Alkoxylation processes using phosphorus and double metal cyanide catalysts

An alkoxylation process, comprising the following steps:

• (I) forming a reaction mixture comprising;
• a) a starter compound having at least one hydroxyl or thiol group and a molecular weight of up to 300, b) at least one cyclic oxide, and c) a catalytically effective amount of a phosphorus catalyst;
• (II) reacting the cyclic oxide b) with the starter compound a) in the presence of the phosphorus catalyst c) to form an intermediate alkoxylated product having a number average molecular weight of 400 to 1500 and containing residues of the phosphorus catalyst;
• and
• (III) further alkoxylating the intermediate alkoxylated product containing residues of the phosphorus catalyst in the presence of a catalytically effective amount of a double metal cyanide catalyst complex to produce a polyether having a number average molecular weight at least 200 g/mol greater than that of the intermediate alkoxylated product;
• wherein the phosphorus catalyst c) has any of the following structures;
• wherein R1, R2 and R3 independently are groups having unsubstituted or substituted, optionally heteroatomic, aromatic five- or six-member rings having a direct bond between a carbon atom of the optionally heteroatomic aromatic five- or six-member ring and the phosphorus atom, each R is independently hydrogen, halogen, unsubstituted or inertly substituted C1-12 alkoxyl, aryloxy, unsubstituted or inertly substituted linear, branched and/or cyclic alkyl and unsubstituted or inertly substituted aryl, with the proviso that any two R groups may together form a ring structure, Cp* designates an optionally substituted cyclopentadienyl ligand, X is halogen, hydroxyl, unsubstituted or inertly substituted alkyl, unsubstituted or inertly substituted aryl, unsubstituted or inertly substituted alkoxy, or unsubstituted or inertly substituted aryloxy, A represents a weakly coordinating anion, n− represents the valence of A, and n represents the absolute value of the valence of A.