Patent GB-1062016-A (GB)
Title: Polyamines
Inventor: POWERS EUGENE LEROY
IPC: C08G12/08
Filed: 1964-06-12
Abstract: Polyaryl alkylene polyamines of low molecular weight are prepared by condensing an aromatic amine containing one benzene ring with an aldehyde or ketone containing at most 6 carbon atoms, by mixing at least one mole of amine per mole of aldehyde or ketone with the aldehyde or ketone under conditions causing turbulence at Reynolds numbers of 4500 to 100,000, in the presence of a strong Lewis acid in catalytic amount.  Suitable amines are aniline, chloroaniline, o-, m-, p-toluidine, o-, m-, p-phenetidine, o-, m-, p-anisidine, o-, m-, p-xylidine, o-, m-, p-xenyl amines, nitroaniline, 2,4-tolylene diamine, and 2,6-tolylene diamine.  Suitable aldehydes and ketones are formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, cyclohexane aldehyde, acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, hexanone-2, hexanone-3, di-n-propyl ketone, and cyclohexanone.  Suitable catalysts are HCl, H2SO4, HClO4, HBr, BF3, SuCl4, PCl3, POCl3, SOCl2, AlCl3, L2, Br2, benzoyl chloride, phthalyl chloride and benzyl chloride.  The preferred reactants are aniline and formaldehyde, when the chief product is 4: 41-diaminodiphenyl-methane. The preferred molar ratios of amine to aldehyde are 1.4-4:1.  There is preferably present 1 mole of water per 0.2-30 moles of aniline.  The reaction mixture may be digested separately, preferably in two stages at 50-90 DEG  and 90-150 DEG  C., then it is neutralized, and the organic is separated. The mixed products may be reacted directly with phosgene to give polyisocyanates.  In examples aniline is reacted (1) with formaldehyde, (2) with methyl-ethylketone.ALSO:Polyaryl alkylene polyamines are prepared by condensing an aromatic amine containing one benzene ring with an aldehyde or ketone containing at most 6 carbon atoms in the presence of a catalytic amount of a strong Lewis acid, by mixing at least one mole of amine per mole of aldehyde or ketone with the aldehyde or ketone under conditions causing turbulent flow at Reynolds numbers of 4500 to 100,000.  Suitable amines are mono- and di-amines having not more than one other substituent on the benzene nucleus e.g. chloraniline, o-, m-, p-toluidine, o-, m-, p-phenetidine, o-, m-, p-anisidine, o-, m-, p-xylidine, o-, m-, p-xenyl amines, nitroaniline, 2,4-tolylene diamine, and 2,6-tolylene diamine. Aniline is preferred.  Suitable aldehydes and ketones are formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, cyclohexane aldehyde acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, di-n-propyl ketone, hexanone-2, hexanone-3, and cyclohexanone.  Suitable catalysts are HCl, H2SO4, HClO4, HBr, BF3, SnCl4, PCl3, POCl3, SOCl2, AlCl3, I2, Br2, benzoy chloride, phthalyl chloride, and benzyl chloride.  The preferred reactants are aniline and formaldehyde. The preferred molar ratios of amine to aldehyde are 1.4: 1 to 4: 1.  There is preferably present 1 mole of water per 0.2-30 moles of aniline.  The reaction mixture may be digested separately, preferably in two stages at 50-90 DEG  and 90-150 DEG  C., then it is neutralized, and the organic layer is separated.  The mixed products may be used directly in reaction with phosgene to give polyisocyanates.  In examples, aniline is reacted with (1) formaldehyde, (2) methylethylketone.