Patent GB-680997-A (GB)
Title: Compositions of matter containing glycidyl ethers and diamines and resinous productsobtained therefrom
IPC: E21D20/02
Filed: 1949-02-25
Abstract: Resinous products which are heat curable and are employed in the manufacture of surface coating compositions, moulding powders, films and fibres are obtained by heating together at temperatures from 50-250 DEG  C. a glycidyl ether formed by reacting a compound containing a glycidyl radical or a radical capable of yielding a glycidyl radical under the reaction conditions with a polyhydric compound and having a 1,2-epoxy equivalency greater than one and a saturated aliphatic diamine containing two primary amino groups one of which is linked directly to a tertiary carbon atom and the other to a secondary carbon atom.  The term "epoxy equivalency" defines the average number of 1.2-epoxy groups contained in the average molecule of the epoxy ether.  Preferably 5-300 per cent of the equivalent amount of the diamine is employed.  Diamines specified are: 1,2-diamino-2-methyl-propane, -butane, -pentane; 2,3-diamino-2,3-dimethylbutane, 2,5-diamino - 2,5 - dimethylhexane and the corresponding heptane.  2,4-diamine-2-methylpentane (diacetone diamine) is preferred.  The glycidyl ethers are ethers of polyhydric alcohols, e.g. glycols, glycerol, diglycerol, erythritol, pentaglycerol, pentaerythritol, mannitol, sorbitol, polyvinyl alcohol, polyallyl alcohol, obtained by reacting the polyhydric alcohol with epichlorhydrin in presence of boron trifluoride, hydrofluoric acid, stannic chloride, &c. as catalyst and dehydrochlorinating the product; or (2) ethers of polyhydric phenols obtained by reacting a dihydric phenol with epichlorhydrin in alkaline solution, e.g. 4 mols. bis-(4-hydroxyphenyl)-2,2-propane, 5 mols. epichlorhydrin and 6.43 mols. 10 per cent NaOH solution are heated while stirring to 100 DEG  C. for 80 minutes and then refluxed at 100 DEG  C. for a further 60 minutes; the resinous layer is separated, dried and dehydrated. Compositions specified are (1) 90 parts diacetone diamine and 100 parts diglycidyl ether; (2) 100 parts of the epoxy ether prepared as above and 6.7 parts diacetone diamine. They may be applied as coatings dissolved in ketones, esters and alkylethers of ethylene glycol with or without the addition of aromatic hydrocarbons; pigments, e.g. titanium oxide, antimony oxide, carbon black, chrome yellow, zinc oxide, para red &c. may be added. Moulding powders incorporating the usual fillers, e.g. wood flour, talc, cellulose, zinc sulphide, have the property of expanding on moulding.  The Specification as open to inspection under Sect. 91 includes simple ethers, e.g. diglycidyl ether or di (3-methyl glycidyl) ether.  This subject-matter does not appear in the Specification as accepted.ALSO:Amines containing two primary amino groups one of which is directly linked to a saturated tertiary carbon atom, are prepared by reacting lower aliphatic saturated ketones with liquid ammonia at 30-40 DEG  C. in presence of hydrochloric acid with formation of a pyrimidine which is recovered by distillation and heated with 1-5 mols. liquid ammonia in presence of a hydrogenation catalyst under hydrogen pressure to yield the diamine.  Thus, acetone and liquid ammonia are reacted to form 2,2,4,4,6-pentamethyl tetrahydropyrimidine which is further reacted to form 2,4-diamino-2-methyl pentane; methyl ethyl ketone similarly yields the isomers 2,4,5,6 - tetramethyl - 2,4 - diethyl tetrahydro pyrimidine and 2,4-dimethyl-2,4,6-triethyl tetrahydro pyrimidine which in turn yield a mixture of 3,5-diamino-3,4-dimethyl-hexane and 3,5 - diamino - 3 - methyl - heptane.  Other ketones mentioned are methyl propyl ketone and diethyl ketone.  Condensation products are prepared by reacting polyhydric alcohols with epichlorhydrin in the presence of 0.1 to about 2 per cent of an acid reacting compound, e.g. BF3, hydrofluoric acid or stannic chloride at a temperature of about 50 DEG  to 125 DEG  C., there being about one mole. of epichlorhydrin for each molar equivalent of hydroxyl group in the alcohol and dehydrochlorinating the product by heating at about 50 DEG  to 125 DEG  C. with, say, 10 per cent stoichiometric excess of a base, e.g. sodium aluminate.  The products contain an average of more than 1 epoxy group per molecule.  An example describes the production of such a product from glycerol.  Other alcohols mentioned are ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, di- and tri-ethylene glycol, dipropylene glycol, di- and penta - glycerol, erythritol, pentaerythritol, mannitol, sorbitol, polyallyl alcohol and polyvinyl alcohol.  The formation of such condensation products from the polyhydric alcohols and dichlorhydrin is referred to.  The amines and condensation products are used in resin forming compositions (see Group IV (a)).