Patent GB-465105-A (GB)
Title: Manufacture of organic compounds of high molecular weight containing basic substituents
IPC: C08B37/00
Filed: 1935-09-25
Abstract: A natural or artificial polymeric substance containing a hydroxy, carboxyl or mercapto group is converted into a basic substituted ether or ester by treatment, in presence or absence of a catalyst, with an alkylene oxide containing a group which does not react or reacts only slowly with the alkylene oxide group under the conditions of treatment and is either already basic or is rendered basic by subsequent alkylation of a thioether group or by hydrolysis or reduction.  Specified polymeric substances are cellulose and derivatives thereof containing hydroxyl groups, starch, polyvinyl alcohol, partially saponified polyacrylic acid esters, partially saponified polyvinyl acetate or chloracetate and phenol aldehyde condensation products and specified catalysts are boric acid, borax, calcium sulphocyanide, lithium iodide, toluenesulphonic acids, diethylaniline, pyridine and tripropylamine.  Specified alkylene oxides containing basic groups (obtainable by splitting off hydrogen chloride from the corresponding g -chloro-b -oxypropyl compounds by means of potassium hydroxide) are piperidopropene oxide and its addition compounds with methyl iodide or dimethyl sulphate, oxidopropyltriethylammonium chloride and dioxidopropylcyclohexylamine.  Specified alkylene oxides containing thioether groups which can be made basic by alkylation are methylglycidethioether and oxidopropyl-thioglycollic acid. An alkylene oxide which can be made basic by hydrolysis is N - acetyl-2 : 3-oxidopropyl-N-methylamine.  Alkylene oxides which can be made basic by reduction, e.g. with sodium bisulphite, are the amino-oxides obtainable by the action of hydrogen peroxide upon basic alkylene oxides containing tertiary nitrogen.  The products are applicable as textile assistants, particularly for fixing dyestuffs containing acid groups, and as starting materials or as adjuvants to materials for the production of artificial fibres and other artificial shaped objects.  The following examples are specified: (1) a cellulose acetate having an acetic acid content of 51 per cent is heated for 10 hours at 100 DEG  C. with piperidopropene oxide in dioxane; the resulting solution may be worked up into films or artificial silk having a strong affinity for acid dyestuffs or components; (2) an ethyl cellulose having an ethoxyl content of 45 per cent is heated with piperidopropene oxide for 12 hours at 100 DEG  C.; the product may be converted into films or threads which are intensely dyed by acid dyestuffs; (3) a partially saponified polyvinyl acetate is similarly treated; the product is applicable as a textile assistant or as an addition to solutions to be spun or cast; (4) a viscose artificial silk, advantageously after a preliminary swelling in dilute caustic soda, is heated for 8 hours at 50 DEG  C. with a solution of piperidopropene oxide to increase its affinity for acid dyestuffs; the treatment may be applied locally with simultaneous application of a dyestuff and mixed fabrics of wool and viscose artificial silk may be treated; (5) a novolak made by condensing phenol with formaldehyde in presence of hydrochloric acid is treated with piperidopropene oxide in toluene at 110 DEG  C. the product may be added to acetate artificial silk spinning solutions; (6) a similar novolak is heated in dioxane for 8 hours at 100 DEG  C. with the amino-oxide obtainable by treating piperidopropene oxide with hydrogen peroxide and the amino-oxide group is then reduced; the product is applicable as in (5); (7) cellulose, pre-swollen and treated with piperidopropene oxide as in (4) is acetylated with acetic acid and acetic anhydride in presence of sulphuric acid and the product is hydrolyzed to the stage at which solubility in acetone commences, precipitated with water containing sodium acetate, dissolved in a mixture of methylene chloride and alcohol and dry spun to obtain an artificial silk which is powerfully dyed by acid dyestuffs; the non-acetylated cellulose may also be worked up into artificial silk.  The Specification as open to inspection under Sect. 91 comprises also (a) the use, as alkylene oxides containing basic groups or groups convertible into basic groups, of diethylaminopropene oxide and phthalimidopropene oxide and, as alkylene oxide containing a thioether group, of 8-oxyquinoline-glycide ether, (b) the reaction of the alkylene oxides with aliphatic alcohols and mercaptans, fatty acids, dyestuffs, intermediates and pharmaceutical products containing hydroxy, amino, imino or carboxyl groups, e.g. aminoazo dyestuffs, N - oxyethylaminoanthraquinones, acetylsalicylic acid, aminoquinolines, aminoacridines, sugar and proteins, e.g. casein or gelatine, (c) the use as catalysts of zinc chloride, ferric chloride, aluminium chloride, tin chloride or boron fluoride, (d) example of the treatment of casein with piperidopropene oxide and the propene oxide from methyldodecylamine, (e) an example of the treatment of oleyl alcohol with piperidopropene oxide and alkylation of the product, (f) an example of the treatment of dodecylmercaptan with diethylaminopropene oxide, (g) an example of the treatment of the fatty acid of coco butter with the addition product from piperidopropene oxide and dimethyl sulphate, (h) an example of the treatment of dodecylamine (1 mol.) with piperidopropene oxide (2 mols.) followed by alkylation; the product may be used for improving the fastness to water of dyeings with direct dyestuffs, (i) an example of the treatment of N-methylaniline with piperidopropene oxide and, if desired, peralkylation of the piperidine N-atom, the product may be coupled with diazo compounds to obtain a dyestuff especially suitable for dyeing wool or silk pre-treated with propylene oxide sulphonic acid.  This subject-matter does not appear in the Specification as accepted.