Patent GB-1017270-A (GB)
Title: Epoxy compounds and process for their preparation
Inventor: BREMMER BART JACOB
IPC: C07D303/36
Filed: 1964-10-21
Abstract: The invention comprises epoxy compounds containing more than one terminal oxirane group, which are liquid or thermoplastic and can be cured, and which contain, between oxirane groups, at least one radical of formula <FORM:1017270/C3/1> or <FORM:1017270/C3/2> where R is C1-C6 alkylene, at least one X of each N-arylalkylene-diamine moiety is Br or Cl, and the remaining X substituents are Br, Cl, H, Me or Et, said compounds containing at least 10% by weight of Br or at least 18% by weight of Cl or a calculable intermediate value when both Br and Cl are present; and their production by reacting an epihalohydrin or a polyepoxy compound at elevated temperature with a compound of formula <FORM:1017270/C3/3> or <FORM:1017270/C3/4> Specific types of product are those of formula Y-Z where Y is J2Q-, each J being one of the following radicals (1) to (5): <FORM:1017270/C3/5> <FORM:1017270/C3/6> <FORM:1017270/C3/7> <FORM:1017270/C3/8> <FORM:1017270/C3/9> where R1 is H or Me; Q is one of the following radicals (6) to (11): <FORM:1017270/C3/100> <FORM:1017270/C3/111> <FORM:1017270/C3/122> <FORM:1017270/C3/133> <FORM:1017270/C3/144> <FORM:1017270/C3/155> where R is C1- 6 alkylene and X is 1-4 Br or Cl, remaining X radicals being Br, Cl H or C1- 4 alkyl, n is 0-20 and R1 is one of the following radicals (a to (d): <FORM:1017270/C3/166> <FORM:1017270/C3/177> <FORM:1017270/C3/188> where m is 1-5 and p is 2-6; and Z is X or Y and is attached to a carbon atom of the phenylamine group or groups of Q other than that to which the N is attached.  In specified procedures, a C1- 6 aliphatic polyamine is heated with a nuclear halogenated aromatic hydrocarbon, and the product heated with (i) an excess of epibromohydrin or epichlorohydrin in the presence of aqueous alkali metal hydroxide; (ii) a polyepoxy compound such as the diglycidyl ether of 4,41-isopropylidene-diphenol or of propylene glycol or similar products with repeating oxyarylene or oxyalkylene units; or (iii) a non-ether diepoxide such as vinylcyclohexene dioxide.  A product of these procedures may also be heated with a polyhydric phenol or a bisphenol, e.g. bisphenol A.  The compounds as defined above may be cured by treatment with an amine, a dicarboxylic acid or anhydride, a polyphenol, a diglycidyl ether or polyether, or a Lewis acid, especially a polyalkylene polyamine.  The compounds of the invention may be blended with known epoxy resins, e.g. (in examples) an epoxylated phenolformaldehyde novolac resin or 4,41-isopropylidenediphenol diglycidyl ether, and the blends may be cured.ALSO:The invention comprises epoxy compounds containing more than one terminal oxirane group, which are liquid or thermoplastic and can be cured, and which contain, between oxirane groups, at least one radical of formula <FORM:1017270/C2/1> or <FORM:1017270/C2/2> where R is C1- 6 alkylene, at least one X of each N-arylalkylene-diamine moiety is Br or Cl, and the remaining X substituents are Br, Cl, H, Me or Et, said compounds containing at least 10% by weight of Br or at least 18% by weight of Cl or a calcurable intermediate value when both Br and Cl are present; and their production by reacting an epihalohydrin or a polyepoxy compound at elevated temperature with a compound of formula <FORM:1017270/C2/3> or <FORM:1017270/C2/4> Specific types of product are those of formula Y-Z, where Y is J2Q-, each J being one of the following radicals (1) to (5); <FORM:1017270/C2/5> <FORM:1017270/C2/6> <FORM:1017270/C2/7> <FORM:1017270/C2/8> <FORM:1017270/C2/9> where R1 is H or Me; Q is one of the following radicals (6) to (11): <FORM:1017270/C2/10> <FORM:1017270/C2/11> <FORM:1017270/C2/12> <FORM:1017270/C2/13> <FORM:1017270/C2/140> <FORM:1017270/C2/151> where R is C1- 6 alkylene and X is 1-4 Br or Cl, remaining X radicals being Br, Cl, H or C1- 4 alkyl, n is 0-20 and R1 is one of the following radicals (a) to (d): <FORM:1017270/C2/162> <FORM:1017270/C2/173> <FORM:1017270/C2/184> <FORM:1017270/C2/195> where m is 1-5 and p is 2-6; and Z is X or Y and is attached to a carbon atom of the phenylamine group or groups of Q other than that to which the N is attached.  In specified procedures, a C1- 6 aliphatic polyamine is heated with a nuclear halogenated aromatic hydrocarbon, and the product heated with (i) an excess of epibromohydrin or epichlorohydrin in the presence of aqueous alkali metal hydroxide; (ii) a polyepoxy compound such as the diglycidyl ether of 4,41-isopropylidene-diphenol or of propylene glycol or similar products with repeating oxyarylene or oxyalkylene units; or (iii) a nonether diepoxide such as vinylcyclohexene dioxide. A product of these procedures may also be heated with a polyhydric phenol or a bisphenol, e.g. bisphenol A.  Starting materials.-N - Pentachlorophenylethylenediamine was prepared from C6C16 and NH2CH2CH2NH2; the corresponding bromo compound is similarly prepared.  Chlorinated 4,41 - bis - (aminoethylamino) - biphenyl having an average of 6.5 Cl atoms was obtained from chlorinated biphenyl (n8 Cl) and ethylenediamine.