Integrated process for the preparation of substantially linear high molecular weight thermoplastic polymers from aryl polyhalide monomers

An integrated process for preparing a substantially linear thermoplastic polymer derived from an aryl polyhalide monomer which comprises:

• (i) contacting a phenol compound with about stoichiometric amounts of an alkali metal carbonate or hydroxide sufficient to form an alkali metal salt of the phenol compound in a liquid phase of an aprotic solvent and an azeotrope former and for a time and at a temperature sufficient to form the alkali metal salt of the phenol compound;
• (ii) contacting the alkali metal salt of the phenol compound with a dihalobenzenoid compound sufficient to form an aryl polyhalide monomer in a liquid phase of an aprotic solvent and an azeotrope former for a time and at a temperature sufficient to form the aryl polyhalide monomer, wherein the dihalobenzenoid compound has an inert electron withdrawing group in one or more of the positions ortho and para to the halogen atoms thereby activating the halogen atoms to a level sufficient to react with said alkali metal salt of the phenol compound;
• (iii) removing water from the reaction mass of (i) and (ii) as an azeotrope with said azeotrope former until substantially anhydrous conditions are attained and excess azeotrope former is substantially removed;
• and
• (iv) coupling aryl polyhalide monomers by contacting said monomers with a catalyst mixture in the presence of a reducing metal selected from the group consisting of zinc, magnesium and manganese or mixtures thereof and in a liquid phase of an aprotic solvent under substantially anhydrous conditions for a time and at a temperature sufficient to form a substantially linear thermoplastic polymer, wherein the catalyst mixture comprises an anhydrous nickel compound and at least one ligand selected from the group consisting of a triarylphosphine having from about 6 to about 14 carbon atoms in each aryl moiety and an aromatic bidentate compound containing at least one ring nitrogen atom and from about 5 to about 30 carbon atoms and wherein the ratio of gram atoms of nickel per mole of aryl polyhalide monomer is from about 0.001 to about 0.1, the amount of ligand is from about 1 to about 50 moles per gram atom of nickel and the amount of reducing metal is at least about 1 mole of reducing metal per mole of aryl polyhalide monomer.