JPH0331320A - 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<1> is H or 1-5C alkyl; R<2> is 5-15C alicyclic alkylene; 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 a novel diamine having a polyarylene alkylene ether structure and a method for producing the same.

The diamine compound 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.

[Conventional technology and issues]

Regarding the production of diamine compounds, many attempts have been made in the past, and unique ones have been provided. (Japanese Unexamined Patent Publication No. 15420/1983), or sodium phenolate is produced by reacting bisphenol-A with caustic soda, which is then reacted with dichlorodiphenyl sulfone, and then esterified with nitrobenzoic acid. Diamine compounds obtained by reaction and reduction of the nitro group (Japanese Unexamined Patent Publication No. 63-250350) 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 has a skeleton structure composed of alternating copolymers of alicyclic cybaride and bisphenols, and is applicable to such new application fields, and diamines and This paper attempts to provide a manufacturing method for the same.

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]

As a result of intensive studies to achieve the above object, the present inventors discovered the following new diamine and method for producing the same, and completed the present invention.

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

(However, in the above formula (1), Y is a single bond, -5--SO, -
1-〇〇- or represents an alkylene group or aralkylene group having 1 to 10 carbon atoms, R1 represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and R2 represents an alicyclic alkylene group having 5 to 15 carbon atoms. , where n is a number of 20 or less.

) Another aspect of the present invention is to provide a method for producing a novel diamine represented by (1) below.

That is, the manufacturing method is to react the compound shown in the following maximum (2) with the compound shown in the following maximum (3) in an organic polar solvent to convert it into the compound shown in the following maximum (4). and then connect the halogen groups at both ends (however, in the above formula (1), Y is a single bond, -5--SO2-
1-CO- or an alkylene group or aralkylene group having 1 to 1 carbon atoms, R1 is hydrogen or an alkyl group having 1 to 5 carbon atoms, and R2 is an alicyclic alkylene group having 5 to 15 carbon atoms. , where n is a number of 20 or less.

)X-CH2-R”-CH2-X (2)
(However, in the above formula (2), X represents F, C1, Br,
R2 is the same as that in formula (1) above. ) (However, in the above formula (3), M represents an alkali metal, and Y and R1 are the same as those in the above formula (1).) (However, in the above formula (4), Y, R'R ” and n are the same as those in the above formula (1), and X is the same as that in the above formula (2).) 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 yield of the dihalogen compound decreases, and when it is more than 5.0, the amount of remaining compound (2) increases, both of which are disadvantageous.

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 r 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 many known methods can be used for the conversion, and there is no need to limit the method. For example, by deriving aminophenol into an alkali metal phenolate,
By reacting with dihalide (4) in a polar solvent, the diamine compound shown in -maximum (1) can be obtained.

〔Example〕

The present invention will be specifically explained below using 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)
, 50 ml of dimethylsulfoxide doluene was charged, and the resulting water was distilled off as an azeotrope with toluene while stirring at 123°C for 5 hours.
Sodium phenolate was synthesized.

Next, 9.95 g (0.05 mol) of 4.4'-bis(chloromethyl)cyclohexane was mixed with 50.5 g of dimethyl sulfoxide. Add the dissolved material to the solution and heat at 125℃ for 7
Time reacted.

After the reaction mixture was cooled to room temperature, the precipitated sodium chloride was separated in a furnace, and 400 mN of methanol was added to the obtained r liquid to precipitate a solid substance. The resulting slurry was filtered, 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 15.4g.

In a fourth 300+S1 flask equipped with a thermometer, a water separator with a Dimroth condenser, a nitrogen inlet tube, and a stirrer with Teflon blades, add 1.0 9 g of p-aminophenol (
0.01 mol), sodium hydroxide 0.432 (0.01 mol as purity 95%), 50 l of dimethylthrephoxide, and 25 l of toluene, and the water produced was distilled as an azeotrope with toluene. The mixture was stirred at 120° C. for 5 hours while removing water, and sodium phenolate was synthesized.

After cooling, a solution of 13.9 g of the dihalide obtained earlier in 50 ml of dimethyl sulfoxide was added, and
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, and 300 ml of methanol was added to the obtained liquid to precipitate a solid. 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 12.2y. The I R,'H-NMR spectrum measured for this product is shown in Figures 1 and 2. From the ratio of the proton numbers of aliphatic groups, aromatic groups, and amino groups in the IH-NMR spectrum, the following is shown. It was determined that the compound was

Example 2 500s+t'4 with thermometer, water separator with Dimroth cooling tube, nitrogen introduction tube, and stirrer with Teflon blades
In a double flask, add 9.3y (0) of 4.4'-biphenol.
, 05 mol), 4.3 g of sodium hydroxide (95% purity)
(0.1 mol), dimethyl sulfoxide 150 ml
, 50 ml of toluene was charged, and the resulting water was distilled off as an azeotrope with toluene while stirring at 121°C for 5 hours to synthesize sodium phenolate.
'-Bischloromethylcyclohexane 9.95g (0,
A solution of 055 mol) in dimethyl sulfoxide (50 mN) was added, and the mixture was reacted at 127°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 resulting 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 11.4y.

In a 300 mf four-loop flask equipped with a thermometer, a water separator with a Dimroth condenser, a nitrogen inlet tube, and a stirrer with Teflon blades, 1.09 g of p-aminophenol (0,0
1 mol), sodium hydroxide 0.43 g (0.01 mol as purity 95%), dimethyl sulfoxide 50sZ,
Toluene 25-1 was charged, and while the water produced was distilled off as an azeotrope with toluene, the mixture was stirred at 120°C for 5 hours to synthesize sodium phenolate.

After cooling, a solution of the dihalide to, 2y obtained earlier in 50 ml of dimethyl sulfoxide 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 in a furnace, 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. The yield was 8.9y, and the IR1'H-NMR spectrum measured for this product is shown in Figures 3 and 4. The aliphatic group in the 'H-NMR spectrum,
The compound was determined to be the one shown below based on the ratio of the proton numbers of the aromatic group and the amino group.

Example 3 10.9 g of 4,4'-dihydroxydiphenyl sulfide (10.9 g of 4,4'-dihydroxydiphenyl sulfide, 05 mol), sodium hydroxide 4
．． 3 g (0.1 mol as purity 95%), 150 mN of dimethyl sulfoxide, and 50 ml of toluene were added, and while the water produced was distilled off as an azeotrope with toluene, 1
The mixture was stirred at 26°C for 5 hours to synthesize sodium phenolate. Next, a solution of 9.95 g (0,055 mol) of 4,4'-bischloromethylcyclohexane in 50-1 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 from the furnace, and methanol 400IIe 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 repeated washing with water until the temperature reached 100° C., it was dried at 60 to 70° C. under vacuum. The yield was 12.8y.

300II11-4 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
0.01 mol), dimethyl sulfoxide 50 m
#, 25 ml 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 11.3 g of the dihalide obtained previously in 50 mN of dimethyl sulfoxide was added, and 12.
The reaction was carried out at 6°C for 7 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium chloride was separated in a furnace, and 3001 Il of methanol was added to the obtained r liquid.
A solid was precipitated by adding . The generated slurry is treated, and the resulting solids are collected until the pH of the cleaning 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 9.2g. The I R,'H-NMR spectrum measured for this product is shown in Figures 5 and 6. 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 4 12.5y (0.05 mol) of 4,4'-dihydroxydiphenylsulfone was placed in a 500+e1 four-bottle flask equipped with a thermometer, a water separator with a Dimroth condenser, a nitrogen inlet tube, and a stirrer with Teflon blades. ), sodium hydroxide 4
．． 3y (0.1 mol as purity 95%), 150 ml of dimethyl sulfoxide, and 50 ml of toluene, and while distilling off the water produced as an azeotrope with toluene,
The mixture was stirred at 22°C for 5 hours, and then a solution of 9.9'5 y (0,055 mol) of 4,4'-bischloromethylcyclohexane (0,055 mol) to which sodium phenolate had been synthesized was added, and the mixture was heated at 125°C. It reacted for 7 hours.

After the reaction mixture was cooled to room temperature, the precipitated sodium chloride was separated, and 400 ml of methanol was added to the obtained liquid to precipitate a solid. The resulting slurry was filtered, 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. The yield was 14.1y.

In a 300nf 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 mole), 0.43 g of sodium hydroxide (0.01 mole assuming 95% purity), 50 g of dimethylsulfoxide!
, Toluene 25-1 was charged, and while the water produced was distilled off as an azeotropic mixture with toluene, the mixture was stirred at 129°C for 5 hours to synthesize sodium phenolate.

After cooling, 13.6 g of the halide obtained above dissolved in 50+5ffi of dimethyl sulfoxide was added, and the mixture was reacted at 127° C. for 7 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium chloride was separated, and 300 methanol was added to the obtained P solution 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 12.9y, and the IR,'H-NMR spectrum measured for this product is shown in Figure 7.
From the ratio of the number of protons of aliphatic groups, aromatic groups, and amino groups in the 'H-NMR spectrum shown in FIG. 8, it was determined that the compound was as shown below.

Example 5 11.4 g of bisphenol A (0,0
5 mol), sodium hydroxide 4.3 g (0.1 mol assuming 95% purity), dimethyl sulfoxide 150a+4'
, 50m&' of toluene was charged, and the water produced was distilled off as an azeotrope with toluene while stirring at 125°C for 5 hours to synthesize sodium phenolate.
4'-bischloromethylcyclohexane 9.95y (0
, 055 mol) dissolved in 50 ml of dimethyl sulfoxide was added, and the mixture was reacted at 122°C for 7 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium chloride was separated from the furnace, and 400 ral 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 repeated washing with water until the temperature reached 100° C., it was dried at 60 to 70° C. under vacuum. Yield: 9.5y.

1.09 g of p-aminophenol (0,0
1 mol), sodium hydroxide 0.43y (0.01 mol as purity 95%), dimethyl sulfoxide 50111
, toluene 251111 was charged, and while the produced water was distilled off as an azeotropic mixture with toluene, the mixture was stirred at 123° C. for 5 hours to synthesize sodium phenolate.

After cooling, a solution of 8.4 g of the dihalide obtained earlier in dimethyl sulfoxide 50-1 was added, and 126
The reaction was carried out at ℃ for 7 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium chloride was separated from the furnace, and 300 IIl of methanol was added to the resulting 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 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: 7.6g. The IR, '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 IH-NMR spectrum, it is shown below. It was determined to be a compound.

Example 6 4.4'-biphenol 9.31? (0,
05 mol), sodium hydroxide 4.3 g (0.1 mol assuming 95% purity), dimethyl sulfoxide 150 ml,
50 ml of toluene 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, 23.3 g of tricyclodecane (5,2゜1.0.'.'') dimethyl chloride <0.1 mol) was added to dimethyl sulfoxide 5
The solution dissolved in 0ml1 was added and reacted at 127°C for 7 hours.

After the reaction mixture was cooled to room temperature, the precipitated sodium chloride was separated by P, and 400 mN of methanol was added to the obtained r liquid to precipitate a solid substance. The resulting slurry was filtered, 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 24.8g.

10.9 g of p-aminophenol (0,0
1 mol), 4.3 g of sodium hydroxide (0.1 mol assuming 95% purity), 100 m of dimethyl sulfoxide,
50 mf of toluene was charged, and while the produced water was distilled off as an azeotropic mixture with toluene, the mixture was stirred at 125°C for 5 hours to synthesize sodium phenolate.

After cooling, a solution of 21.9 g of the dihalide obtained earlier in 100 ml of dimethyl sulfoxide was added, and 1
The reaction was carried out at 27°C for 7 hours.

After the reaction mixture was cooled to room temperature, the precipitated sodium chloride was separated in a furnace, and 400 mN of methanol was added to the obtained furnace liquid to precipitate a solid substance. The resulting slurry was filtered, and the resulting solid was washed repeatedly with water until the DH of the washing solution became 6 to 7, and then dried under vacuum at 60 to 70°C to obtain yellow crystals. Yield: 17.6L The IR, 'H-NMR spectra measured for this product are shown in Figures 11 and 12. The ratio of proton numbers of aliphatic groups, aromatic groups, and amino groups in the 'H-NMR spectra It was determined to be the compound shown below.

〔Effect of the invention〕

Since the present invention is configured as described above, a novel diamine can be obtained in high yield. Further, this novel 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]

1, 3, 5, 7, 9 and 11 are IR spectrograms of the compounds according to the present invention. Figures 8, 10 and 12 are 'H-NMR spectrograms of compounds according to the present invention.

Claims (1)

[Claims] 1. Diamine represented by the following general formula (1): ▲ Formula,
There are 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^1 represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and R^2 represents an alkyl group having 5 carbon atoms.
~15 alicyclic alkylene groups, 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 A method for producing a diamine represented by the following general formula (1), which is characterized by converting the halogen group at both ends into an aminophenoxy group ▲ Numerical formula, chemical formula, table, 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^1 represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and R^2 represents an alkyl group having 5 carbon atoms.
~15 alicyclic alkylene groups, and n is a number of 20 or less. ) There are mathematical formulas, chemical formulas, tables, etc.▼(3) (However, in the above formula (3), M represents an alkali metal, and Y
and R^1 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^1, R^2 and n are those of the above formula (1), and x is the above formula (2) )