JPH0331321A - Aromatic diamine and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (Y is single bond, -S-, -SO2-, -CO-, 1-10C alkylene or aralkylene; R is H or 1-5C alkyl; n is <=20). EXAMPLE:A compound expressed by formula II. USE:A raw material for polyamide, polyimide, polyamide-imide resins, etc., and curing agent for urethane compounds, epoxy compounds, etc. PREPARATION:A compound expressed by formula III (X is F, Cl or Br) is reacted with a compound expressed by formula IV (M is alkali metal) in an organic polar solvent and converted into a compound expressed by formula V. Both terminal halogen groups thereof are then converted into aminophenoxy groups expressed by formula VI.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an aromatic diamine having a polyarylene alkylene ether structure and a method for producing the same. Aromatic diamine compounds are compounds useful as monomers for polymeric materials, such as raw materials for polyamide, polyimide, and polyamideimide resins, or as curing agents for urethane compounds, epoxy compounds, and the like.

[Conventional technology and issues]

Many attempts have been made to produce aromatic diamine compounds, and some unique products have been provided.
For example, one produced by reacting bisphenol-A and dichlorodiphenyl sulfone in the presence of potassium carbonate and then reacting with aminophenol (Japanese Unexamined Patent Publication No. 80-15
420), or by reacting bisphenol-A and caustic soda to form sodium phenolate, reacting it with dichlorodiphenyl sulfone, and then carrying out an esterification reaction using nitrobenzoic acid to reduce the nitro group. Diamine compounds obtained (Japanese Patent Laid-Open No. 63-250350) and the like are known. However, this is not sufficient to expand the field of application of polymeric materials, and there is a need for monomer materials with even newer skeleton structures.

Therefore, the present invention provides a diamine that has a skeleton structure composed of an alternating copolymer of xylylene civalide and bisphenols and is useful as a monomer for polymeric materials, which can be applied to such new application fields, and the production thereof. It seeks to provide law.

The skeleton structure of the conventionally known diamine compound is composed of an alternating copolymer of bisphenol-A and dihalodiphenylsulfone or dihalobenzophenone, and is different from that of the present invention.

[Means to solve the problem]

The present inventors conducted intensive studies to achieve the above object, and as a result, discovered the following novel aromatic diamine and its manufacturing method, and completed the present invention.

That is, one aspect of the present invention is to provide a novel diamine represented by the following general formula (1).

(However, in the above formula (1), Y is a single bond, -3--so, -
-co- or represents an alkylene group or aralkylene group having 1 to 10 carbon atoms, and R is hydrogen or
~5 alkyl group, n is a number of 20 or less. ) Another aspect of the present invention is to provide a method for producing a novel aromatic diamine represented by the following general formula (1). That is, the manufacturing method involves reacting a compound represented by the following general formula (2) with a compound represented by the following general formula (3) in an organic polar solvent to convert it into a compound represented by the following general formula (4). and then converting the halogen groups at both ends into aminophenoxy groups.

(However, in the above formula (1), Y is a single bond, -5--SO2-
1-〇〇- or represents an alkylene group or an aralkylene group having 1 to 10 carbon atoms, R represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n is a number of 20 or less.

) x-co2+CH,-X (2) (However, in the above formula (2), X represents F, C1, Br.) RR (However, in the above formula (3), M represents an alkali metal, and Y
and R are the same as those in formula (1) above. )RR (However, in the above formula (4), Y, R and n are the above formula (・1
) and X are the same as those in formula (2) above.

) In order to produce the diamine compound of the present invention, the above formula (2
) and the compound represented by the above formula (3) are reacted in an organic polar solvent to synthesize the dihalogen compound represented by the above formula (4).

Examples of the organic polar solvent used here include dimethylsulfone, diethylsulfone, dimethylsulfoxide, diethylsulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, N,N'-dimethylimidazolidinone, and the like.

The reaction temperature is generally preferably in the range of 50°C to 250°C, more preferably in the range of 80°C to 230°C.

If the temperature is too low, the reaction rate is slow, and in extreme cases there is no reaction at all; on the other hand, if the temperature is too high, no particular advantage is observed by increasing the temperature.

The molar ratio of compound (2) and compound (3) is not particularly limited, but is usually 1.0 to 5.0:1. When the molar ratio of compound (2) is less than 1.0, the amount of terminal hydroxyl groups increases and the yield of the dihalogen compound decreases, and when it is more than 5.0, the amount of remaining compound (2) increases, which is disadvantageous. I can't escape it.

The method of charging the raw materials may be -batch charging, and the compound (2
) may be divided and charged either way, but preferably the method is to divide and charge compound (2).

The produced dihalogen compound (4) is isolated by cooling the reaction mixture, separating the precipitated alkali metal halide by a method such as filtration, and concentrating the resulting liquid as necessary, or adding methanol or the like. This can be achieved by adding a solid to precipitate. The purity of the obtained solid can be improved by dissolving it in a polar solvent again and then reprecipitating it.

The dihalogen compound (4) is then converted into the compound represented by the general formula (1), and the method is not limited to this, and many known methods can be used.6 For example, aminophenol is converted into an alkali. Induction into metal phenolate and dihalogenation in polar solvent? ! By reacting with J(4), a diamine compound represented by general formula (1) can be obtained.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 3.3',5.5'-tetramethyl-4,
4'-biphenol 12.1g (0.05 mol), sodium hydroxide 4.3g (0.1 mol assuming 95% purity)
, diethyl sulfoxide 150effi, toluene 50
mf was charged, and the resulting water was stirred at 124° C. for 5 hours while distilling off the water as an azeotrope with toluene to synthesize sodium phenolate.

Next, 8.3 g of m-xylylene dichloride (0,055
mol) dissolved in 50 si of dimethyl sulfoxide was added, and the mixture was reacted at 126°C for 7 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium chloride was separated from P, and 400 ml of methanol was added to the obtained furnace liquid.
A solid was precipitated by adding . The generated slurry is filtered, and the resulting solids are collected until the pH of the washing solution is 6 to 7.
After repeated washing with water until the temperature reached 100° C., it was dried at 60 to 70° C. under vacuum. The yield was 16.21F.

300 affi 4 with thermometer, water separator with Dimroth cooling tube, nitrogen inlet tube, and stirrer with Teflon blades.
In a double flask, add 1.09 g of p-aminophenol (0.
, 01 mol), sodium hydroxide 0.43 g (purity 95
%), dimethyl sulfoxide and the resulting water was distilled off as an azeotrope with toluene while stirring at 121'C for 5 hours to synthesize sodium phenolate.

After cooling, a solution of the previously obtained dihalide 14.8y in 50 ml of dimethyl sulfoxide was added, and 12.
The reaction was carried out at 5°C for 7 hours.

After the reaction mixture was cooled to room temperature, the precipitated sodium chloride was separated in a furnace, and 300 mf of methanol was added to the obtained furnace liquid to precipitate a solid substance. The resulting slurry was filtered, and the resulting solid was repeatedly washed with water until the pH of the washing solution became 6 to 7, and then dried under vacuum at 60 to 70°C to obtain yellow crystals. The yield was 13.6y.

The IR1'H-NMR spectrum measured for this product is shown in Figures 1 and 2, and the ratio of the 10 tons of aliphatic groups, aromatic groups, and amino groups in the 'H-NMR spectrum is shown below. It was determined that the compound was

n=6.4 Example 2 4.4'-biphenol 9.3 was added to a 500@1 four-bottle flask equipped with a thermometer, a water separator with a Dimroth condenser, a nitrogen inlet tube, and a stirrer with Teflon blades. g<0.
05 mol), sodium hydroxide 4.3 g (0.1 mol assuming 95% purity), dimethyl sulfoxide 150+*l
, 50 ml of toluene was charged, and the resulting water was stirred at 122° C. for 5 hours while distilling off the water as an azeotrope with toluene to synthesize sodium phenolate. Then m-
A solution of 8.3 g (0,055 mol) of xylylene dichloride dissolved in 50+sl of dimethyl sulfoxide was added, and 1
The reaction was carried out at 26°C for 7 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium chloride was separated from P, and 400 esl of methanol was added to the obtained furnace liquid.
A solid was precipitated by adding . The generated slurry is filtered, and the resulting solids are collected until the pH of the washing solution is 6 to 7.
After repeated washing with water until the temperature reached 100° C., it was dried at 60 to 70° C. under vacuum. Yield was 14.5g.

A thermometer, a water separator with a Dimroth condenser, a nitrogen inlet tube, a 300 ml four-loaf flask with a Teflon-bladed stirrer, and 1.09 g of p-aminophenol (0,
01 mole), sodium hydroxide 0.43 g (purity 95%
(0.01 mol), dimethyl sulfoxide 50ef
, 25-l of toluene was charged, and while the produced water was distilled off as an azeotropic mixture with toluene, the mixture was stirred at 124°C for 5 hours to synthesize sodium phenolate.

After cooling, a solution of 12.6 g of the dihalide obtained earlier in 50 mf of dimethyl sulfoxide was added,
The reaction was carried out at 5°C for 7 hours.

After the reaction mixture was cooled to room temperature, the precipitated sodium chloride was separated, and 300 ml of methanol was added to the obtained r liquid to precipitate a solid substance. The resulting slurry was washed with water until the pH of the washing solution reached 6 to 7, and then dried under vacuum at 60 to 70°C to obtain yellow crystals. Yield was 11.5g.

The I R, 'H-NMR spectrum measured for this product is shown in Figures 3 and 4. From the ratio of the proton numbers of aliphatic groups, aromatic groups, and amino groups in the 'H-NMR spectrum, the following is obtained. It was determined that the compound shown is

Example 3 Into a fourth 500 liter flask equipped with a thermometer, a water separator with a Dimroth condenser, a nitrogen inlet tube, and a stirrer with Teflon blades, 10.911 (0.0 , 05 mol), sodium hydroxide 4.39 (0.1 mol as purity 95%), and dimethyl sulfoxidone 50 ml, and stirred at 125°C for 5 hours while distilling off the produced water as an azeotrope with toluene. and synthesized sodium phenolate. Next, a solution of 8.3 g (0.05 mol) of m-xylylene dichloride dissolved in 50 mf of dimethyl sulfoxide was added, and the mixture was heated at 123°C.
It reacted for 7 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium chloride was separated from P, and 400 mj of methanol was added to the obtained P solution.
A solid was precipitated by adding . The generated slurry is filtered, and the resulting solids are collected until the pH of the washing solution is 6 to 7.
After repeated washing with water until the temperature reached 100° C., it was dried at 60 to 70° C. under vacuum. The yield was 11.8y.

In a 300 ml four-loaf flask equipped with a thermometer, a water separator with a Dimroth condenser, a nitrogen inlet tube, and a stirrer with Teflon blades, 1.09y<0.0 of p-aminophenol was added.
1 mol), sodium hydroxide 0.43y (0.01 mol as purity 95%), dimethyl sulfoxide 50-1,
25 liters of toluene was charged, and while the water produced was distilled off as an azeotrope with toluene, the mixture was stirred at 126°C for 5 hours to synthesize sodium phenolate.

After cooling, a solution of 10.9# of the dihalide obtained earlier in dimethyl sulfoxide 50+ef was added, and 1
The reaction was carried out at 25°C for 7 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium chloride was separated from the furnace, and 300 vsl of methanol was added to the obtained R liquid.
A solid was precipitated by adding . The generated slurry is filtered, and the resulting solids are collected until the pH of the washing solution is 6 to 7.
After repeating washing with water until the temperature was 20°C, it was dried under vacuum at 60 to 70°C to obtain yellow crystals. Yield was 9.4g.

The I R,'H-NMR spectrum measured for this product is shown in Figures 5 and 6. It was determined that the compound was

Example 4 11.4 g of bisphenol-A (0,0
5 mol), 4.3 y of sodium hydroxide (0.1 mol as purity 95%), 150 ml of dimethyl sulfoxide & 50 ml of toluene, and heated at 126°C for 5 hours while distilling off the produced water as an azeotrope with toluene. Stir and
Next, a solution of 8.3 g (0,055 mol) of m-xylylene dichloride, which had been synthesized from sodium phenolate, dissolved in 50 l of dimethyl sulfoxide was added, and the mixture was reacted at 124°C for 7 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium chloride was separated, and 400 ml of methanol was added to the obtained P solution to precipitate a solid substance. The resulting slurry was filtered, and the resulting solid was washed with water repeatedly until the 98 of the washing solution became 6 to 7, and then dried under vacuum at 60 to 70°C. Yield was 15.2g.

300mj with thermometer, water separator with Dimroth cooling tube, nitrogen introduction tube, and stirrer with Teflon blades! 1.09 g of p-aminophenol (0,
01 mol), sodium hydroxide 0.439 (purity 95%
(0.01 mol) and dimethyl sulfoxide were stirred at 126° C. for 5 hours while distilling off the resulting water as an azeotrope with toluene to synthesize sodium phenolate.

After cooling, a solution of 13.8 g of the dihalide obtained earlier in dimethyl sulfoxide 50-1 was added, and 12.
The reaction was carried out at 4°C for 7 hours.

After the reaction mixture was cooled to room temperature, the precipitated sodium chloride was separated from P, and 300 d of methanol was added to the obtained P solution to precipitate a solid. The resulting slurry was washed with water until the pH of the washing solution reached 6 to 7, and then dried under vacuum at 60 to 70°C to obtain yellow crystals. The yield was 12.3y.

The IR and 'H-NMR spectra measured for this product are shown in Figures 7 and 8. l) (From the ratio of proton numbers of aliphatic groups, aromatic groups, and amino groups in the NMR spectrum, it is shown below. It was determined to be a compound.

Example 5 500 mffi 4 with thermometer, water separator with Dimroth cooling tube, nitrogen inlet tube, stirrer with Teflon blades
In a double flask, add 3.3',5.5'-tetramethyl-
4.4'biphenol 12.1y (0.05 mol), sodium hydroxide 4.3 g (0.1 mol based on 95% purity), dimethyl sulfoxide 150 mff1, toluene 5
0s+1 was charged, and the resulting water was distilled off as an azeotrope with toluene while stirring at 122°C for 5 hours to synthesize sodium phenolate.

Next, 8.3 g (0,055 g) of p-xylylene dichloride
mol) dissolved in 50 l of dimethyl sulfoxide was added and reacted at 1.125°C for 7 hours.

After the reaction mixture was cooled to room temperature, the precipitated sodium chloride was separated in a furnace, and 400 mZ of methanol was added to the obtained r liquid to precipitate a solid. The resulting slurry was filtered, and the resulting solid was washed repeatedly with water until the pH of the washing solution became 6 to 7, and then dried under vacuum at 60 to 70°C. Yield was 16.2g.

10.9 g of p-aminophenol (0-
1 mole), 4.3y of sodium hydroxide (0.1 mole assuming 95% purity), 100ml of dimethyl sulfoxide, 50ml of toluene! was charged and stirred at 124° C. for 5 hours while distilling off the produced water as an azeotropic mixture with toluene to synthesize sodium phenolate.

After cooling, the previously obtained dihalide i4. Add st dissolved in dimethyl sulfoxide 100+*1,
The reaction was carried out at 126°C for 7 hours.

After the reaction mixture was cooled to room temperature, the precipitated sodium chloride was separated from the P solution, and 400 ml of methanol was added to the obtained P solution to precipitate a solid substance. The resulting slurry was treated with P, and the resulting solid was washed with water repeatedly until the pH of the washing solution became 6 to 7, and then dried under vacuum at 60 to 70°C to obtain yellow crystals. The yield was 12°Og.

The I R, H-NMR spectrum measured for this product is shown in Figures 9 and 10. From the ratio of the proton numbers of aliphatic groups, aromatic groups, and amino groups in the 'H-NMR spectrum, the following is shown. It was determined that the compound was

n4.8 Example 6 500 WAIl 4 with thermometer, water separator with Dimroth cooling tube, nitrogen inlet tube, stirrer with Teflon blades
In a double flask, add 3.3', 5.5'-tetramethyl-
4,4'-biphenol 12.1 g (0.05 mol),
4.3 g of sodium hydroxide (0.1 mol as 95% purity), 150 s of dimethyl sulfoxide & 50 s of toluene
sN was charged, and the resulting water was stirred at 124° C. for 5 hours while distilling off the water as an azeotrope with toluene to synthesize sodium phenolate.

Next, 8.3 g of 0-xylylene dichloride (0,055
A solution of 1 mole) dissolved in 50 liters of dimethyl chloride was added, and the mixture was reacted at 126°C for 7 hours.

After the reaction mixture was cooled to room temperature, the precipitated sodium chloride was separated, and 400 mN of methanol was added to the obtained P solution to precipitate a solid substance. The resulting slurry was filtered through a V-filter, and the resulting solid was washed with water repeatedly until the pH of the washing solution became 6 to 7, and then dried under vacuum at 60 to 70°C. Yield was 15.8g.

In a 500 liter four-loaf flask equipped with a thermometer, a water separator with a Dimroth condenser, a nitrogen inlet tube, and a stirrer with Teflon blades, 10.9 y of p-aminophenol (0-1
mol), sodium hydroxide 4.3y (0.1 mol as purity 95%), dimethyl sulfoxide 10C)t', and toluene 5C1++Z, and while distilling off the water produced as an azeotrope with toluene, the mixture was heated at 125°C. The mixture was stirred for 5 hours to synthesize sodium phenolate.

After cooling, a solution of the previously obtained dihalide 13.9y in 100 mN of dimethyl sulfoxide was added, and 1
The reaction was carried out at 28°C for 7 hours.

After the reaction mixture was cooled to room temperature, the precipitated sodium chloride was separated in a furnace, and 400 mf of methanol was added to the obtained P solution to precipitate a solid substance. The resulting slurry was washed with water until the pH of the washing solution reached 6 to 7, and then dried under vacuum at 60 to 70°C to obtain yellow crystals. The yield was 11.19.

The IR and H-NMR spectra measured for this product are shown in Figures 11 and 12. From the ratio of the proton numbers of aliphatic groups, aromatic groups, and amino groups in the IH-NMR spectra, the compound is shown below. It was determined that

1 is a 'H-NMR spectrogram of a compound.

〔Effect of the invention〕

Since the present invention is configured as described above, a novel aromatic diamine can be obtained in high yield. Furthermore, this novel aromatic diamine is a compound useful as a monomer for polymeric materials, such as a raw material for polyamide, polyimide, and polyamideimide resin, or as a curing agent for urethane compounds, epoxy compounds, and the like.

[Brief explanation of drawings]

Claims (1)

[Claims] 1. Aromatic diamine represented by the following general formula (1): ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (However, in the above formula (1), Y is a single bond, -S −, −SO_
2-, -CO-, or an alkylene group or aralkylene group having 1 to 10 carbon atoms, R represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n is a number of 20 or less). 2. A compound represented by the following general formula (2) and a compound represented by the following general formula (3) are reacted in an organic polar solvent to convert it into a compound represented by the following general formula (4), and then both of them are A method for producing an aromatic diamine represented by the following general formula (1), which is characterized by converting a terminal halogen group into an aminophenoxy group (numerical formula, chemical formula, table, etc.). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (However, in the above formula (1), Y is a single bond, -S-, -SO_
2-, -CO-, or an alkylene group or aralkylene group having 1 to 10 carbon atoms, R represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and n is a number of 20 or less. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (However, X in the above formula (2) represents F, Cl, Br.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(3) (However, , M in the above formula (3) represents an alkali metal, Y
and R are the same as those in formula (1) above. )▲There are mathematical formulas, chemical formulas, tables, etc.▼(4) (However, in the above formula (4), Y, R, and n are the above formula (1)
and x are the same as those in equation (2) above. )