AbstractThis study involved the synthesis and characterization of tetraoxaspiroalkane monomers and evaluated their potential to reduce polymerization stress when formulated in a Silorane resin system. The tetraoxaspiroalkane monomers had two main structural features (a) two different types of core ring structures (a 1,5,7,11‐tetraoxaspirocyclic ring or a 2,4,8,10‐tetraoxaspirocyclic ring) and (b) four different types of ring substituents (normal alkyl, allyloxyalkyl, trimethylsilylalkyl, or oxabicycloalkyl). The resin formulations contained (a) 20 mol % of a 1,5,7,11‐ or 2,4,8,10‐tetraoxaspiroalkyl monomer; (b) a phenylmethylsilane containing two oxabicycloheptyl groups; (c) a cyclotetrasiloxane containing four oxabicycloheptyl groups; and (d) a photocationic initiator system. Three main aspects were studied (a) the photoreactivity of the formulations using PDSC, (b) photopolymerization stress, and (c) mechanical properties (flexural elastic modulus, ultimate strength, and work of fracture) which were measured using an electromagnetic mechanical testing machine. The main findings were (a) formulations containing 2,4,8,10‐tetraoxaspiroalkane monomers had measured net enthalpies greater than those containing 1,5,7,11‐tetraoxaspiroalkane monomers, and above those calculated for addition of an inert diluent; (b) all formulations containing tetraoxaspiroalkane monomers exhibited photopolymerization stress values that were 40–99% less than the nonaddition control; (c) the formulation containing a 1,5,7,11‐tetraoxaspiroalkane monomer with an oxirane functionality had mechanical properties that were not significantly different from the nonaddition control. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008