Synthesis and characterization of thiol–ene functionalized siloxanes and evaluation of their crosslinked network properties

Three types of linear thiol‐functionalized siloxane oligomers and three types of ene‐functionalized oligomers were synthesized and subsequently photopolymerized. Within each type of thiol‐functionalized oligomer, the ratio of mercaptan repeat units to nonreactive phenyl repeat units was varied to manipulate both the crosslink density and the degree of secondary interactions through π–π stacking. Similarly, the repeat units of the three ene‐functionalized oligomers are composed of allyl‐functional monomers, benzene‐functional monomers, and octyl‐functional monomers in varying ratios of benzene:octyl but with a constant fraction of allyl moieties. The structural composition of the siloxane oligomers plays a pivotal role in the observed material properties of networks formed through thiol–ene photopolymerization. Networks with a high concentration of thiol functionalities exhibit higher rubbery moduli, ultimate strengths, and Young's moduli than networks with lower thiol concentrations. Moreover, the concentration of functionalities capable of participating in secondary interactions via hydrogen bonding or π–π stacking directly impacts the network glass transition temperature and elasticity. The combination of low crosslink density and high secondary interactions produces networks with the greatest toughness. Finally, the fraction of octyl repeats correlates with the hydrophobic nature of the network. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012