Patent GB-535577-A (GB)
Title: Manufacture of quartenary ammonium compounds
Filed: 1939-09-13
Abstract: 535,577. Resinous condensation products. DU PONT DE NEMOURS & CO., E.I. Sept. 13, 1939, No. 25700. Convention date, Sept. 15, 1938. [Class 2 (iii)] Polymeric quaternary ammonium compounds are prepared by reacting, under anhydrous conditions, formaldehyde, a diol, a ditertiary diamine and a non-oxidizing inorganic anhydrous acid. The term diol is used to include a glycol, a dithiol or a compound including one thiol and one hydroxyl group wherein the hydroxyl or the thiol groups are attached to a carbon atom having attached thereto a hydrogen atom.,the said carbon atom not forming part of an aromatic ring : such compounds include decamethylene glycol, #-mercaptoethanol, decamethylenedithiol, α-α<SP>1</SP>-diphenylhexamethylene glycol, ethylene glycol, hexamethylene glycol, octadecamethylene glycol, diethylene glycol, 1:4-cyclohexylene glycol, p-xylylene glycol, camphene glycol, 2:4-dihydroxyhexane, di- (#-mercaptoethyl ether, di- (#-mercaptoethyl) sulphide, 1:6-dihydroxy-2:5-dimethylhexane, 2-mercaptoethanol and conylene glycol ; other glycols, which may be aliphatic, aromatic (subject to certain restrictions), cyclic, acyclic, homocyclic, heterocyclic, saturated, unsaturated, unsubstituted or substituted by groups which do interfere with the reaction such as ether, sulphur, ester, nitro, ketone, tertiary amide, and nitrile groups, may also be used. Diamines, wherein each nitrogen must be attached to at least two saturated radicals include aliphatic, aromatic, cyclic, acyclic, homocyclic, heterocyclic, saturated, unsaturated, substituted and unsubstituted diamines. such as N:N:N<SP>1</SP>:N<SP>1</SP>-tetramethylethyleneglycol diamine, N:N:N<SP>1</SP>:N<SP>1</SP>-tetramethyl-1:4-cyclohexylenediamine, 1:10-bis (diethylaminomethoxy)- decane, N:N<SP>1</SP>-bis-(2-hydroxyethyl) piperazine, bis-(4-morpholine) dodecane, bis-(1-piperidyl) octane, 1:6-bis (dimethylamine) - 2:5-dimethylhexane, N:N:N<SP>1</SP>-N<SP>1</SP>-tetramethylp-phenylene diamine, N:N:N<SP>1</SP>:N<SP>1</SP>-tetraethyl- 1:6-diamino-3-hexene, N-allyl-N-N<SP>1</SP>-N<SP>1</SP>- trimethyloctadecamethylenediamine and N:N:N<SP>1</SP>:N<SP>1</SP>-diethylene-1.2- ethylene diamine; other radicals that may occur in the diamine and which do not interfere with the basic reaction include ether, sulphide, ketone, nitro, amide, hydroxyl and thiol radicals. Inorganic acids which include the corresponding anhydrides; include sulphur dioxide, sulphur trioxide, sulphuric acid, hydrogen chloride, hydrogen bromide, hydrogen sulphide, hydrogen fluoride, phosphoric acid, hydrogen cyanide, hydrogen iodide, nitrogen trioxide, and carbon dioxide. Diluents, which may be present in reaction mixture, include xylene, toluene, benzene, dioxan, ligroin, ethylene glycol dimethylether, cyclohexane, dibutylether, or diethyl ether. In examples (1) sulphur dioxide or hydrogen chloride is bubbled through a mixture of decamethylene glycol, paraformaldehyde and tetramethylhexamethylenediamine if necessary in solution in benzene ; (3) sulphuric acid is. added to a solution of #-mercaptoethanol, paraformaldehyde and tetramethylhexamethylenediamine in benzene ; (4) carbon dioxide is bubbled through a solution of decamethylenedithiol, paraformaldehyde and tetramethylhexamethylene: diamine in benzene ;  (5) hydrogen sulphide is bubbled through a solution of α-α<SP>1</SP>-diphenylhexamethyleneglycol, paraformaldehyde and tetramethylhexamethylenediamine in benzene to obtain the various polymeric products. The products may be used as mould inhibitors, bactericides, pourpoint depressants, surface-active agents, and modifying agents for viscose.