NO161917B - ANALOGY PROCEDURE FOR THE PREPARATION OF THERAPEUTIC ACTIVE DERIVATIVES OF TIENO AND FURO (2,3-C) PYROLES. - Google Patents

Abstract

preparation of thieno and furo [2,3-c] pyrroles represented by the formula. wherein X and X represent an oxygen or sulfur atom; R. represents a straight or branched chain alkyl radical containing from 1 to 8 carbon atoms, an alkynyl radical, an alkoxyalkyl radical containing from 3 to 8 carbon atoms or an aromatic radical; R 1 represents a hydrogen atom or a straight or branched alkyl radical; m = 2 or 3, when m = 2 represents X and Xet sulfur atom, U represents a 3,4-diamino-cyclobutene-1,2-dione or aminosulfonylformamidine radical; U can also represent a nitrogen structure. wherein V represents a nitrogen atom or a CH fragment; W represents NO or CN; R represents a hydrogen atom, a straight or branched alkyl radical of from 1 to 8 'carbon atoms, an alkynyl radical; R represents an alkyl group containing from 1 to 3 carbon atoms.

Description

Process for increasing the dye uptake capacity for acid dyes for polyamides from lactams.

It is known that one can improve

the dye absorption capacity for acid dyes

for polyamides when it is ensured that the polyamides have an increased number of amino end groups. This can be achieved by addition

of free 1 amides to the polyamide-forming ones

starting materials before the polycondensation. To

the amines used for this purpose belong

aliphatic mono- or diamines and heterocyclic amines. While the addition of such

amines to dicarboxylic acids and diamines which

polyamide-forming starting materials only have

led to a small profit, must

the amounts of lactams as1 monomers

be considerably larger. Polyamides such as

produced by this method and

has an increased number of amino end groups, is

however, difficult to spin. When you want

achieve a noticeable improvement in dyeability and add a correspondingly larger amount of amine, the polyamide mass tends to

spinning to dripping, i.e. a spinning is

practically no longer possible. After one

known method, this shortcoming must now be eliminated by adding the polyamide

before spinning sets phosphorus compounds.

Hypophosphites of alkali-alkaline and alkaline-earth metals as well as of

zinc, cadmium, manganese, aluminum and

tin and salts of phosphinic acids.

According to another known method

the color affinity of polyamides must be increased

by adding alkyl or arylphosphinic acids, resp. their amine salts. It is shown that

the addition of these compounds, especially of the amine salts of phosphinic acids, results in a noticeable improvement in the color absorption capacity, while the metal salts of phosphinic acids produce no effect. However, the known method is limited to polyamides of dicarboxylic acids and diamines. When one tries to transfer the prescription for the working method to polyamides of lactams, it is determined that the achievable improvement in color affinity is only small.

It has now been found that the dye absorption capacity of polyamides of lactams for acid dyes can be significantly improved by the addition of organic phosphorus compounds

when using 0.05-3% by weight. of one

phosphorous or phosphonic acid ester together with 0.02-0.5 wt. of an amine of the general formula

where n means 2-5 and m means 0-3.

The best results are obtained with amines of the above formula', where n is 2 and mi is 1-3, especially with diethylenetriamine as well as triethylenetetramine or tetraethylenepentamine.

Phosphorous compounds and amines can be added to lactams before or at a suitable point in time during the polycondensation. It is also possible to add additives to the finished polyamide, which is available in cut or powder form, before spinning, e.g. by "breading" the cuts.

Phosphorus compounds that can be used according to the invention include phosphorous or phosphonic acid esters of the general formulas

wherein X means an aryl or alkyl residue and Y means an aryl or alkyl residue or hydrogen.

When, in order to increase the color affinity of polyamides of lactams, only a phosphoric or phosphonic acid ester is added, there is already an, albeit relatively small, effect, while this is not the case with the known phosphinic acids, resp. phosphinic acid derivatives. However, the phosphorus compounds to be used according to the invention also do not succeed in enhancing this effect by adding correspondingly larger quantities without at the same time reducing the viscosity of the polyamide. When, on the other hand, a phosphoric or phosphonic acid ester is used together with a smaller amount of the di- or polyamine, the color absorption capacity increases greatly. Although the amines, as well as the phosphorus compounds, have a viscosity-reducing effect, with a suitable combination of phosphorus compounds and amines as well as with the choice of additive quantities, an optimal improvement of the color affinity can be achieved with the least possible reduction in viscosity. Here, in particular, amines of the aforementioned general formula, in which m is 1-3, offer great advantages because even in very small quantities they show a strong effect on the color ratio of the polyamides, and these quantities only have a small effect on the viscosity.

A further precaution which leads to the achievement of particularly favorable results is the addition of a phosphorus compound and amine to the finished polyamide. In this form of implementation of the method, the viscosity of the polyamide is hardly influenced. It is therefore surprising that the improvement in color absorption is considerable. This was not to be foreseen, especially with knowledge of known methods, because these assume that in order to increase the number of amino end groups and thus the color affinity, the additives, and especially the amines, must be added unconditionally to the polyamide-forming starting materials.

The procedure shall be explained in more detail by means of examples. A) Caprolactam is polycondensed in a known manner and 1 part by weight of ethanephosphonic acid ester and 0.3 parts by weight of diethylenetriamine are added to the liquid monomer. The polyamide formed has a solution viscosity of 2.05 and is easily spinnable. (The solution viscosity is determined by measuring the flow rate of a 1% solution of the polyamide in formic acid.) To determine the color improvement achieved, threads of the above-mentioned additives containing polyamide are dyed together with polyamide threads that do not contain additives, in the same bathroom with "Antralan blue B". The dye taken up by the two thread samples is then completely washed out with a pyridine-water mixture. One measures the extinction of the two dye solutions whose ratio is 1:3.8 (polyamide without addition: polyamide + phosphorus compound and amine).

As described in example A, further tests are carried out while changing the conditions indicated in the following table.

<*>) = Comparison test. ;B) Ready-to-spin dried polyamide cut from caprolactam with a solution viscosity of 2.55 is mixed in a Taumel dryer one after the other with 0.3% by weight of hexamethylenediamine and 1% by weight. tributyl phosphate. These cuts are then re-granulated in an extruder. After re-granulation, the dissolution viscosity of 2.53 must be read. The cuts are then spun and the threads formed are dyed as described in example A. By measuring the extinction ratio of the amounts of dye taken up by the thread samples, the achieved color improvement in relation to unmodified polyamide is determined. The extinction ratio amounts to 1:2.63 (polyamide without addition: polyamide and phosphorus compounds and amine). As described in example B, a further difference is carried out by changing the compounds indicated in the table, resp. tilseitoinig quantities. A further advantage of the method according to the invention must be seen in that addition of the phosphorus compounds under (<*>) = Comparison test.

the spinning triggers considerable after-condensation so that it also then, when

the solution viscosity of additive-containing cuts compared to normal polyamide is

somewhat lower, enters the spinning process one

increase in viscosity so that also i

in these cases, a sufficient

high viscosity of the finished threads ("Ge-■wølle viscosity"). The addition of the amine as a viscosity stabilizer prevents the increase

of "Gewølle viscosity" during the spinning process assumes an excessive degree. Also this one

effect is possible, as the following examples

shows clear coating.

C) This example's experiment was through-

led to show that phosphoric acid ester-containing polyamide of caprolactam during spinning is also subject to considerable post-condensation when the cuts contain amine.

Polyamide cuts containing the additives specified in Table C are spun with an extruder spinning machine at a temperature of 275°C. From the ready-to-use cuts and the "Gewølle samples", the solution viscosity was determined in the manner described in example A. The high increase in solution viscosity during spinning increases the reducing effect of the solution viscosity of the phosphonic acid ester and the amine during polymerization.

Claims (2)

1. Process for increasing the color absorption capacity of acidic dyes for polyamides from lactams by adding organic phosphorus compounds and amines, characterized by using 0.05-3% by weight of phosphoric or phosphonic acid ester together with 0.02-0.5% by weight of an amine with the general formula H2N- (CH2)n- (NH- (CH2)J ,,,-NIL, where n equals 2-5 and m equals 0-3. 2. Method according to claim 1, characterized in that 0.05-3% by weight of phosphoric or phosphonic acid ester is used together with 0.02-0.5% by weight of an amine with the general formula H2N-(CH2)n-(NH-(CH2)„)I11-NH2 where n is 2 and m is 1-3.