High-temperature, aromatic coating materials from aryl polyhalides

Claim 1

Method of preparing high temperature, cross-linked, solvent-resistant coating materials which comprise the steps in order of: (A) contacting one or more unsubstituted aryl polyhalide monomers wherein the unsubstituted aryl polyhalide monomer is produced: (1) by the reaction of a dihalobenzenoid compound with a phenolic compound and at least one alkali metal carbonate in a liquid phase of an aprotic solvent and an azeotrope former for a time and at a temperature sufficient to form the "unsubstituted" aryl dichloride 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 the alkali metal carbonate reaction product of the phenolic compound; and (2) removing water from the reaction mass of 1 as an azeotrope with said azeotrope former until substantially anhydrous conditions are attained and excess azeotrope former is substantially removed; with a catalyst mixture in the presence of a reducing metal selected from the group consisting of zinc, magnesium and manganese or mixtures thereof in a dipolar aprotic solvent in which said monomer is soluble, under essentially anhydrous conditions for a period of time and at a temperature sufficient to couple said monomer until macromolecules having a degree of polymerization representative of an oligomer or a polymer are produced, wherein the catalyst mixture comprises an anhydrous nickel compound and at least one liquid 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; (B) adding to the reaction mixture of (A) about 0.01 to about 1.0 moles of a substituted organic halide having at least one substitutent per molecule selected from the class consisting of acetoxy, amide, ester, amine, vinyl, alkyne, cyano, silane, epoxide, and isocyanate groups, per mole of unsubstituted aryl polyhalide whereby said macromolecule in (A) further couples with said substituted organic halide to form mixed macromolecules; and (C) cross-linking the mixed macromolecules from (B).