The present invention is related to novel preparative methods to a novel class of polymer network materials with a highly branched poly(glycidyl ether) (PGE) structure. Said polymer networks are prepared by a simple procedure involving cationic ring-opening polymerisation and the method is applicable to a wide range of glycidyl ether containing monomers. The method comprises either the step of homopolymerising at least one multi-topic glycidyl ether comprising at least three glycidyl ether groups or the step of copolymerising (A) at least one multi-topic glycidyl ether comprising at least three glycidyl ether groups with (B) at least one glycidyl ether component comprising at least one glycidyl ether group by ring opening polymerisation.
