JPH02247155A - Novel diamine and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (Y is -SO2- or -CO-; R is 5-15C alicyclic alkylene; n is degree of polymerization and 1-20). USE:Useful as a monomer for polymer materials such as a raw material for polyamide, polyimide or polyamide-imide resins or a curing agent for urethane compound, epoxy compound, etc. PREPARATION:A compound shown by formula II (X is F, Cl or Br) is reacted with a compound shown by formula III (M is alkali metal salt) in a solvent such as dimethyl sulfoxide at 50-250 deg.C to give a compound shown by formula IV. Then both end halogen groups are converted into a group shown by formula V to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel diamine having a polyoxyarylene alkylene sulfone and polyoxyarylene alkylene ketone structure, and a method for producing the same. Diamine compounds are monomers for polymeric materials, such as raw materials for polyamides, polyimides, and polyamide-imide resins.
Alternatively, it is a compound useful as a curing agent such as a urethane compound or an epoxy compound.

<Prior Art> Many attempts have been made to develop diamine compounds, and unique ones have been provided. For example, those produced by reacting bisphenol-A and dichlorodiphenyl sulfone in the presence of potassium carbonate and then reacting with aminophenol (Japanese Unexamined Patent Publication No. 15420/1983), or those produced by reacting bisphenol-A and dichlorodiphenyl sulfone with caustic soda. After converting it into sodium phenolate, it was reacted with dichlorodiphenyl sulfone, and then subjected to an esterification reaction using nitrobenzoic acid.
Diamine compounds obtained by reducing a nitro group (Japanese Unexamined Patent Publication No. 63-250350) are known.

<Problems to be Solved by the Invention> The object of the present invention is to solve the problems of the general formula (1). represents an alicyclic alkylene group, and n is a number of 20 or less indicating the average degree of repeated polymerization.'' The purpose of the present invention is to provide a novel diamine and a method for producing the same.

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

The present inventors obtained a compound represented by the following general formula (4) by reacting the compound represented by the general formula (3) with the compound represented by the general formula (3) in an organic polar solvent. As a result of extensive research, we have completed the present invention.

That is, the present invention provides: (1) a novel diamine represented by the following general formula (1); represents an alicyclic alkylene group, and 11 is a number of 20 or less indicating the average degree of repeated polymerization.""However, in the above formula (1), Y is 18○2- or -C
◯-, R represents an alicyclic alkylene group having 5 to 15 carbon atoms, and 11 is a number of 20 or less indicating the average degree of repeated polymerization. (2) A compound represented by the following general formula (2) and the following "However, in the above formula (2), X represents F, C2, or Br, and Y is the same as that in the above formula (1>). "MO-C)-12-
R-(:, H2-0M (3) However, in the above formula (3), M represents an alkali metal salt, and R represents the above formula (
It is the same as that in 1).

However, in the above formula (4), Y and n are the same as those in the above formula (1), and X is the same as that in the above formula (2).

The novel diamine according to the present invention is a monomer of a polymeric material,
For example, it is a compound useful as a raw material for polyamide, polyimide, and polyamideimide resin, or a curing agent for urethane compounds, epoxy compounds, and the like.

In order to produce the diamine compound of the present invention, the 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 will be slow, and in extreme cases there will be 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) to compound (3) is not particularly limited, but is usually 1.0 or more and 5.0 or less.

If it is less than 1.0, the amount of terminal hydroxyl groups increases and the yield of dihalogen compounds decreases, and if it is more than 5.0, the remaining compounds (
The amount of 2) increases, and both are unavoidable.

The raw materials may be charged in batches, and the compound (2
) may be divided and charged, but the preferred method is to divide and charge compound (2).

The generated 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 obtained filtrate as necessary, or adding methanol. This can be achieved by obtaining a solid that precipitates. 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,
The diamine compound represented by general formula (1) can be obtained by converting aminophenol into an alkali metal phenolate and reacting it with dihalide (4) in a polar solvent.

<Example> The present invention will be specifically explained below using Examples.

Example 1 1,4-cyclohexane dimetatool 14 in a 500n 120 flask equipped with a thermometer Zimrow I, a water separator with a cooling tube, a nitrogen inlet tube, and a stirrer with Teflon blades.
．． 4 (0.1 mol), sodium hydride 8.0 g (
0.0 as purity 60%. 2 mol> and 150 mg of dimethyl sulfoxide were charged, and the mixture was stirred at room temperature under a nitrogen atmosphere for 1 hour to synthesize sodium alcoholade. Then “4,
41-dichlorodiphenylsulfone 35.9g (0,1
A solution of 25 mol) of dimethylsulfoxy F' dissolved in 50 m 2 of dimethylsulfoxy F' was added, and the mixture was reacted at 125°C for 5 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium chloride was filtered off, and 400 m of methanol was added to the resulting filtrate.
A solid was precipitated by adding l+. The resulting slurry was filtered, and the resulting solid matter was filtered until the pH of the washing solution was 6.
After repeating washing with water until the temperature reaches 7, then 60 to 70 under vacuum.
Dry at °C. Collection j140. ．． 1g, which was determined to be the compound shown below based on the ratio of proton numbers of aliphatic groups and aromatic groups in 1H NMR.

10- Water separator with thermometer Dimroth cooling tube, nitrogen introduction tube,
Into 40 flasks of 300 m2 equipped with a stirrer with Teflon blades, 4°36 g (0.04 mol) of p-aminophenol and 1°69 g of sodium hydroxide (0.02 g (95% purity) were added.
．． 04 mol), dimethyl sulfoxide 50 ml! ,
25 tn 2 of toluene was charged, and the resulting water was distilled off as an azeotropic mixture with toluene, and the mixture was stirred at 120° C. for 6 hours to synthesize sodium phenolate.

After cooling, a solution of 17.2 g of the previously obtained dihalogenated compound in 50 mQ of dimethyl sulfoxide was added,
The reaction was carried out at 124°C for 5 hours.

After the reaction mixture was cooled to room temperature, the precipitated sodium chloride was separated, and the obtained t! 300 m of methanol in the liquid
A solid was precipitated by adding 2. The resulting slurry was filtered, and the resulting solid matter was filtered until the pH of the washing solution was 6.
~7; After repeated washing with water until solid, 60~7 under vacuum
It was dried at 0°C to obtain yellow crystals. Yield 18.3g,
The IR and IH-NMR spectra measured for this product are shown in FIGS. 1 and 2. It was determined to be the compound shown below based on the ratio of proton numbers of aliphatic groups, aromatic groups, and amino groups in the 'H-NMR spectrum.

Example 2 Water separator with thermometer Dimroth cooling tube, nitrogen introduction tube,
Tricyclodecane (5°2, 1.0.
26) Dimethatol 19.6g (0°1 mole), sodium hydride 8.0g (0.2 mole assuming purity 60%)
5 Charge 150 m fl of dimethyl sulfoxide,
The mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere to synthesize sodium alcoholade. Next, a solution of 35.9 g (0,125 mol) of 4,4''-dichlorodiphenylsulfone dissolved in 50 m2 of dimethyl sulfoxide was added, and the mixture was heated to 125°C.
It reacted for 5 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium chloride was filtered off, and the resulting solution was mixed with 400% methanol.
mS! A solid was precipitated by adding . The generated slurry is filtered, and the resulting solid is adjusted to the pH of the washing solution.
After repeating washing with water until the value reaches 6~7, wash under vacuum at 60~
It was dried at 70°C. Yield: 42.6 g. This product was determined to be the compound shown below from the ratio of proton numbers of aliphatic groups and aromatic groups measured by IHNMR. Water separator with thermometer and Dimroth cooling tube, nitrogen introduced 300m2 with tube, Teflon bladed stirrer
4.36 g of p-aminophenol in 4 flasks.
(0.04 mol), sodium hydroxide 1-69 g
(0.04 mol at 95% purity), 50 mQ of dimethyl sulfoxide, and 25 m2 of toluene were stirred at 120°C for 7 hours while distilling off the water produced as an azeotrope with toluene. Synthesized Lato.

After cooling, a solution of 19.3 g of the previously obtained dihalide in 50 mL of dimethyl sulfoxide was added, and the mixture was reacted at 124° C. for 5 hours.

After cooling the reaction mixture to room temperature, precipitated sodium chloride was filtered off, and methanol 30011 was added to the obtained filtrate.
1 j! A solid was precipitated by adding . The generated slurry is filtered, and the resulting solid is adjusted to the pH of the washing solution.
After repeating washing with water until the value reaches 6~7, wash under vacuum at 60~
It was dried at 70°C to obtain yellow crystals. Yield 15.0g,
The IR,'H-NMR spectra measured for this product are shown in FIGS. 3 and 4. It was determined to be the compound shown below based on the ratio of the proton numbers of aliphatic groups, aromatic groups, and amino groups in the IH-NMR spectrum.

Example 3 4 of 500 m2 with thermometer, water separator with Dimroth cooling tube, nitrogen inlet tube and stirrer with Teflon blades
In a double flask, 11.5 g (0.08 mol) of 1,4-cyclohexane dimetatool, 6.4 mol of sodium hydride.
(0°16 moles assuming a purity of 60%) and 150 m2 of dimethyl sulfoxide were charged, and the mixture was stirred at room temperature under a nitrogen atmosphere for 1 hour to synthesize sodium alcoholade. Then,
A solution of 21.8 g (0.1 mol) of 4°4'-difluorobenzophenone dissolved in 200 m 2 of dimethyl sulfoxide was added, and the mixture was reacted at 130°C for 5 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium fluoride was filtered off, and 400 m of methanol was added to the resulting filtrate.
j! A solid was precipitated by adding . The resulting slurry was filtered, and the resulting solid was washed with water repeatedly until the pH of the washing solution became 6-7, and then washed under vacuum at 60-7.
Dry at 0°C.

Yield f126.8g. 1HN measured for this
Based on the ratio of the proton numbers of aliphatic groups and aromatic groups in MR, it was determined that the compound was as shown below. In a double flask, 4.36 g (0.04 mol) of p-aminophenol, 1.69 g (0.04 mol assuming purity of 95%) of sodium hydroxide
, dimethyl sulfoxide 50 m2, toluene 25 m
2 was charged, and the resulting water was distilled off as an azeotropic mixture with toluene, and the mixture was stirred at 126° C. for 6 hours to synthesize sodium phenolate.

After cooling, 7.4 g of the previously obtained dihalide was mixed with 50 m S! of dimethyl sulfoxide. Add the solution dissolved in
The reaction was carried out at 124°C for 5 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium fluoride was filtered off, and 300 m of methanol was added to the obtained filtrate.
A solid was precipitated by adding 9. The resulting slurry was filtered, and the resulting solid matter was filtered until the pH of the washing solution was 6.
After repeating washing with water until the temperature reaches 7, then 60 to 70 under vacuum.
It was dried at °C to obtain yellow crystals. The yield was 6.4 g. The IR and IH-NMR spectra measured for this product are shown in FIGS. 5 and 6. It was determined to be the compound shown below based on the ratio of proton numbers of aliphatic groups, aromatic groups, and amino groups in the 'H-NMR spectrum.

7'Jm: 10 Example 4 Water separator with thermometer Dimroth cooling tube, nitrogen introduction tube,
Tricyclodecane (5°2, 1.0.
26) Prepare 15.7 g (0°08 mol) of dimethatol, 6.4 g (0.16 mol as purity 60%) of sodium hydride, and 150 m Q of dimethyl sulfoxide.
The mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere to synthesize sodium alcoholade.

Then, 4,4'-difluoropentuphenone 21,
8 g (0.1 mol) of dimethyl sulfoxide 200
mS! The solution was added to the mixture and reacted at 130°C for 5 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium fluoride was filtered off, and 400 m of methanol was added to the resulting filtrate.
By adding 2, a solid was precipitated. The resulting slurry was filtered, and the resulting solid matter was filtered until the pH of the washing solution was 6.
After repeating washing with water until the temperature reaches 7, then 60 to 70 under vacuum.
Dry at ℃.

Yield 29.1g, measured on this one.
The compound was determined to be the one shown below based on the ratio of the proton numbers of the fatty membrane group and the aromatic group in H-NMR.

n=32 4.36 g of p-aminophenol (0,0
4 mol>, sodium hydroxide 1.69 g (0.04 mol assuming 95% purity), dimethyl sulfoxyl" 50
m 2, toluene 25 m2 were charged, and the resulting water was distilled off as an azeotropic mixture with toluene, and heated at 122 °C for 6 m2.
The mixture was stirred for hours to synthesize sodium phenolate.

After cooling, add a solution of 8.4 g of the dihalide obtained earlier in 50 m2 of dimethyl sulfoxide, and
The reaction was carried out at 5°C for 5 hours.

After cooling the reaction mixture to room temperature, the precipitated sodium fluoride was filtered off, and 300 mR of methanol was added to the resulting filtrate.
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
to obtain yellow crystals. The yield was 5.6 g. The IR and IH-NMR spectra measured for this product are shown in FIGS. 7 and 8. ' From the ratio of the proton numbers of aliphatic groups, aromatic groups, and amino groups in the H-NMR spectrum, it was determined that the compound was as shown below.

Figures 1, 3, 5 and 7 are IR spectrograms of such compounds according to the present invention;
Figures 6 and 8 show the compounds according to the present invention.
It is an H-NMR spectrogram.

Claims (1)

[Claims] [1] New diamine represented by the following general formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (1) “However, in the above formula (1), Y is -SO_2-, or -
represents CO-, R represents an alicyclic alkylene group having 5 to 15 carbon atoms, and n is a number of 20 or less indicating the average degree of repeated polymerization. [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 novel diamine compound represented by the following general formula (1), which is characterized by converting the halogen groups at both ends of the halogen group into a ▼ group, which has a numerical formula, a chemical formula, a table, etc. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) ``However, in the above formula (1), Y is -SO_2-, or -
represents CO-, R represents an alicyclic alkylene group having 5 to 15 carbon atoms, and n is a number of 20 or less indicating the average degree of repeated polymerization. ” ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) “However, in the above formula (2), X represents F, Cl, Br,
Y is the same as that in formula (1) above. "MO-CH_2-R-CH_2-OM(3) "However, in the above formula (3), M represents an alkali metal salt, and R
is the same as that in equation (1) above. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (4) "However, in the above formula (4), Y and n are the same as those in the above formula (1), and X is the same as that in the above formula (2)."