Polyarylene polyether made using mixed base system

In a method of producing polyarylene polyethers by reacting a dihalobenzenoid compound in which halogen is attached directly to a ring carbon atom and a dihydroxy phenol at a temperature in a range between 100.degree. and 200.degree. C. and in the presence of a polar solvent, the improvement which provides an amine-terminated polyarylene polyether with a select degree of polymerization, between 6 and 15, and a ratio between weight average and number average molecular weight between about 2 and 4, said improvement comprising:

• (a) providing a dihydroxy phenol, a strong alkali metal base, a weak alkali metal base comprising a carbonate, a polar solvent, an azeotrope former and optionally water in a first reactor, said dihydroxy phenol and said strong alkali metal base being at a molar ratio between 1:1.50 and 1:1.98 and there being sufficient alkali metal weak base to provide a total of at least one equivalent of alkali metal in the combination of said strong and weak bases for each equivalent of hydroxy in said dihydroxy phenol, the molar amount of said weak alkali metal base not being greater than about 50% of the molar amount of said strong alkali metal base;
• (b) maintaining the contents of said first reactor at a temperature in a range sufficient for dehydration of said dihydroxy phenol and formation of a double salt of said dihydroxy phenol, said dehydration continuing until there is less than about 1% by weight water in said first reactor;
• (c) combining said dihalobenzenoid compound and said double salt of (b) in said first or a different reactor at a molar ratio between 1.167:1 and 1.067:1 dihalobenzenoid compound to double salt, the combination of this step (c) being in the presence of a polar solvent;
• (d) maintaining the contents of the reactor in step (c) at a temperature and for a time sufficient to provide a halogen-terminated polyarylene polyether with said select degree of polymerization and ratio between weight average and number average molecular weight;
• (e) providing a hydroxy aromatic amine, a strong alkali metal base, a weak alkali metal base, a polar solvent, an azeotrope former and optionally water in a reactor, said dihydroxy aromatic amine and said strong base being at a molar ratio between 1:0.50 and 1:0.98 and there being sufficient weak alkali metal base to provide a total of at least one equivalent of alkali metal in the combination of said strong and weak bases for each equivalent of hydroxyl in said hydroxy aromatic amine;
• (f) maintaining the contents of said reactor of (e) at a temperature in a range sufficient for dehydration of said hydroxy aromatic amine and formation of an alkali metal salt of said hydroxy aromatic amine, said dehydration continuing with water removal until there is less than about 3% water remaining in the contents of said reactor of the step (f);
• (g) combining said alkali metal salt of (f) and said halogen-terminated polyarylene polyether of (d) in said reactor of (f) or (d) or a different reactor either in an equivalent ratio of 1:1 between halogen of said halogen-terminated polyether and hydroxyl of said alkali metal salt of (f) or a slight excess of said alkali metal salt in the event a molecular weight reduction is desired;
• (h) maintaining the contents of said reactor of (g) at a temperature sufficient to cause displacement of halogen in said halogen-termninated polyarylene polyether and provide an amine-terminated polyarylene polyether with a select degree of polymerization and ratio between weight average and number average molecular weights;
• (i) isolating said amine-terminated polyarylene polyether.

An amine-terminated polyarylene polyether having the formula:

• ##STR2## wherein O is oxygen;
• n is between 6 and 15;
• X is halogen, hydroxyl, or O--R(NH.sub.2).sub.m where m is 1 or 2;
• Y is QX or hydrogen;
• Q is the residuum of a dihalobenzenoid compound having two replaceable halogens which are attached directly to ring carbon atoms;
• D is the residuum of a dihydroxy phenol;
• R is a di or trivalent aromatic group having up to four aromatic nuclei;
• at least about 70% of the total of said X and Y groups comprises --NH.sub.2 and at least about 5% of said X and Y groups comprise hydroxyl and halogen;
• said amine-terminated polyarylene polyether having a weight average molecular weight that is between 2.0 and 3.6 times its number average molecular weight.

An amine-terminated polyarylene polyether having the formula:

• ##STR3## wherein O is oxygen;
• n is between 8 and 12;
• X is halogen, hydroxyl, or O--R(NH.sub.2).sub.m where m is 1 or 2;
• Y is QX or hydrogen;
• Q is the residuum of a dihalodiphenylsulfone having two replaceable halogen which are attached directly to ring carbon atoms;
• D is the residuum of bisphenol A;
• R is a phenylene group having up to four aromatic nuclei;
• at least about 80% of the total of said X and Y groups comprises --NH.sub.2 and at least about 5% of said X and Y groups comprise hydroxyl and halogen;
• said amine-terminated polyarylene polyether having a weight average molecular weight that is between 2.0 and 3.6 times its number average molecular weight and being made by a process comprising reacting a dihalodiphenyl sulfone and bisphenol A at a molar ratio of about 1.1:1.0.