DE2000927A1 - Aromatic polyamides containing disulphimide - groups - Google Patents

Abstract

High-molecular aromatic polyamides which can be dyed by means of basic dyes contain 2-20 mol % (of the total units derived from the diamine or from the dicarboxylic acid dihalide) of a disulphimide group containing units of formula: where Ar1 and Ar2 are divalent aromatic residues consisting of 1, or several condensed, aromatic rings, or aromatic rings joined by a simple bond or a -CH2-, -O-, or -SO2- group, and which may carry alkyl or halogen substituents, Ar3 is a trivalent aromatic residue, R is Cl-4 alkyl or a residue which may be alkyl- or halogen-substd, Z is H or an alkali metal and A is -CONH- or -NHCO-, and 98-80 mol % of units from known aromatic polyamides. The polyamide has a relative solution viscosity (using a 0.5% solution in N-methyl-pyrrolidone at 20 degrees C)>1.3. The polyamides are almost colourless and are very easily dyed with basic dyes.

Description

Basic dyeable, high molecular weight aromatic polyamide object of the invention are basic dyeable, high molecular weight aromatic polyamides, the additionally have disulfimide structures, as well as threads made therefrom.

Those through interfacial polycondensation and polycondensation in solution from aromatic or aromatic, heterocyclic-containing diamines and aromatic High molecular weight polyamides obtained from dicarboxylic acid dihalides are generally obtained cannot be dyed with basic dyes. To the wide range of basic hard materials to be able to use it for coloring aromatic polyamides, it is necessary to the polyamides by introducing acidic groups the necessary affinity for these Parbstoffe to rent. It is known, for example, by adding carboxylic acid derivatives capable of cocondensation (US Pat. No. 3,380,969) or of cocondensable sulfonic acid derivatives (NE 6 717 240) to improve the dye uptake of aromatic polyamides.

A disadvantage of the cocondecsationa capable carboxylic acid derivatives is that often the acidity of the carboxyl group to achieve good dyeability is not sufficient. The sulfonic acid derivatives are usually less easy to digest condense the polyamides.

Objects of the @findurch very owned, uncoloured ho @@ me. The aromati @@ @@ @@. @@@ -i. -; (based on the total amount of the structural segments derived from the diamines or from the dicarboxylic acid dihalides) from structural segments of the general formulas containing a disulfimide group where hr1 and Ar2 can be the same or different and bivalent atomic radicals, consisting of one or more condensed aromatic rings or aromatic rings which have a single bond or a -CH2-, -0-, -5- or -SO2- Group are connected to one another, as well as their alkyl and halogen substitution products, Ar³ is a trivalent aromatic radical, R is a C1-C4-alkyl radical or an optionally alkyl or halogen-substituted radical, Z can be hydrogen or an alkali metal and A represents the amide grouping of the Formula -CONH- or -NHCO- stands, and @@@ known aromatic consists, @@@ the @@ es # @@@ me @@@@ en hang in @@@ @@@.

These new polyamides show due to the strong acidity of the disulfimide group extremely good dyeability with basic dyes.

Another object of the invention is a process for the preparation of basic dyeable, high molecular weight aromatic polyamides by condensation of components with acidic groups, which is characterized in that 2 to 20 mol%, based on the total amount of diamines, diamines of the general formulas in which Ar1, Ar2, Ar3, R and Z have the abovementioned meaning, or 2 to 20 mol%, based on the total amount of dicarboxylic acid dihalides, dicarboxylic acid dihalides of the general formulas where Ar1, Ar2, Ar3, R and Z have the abovementioned meaning and Hal is chlorine or bromine, polycondensed together with customary polyamide-forming aromatic diamines and aromatic ticarboxylic acid dihalides.

So there are cocondensable disulfimide compounds in a concentration of 2 to 20 mol%, preferably 4 to 10 mol, based on the Total amount of one of the two condensation components, also condensed. Because of the excellent condensation ability of the built-in disulfimide compounds practically complete condensation of these compounds is obtained.

For the purposes of this invention, only aromatic polyamides are used as aromatic polyamides Polyamides understood, which consist of purely aromatic components or such components, which in addition to aromatic radicals also contain heterocyclic radicals in the chain, but not those that also have aliphatic radicals within the chain structure, are constructed.

The aromatic I) isulfimide compounds correspond to the general formulas X denotes an —NH2 group or the —CO — Hal group, where Hal is preferably C1 and Br, Ar1, Ar2, Ar3, R and Z have the abovementioned meanings.

Ar3 is preferably a trivalent aromatic radical of the following formulas: The following disulfimides, which correspond to the formulas given above, can be used, for example: 4,4'-diamino-diphenyl-disulfimide 3,3'-diamino-diphenyl-disulfimide 3,4'-diamino-diphenyl-disulfimide 3,3'- Diamino-4,4'-dichloro-diphenyl-disulfimide 4,4'-diamino-3,3'-dichloro-diphenl-disulfimide 3,3'-diamino-4-chloro-diphenyl-disulfimide diphenyl-disulfimide-dicarboxylic acid dichloro-4 , 4 'Diphenyl-disulfimide-dicarboxylic acid dichloro-3,3' Diphenyl-disulfimide-dicarboxylic acid dichloro-3,4 '4- (p-aminophenoxy) -3'-amino-diphenyl-disulfimide 5-aminophenyl-4'-amino-naphthyl- (1) -disulfimide 3,5-diamino-diphenyl-disulfimide 3,5-diamino-4-chloro-diphenyl-disulfimide in which 3,5-diaminophenyl-methyl-disulfimide diphenyl-disulfimide-dicarboxylic acid-dichloride-3,5 phenyl- methyl-disulfimide-dicarboxylic acid-dichloride-3, 5 1, 5-diamino-naphthyl- (3) -phenyl-disuifimid 1, 4-diamino-naphthyl- (6) -phenyi-disuifimid 1,5-diamino-naphthyl- ( 3) -methyl-disulfimid The disulfimides described above can by reaction of sulfonic acid chlori those with sulfonic acid amides in an alkaline medium (Ber. 75, 532 (1942)) or by reacting sulfonylthionylamines with sulfonic acids (DBP 1 235 300).

The disulfimides described above are suitable for cocondensation for all polyamides and copolyaniides made from aromatic or aromatic, Diamines and dicarboxylic acid halides containing heterocycles can be produced and, for example, in U.S. Patents 3,094,511 and 3,376,268, French Patents 1,199,458 and 1,430,480, Belgian patents 718 033 and 718 034, as well as in the German patent applications P 17 20 728.2, P 18 07 297.4, P 19 46 789.1 and P 19 53 358.5 are described.

For the production of the basic dyeable, disulfimide-containing, Polyamides containing aromatic or heterocycles are preferably used polycondensation in solution, but in principle interfacial polycondensation can also be used use. The procedure here is preferably such that a fully aromatic diamine is used or a diamine containing heterocycles together with 2-20 ol, preferably 4 - 10 mol, of a diamine with a disulfimide structure, based on the total amount of diamine, in a polar organic solvent and then the aromatic dicarboxylic acid dichloride slowly and in portions. But you can also proceed in such a way that you get a fully aromatic or a Diamine containing heterocycles in a polar organic Submitted solvent and an aromatic dicarboxylic acid dihalide in mixture with 2 to 20 mol, preferably 4 to 10 mol%, of a dicarboxylic acid dihalide with a disulfimide structure (based on the total amount of dicarboxylic acid dichloride) added.

NN-dialkylearboxamides serve as polar, organic solvents, for example N, N-dimethylacetamide, or N-substituted lactams, such as. B. N-methylpyrrolidone. The great advantage of these solvents is that in the absence of additional Acid acceptors can be worked. To achieve the highest possible molecular weight It is advantageous to use reaction products, the diamine component and the dicarboxylic acid dihalide component to be used in equivalent or nearly equivalent amounts. The condensation will at temperatures between -30 and + 1500C, but preferably at temperatures between -10 and +5000. The reaction times are between 1 and 30 hours. The solids content of the solutions is 5-40, preferably 10-25 fo.

Are diamines and dicarboxylic acid dihalides by their structure so designed that they are mutually insoluble in polar, organic solvents If polyamides are formed, up to 5;, (related on the amount of solvent) of an alkali or alkaline earth salt as a solubilizer, preferably LiOl or CaC12, can be added to prevent the precipitating of the resulting Prevent polyamide from the solution.

In the manufacture of some polyamides, palycondensation occurs very high viscosities due to very high molecular weights of the polyamides, so that it is recommended before or during the condensation or immediately after addition of the dicarboxylic acid dihalide is a chain termination causing Connection, e.g. B. an amine, an alcohol, water, an amino acid or hydroxycarboxylic acid, to be added to the batches as a chain regulator in small amounts.

The polyamides produced according to the invention are colorless or almost completely colorless and can be colored very easily with basic dyes. You let parts according to the known methods to form parts and to threads, fibers or bristles to process. Dyed textiles made from these polyamides have high washfastnesses.

Example 1 a :) Production of the disulfimide compound A suspension of 202 parts by weight of m-nitrobenzenesulfonamide in 1200 parts by weight of water was with 200 parts by weight of a 20 show added sodium hydroxide solution. Were at room temperature at the same time a solution of 242 parts by weight of m-nitrobenzenesulfonyl chloride in 400 parts by weight Acetone and 210 parts by weight of a 20% own sodium hydroxide solution are added dropwise so that a pH value from 10 - 11 was maintained. After stirring for two hours at 50 ° C., the mixture was cooled and suctioned off and washed with sodium hydroxide solution and water. The residue is sodium di- (m-nitrophenyl) disulfimide (Mp. 254-255 ° C), from which the di- (m-aminophenyl) -disulfimide sodium by catalytic hydrogenation with a melting point of 285-2870C.

b) Preparation of the polyamide 153 parts by weight of 3- (p-aminophenyl) -7-amino-2,4- (1H, 3H) -quinazolinedione and 10.8 parts by weight of di- (m-aminophenyl) disulfimide sodium were in 860 parts by weight absolute dimethylacetamide entered. Then were steady at 5 - 1000 under Stirring 122 parts by weight of isophthalic acid dichloride added in portions and the viscous The solution was stirred for a further 12 hours at room temperature. In between had to to adjust a viscosity between 2000 and 3000 poise, another 440 parts by weight Dimethylacetamide are added.

c) creation of threads This spinning solution with a viscosity of 2850 poise at 200C (rel. Rel = 2.3, measured on a 0.5% solution in N-methylpyrrolidone at 200 ° C.) through a 10-hole nozzle (diameter 0.1 mm) into a precipitation bath (bath temperature 2000), consisting of 70 parts by weight of water and 30 parts by weight of dimethylacetamide, spun. The threads were with a Speed of 10 m / minute withdrawn from the nozzle, then washed in water at 20 0C and finally pre-stretched in water at almost 1000C in a ratio of 1: 1.5. After drying the threads were at 380 -3900C over a heating bracket of 30 cm length in proportion 1: 1.5 stretched. Extremely thermally stable threads with a high temperature strength are obtained from 2.9 - 3.3 g / dtex at 5% elongation.

d) Dyeing of the threads 10 g fiber each from this polyamide and from the unmodified Homopolycondensate of 3- (p-aminophenyl) -7-amino-2,4- (1H, 3H) -quinazolinedione and Isophthalic acid dichloride were colored at 120 ° C. The liquor is made up of 5% Astrazon red RL (Color Index I, p. 162), 1 g / liter of the reaction product of 1 mol of oleyl alcohol with 50 moles of ethylene oxide and 2 g / liter of methyl o-cresotinate together. the The liquor was adjusted to pH = 4.5 and heated to 1200C over the course of 45 minutes and leave at 1200C for 1.5 hours.

After dyeing, the strands were made with a 0.1 of their own water Solution from Blankit treated at 500C.

For the exact determination of the better stainability, 500 mg of the treated fibers dissolved in 25 cm3 of dimethylacetamide and placed in a photometer (BFK from Kipp + Zonen) at 475 m / u the extinctions compared to pure dimethylacetamide measured. The extinctions are E = 1.8 for the disulfimide-modified polyamide compared to E = 0.15 for the unmodified homopolycondensate.

Example 2 a) Production of the disulfimide compound A suspension of 236.5 parts by weight of 4-chloro-3-nitrobenzenesulfonamide in 1000 parts by weight of water was with 200 parts by weight of a 20% strength sodium hydroxide solution are added. Then a solution of 242 parts by weight of 4-chloro-3-nitro-benzenesulfochloride were simultaneously at room temperature in 300 parts by weight of acetone and 210 parts by weight of a 20 show sodium hydroxide solution added dropwise in such a way that that a pH value between 11 and 12 was maintained. After two hours of stirring The mixture was cooled at 50 ° C. and the sodium di- (4-chloro-3-nitrophenyl) disulfimide formed (Melting point: 311-330C) and washed with sodium hydroxide solution. From this dinitro compound the di- (4-chloro-3-aminophenyl) disulfimide sodium with a melting point of 298-300 0C smoothly obtained by catalytic hydrogenation.

b) Preparation of the polyamide 134 parts by weight of 3- (p-aminophenyl) -7-amino-2,4- (1H, 3H) -quinazolinedione were used and 16.7 parts by weight of di- (4-chloro-3-aminophenyl) disulfimide sodium in 780 parts by weight Submitted absolute dimethylacetamide and then at 5 - 10 ° C with constant stirring added in portions 109.5 parts by weight of isophthalic acid dichloride and the viscous The solution was stirred for a further 12 hours at room temperature.

c) Production of threads From this 23 show polyamide solution with a Viscosity of 1500 poise (#el. = 1.5, measured on a 0.5% solution of the polyamide in N-Methsrlpyrrolidon at 200C) were through a 10-hole nozzle into an aqueous Felling bath threads are spun. The take-off speed was 15 m / 8 minute.

After a two-stage stretching in boiling water and on a Bail of 4000C with a total draw ratio of 1: 2.0 resulted in threads with a tear strength of 3.0-3.5 g / dtex.

a) Dyeing of the threads As described in Example 1 d), was also with these Polyamid threads carried out a comparative dyeing. The solution of the dyed threads in dimethylacetamide had an extinction of E = 2.54 (compared to E = 0.15 of the solution of the unmodified homopolymer).

Stains were also made with other astrazone dyes, such as e.g. B. Astrazon blue B (Color-Index II / 42140) and Astrazon orange G (Color-Index II / 48035), carried out.

Example 3 a) Preparation of the disulfimide compound A slurry of 303 parts by weight of 3-nitrobenzenesulfonamide in 1600 parts by weight of water was mixed with 300 parts by weight of a 20% strength sodium hydroxide solution are added. Then at room temperature both a solution of 384 parts by weight of 4-chloro-3-nitro-benzenesulfochloride in 500 Parts by weight of acetone as well as 300 parts by weight of a 20 show sodium hydroxide solution at the same time added dropwise in such a way that a pI ert of 10-11 was retained.

After stirring for 1 to 2 hours at about 50 ° C., the mixture was cooled, Sucked off and washed with sodium hydroxide solution and water.

The residue is 4-chloro-3-nitrophenyl-3'-nitrophenyl disulfimide (M.p .: 246-2470C), from which the 4-chloro-3-aminophenyl-3'-aminophenyl-disulfimide is smoothly obtained by catalytic hydrogenation.

b) Production of the polyamide 155 parts by weight of 1,3-bis (p-aminophenyl) -5,5-dimethylhydantoin and 22.2 parts by weight of 4-chloro-3-aminophenyl-3'-aminophenyl disulfimide were in 870 Parts by weight of absolute X-methylpyrrolidone dissolved and then 111.6 parts by weight of isophthaloyl chloride added in small portions at 5-100C. The viscous solution was still about Stirred for 12 hours at room temperature.

c) Production of threads This very viscous solution (# = 2750 poise, #rel. = 1.5, measured on a 0.5% solution of the polyamide in N-methylpyrrolidone at 200C) was spun according to the wet spinning process. The threads were at 10 m / minute deducted from a 10-hole nozzle hole diameter 0.1 mm).

Water at 20 ° C. was used as the precipitation bath. After the washing process, the Threads stretched in boiling water in a ratio of 1: 1.5, dried and stored at 390-400 ° C stretched on a stretching stirrup in a ratio of 1: 1.5. Threads with excellent Thermal stability and with a tensile strength of 3.0-3.3 g / dtex at 8% elongation.

d) Dyeing of the threads A comparison dyeing according to that in the example was used 1 d) described method carried out. Also as indicated in example 1 d), the absorbance of a solution of the dyed threads was measured; it is E = 2.1 (compared to E = 0.18 of the solution of the unmodified homopolycondensate from 1,3-bis- (p-aminopehyl) -5,5-dimethyl-hydantoin and tsophthalic acid dichloride).

Claims (7)

Patent claims: ; ij)) Base dyeable, high molecular weight aromatic polyamides, consisting of 2-20 mol% (based on the total amount of the structural segments derived from the diamines or from the dicarboxylic acid dihalides) of structural segments of the general formulas containing a disulfimide group where Arl and Ar can be the same or different and divalent aromatic radicals, consisting of one or more condensed aromatic rings or of aromatic rings, which have a single bond or a -CH2-, -0-, -S- or -S02- Groups are linked to one another and their alkyl and halogen substitutions are products, hr3 is a trivalent aromatic radical, a C1-C4-alkyl radical or an optionally alkyl or halogen-substituted est, Z can be hydrogen or an alkali metal and A is the amide group of the formula -CONH- or -NHCO-, and 98-80 mol.% of structural segments of known aromatic polyamides, the polyamides having a relative solution viscosity if 'rel. (measured on a 0.5% solution in N-methylpyrrolidone at 20 ° C.) above 1.3. 2.) Base dyeable, high molecular weight aromatic polyamides according to claim 1, characterized in that the structural segments containing a disulfimide group have the general formula where Ar1, Ar2 and Z have the meaning given in claim 1. 3) basic dyeable, high molecular weight aromatic polyamides according to claim 1, characterized in that the 3 structure segments containing a disulfimide group have the general formula in which A, R and Z have the meaning given in claim 1. 4) Process for the preparation of basic dyeable, high molecular weight aromatic polyamides by condensation of components with acidic groups, characterized in that 2 - 20 mol, based on the total amount of diamines, diamines of the general formulas wherein Ar1, Ar2, Ar3, R and Z have the meaning given in claim 1, or 2 to 20 mol%, based on the total amount of dicarboxylic acid dihalides, dicarboxylic acid dihalides of the general formulas in which Ar1, Ar2, Ar3, R and Z have the meaning given in claim 1 and Hal is chlorine or bromine, polycondensed together with customary polyamide-forming aromatic diamines and aromatic dicarboxylic acid dihalides. 5) Method according to claim 3, characterized in that the Carries out polycondensation in a solvent. 6) Method according to claim 3, characterized in that the Carries out polycondensation as interfacial condensation. 7) Threads made from high molecular weight aromatic polyamides according to claim 1.