JPS5941453B2 - Polyamide having sulfonamide group in side chain and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a novel polyamide sulfonamide having a sulfonamide group in its side chain.

[Background of the invention]

So-called aromatic polyamides, in which amide bonds are directly bonded to aromatic nuclei, have excellent mechanical properties, shape stability at high temperatures, thermal decomposition resistance, electrical insulation properties, etc. due to their rigid molecular chains, and are useful for heat-resistant fibers and Industrially, it is extremely valuable as an 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, the production of films from these aromatic polyamides has been subject to various limitations. Furthermore, when these conventional aromatic polyamide films are used as semipermeable membranes, it has been pointed out that they have drawbacks in their properties, such as insufficient water permeability due to their remarkable hydrophobicity. [Object of the invention] The present invention was made in view of the drawbacks of the conventional aromatic polyamides,
The purpose is to provide a material that retains the mechanical strength and heat resistance inherent to aromatic polyamide, has excellent solubility in organic solvents, and is easy to form into a film. The goal is to provide useful materials.

[Summary of the Invention] The aromatic polyamide of the present invention is a polyamide having a sulfonamide group in the side chain, and is characterized by a reduced viscosity of at least 0.5 dt/g (solvent, dimethylacetamide, concentration 0.1 g/Dtl3O°C). ) and consists of repeating units represented by the general formula below.

(In the formula, Ar has n SO2NH2 groups bonded to the aromatic nucleus, and each of the SO2NH2 groups has an NH It represents a divalent aromatic residue bonded to the group, and Q represents a divalent aromatic or aliphatic residue.

) Specifically, Ar is - Kuwa≦ ~▼VC Todoroki? Number C' Society - (n is 0 or 1, X is -0-, -S-, -SO2- or -CH2-.

), and Q is a m-phenylene group, (Y is -0-, -SO2- or -CO-), and a divalent group selected from +CH2》2 to 8. be. The above-mentioned aromatic polyamide having a sulfonamide group in the side chain is a corresponding aromatic diaminosulfonamide (H2N
-Ar-NH2) and a dibasic acid halide in an inert solvent at a temperature below room temperature. Specific examples of such aromatic diaminosulfonamide (H2N-Ar-NH2) are as follows.

3,5-diaminobenzenesulfonamide benzidine-2-sulfonamide (synonymous with 4,4'-diaminodiphenyl-2-sulfonamide) Two or more of these aminosulfonamides can be used in combination.

Further, the dibasic acid halide, which is another raw material component (Q-containing compound), is specifically shown below.

Isophthalic acid halides Two or more of these dibasic acid halides can be used in combination.

In particular, it is advantageous to use an aromatic dicarboxylic acid halide in combination with the aliphatic dicarboxylic acid halide in terms of the strength of the membrane. For example, N-methyl-2-pyrrolidone N,N
- A solvent inert to the reaction components, such as dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoramide, and N,N-diethylformamide, is used.

An acid acceptor may also be used to capture the hydrogen halide generated.

There are various 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 aromatic polyamide of the present invention is produced by reacting the aromatic diaminosulfonamide and a dibasic acid halide in an inert solvent at a temperature around room temperature or lower.

In this case, both reaction components are mixed in a substantially equimolar ratio (in practice, 0
．． There is no problem even if the amount is increased or decreased within the range of 2 moles or less. ), and by doing so, it is possible to obtain an aromatic polyamide having a high molecular weight, that is, exhibiting a high reduced viscosity. Low molecular weight aromatic 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, at least 0.5 dt/g
, preferably with a reduced viscosity of 0.8 dt/g or more (solvent, N
, N-dimethylacetamide, concentration 0.1 g/Dt. 3
Aromatic polyamides having a temperature of 0.degree. The aromatic polyamide obtained as described above has a wave number of 3 in its infrared absorption spectrum.
Absorption by amide groups in the region of 400 to 3200 an-1, wave numbers 1350 to 1320 and 1170 to 1150 α
Absorption due to sulfonamide groups was shown in the -1 region, and the elemental analysis values also matched the calculations.

The aromatic polyamide of the present invention has a highly polar sulfonamide group as a side chain, and this group allows the membrane to exhibit permselectivity, and also provides rigidity to the main chain of the polyamide containing the aromatic nucleus. It is extremely unique in that it gives the membrane high mechanical strength and excellent resistance to corrosion.

The aromatic polyamide of the present invention is easily soluble in polar solvents such as amides, and can be formed into a film from the solution by inertial means.

The film also exhibits good water permeability and salt rejection, and is useful as a semipermeable membrane. Next, the present invention will be explained with reference to Examples. [Embodiments of the invention] Example 1 In a four-hole flask with a capacity of 1 ton equipped with a thermometer, a stirrer, a dropping funnel and an air-cooled tube with a calcium chloride tube, 4,4'
-Diaminodiphenyl ether-2,2'-disulfonamide 71.6 gsN-methyl-2-pyrrolidone 500
g and 25 g of lithium chloride, stir the contents,
Cool the flask in an ice bath.

40.6 g of isophthaloyl chloride was gradually added, and the temperature of the contents was maintained at 10° C. or lower. After the addition was completed, the reaction temperature was maintained at 7° C. and the reaction was continued for 6 hours. During this time, the viscosity of the solution increased. The resulting solution was poured into ice water, and the resulting polyamide precipitate was pulverized and thoroughly washed with water until the acidity of the solution was no longer recognized. Finally, it was washed with methanol, and the pale gray white powder was dried under reduced pressure at 120°C. The yield was 95g. Elemental analysis results of the product (calculated values are shown in brackets).

C5O. O% (49.18%), H3.9% (3.28
%), Nll. 5% (11.48%), Sl2. l%(
13.11%) The aromatic polyamide did not soften up to 300°C.

The infrared absorption vector is shown in the figure.

Wave number 3300? -1 absorption by amide group, wave number 132
0an-1 and 1150? -1 shows absorption by sulfonamide. Example 2 The aromatic polyamide powder obtained in Example 1 was N-methyl-2
-pyrrolidone, N,N-dimethylacetamide, N,N
-Soluble in dimethylformamide, N,Nl-diethylformamide, and dimeryl sulfoxide.

The reduced viscosity of this aromatic polyamide was 1.5 dt/g (solvent dimethylacetamide, concentration 0.1 g/Dt solution, temperature 30°C, measurement conditions the same below).

, 20% dimethylacetamide of this aromatic polyamide
A solution was prepared, cast on a glass plate, and dried at 180 to 200°C to produce a film (thickness: 50 μm). The tensile strength of this film is 15k9/M7il, and the elongation rate is 10%.
It was hot. In addition, this film C did not lose weight up to 400°C when thermogravimetrically analyzed in air (heating rate 5°C/MO).
[dissolved in dimethylacetamide] was cast on a glass plate, the solvent was evaporated at 110°C for 15 minutes, and then the solution was immersed in ice water for gelation to obtain a transparent film.

5000 PI as feed for this membrane] 10)N
A reverse osmosis experiment was conducted using the ACT aqueous solution under the conditions of an operating pressure of 50 kg/d. Water permeation amount is 1.7m'/M゜・D
ay, the salt rejection rate was 65%. Example 3 Two sets of devices similar to those in Example 1 were prepared, and 4,4-diaminodiphenyl ether-2,2'-disulfonamide 71 was added to each set.
．． 6. Add 500 g of N-methyl-2-pyrrolidone and 25 g of lithium chloride, stir the contents, and keep one flask at 20°C and the other at 40°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 aromatic polyamide and the tensile strength and elongation of the formed dry film were measured. The results are shown in the table. Example 4 Into the same apparatus as in Example 1, 71.2 g of 4,4'diaminodiphenylmethane-2,2'-disulfonamide and 250 g of N-methyl-2-pyrrolidone were added. ．． Add 250 g of N,N-dimethylacetamide and 25 g of lithium chloride, stir the contents, and cool the flask in an ice bath.

28.42 g of isophthalic acid chloride and 12.18 g of terephthalic acid chloride are gradually added to this. After the addition was completed, the reaction was carried out at 8° C. for 5 hours. The resulting solution was treated in the same manner as in Example 1 to obtain 94 g of aromatic polyamide powder. The reduced viscosity of this aromatic polyamide was 2.4 dt/g. Further, the temperature at which weight loss started was 350°C as determined by thermogravimetric analysis. Elemental analysis results (calculated values in brackets) C5O. 5% (49.18%), H4. O% (3.28
(:F6), Nll. O% (11.4801)), Sl
1,5% (13.11%) This aromatic polyamide is N-
It was soluble in methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, and dimethylsulfoxide.

Example 5 3,5-diaminobenzenesulfonamide 18
．． Add 7 g, 1 N-methyl-2-pyrrolidone, 200 g, and 10 g of lithium chloride.Stir the contents and cool the flask in an ice bath.

29.5 g of 4,4'-diphenyl ether dicarboxylic acid chloride was gradually added, and after the addition was completed, the reaction was carried out at 7°C for 5 hours.

This solution was treated in the same manner as in Example 1 to obtain 39 g of aromatic polyamide powder. The reduced viscosity of this aromatic polyamide was 2.05 dt/g. As a result of infrared spectroscopy, the wave number of 3300 cm-1 is the absorption of amide group of 1150 cfn-
Absorption of sulfonamide was observed in 1 and 1320c1n-1. Example 6 Into the same apparatus as in Example 1, 132.5 g of 4,4'-diaminodiphenyl-2-sulfonamide, . Add 500 g of N-methylpyrrolidone and 25 g of lithium chloride, stir the contents, and cool the flask in an ice bath.

91 g of adipic acid chloride is gradually added to this.
After addition. The reaction was carried out for 5 hours at a temperature below 10°C.
The resulting solution was treated in the same manner as in Example 1 to obtain 120 g of aromatic polyamide powder. The reduced viscosity of this aromatic polyamide was 1.05 dt/g. Elemental analysis results (calculated values in brackets) C58.5% (57.9%), H5. O% (5.1%)
, NlO. 9% (11.3%), S8. O% (8.6%
) As a result of infrared spectroscopy, amide group absorption at a wave number of 3300 an-1 and sulfonamide absorption at 1150 an-1 and 1330 an-1 were observed.

This polyamide is N-methyl-2-pyrrolidone, N,N
-It was soluble in dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide. This aromatic polyamide film had a tensile strength of 12k9/m and an elongation of 6%. Example 7 In a flask similar to Example 1, 27.9 g of 4,4'-diaminodiphenyl ether-2-sulfonamide, . N
-200 g of methyl-2-pyrrolidone, 10 g of lithium chloride
Stir the contents and keep the flask cooled in an ice bath.

20.3 g of isophthalic acid chloride was gradually added to this, and after the addition was completed, the reaction was carried out at 7° C. for 6 hours. It was treated in the same manner as in Example 1 to obtain 38 g of aromatic polyamide powder. The reduced viscosity of this aromatic polyamide was 1.65 dt/g. It was prepared in the same manner as in Example 1 from the N,N-dimethylacetamide solution. The tensile strength of the film is 11
The kg/MilS elongation rate was 13%. Example 8 Into the same flask as in Example 1, 71.6 g of 4,4'-diaminodiphenyl ether-2,2'-disulfonamide was added.
g. ．． Add 500 g of N-methyl-2-pyrrolidone and 25 g of lithium chloride, stir the contents, cool the flask in an ice bath, and gradually add 68.4 g of 4,4'-diphenylsulfonedicarboxylic acid chloride. , after addition,
The reaction was carried out at 7°C for 5 hours.

This solution was treated in the same manner as in Example 1 to obtain 130 g of aromatic polyamide powder. This aromatic polyamide is N-methylpyrrolidone, N,N-dimethylacetamide, N,
Soluble in N-dimethylformamide, N,N-diethylformamide, and dimethylsulfoxide.

The reduced viscosity of this polyamide was 1.3 dt/g.

As a result of infrared spectroscopy, the wave number 3300an-1 is the absorption of amide group 1150? Absorption of sulfonamide was observed in -1 and 1320a1-1. A 15% solution of this polyamide in N-methylpyrrolidone was prepared, cast onto a glass plate, and dried at 150 to 200°C to form a film (40μ thick).
m) was prepared.

The tensile strength of this film is 12k9/the elongation rate is 8%
It was hot. Further, when this film was subjected to thermogravimetric analysis in air, it did not lose weight up to 380°C. Example 9 In a flask similar to Example 1, 71.6 g of 4,4'-diaminodiphenyl ether-2,2'-disulfonamide was added.
g. Add 500 g of N-methyl-2-pyrrolidone and 25 g of lithium chloride, stir the contents, and cool the flask in an ice bath. Gradually add 61.2 g of 4,4'-diphenylsulfonedicarboxylic acid chloride. After addition, 7
The reaction was carried out at ℃ for 5 hours.

This solution was treated in the same manner as in Example 1 to obtain 120 g of aromatic polyamide powder. This aromatic polyamide is N-methylpyrrolidone N,N-dimethylacetamide, N,N
-Soluble in dimethylformamide, N,N-diethylformamide, and dimethylsulfoxide.

The reduced viscosity of this polyamide was 1.8 dt/g.

As a result of infrared spectroscopy, absorption of amide group at 1150c1n-1 and sulfonamide absorption at 13200n-1 was observed at wave number 3300CTL-1. A 15% solution of this polyamide in N-methylpyrrolidone was prepared, cast on a glass plate, and dried at 150 to 200°C to produce a film (40 m thick).

The tensile strength of this film is 13k9/CII! ．． The elongation rate was 9%. Further, when this film was subjected to thermogravimetric analysis in air, there was no weight loss L up to 380°C. Example 10 Into the same apparatus as in Example 1, 279 g of 4,4-diaminodiphenyl ether-2-sulfonamide was added. ．． Add 200 g of N-methyl-2-pyrrolidone and 10 g of 1,000 chloride, stir the contents, and cool the flask in an ice bath.

15.4 g of succinic acid chloride is gradually added to this. After the addition was completed, the reaction was carried out at a temperature of 10° C. or lower for 5 hours.
The resulting solution was treated in the same manner as in Example 1 to obtain 40 g of aromatic polyamide powder. The reduced viscosity of this aromatic polyamide was 1.0 dt/g. Elemental analysis results (calculated values are shown in the box) C54. O% (53.2%), H4. O% (4.2%)
, Nll. 5% (11.

6%), S8. 1% (8.9%) Infrared spectroscopic analysis results,
Amide group absorption at wave number 3300 an-1, 1150 an-
1 and 1330C7! Sulfonamide absorption was observed in L-1.

This polyamide is N-methyl-2-pyrrolidone, N,N
-Dimethylacetamide, N,N-dimethylformamide, and dimethylsulfoxide. The tensile strength of this aromatic polyamide film is 12k9/Mi7
L, elongation was 5%. Example 11 27.9 g of 4,4'-diaminodiphenyl ether-2-sulfonamide, 200 g of N-methylpyrrolidone, and 10 g of lithium chloride were placed in the same apparatus as in Example 1, the contents were stirred, and the flask was placed on ice. Cool in a bath.

23.8 g of sebacic acid chloride is gradually added to this. After the addition was completed, the reaction was carried out at a temperature of 10° C. or lower for 5 hours. The resulting solution was treated in the same manner as in Example 1 to obtain 45 g of aromatic polyamide powder. The reduced viscosity of this aromatic polyamide was 1.5 dt/g. Elemental analysis results (calculated values in brackets) C6O. O% (59.3%), H6, O% (6.1%)
, N9. l% (9.

4%), S6.9% (7.2%) Infrared spectroscopic analysis results,
Amide group absorption with wave number 3300an-1 1150an-1
And sulfonamide absorption was observed in 1330an-1.

This polyamide is N-methyl-2-pyrrolidone N,N
-It was soluble in dimethylacetamide, N,N-dimethylformamide, and dimethylsulfoxide. This aromatic polyamide film had a tensile strength of 9k9/m and a length elongation of 8%. Example 12 In a flask similar to Example 1, 4,4'-diaminodiphenylsulfide-2,2'-disulfonamide 74
．． 8g. Add 500 g of N-methyl-2-pyrrolidone and 25 g of lithium chloride, stir the contents, and cool the flask in an ice bath.

40.6 g of isophthalic acid chloride was gradually added to this flask, and after the addition was completed, the reaction was carried out at 7° C. for 5 hours. This solution was treated in the same manner as in Example 1 to obtain 132 g of aromatic polyamide powder. This aromatic polyamide is N-methylpyrrolidone N-N-dimethylacetamide, N,N-
Dimethylformamide N-N-diethylformamide Soluble in dimethyl sulfoxide.

The reduced viscosity of this polyamide was 1.5 dt/g.

As a result of infrared spectroscopy, absorption of amide group at wavelength 3300CTII-1, 1150an-1 and 1320aL-1
Absorption of sulfonamide was observed. A 15% solution of this aromatic polyamide in N-methylpyrrolidone was prepared, cast on a glass plate, and dried at 150 to 200°C to produce a film (thickness: 35 μm). The tensile strength of this film was 16 kg/Cml, and the elongation rate was 5%. When this film was heated in air, it did not lose weight up to 410°C. [Effects 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 aromatic polyamide, has excellent solubility in organic solvents, and is easy to form into a film. be.

[Brief explanation of drawings]

The figure shows an infrared absorption spectrum.

Claims (1)

[Claims] 1. An aromatic polyamide having a reduced viscosity of at least 0.5 dl/g (solvent, dimethylacetamide, concentration 0.1 g/dl, 30°C) and consisting of repeating units represented by the following general formula: . ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼ (n is 0 or 1, X is O, S, SO_2 or CH_
2), and Q is m-
2 selected from phenylene group, p-phenylene group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Y is O, SO_2 or CO), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
It is the basis of valence. )2 (A) General formula H_2N-Ar-NH_2 (in the formula A
r is ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, (n is 0 or 1, X is O, S
, SO_2 or CH_2) and (B) a dibasic acid halide are polycondensed in an inert solvent at a temperature below room temperature. An aromatic polyamide having a reduced viscosity of at least 0.5 dl/g (solvent, dimethylacetamide, concentration 0.1 g/dl, 30°C) and consisting of repeating units represented by the following general formula. Manufacturing method. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar and n are as defined in (A) above, and Q is m-phenylene group, p-phenylene group ▲There are mathematical formulas, chemical formulas, tables, etc.) (Y is O, SO_2 or CO), ▲A divalent group selected from ▼There are mathematical formulas, chemical formulas, tables, etc.)