IL30837A - Process for the manufacture of condensation products of heterocyclic compounds with thiourea compounds and alkanolamines - Google Patents

Description

30837/2 Process for the manufacture of condensation products of heterocyclic compounds with thiourea compounds and alkanolamines CIBA-GEIGY A.G.

C, 29062 It has been found that valuable new condensates are obtained that are capable of substantially counteracting the impairment of the mechanical properties Occurring when finishing cellulosic textile materials with aminoplasts, when in an aqueous medium at a temperature rom -10° to +j50°C, in each case at a molecular ratio of 1 : 2 to 1 : 0.5, preferably from 1 : 1.5 to 1 : 0.5, a colourless heterocyclic compound that contains at least 2 nitrogen atoms in the hetero ring and at least 2 halogen atoms linked with carbon atoms of the hetero ring, is reacted with (A) a thiourea compound that contains at least one hydrogen atom linked with nitrogen preferably thiourea itself, or with an alkali metal or ammonium hydrogensulphide and (B) a mono- or di-alkanolamine containing 1 to 4 carbon atoms, preferably with mono- or di-ethanolamine , the reaction is then finalized at a temperature from JO to 100°C, preferably from 5 to 70°C and, if desired, water, is distilled out of the mixture formed.

The heterocyclic compound used as starting material i-in the present process must be practically colourless and contain at least one, preferably only one, heterocycle which may be altogether the only ring of the compound or, for example, may also contain a fused-on aromatic six-membered ring. Speci-ally useful are- compound with six-membered heterorings, especi ally those whose ring contains 2 or 5 nitrogen atoms and .4 or 5 carbon atoms, such as pyridazine, pyrimidine, quinazoline and especially 1 ,5,5-triazine compounds. These compounds contain at least 2 halogen atoms linked with carbon atoms of of the alkali, or of its last portion, the reaction medium reveals a pH value of about 7· The reaction is then finalized at a temperature from }0 to 100°C, preferably from 40 to 70QC, and may' be terminated after 2 to 5 hours. The pH value of the reaction mixture during this time should be within' the neutral or. slightly alkaline region. A drop in pH value impairs the solubility of the reaction product substantially and can be prevented by adding more alkali. The condensates are also obtained, when in an aqueous medium at a temperature from -10 to +25°C at a pH value from 6 to 9 and at a molecular ratio from 1 : 1.5 to 1 : 0.5, a colourless heterocyclic compound that contains at least 2 nitrogen atoms in the hetero ring and at least 2 halogen atoms linked with carbon atoms of the hetero ring, is reacted with a thiourea compound and on completion of this first reaction stage, without intermediate separation, for every mol of heterocyclic halogen compound used 0.5 to 1.5 mols of a monoalkanolamine are added, while maintaining a pH value from 6 to 10 and keeping the temperature of the reaction medium first for at least 8 hours at 50 to 50°C and then for at least 5 hours at 60 to 65°C and, if desired, the water is distilled out of the mixture formed,.

When the starting material used is cyanuric chloride, then, in general, for 1 mol each of this halogen compound a total of about mols of monoacidic base, thus for instance 3 mols of alkali metal hydroxide and lmol of alkanolamine , is consumed. The amount of water used as reaction medium may be freely chosen within a wide range, advantageously so that, on one hand, the reaction mixture is easy to stir from the start and the risk the practical performance problematic. Since as a rule the heterocyclic halogen compounds are sparingly soluble in the ; : ; water serving as reaction medium, it is advantageous first to convert them into a finely distributed state, which. can be done in known manner by dissolution in an organic water-miscible solvent such as acetone and pouring the solution out over ice, As mentioned above, the molecular ratio heterocyclic haloge compound : sulphur-containing compound should range from 1 : 2 to 1 : 0.5, preferably from 1 .": 1.5 to : 0.5, and the molecular ratio of heterocyclic halogen compound : alkanolamine should likewise /be within the range: from ; : ,2 to 1 : 0.5, preferably from 1 : 1. to 1 : O.5.. Especially with cyanuric chloride particularly good results are .obtained by using equimolecular proportions or amounts of the three reactants differing only .■little therefrom. ;.' ,;: '''^■· ¾^ ' ^ ^ '!"■: ' ':■'' ■.

On completion of the reaction the resulting product :. can be used as it is for the purpose indicated above. In view of the concentration of the mixture, whic is not very high : at the end of the reaction, it is, however,, advisable to remove -the water completely or partially by distillation under vacuum.. In this manner generally stable products are obtained which · are t most only slightly tinted:.and are readily and. completely soluble in water.

T e products obtained by the process described above " are suitable, as has already been said, for use in combination with ;aminoplasts in textile finishing, especially for improving the shape retention. Particularly suitable for such a treatment s textile material , of cellulose, if desired in combination ;. '

Claims (2)

1. WHAT WE CLAIM IS: 1. A process for the manufacture of condensation products, characterized in that, in an aqueous medium at a temperature from -10. to +30°C in each case at a molecular ratio from 1 : 2 to 1 : 0.5, a colourless heterocyclic compound containing at least 2 nitrogen atoms in the hetero ring and at least two halogen atoms linked with carbon atoms of the hetero ring, is reacted with (A.) a thiourea compound containing at least one hydrogen atom linked with nitrogen, or with an alkali metal or ammonium hydrogensulphide and (B) a mono- or dialkanolamine with 1 - 4 carbon atoms, then the reaction is finalized at }0 to 100°C and from : the resulting mixture water is removed by distillation.

2. A process according to claim 1, wherein cyanuric chloride is used as halogenous heterocyclic compound. 5. A process according to claim 1 or 2, wherein the thiourea compound used is thiourea itself. . A process according to any one of claims 1 to 2, wherein the alkanolamine used is mono- or diethanolamine . 5. A process according to claim 1, characterized in that in each case the molecular ratio heterocyclic compound: component (A) as well as (B) is from 1 : 1.'5 to 1 : 0.5. 6. A process according to claim ;1, wherein, in an aqueous medium at a temperature from -10 to 25°C and at a pH value from 6 to 9, at a molecular ratio of 1 : 1.5 to 1 : 0.5, a. colourless heterocyclic compound containing at least 2 nitrogen atoms in the hetero ring and at least 2 halogen atoms linked with carbon atoms of thejetero' ring, is reacted with for every mol of heterocyclic halogen compound used .0.5 to 1 .5 mols of a monoalkanolamine are^ added, while maintaining a pH value from 6 to 10 the temperature'-of the reaction medium is first kept for at least 8 hours at 30 to 50°C and then for at least 5 hours at 60 to 65°C and, if desired, water is removed by distillation from the resulting mixture. 7. Any condensate obtained by the process of any one of claims 1 to 6. these materials are , impregnated with an aqueous preparation containing a curable aminoplast precondensate , a curring catalyst and a condensate as claimed in any one of claims 1 to 6 , and the textile material is dried and then hardened by a heat treatment. 10 . A process according to claim 9, wherein urea and/or melamine derivatives are used as aminoplast precondensates . 11-. A process according to claim 9 or 10 , characterized in that the aqueous preparation further contains an emulsified polymer from a minor quantity of an alkaline earth metal salt of an a, β-ethylenically unsaturated monocarboxylic acid,, of an N-methylolamide or N-methylolamide ether of. an α,β-un- saturated mono- or dicarboxylic- acid and at least one -.further copolymerizable compound. For the