Foam-forming compositions containing azeotropic or azeotrope-like mixtures containing cis-1,1,1,4,4,4-hexafluoro-2-butene are disclosed. The foam-forming composition contains (a) an azeotropic or azeotrope-like mixture of cis-1,1,1,4,4,4-hexafluoro-2-butene with methyl formate, 1,1,1,3,3-pentafluorobutane, trans-1,2-dichloroethylene, pentane, isopentane, cyclopentane, HFC-245fa, or dimethoxymethane; and (b) an active hydrogen-containing compound having two or more active hydrogens. Also disclosed is a closed-cell polyurethane or polyisocyanurate polymer foam prepared from reaction of an effective amount of the foam-forming composition with a suitable polyisocyanate. Also disclosed is a process for producing a closed-cell polyurethane or polyisocyanurate polymer foam by reacting an effective amount of the foam-forming composition with a suitable polyisocyanate.