Patent GB-471048-A (GB)
Title: Improvements in the manufacture and production of nitrogenous condensation products of high molecular weight
IPC: C09F1/00
Filed: 1935-12-23
Abstract: Resinous condensation products, useful as textile assistants, of the general formula R--X--R1--N, where R represents the cyclic radicle of abietic acid or its hydrogenation products, R1 an alkylene or hydroxyalkylene radicle, N represents tri- or pentavalent nitrogen and X may comprise the groups --CH2O--, --CH2NY, --CH2NYCO--. --CH2OCO----COO--, or --CONY--, Y being a hydrogen atom or an organic radicle, are obtained by (1) causing abietinyl derivatives containing a reactive halogen atom, such as abietinyl halogen alkyl ethers, amines, esters or amides, to act on amines or nitrogenous heterocyclic bases or their substitution products, or (2) reacting resin alcohols with halogen alkylamines, chlorides of amino acids, alkylolamines or polyamines; reacting resin amines with halogen alkylamines, chlorides of amino acids or alkylolamines; or reacting resin acids with alkylolamines or polyamines.  Starting materials for (1) may comprise abietinyl halogen alkyl ethers obtainable by reacting abietinol or tetrahydroabietinol with halogenated alcohols, with ethylene oxide followed by treatment with phosphorus oxychloride, or with halogenated hydroxyethers, e.g. b -chlorb <1>-hydroxy-diethyl ether; abietinyl halogenalkylamines obtainable by treating abietinylamine with alkylene oxide and subsequently replacing the terminal hydroxyl group by halogen, or by condensing abietinylamine with halogenated hydroxy ethers or halogenated alcohols; abietinyl halogen-alkyl esters obtainable by reacting abietic acid with halogenated alcohols, with epichlorhydrin or with alkylene oxides followed by treatment with phosphorus oxychloride, or by reacting abietinol or tetrahydroabietinol with halogenated aliphatic acids; and abietinyl halogen alkyl amides obtainable by condensing resin acids with halogen alkylamines, or by condensing abietinylamines with halogenated aliphatic acids. The abietinyl halogen alkyl derivatives are caused to react at elevated temperature and, if desired, under pressure and/or in the presence of diluents, with amines, e.g. aliphatic, cycloaliphatic, aromatic, aliphatic-aromatic or with nitrogenous heterocyclic bases.  Suitable amines and heterocyclic bases are diethylamine, trimethylamine, ethylenediamine, dodecylamine, oleylamine, piperidine, aniline, methylaniline, and pyridine.  Substituted amines containing carboxyl, ether, ester or sulphonic groups, e.g. sarcosine and taurine, may be employed.  Halogen alkylamides or polyamines, alkylolamines and chlorides of amino acids for method (2) are obtainable by reacting halogenated amines, alcohols and acid chlorides with amines or nitrogenous heterocyclic bases.  In examples: (1) dihydroabietinol is heated, under reflux, with monochloracetic acid and the viscous ester is further heated with trimethylamine dissolved in alcohol, yielding a brown crystalline product which, in aqueous solution, has good wetting and foaming power; wax-like products may be obtained by using pyridine, aniline, methylaniline, glycocoll or sarcosine in place of trimethylamine; the sodium salts of the glycocoll and sarcosine products have soap-like properties and may be employed as fixatives for tanning agents and for rendering artificial silk fabrics slip-proof; (2) dihydroabietinylamine is reacted with monochloracetyl chloride and the amide further reacted with trimethylamine or pyridine giving a water-soluble, wax-like product; (3) a chlorinated ether is obtained by treating an industrial mixture of di- and tetrahydroabietinol with epichlorhydrin, or with ethylene oxide followed by phosphorus oxychloride, and is further reacted with trimethylamine or pyridine; (4) colophony or hydrogenated abietic acid is reacted with epichlorhydrin and further reacted with trimethylamine; (5) abietinylamine is slowly introduced into a boiling mixture obtained by running pyridine into a benzene solution of chloracetyl chloride, the benzene is distilled off and the residue heated at 130--150 DEG  C. until the reaction product is soluble in water; (6) abietic acid is heated with the reaction product of pyridine and b -chlor-b <1>-hydroxy-diethyl ether. Specification 369,614 is referred to.