Low-molecular-weight atactic poly(propylene oxide) and poly(epichlorohydrin) (PECH) were chlorinated on average up to 4.42 chlorine atoms per repeat unit. A study of the products showed that chlorine substitution preferentially occurred on already chlorinated repeat units, yielding chlorine -rich and chlorine -poor sequences. As the extent of chlorine substitution increased, the glass-transition temperature of the polymers markedly increased, and their solubility in most of the organic solvents drastically decreased. The chlorinated polymers were azidified with NaN3 in dimethyl sulfoxide solutions. An analysis showed that azide groups replaced 99.8-99.9% of the initially present chlorine atoms. As the azide content of the samples increased, initially opaque polymers become dark brown, and their solubility increased in water but decreased in organic solvents. Samples with approximately four or more azide groups per repeat unit were only soluble in dimethyl sulfoxide and water. The standard enthalpy of formation of the polymers became increasingly positive as the azide content increased. The enthalpy of formation of a sample with 4.42 N-3/repeat unit was 6929 kJ/repeat unit, whereas this value was only 103 kJ/mol for classical GAP. An azidified sample from PECH (4.42 N-3/repeat unit) was crosslinked with a commercial triisocyanide into a rubbery product. The density and ultimate tensile strength of the rubbery product were 1.44 g/cm(3) and 4.84 MPa, and it swelled about 10% at 20degreesC in water. (C) 2004 Wiley Periodicals, Inc.