Patent GB-799762-A (GB)
Title: Xylylene derivatives and processes for preparing the same
IPC: C08G69/26
Filed: 1956-07-16
Abstract: The invention comprises diamines of the formula <FORM:0799762/IV (b)/1> in which R1 is hydrogen or a hydrocarbon radical of 1-6 carbon atoms, R2 is a hydrocarbon radical of 1-6 carbon atoms, each R2 being the same or different, and each X is an alkylene hydrocarbon radical of 1 to 5 carbon atoms, and salts thereof with aliphatic dicarboxylic acids of 4 to 20 carbon atoms per molecule.  The diamines may be made by catalytic hydrogenation of the corresponding dinitriles or nitro compounds, or by the addition of ammonia to the corresponding di-halo-alkyl compounds or to the olefinic double bonds of the corresponding di-alkenyl compounds.  Thus, 1 : 4-bis-(delta-aminobutyl) tetraethyl benzene is made by hydrogenating 1 : 4 - bis - (gamma - cyanopropyl) tetraethyl benzene obtained from the corresponding bis-(gamma-chloro-propyl) compound and sodium cyanide.  Also bis-(gamma-nitro-n-butyl) tetrabutyl benzene is hydrogenated and bis-(tertiary-butenyl) durene is reacted with ammonia, the corresponding diamines being obtained.  Hydrogenation of the di-nitriles is conducted in liquid phase in the presence of a nickel, copper chromite or palladium black catalyst and in the presence of ammonia at between 80 DEG  and 120 DEG  C. at 70-210 atmospheres pressure, if desired using solvents such as ethanol, tertiary butanol, dioxane, and tetrahydrofuran.  Addition of ammonia to the halogen compounds is effected by mixing the compound with a large excess of liquid ammonia at 20-80 DEG  C. under pressure and if desired in the presence of solvents such as benzene or diethyl ether. The di-nitriles may be made from the corresponding di-halo-alkyl compounds by reaction with 2.1-2.5 mols. of alkali-metal cyanide in a solvent such as dioxane, acetone, methyl ethyl ketone or dimethoxy ethane at temperatures of 75-125 DEG  C.  The nitriles may be isolated or the reaction mixture hydrogenated directly to give the diamines.  The di-(halo-alkyl) compounds may be made by halogenation, e.g. hexamethyl benzene is chlorinated to give bis-(chlormethyl) tetramethyl benzene, or by chlormethylation using formaldehyde and hydrogen chloride.  Thus, bis-(chlormethyl) tetraethyl benzene is made by chlormethylation of tetra-ethyl benzene.  In examples: bis-(cyanomethyl) durene, bis - (beta - cyano - n - propyl) durene, bis - (5-cyano - 2 - pentenyl) durene, bis - (gamma-cyanopropyl) prehnitene, 1 : 4 - bis - (cyanomethyl) - 2 : 3 : 6 - trimethyl benzene, and 1 : 2 - bis - (alpha - cyanoethyl) - 3 : 4 : 6 - trimethyl benzene, prepared by reacting the corresponding chloro-compounds with sodium or potassium cyanides, are hydrogenated in presence of ammonia to give the corresponding diamines; bis - (beta - chloro - n - propyl) durene and bis-(gamma-chloropropyl) isodurene are reacted with liquid ammonia to give the corresponding diamines; in further examples, bis-(beta-aminoethyl) durene adipate, sebacate, and 1 : 2-eicosanedioate, bis - (beta - methyl - gamma-amino - n - propyl) durene adipate, bis - (beta-amino - n - propyl) durene sebacate, bis-(omega - aminohexyl) durene adipate, bis-(delta-aminobutyl) prehnitene adipate, and bis-(gamma-aminopropyl) isodurene sebacate, are made by mixing alcoholic solutions of the appropriate diamine and acid.ALSO:The invention comprises resinous polyamides of a diamine of the formula: <FORM:0799762/IV (a)/1> in which R1 is hydrogen or a hydrocarbon radical of 1-6 carbon atoms, R2 is a hydrocarbon radical of 1-6 carbon atoms, R2 is a hydrocarbon radical of 1-6 carbon atoms, each R2 being the same or different, and each X is an alkylene hydrocarbon radical of 1-5 carbon atoms, and a polycarboxylic acid having 2-22 carbon atoms per molecule.  The polyamides are made by reacting the diamine and acid in approximately equimolar proportions, with or without a solvent, to form a salt and heating the latter at between 175 DEG  and 350 DEG  C. in the presence or absence of a solvent or diluent, the last stages of reaction being conducted under sub-atmospheric pressure.  In examples, polyamides are made by heating bis-(beta-aminoethyl) durene sebacate, the corresponding 1 : 20-eicosanedioate, bis-(beta-methyl-gamma-amino-n - propyl) durene adipate bis - (beta - amino-n-propyl) durene sebacate, bis-(omega-amino-hexyl) durene adipate, bis-(delta-aminobutyl) prehnitene adipate, and bis-(gamma-amino-propyl) isodurene sebacate. Other carboxylic acids which may be used are maleic acid, succinic acid, terephthalic acid and durene-dicarboxylic acid.  The polyamides may be used in admixture with other resins, plasticizers, pigments and dyes.  The polyamides of the above diamines with dicarboxylic acids may be copolymerized with dicarboxylic acid amides of primary and secondary diamines.  In particular, a copolymer of 20 to 80 mol. per cent of an amide of an aliphatic dicarboxylic acid of 4-22 carbon atoms and a diamine of the above general formula with an amide of an aliphatic dicarboxylic acid of 4-22 carbon atoms and an aliphatic diamine of 4-18 carbon atoms having at least one hydrogen atom attached to each nitrogen atom, is described.  In an example, bis - (beta - aminoethyl) durene adipate and hexamethylene diamine adipate in equimolar quantities are heated together to form a copolymer.