Rigid polyurethane (PUR) foams have been the most effective insulation material used in space launchers since the beginning of cryogenic fuel use, due to their outstanding thermal and mechanical properties. In this study, spray-applied PUR foams using different ratios of amine-based catalysts were produced. Due to climate change, several restrictions have been made regarding the usage of blowing agents used for PUR foam production. Lately, hydrofluoroolefins (HFOs) have been suggested as an alternative for PUR foam production due to their low global warming potential (GWP) and ozone depletion potential (ODP), replacing the hydrofluorocarbons (HFCs) so far used. This change in blowing agents naturally altered the usage of catalysts. Reactive amine-based catalysts are less hazardous because of their low volatility and ability to react successfully with isocyanate or polyols. Spray-applied PUR foams with a potential application for cryogenic insulation were produced and tested for long-term storage, analyzing parameters such as the pH value of polyol composition, foaming kinetics (trise, tcream), etc. Athermal analysis (TG, DSC) was also applied to developed materials, as well as artificial ageing by exposing samples to UV light. It was discovered that PUR foams obtained using reactive amine-based catalysts, such as Polycat 203 and 218, have a higher integral heat capacity, but polyol mixtures containing these catalysts cannot exceed a storage time of more than 4 months. It was also observed from artificial ageing tests of PUR cryogenic insulation by exposure to UV light that the thickness of the degraded layer reached 0.8 mm (after 1000 h), but no significant destruction of cellular structure deeper in the material was observed.