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Segmented polyurethanes based on aliphatic diisocyanate (hexamethylene diisocyanate) were synthesised varying the chemical nature (polyester or polyether) and molecular weight of the soft segment. These polymers were exposed to UV radiation and changes in the chemical structure were analysed by FTIR spectroscopy. Chemical nature and molecular weight of the soft segment are shown to be important factors which control the photodegradative behaviour of the urethane linkages.