Patent GB-1008161-A (GB)
Title: Aromatic amino glycidyl ethers and epoxy resins
Inventor: WINFIELD GRAHAM
IPC: C08G59/28
Filed: 1961-04-13
Abstract: Glycidyl ethers containing, directly attached to an aromatic nucleus, at least one group of the general formula:  <FORM:1008161/C3/1> wherein A represents a monovalent aliphatic, cycloaliphatic or araliphatic hydrocarbon group or a benzene nucleus or a grouping of the general formula: <FORM:1008161/C3/2> and where R1 and R2 when taken separately represent hydrogen atoms or monovalent saturated aliphatic or araliphatic hydrocarbon groups, or benzene nuclei or when taken together represent a chain of three or four methylene groups and R3 represents a hydrogen atom or a methyl radical, not more than two such groups being attached to any one aromatic nucleus and in particular glycidyl ethers represented by the following general formulae: <FORM:1008161/C3/3> where X represents hydrogen or not more than two monovalent substituents, Z is a monofunctional aliphatic cycloaliphatic, araliphatic hydrocarbon group or benzene nucleus, n is one or two, Y represents an oxygen or sulphur atom, sulphone (SO2) grouping or a disubstituted carbon atom of the type <FORM:1008161/C3/4> where a and b taken singly may be hydrogen atoms or C1 to C4 alkyl groups or where a and b taken together represent an oxygen atom or a chain of 4 or 5 methylene groups, p is one or two, X1 and X11 represent hydrogen or halogen atoms, alkoxy groups or aliphatic, cycloaliphatic or araliphatic hydrocarbon groups or benzene nuclei, c and d represent hydrogen atoms or alkyl groups of not more than 4 carbon atoms and q is an integer, may be cured alone or in admixture with other epoxide containing resins together with conventional hardening agents, accelerators, fillers, plasticizers and colouring agents, for example, asphalt, bitumen, glass fibres, mica, quartz powder, cellulose, kaolin, finely divided silica, especially of large surface area available under the Registered Trade Mark "Aerosil" or metal powder to give hard, tough, resinous compositions.ALSO:Glycidyl ethers containing directly attached to an aromatic nucleus at least one group of the general formula <FORM:1008161/C2/1> wherein A represents a monovalent aliphatic, cycloaliphatic or araliphatic hydrocarbon group or a benzene nucleus or a grouping of the general formula <FORM:1008161/C2/2> and where R1 and R2 when taken separately represent hydrogen atoms or monovalent saturated aliphatic or araliphatic hydrocarbon groups or benzene nuclei or when taken together represent a chain of three or four methylene groups and R3 represents a hydrogen atom or a methyl radical, not more than two such groups being attached to any one aromatic nucleus and in particular glycidyl ethers of the formula <FORM:1008161/C2/3> where the benzene nucleus may be fused to another benzene nucleus and Z is a monofunctional aliphatic, cycloaliphatic araliphatic hydrocarbon group or benzene nucleus and X represents hydrogen or not more than two monovalent substituents, or of the formula <FORM:1008161/C2/4> or alternatively of the formula <FORM:1008161/C2/5> wherein n is one or two, or a glycidyl ether of the formula <FORM:1008161/C2/6> where each of the benzene nuclei may be fused to another benzene nucleus n is one or two, Y represents an oxygen or sulphur atom, a sulphone (SO2) grouping or a substituted carbon atom of the type <FORM:1008161/C2/7> where a and b taken singly may be hydrogen atoms or alkyl groups of 1 to 4 carbon atoms or where a and b taken together represent an oxygen atom or a chain of 4 or 5 methylene groups, p is 1 or 2, and X1 and X11 represents hydrogen or halogen atoms, alkoxy groups or monovalent aliphatic, cycloaliphatic or araliphatic hydrocarbon groups, or benzene nuclei, or a glycidyl ether having the formula <FORM:1008161/C2/8> wherein c and d represent hydrogen atoms or alkyl groups of not more than 4 carbon atoms and q is an integer, are produced by reacting a compound containing one or more groupings of the general formula <FORM:1008161/C2/9> attached to an aromatic nucleus and A1 represents an aliphatic, cycloaliphatic or anraliphatic hydrocarbon groups or a benzene nucleus or a group of the general formula <FORM:1008161/C2/100> with an epihalohydrin, glycerol dihalohydrin, or with a 3-methyl analogue thereof in the presence of an inorganic base, wherein the base is preferably sodium or potassium hydroxide and wherein the temperature at which the reaction is effected is preferably between 40 DEG  C. and the boiling point of the mixture. N-arylethanolamine starting materials may be readily obtained by condensation of 1 : 2 oxides or the corresponding halohydrins with aromatic amines or polyamines.  1 : 2 oxides stated to be suitable are ethylene oxide, propylene oxide, 1 : 2-epoxybutane, 2 : 3-epoxybutane, butadiene monoxide, allyl glycidyl ether, cyclohexene oxide, cyclopentene oxide and styrene oxide.  Suitable primary starting materials include N-methylaniline, N-methyltoluidine, N-ethyl-toluidine, N-ethyl, o-ethyl and p-ethyl-aniline, p-chloro-N-methyl aniline, p - chlorotoluidine, p - methoxy - N - methylaniline, diphenylamine, N-cyclohexylaniline, and N-methyl alpha and beta-naphthylamine. Other suitable amines as starting materials are N,N1-dimethyl o-, m- and p-phenylene diamines, N,N1-diethyl o-, m- and p-phenylene diamines, N,N1 - dimethyl - 2,4 - diaminotoluene, and N,N1 - dimethyl - 2,4 - diamino chlorobenzene. Further suitable starting materials are aniline, o-, m- and p-toluidines, o-, m- and p-nitro-anilines, 2,4-dinitroaniline, o-, m- and p-anisidines, the chloroanilines, the bromoanilines, o-, m- and p-phenylene diamines, o-, m- and p-ethylanilines, and alpha, and beta-naphthylamines. Numerous other starting materials are also specified.  In the examples, N1-phenyldiethanolamine is reacted with epichlorohydrin, using as condensing agent sodium hydroxide in a one-stage reaction or in two stages using stannic chloride as the first stage and reforming the epoxide by means of sodium hydroxide in the second stage.  In the other examples the following ethanolamines are condensed with epichlorohydrin: N - phenyldiethanolamine, N,N - methylphenylethanolamine, N - phenyldi - 2 - propanolamine, N - m - tolyldiethanolamine, N - o - tolyldiethanolamine, bis - (p-diethanolanilino) ketone, N,N,N1,N1 - tetraethanolbenzidine, methylene-bis-(p-diethanolaniline), isopropylidene - bis - (p - diethanolaniline), methylene (p - diethanolaniline), (m-ethyl - p - diethanolaniline), methylene bis - (p-N - methylethanolaniline), bis - (p - diethanolaniline) ether, bis-(p-diethanolanilino) sulphone and a poly nuclear ethanolamine formed from N-phenyldiethanolamine and from aldehyde in the presence of concentrated hydrochloric acid; the epoxide formed from N-phenyldiethanolamine and 2,3-epoxybutylchloride by reaction with sodium hydroxide is also described.  The products are suitable as components for making epoxy resins.