonded (48.3 ppm), quaternary carbon at position 9 (61.0 ppm), and aromatic ring carbon (120.0-146.5 ppm) was confirmed.

IR spectrum (reflection ATR): 3385 to 3196 cm ⁻¹ (NH stretching), 3062 cm ⁻¹ (= CH stretching), 2915,2860 cm ⁻¹ (CH stretching), 1960 to 1811 cm ⁻¹ (aromatic ring), 1606 cm ⁻¹ ( NH out-of-plane variable angle), 1221, 1113 cm ⁻¹ (ArH out-of-plane variable angle), 877 cm ⁻¹ (NH ₂ out-of-plane variable angle), 766,737 cm ⁻¹ (ArH out-of-plane variable angle)
The presence of amino group, methylene group and aromatic ring was confirmed.

[Example 3] Synthesis of 9,9-bis (aminomethyl) fluorene In a 100 ml three-necked flask, 3.04 g (6.27 mmol) of 9,9-bis (phthalimidomethyl) fluorene and 50 ml of ethanol were placed under a nitrogen atmosphere. At reflux. To this suspension, a solution of 4.64 g (74.2 mmol) of 80% hydrazine monohydrate in 10 ml of ethanol was added dropwise over 15 minutes, followed by refluxing for 4.4 hours. The reaction solution was cooled to room temperature and filtered, and the filtrate (white powder, phthalic acid hydrazide as a main component) was rinsed once with 25 ml of ethanol and twice with 50 ml, and the filtrate and the rinse solution were combined. Since some turbidity was observed in this liquid, it was filtered to obtain a clean liquid. The filtrate was concentrated to dryness under reduced pressure to obtain 1.68 g of a white yellow viscous product. When the content of 9,9-bis (aminomethyl) fluorene was determined by high performance liquid chromatography absolute calibration curve method, it was 82.4% by mass, and the yield relative to 9,9-bis (phthalimidomethyl) fluorene charged. Was 98.4%.

^{1 is} a ¹ H-NMR spectrum of 9,9-bis (mesyloxymethyl) fluorene obtained in Reference Example. 2 is a ¹ H-NMR spectrum of 9,9-bis (phthalimidomethyl) fluorene obtained in Example 1. FIG. 2 is a ¹³ C-NMR spectrum of 9,9-bis (phthalimidomethyl) fluorene obtained in Example 1. FIG. 2 is a ¹ H-NMR spectrum of 9,9-bis (aminomethyl) fluorene obtained in Example 2. FIG. 3 is a ¹³ C-NMR spectrum of 9,9-bis (aminomethyl) fluorene obtained in Example 2. FIG. 3 is an IR spectrum of 9,9-bis (aminomethyl) fluorene obtained in Example 2.

Claims (4)

The following general formula (1)

(Wherein, A is hydrogen, halogen or an alkoxy group having 1 to 3 carbon atoms, and B is hydrogen, an alkyl group, an aryl group or an alkoxy group). The following general formula (2)

The fluorene skeleton containing diamine represented by these (In formula, A is hydrogen, a halogen, or a C1-C3 alkoxy group). The following general formula (3)

A fluorene skeleton-containing bismethyl compound represented by the formula (wherein A is hydrogen, halogen or an alkoxy group having 1 to 3 carbon atoms, and X is a mesyloxy group of a leaving group) and the following general formula (4)

(Wherein B is hydrogen, an alkyl group, an aryl group or an alkoxy group, and Y is an alkali metal or 1,8-diazobicyclo [5,4,0] undecene-7) The method for producing a fluorene skeleton-containing phthalimide according to claim 1, wherein:   The method for producing a fluorene skeleton-containing diamine according to claim 2, wherein the fluorene skeleton-containing phthalimides according to claim 1 are reacted with hydrazines.

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