JPS6129974B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel polyamide having an alkylsulfonamide group in its side chain. So-called aromatic polyamides, in which amide bonds are directly bonded to aromatic nuclei, have rigid molecular chains, so
Mechanical properties, shape stability at high temperatures, thermal decomposition resistance,
It has excellent electrical insulation properties and is extremely valuable industrially as a heat-resistant fiber and insulating film. However, aromatic polyamides generally have poor solubility in organic solvents; for example, poly(m-phenylene isophthalamide) can be dissolved even in polar solvents such as N.N-dimethylacetamide with a few percent of inorganic salts (e.g. lithium chloride, nitric acid, etc.). It only dissolves in the presence of lithium, calcium chloride, etc.).
Therefore, there are limitations to the production of films from these polyamides. Also, when using these conventional aromatic polyamide films as semipermeable membranes,
Due to its remarkable hydrophobicity, it was also pointed out that it had insufficient water permeability and other drawbacks in its properties. The present invention was developed in view of the drawbacks of the conventional aromatic polyamides, and its purpose is to maintain the mechanical strength and heat resistance observed in aromatic polyamides, have excellent solubility in organic solvents, and be easy to form into films. Another object of the present invention is to provide a material that is useful as a semipermeable membrane with good water permeability. The material of the present invention has the general formula [-NH-Ar-NHCO-Q-CO]- (where Ar is

【formula】

[Formula] (n is 0 or 1, R ₁ and R ₂ are hydrogen or a lower alkyl group, only the hydrogen atom is substituted in either R ₁ or R ₂ ), (When R ₃ is H, R ₄ is CH ₃ , C ₂ H ₅ , when R _{3 is CH 3 , R 4 is CH 3} , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , R ₃ is C ₂ H ₅ then R ₄ is C ₂ H ₅ ), ( _R5 is _CH3 , _R6 is H or _CH3 ), and Q is m-phenylene group, p-phenylene group, O-phenylene group, (Y=-O-, _-SO2- ), -( _CH2 )n- (n is 1, 2, 4 to 8), ), and has a reduced viscosity of 0.5 dl/g or more (dimethylacetamide solvent, 0.1 g/g)
It is a polyamide with an alkylsulfonamide group in the side chain that exhibits a dl concentration of 30℃). The polyamide having an alkylsulfonamide group in the side chain of the present invention described above has the general formula H ₂ N-Ar-
NH ₂ (wherein Ar is

【formula】

[Formula] (n is 0 or 1, R ₁ and R ₂ are hydrogen or a lower alkyl group, only the hydrogen atom is substituted in either R ₁ or R ₂ ), (When R ₃ is H, R ₄ is CH ₃ , C ₂ H ₅ , when R _{3 is CH 3 , R 4 is CH 3} , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , R ₃ is C When ₂ H ₅ , R ₄ is C ₂ H ₅ ), (R ₅ is CH ₃ , R ₆ is H or CH ₃ ), aromatic diaminoalkylsulfonamide represented by the general formula XOOC-Q-COOX (wherein Q is m-
Phenylene group, p-phenylene group, O-phenylene group, (Y=-O-, _-SO2- ), -( _CH2 )n-(n is 1, 2, 4 to 8), It is. X is Cl or Br. ) can be produced by polycondensing a dibasic acid halide represented by the following in an inert solvent at a temperature of 25° C. or lower. The aromatic diaminoalkylsulfonamide used in the present invention has the general formula H ₂ N-Ar-NH ₂ (in the formula
Ar is

【formula】

[Formula] (n is 0 or 1, R ₁ and R ₂ are hydrogen or a lower alkyl group, only the hydrogen atom is substituted in either R ₁ or R ₂ ), (When R ₃ is H, R ₄ is CH ₃ , C ₂ H ₅ , when R _{3 is CH 3 , R 4 is CH 3} , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , R ₃ is C _{2H5 , R4} is _{C2H5 )} . Such aromatic aminosulfonamides (H ₂ N
-Ar-NH ₂ ) is specifically shown as follows. 3,5-diaminobenzene-N-methylsulfonamide 3,5-diaminobenzene-N/N-dimethylsulfonamide 3,5-diaminobenzene-N-ethylsulfonamide 3,5-diaminobenzene-N/N-diethylsulfonamide 3,5-diaminobenzene-(N-methyl, N
-ethylsulfonamide) 3,5-diaminobenzene-(N-methyl, N
-n-propylsulfonamide) 3,5-diaminobenzene-(N-methyl, N
-n-butylsulfonamide) 3,5-diaminobenzene-(N-ethyl, N
-n-propylsulfonamide) 3,5-diaminobenzene-(N-ethyl, N
-n-butylsulfonamide) 3,5-diaminobenzene-(N-n-propyl, N-butylsulfonamide) 4,4'-diaminodiphenyl ether-2-N
-Methylsulfonamide 4,4'-diaminodiphenyl ether-2-
N・N-dimethylsulfonamide 4,4'-diaminodiphenyl ether-2-
(N-methyl, N-ethylsulfonamide) 4,4'-diaminodiphenyl ether-2-
(N-methyl, N-n-propylsulfonamide) 4,4'-diaminodiphenyl ether-2-
(N-methyl, N-n-butylsulfonamide) 4,4'-diaminodiphenyl ether-2-
(N-ethyl, N-n-propylsulfonamide) 4,4'-diaminodiphenyl ether-2-
(N-ethyl, N-n-butylsulfonamide) 4,4'-diaminodiphenyl ether-2-
(N-n-propyl, N-butylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di(N-methylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di(N・N-dimethylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di(N-ethylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di(N・N-diethylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di(N・N-di-n-propylsulfonamide) 4.4'-diaminodiphenyl ether-2.
2'-di(N-isopropylsulfonamide) 4.4'-diaminodiphenyl ether-2.
2'-di(N・N-diisopropylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di(N-n-butylsulfonamide) 4,4'-diaminodiphenyl ether 2,2'-
Di(N・N-di-n-butylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di-(N-methyl, N-ethylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di(N-methyl, N-n-propylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di(N-methyl, N-n-butylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di(N-ethyl, N-n-propylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di(N-ethyl, N-n-butylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di(N-n-propyl, N-n-butylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di(N-methyl, N-isopropylsulfonamide) 4.4′-diaminodiphenyl ether-2.
2'-di(N-isopropyl, N-isobutylsulfonamide) 4,4'-diaminodiphenylmethane-2,2'-
di(N-methyl, N-n-propylsulfonamide) 4,4'-diaminodiphenylmethane-2,2'-
di(N-ethyl, N-n-butylsulfonamide) 4,4'-diaminodiphenylmethane-2,2'-
di(N-methylsulfonamide) 4,4'-diaminodiphenylmethane-2,2'-
Di(N・N-methylsulfonamide) Benzidine-2-N-methylsulfonamide Benzidine-2-N・N-dimethylsulfonamide Benzidine-2-N-ethylsulfonamide Benzidine-2-N・N-diethylsulfonamide Benzidine-2-(N-methyl, N-ethylsulfonamide) Benzidine-2-(N-methyl, N-ethylsulfonamide) Benzidine-2-(N-methyl, N-n-butylsulfonamide) 4,4'-diaminodiphenylmethane-2-N-
Methylsulfonamide 4,4'-diaminodiphenylmethane-2-N.
N-dimethylsulfonamide 4,4'-diaminodiphenyl sulfide-2
-N-methylsulfonamide 4,4'-diaminodiphenyl sulfide-2
-N・N-dimethylsulfonamide 4,4'-diaminobenzophenone-2-N-methylsulfonamide 4,4′-diaminobenzophenone-2-N・N
-dimethylsulfonamide 4,4'-diaminodiphenyl sulfide-
2,2'-di(N-methylsulfonamide) 4,4'-diaminodiphenyl sulfide-
2,2'-di(N,N-dimethylsulfonamide) 4.4'-diaminodiphenylsulfone-2.
2'-di(N-methylsulfonamide) 4.4'-diaminodiphenylsulfone-2.
2'-di(N・N-dimethylsulfonamide) 4,4'-diaminobenzophenone-2,2'-di(N-methylsulfonamide) 4,4-diaminobenzophenone-2,2'-di(N/N-dimethylsulfonamide) Benzidine-2,2'-di(N-methylsulfonamide) Benzidine-2,2'-di(N/N-dimethylsulfonamide) 3,7-diaminonaphthalene-1,5-di(N
-methylsulfonamide) 3,7-diaminonaphthalene-1,5-di(N/N-dimethylsulfonamide) 2,4-diaminodiphenyl-4'-N-methylsulfonamide 2,4-diaminophenyl-4'-N,N-dimethylsulfonamide 2-[(4-aminophenyl)isopropyl]-
4-amino-N-methylsulfonamide 2-[(4-aminophenyl)isopropyl]-
4-amino-N・N-dimethylsulfonamide Another raw material for the production of the present invention is a dibasic acid halide. Specific examples include isophthalic acid (m-phenylene) halide. Terephthalic acid (p-phenylene) halide Phthalic acid (O-phenylene) halide 4,4'-diphenyl ether dicarboxylic acid halide 4,4' diphenylsulfonedicarboxylic acid halide 2,6-naphthalene dicarboxylic acid halide Malonic acid halide XOOC−CH ₂ −COOX, Succinic acid halide XOOC−(CH ₂ ) ₂ −COOX, Glutamic acid halide XOOC−CH ₂ −CH ₂ −CH(NH ₂ ) −COOX, Adipic acid halide XOOC− (CH ₂ ) ₄ −COOX, pimelic acid halide XOOC− (CH ₂ ) ₅ −COOX, suberic acid halide XOOC− (CH ₂ ) ₆ −COOX, azelaic acid halide XOOC− (CH ₂ ) ₇ −COOX, Sebacic acid halide XOOC-(CH ₂ ) ₈ -COOX, 1,3-cyclopentanecarboxylic acid halide 1,4-cyclohexadicarboxylic acid halide 4,4'-diphenyldicarboxylic acid halide ,and so on. Two or more of these dibasic acid halides can also be used in combination. The present invention uses N-methyl-2-pyrrolidone, N.
N-dimethylacetamide, N・N-dimethylformamide, hexamethylphosphoramide, N・
A solvent inert to the reaction components is used, such as N-diethylformamide. An acid acceptor may also be used to capture the hydrogen halide generated. There are various types of acid acceptors, but generally, for example, pyridine,
triethylamine, tri-n-butylamine,
Tertiary amines such as N.N-dimethylaniline, quinoline, N-methylmorpholine, N-ethylmorpholine are useful. The polyamide of the present invention is produced by reacting the aromatic diaminosulfonamide and a dibasic acid halide in an inert solvent at a temperature of 25° C. or lower. In this case, it is desirable to use both reaction components in a substantially equimolar ratio, whereby a polyamide having a high molecular weight, ie, a high reduced viscosity, can be obtained. Low molecular weight polyamides are difficult to form into films, and even if they can be made into films, they have poor mechanical properties. In the present invention, polyamides having a reduced viscosity of at least 0.5 dl/g, preferably 1.0 dl/g or more (solvent, N·N-dimethylacetamide, concentration 0.1 g/dl, measured at 30°C) are suitable; It is desirable to allow a sufficient reaction. The polyamide obtained according to the above has absorption by amide groups in the wave number region of 3400 to 3200 cm ^-1 of its infrared absorption spectrum, and absorption by the amide group in the wave number region of 1350 to 1320 and 1170 to 3200 cm -1.
Absorption by sulfonamide group in the region of 1150 cm ^-1
Absorption due to alkyl groups was shown at 2960 cm ^-1 , 2920 cm ^-1 , and 2870 cm ^-1 , and the elemental analysis values also agreed with the calculated values. The polyamide of the present invention is easily soluble in polar solvents such as amides, and can be formed into a film from its solution by conventional means. In addition, the film is strong and exhibits good water permeability and solute exclusion rate.
Useful as a semipermeable membrane. Next, the present invention will be explained with reference to Examples. Example 1 4,4'-diaminodiphenylether-
2,2'-di(N-methylsulfonamide), 73.6
g, 500 g of N-methyl-2-pyrrolidone and 25 g of lithium chloride, the contents are stirred and the flask is cooled in an ice bath. 40.6 g of isophthalic acid chloride was gradually added to this, and the temperature of the contents was maintained at 10°C. After the addition was completed, the reaction temperature was kept at 7°C and
Allowed time to react. During this time, the viscosity of the solution increased.
The product was poured into ice water, and the resulting polyamide precipitate was crushed and thoroughly washed with water until the acidity of the salt was no longer observed. Finally, it was washed with methanol, and the pale gray white powder was dried under reduced pressure at 120°C. The yield was 99g. Elemental analysis results of the product (calculated values are shown in brackets). C: 51.8% (51.15%) H: 4.0% (3.90%) S: 12.0% (12.41%) N: 10.3% (10.85%) The above polyamide did not soften up to 290°C. Moreover, its infrared absorption spectrum is as shown in FIG. Absorption by amide group at wave number 3300 cm ^-1 , wave number
Absorption due to sulfonamide groups is observed at 1160 cm ^-1 and 1320 cm ^-1 and absorption due to methyl group is observed at 2850 cm ^-1 . Example 2 The polyamide powder obtained in Example 1 was N-methyl-
It is soluble in 2-pyrrolidone, N·N-dimethylacetamide, N·N-dimethylformamide, N·N-diethylformamide, and dimethylsulfonoxide. The reduced viscosity of this polyamide is 2.0 dl/g (solvent dimethylacetamide, concentration 0.1 g/dl solution, temperature 30
℃ (hereinafter the measurement conditions are the same). A 20% solution of this polyamide in dimethylacetamide was prepared and cast onto a glass plate to a thickness of 200 μm, and dried at 140° C. for 5 hours and at 200° C. for 24 hours to produce a film (45 μm thick). This film had a tensile strength of 9 Kg/mm ² and an elongation rate of 9%. Further, when this film was subjected to thermogravimetric analysis in air (heating rate: 5°C/min), it did not lose weight up to 390°C. In addition, a 10% solution of polyamide in dimethylacetamide containing 10% lithium nitrate was cast onto a glass plate to a thickness of 250 μm, and after the solvent was evaporated at 110°C for 15 minutes, it was immersed in ice water. A transparent film was obtained by gelation. Attach this membrane to a filter and remove 0.5%
Using a sucrose solution, the amount of permeation of water and sucrose was measured at an operating pressure of 5 kg/cm ² . As a result, the water permeation rate was 0.03ml/ ^cm2・min, and the sucrose rejection rate was 90.
It was %. Example 3 Into the same apparatus as in Example 1, 82.90 g of 4,4'-diaminodiphenyl ether-2,2'-di(N,N-dimethylsulfonamide), 250 g of N,N-dimethylacetamide, and lithium chloride were added. Add 25g of flask, stir the contents, and cool the flask in an ice bath.
Gradually add 36.6 g of adipic acid chloride to this. After the addition was completed, the reaction was carried out at 5° C. for 5 hours. The resulting solution was treated in the same manner as in Example 1 to obtain polyamide powder.
Obtained 89g. The reduced viscosity of this polyamide is 0.8dl/
It was hot at g. Furthermore, the temperature at which weight loss started was 400°C as determined by thermogravimetric analysis. Elemental analysis results (calculated values in brackets) C: 50.8% (50.37%) H: 5.5% (5.38%) S: 12.0% (12.22%) N: 10.4% (10.68%) The infrared absorption spectrum of this polyamide is As shown in FIG. Absorption based on amide group at wave number 3300 cm ^-1 , absorption based on sulfonamide group at wave number 1160 cm ^-1 and 1320 cm ^-1 , 2960 cm ^-1 and 2870 cm
^-1 shows absorption due to methyl group. Example 4 Into the same apparatus as in Example 1, 94.06 g of 4,4'-diaminodiphenyl ether-2,2'-di(N-n-butylsulfonamide, 250 g of N-methyl-2-pyrrolidone, N. N-dimethylacetamide 250
g, add 25 g of lithium chloride, stir the contents,
Cool the flask in an ice bath. Gradually add 28.4 g of isophthalic acid chloride and 12.18 g of terephthalic acid chloride to this. After the addition was completed, the reaction was carried out at 5° C. for 5 hours. The resulting solution was treated in the same manner as in Example 1 to obtain 120 g of polyamide powder. The reduced viscosity of this polyamide was 1.5 dl/g. Furthermore, the temperature at which weight loss started was 320°C as determined by thermogravimetric analysis. Elemental analysis results (calculated values in brackets) C: 56.1% (55.98%) H: 5.4% (5.38%) S: 10.2% (10.67%) N: 9.1% (9.33%) The infrared absorption spectrum of this polyamide is As shown in FIG. Absorption by amide group at wave number 3300 cm ^-1 , absorption by sulfonamide group at wave number 1160 cm ^-1 and 1320 cm ^-1 , 2960 cm ^-1 and 2870 cm ^-1
Absorption due to methyl groups is observed at 2920 cm -1 and absorption due to methylene groups is observed at 2920 cm ^-1 . Also, this polyamide is N
-Methyl-2-pyrrolidone, N/N-dimethylacetamide, N/N-dimethylformamide,
Soluble in N.N-diethylformamide and dimethyl sulfoxide. Example 5 Two sets of the same apparatus as in Example 1 were prepared, and 4,4'-diaminodiphenyl ether-2,
2'-di(N-butylsulfonamide) 94.06g,
Add 500 g of N-methyl-2-pyrrolidone and 25 g of lithium chloride, stir the contents, and keep one flask at 25°C and the other at 50°C. 40.6 g of isophthaloyl chloride in each flask.
was gradually added and kept at the specified temperature for 6 hours to complete the reaction. Thereafter, in the same manner as in Example 1 and Example 2, the reduced viscosity of the synthetic polyamide and the tensile strength and elongation of the formed dry film were measured. The results are shown in the table.

〔Effect of the invention〕

As explained above, according to the present invention, it is possible to obtain a material that maintains the mechanical strength and heat resistance inherent to polyamide, has excellent solubility in organic solvents, and is easy to form into a film.

[Brief explanation of the drawing]

1 to 3 are infrared absorption spectra of the polyamide of the present invention.

Claims (1)

[Claims] 1. General formula [-NH-Ar-NHCO-Q-CO]- (However, Ar is [Formula] [Formula] (n is 0 or 1, R ₁ and R ₂ are hydrogen or lower alkyl groups, and the only hydrogen atom is R ₁ or R ₂
), (When R ₃ is H, R ₄ is CH ₃ , C ₂ H ₅ , when R _{3 is CH 3 , R 4 is} CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C _{4 H 3 ,} R ₃ is C ₂ H ₅ then R ₄ is C ₂ H ₅ ), ( _R5 is _CH3 , _R6 is H or _CH3 ), and Q is m-phenylene group, p-phenylene group, O-phenylene group, (Y=-O-, _-SO2- ), -( _CH2 )n- (n is 1, 2, 4 to 8), ), and has a reduced viscosity of 0.5 dl/g or more (dimethylacetamide solvent, 0.1 g/g)
Polyamide with alkylsulfonamide groups in the side chain. 2 (a) General formula H ₂ N−Ar−NH ₂ (Ar is [formula] [Formula] (n is 0 or 1, R ₁ and R ₂ are hydrogen or lower alkyl groups, and the only hydrogen atom is R ₁ or R ₂
), (When R ₃ is H, R ₄ is CH ₃ , C ₂ H ₅ , when R _{3 is CH 3 , R 4 is CH 3} , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , R ₃ is C ₂ H ₅ then R ₄ is C ₂ H ₅ ), (R ₅ is CH ₃ , R ₅ is H or CH ₃ ), (b) an aromatic diaminoalkylsulfonamide represented by the general formula XOOC-Q-COOX (wherein Q is m-phenylene group, p-phenylene group); group, O-phenylene group, (Y=-O-, _-SO2- ), -( _CH2 )n- (n is 1, 2, 4 to 8), It is. X is Cl or Br. ) in an inert solvent at 25°C or below to obtain a reduced viscosity of 0.5 dl/g or more (dimethylacetamide solvent, 0.1
A method for producing a polyamide having an alkylsulfonamide group in the side chain.