Alkoxylations are performed by reacting a cyclic oxide with a starter in the presence of certain phosphonium catalysts. The phosphonium catalysts are highly active and effective in such small quantities that it is often unnecessary to remove catalyst residues from the product. The phosphonium catalysts are very effective in alkoxylating even low molecular weight starters such as glycerol and sorbitol.

The invention provides a method for sequence controllable block copolymerization of a cyclic ester monomer and an epoxy monomer, including: in an inert atmosphere, adding the epoxy monomer and/or the cyclic ester monomer into a catalytic initiating system including an organic base and an alkyl borane for reaction, so as to obtain a sequence controllable polyether-polyester block copolymer of the cyclic ester monomer and the epoxy monomer, i.e. a polyester-b-polyether or a polyether-b-polyester. The invention can prepare various polyether-polyester block copolymers of which the molecular weights, block sequences, block ratios and pendant group combinations can be flexibly adjusted. The invention provides a method for continuously preparing an aliphatic polyester-polyether block copolymer by a one-pot method utilizing a catalytic system of a metal-free Lewis acid-base pair.