Patent GB-1017868-A (GB)
Title: Amine compounds, isocyanates and urethanes obtained therefrom and processes for theirpreparation
IPC: C07C209/68
Filed: 1964-08-04
Abstract: Urethane prepolymers are obtained from one or more diisocyanates obtained from diamino aryl compounds of the general formula <FORM:1017868/C3/1> in which A is the group <FORM:1017868/C3/2> or the group <FORM:1017868/C3/3> in which Y is lower alkyl, amino or halogen' X is lower alkyl or halogen, n is 0 to 4 with the proviso that n is not more than 2 when X is halogen, R and R1 which may be the same or different are each hydrogen, lower alkyl, or aminoaryl, R2 and R3 which may be the same or different, each is hydrogen or lower alkyl q is 1, 2 or 3, m is 0 to 4 such that the sum of m and q does not exceed 6, p is 0, 1 or 2 and is 1 when X is halogen, the groups <FORM:1017868/C3/4> are attached to non-adjacent carbon atoms of the central benzene ring and are not attached to the ring A at a position meta to the amino group -NR2R3, by reacting the former with a difunctional active hydrogen-containing material, especially a polyether, polyester, or polyesteramide, having a molecular weight of 400 to 3000, the amount of the diisocyanate being such as to provide an excess of isocyanato groups over the active hydrogen-containing groups and maintaining the mixture at a temperature of 25 DEG  to 150 DEG  C.  Urethane elastomers can be prepared by reacting the prepolymer with an arylene diprimary amine having a pKb (at 25 DEG C.) of at least 9.5, the arylene diprimary amine being in amount at most substantially equivalent to the free isocyanato groups present in the prepolymer.  In examples a ,a 1 - bis - (4 - isocyanatophenyl) - p - diisopropylbenzene is reacted with 1,4-butane-diol and 1,6-hexane-diol.  A prepolymer obtained by reacting polyoxypropylene-diol with a ,a 1-bis-(4 - isocyanatophenyl) - p - diisopropylbenzene is reacted with 4,41-methylene bis-(2-chloroaniline) to produce an elastomer which is then cured.  A prepolymer obtained by reacting a ,a 1 - bis - (4 - isocyanatophenyl) - p - diisopropylbenzene with a polyester is reacted with 4,41 - methylene bis - (2 - chloroaniline) to produce an elastomer which is then cured.ALSO:The invention relates to amino aryl compounds of the general formula <FORM:1017868/C2/1> in which A is the group <FORM:1017868/C2/2> or the group <FORM:1017868/C2/3> in which Y is lower alkyl, amino or halogen, X is lower alkyl or halogen, n is 0 to 4 with a proviso that n is not more than 2 when X is halogen, R and R1, which may be the same or different, are hydrogen, lower alkyl, or aminoaryl, R2 and R3, which may be the same or different, are each hydrogen or lower alkyl, q is 1, 2 or 3, m is 0 to 4, such that the sum of m and q does not exceed 6, p is 0, 1 or 2 and is 1 when X is halogen, the groups <FORM:1017868/C2/4> are attached to non-adjacent carbon atoms of the central benzene ring and are not attached to the ring A at a position meta to the amino groups, -NR2R3, and to diisocyanates formed therefrom.  Compounds claimed per se are:-a ,a 1-bis(4-aminophenyl)-p-xylene; a ,a 1 - bis - (4 - aminophenyl) - p - diisopropylbenzene; a ,a 1 - bis - (4 - aminophenyl) - m - diisopropylbenzene; a ,a 1 - bis - (2 - amino - 5 - methylphenyl) - p - diisopropylbenzene; a ,a 1,a 11 - tris - (4 - aminophenyl) - 1,3,5 - triisopropylbenzene; a ,a 1 - bis - (4 - N - methylaminophenyl) - p - diisopropylbenzene; a ,a 1 - bis - (4 - N,N - dimethylaminophenyl) - p-diisopropylbenzene; a ,a 1 - bis - (3,5 - dimethyl - 4 - aminophenyl) - p-diisopropylbenzene; a ,a 1 - bis - (4 - aminonaphthyl) - p - diisopropylbenzene a ,a 1 - bis - (4 - amino - 3 - chlorophenyl) - p - diisopropylbenzene; o- or p-a -methylbenzylaniline; tris-(4-N,N-dimethylaminophenyl)methane.  The compounds may be prepared by reacting an aromatic amine containing at least one hydrogen atom in ortho or para position to the amino group having the formula <FORM:1017868/C2/5> with a compound of the formula <FORM:1017868/C2/6> wherein Z is the group <FORM:1017868/C2/7> or the group <FORM:1017868/C2/8> for example an a -hydroxy cumene or a benzyl alcohol derivative or styrene, 2,4-dichlorostyrene, alpha-methylstyrene, 2,4-dichloro-a -methylstyrene, 1,4 - diisopropenylbenzene, 2,6-dimethyl - 1,4 - diisopropenylbenzene or 1,3,5-triisopropenylbenzene, in the presence of, as catalyst, an acid activated clay.  Alternatively, the compounds may be prepared by acetylating the amino groups of the amino-aryl compound, halogenating the resultant acetanilide and subsequently hydrolysing the halogenated derivative to produce the halogenated amino-aryl compound. The amino-aryl compounds may be treated with phosgene to obtain the corresponding di-isocyanates.  Many examples are given.