Effect of Molecular Weight of Methylphenylsiloxy-Containing Vinyl-Functionalized Terpolysiloxanes on Their UV-Activated Crosslinking by Hydrosilylation and Mechanical Properties of Crosslinked Elastomers.

Effects of molecular weight of methylphenyl-containing vinylsiloxy-functionalized terpolysiloxanes on their UV-activated crosslinking by hydrosilylation at room temperature in air, shelf life stability of "all-in-one" pastes prepared from them for additive manufacturing, and mechanical properties of the resulting crosslinked elastomers, are investigated. It is found that while rheology of pastes containing base polymers, trimethylsilylated silica fillers, and thixotropic additives is not significantly affected by the base polymer molecular weight but is dominated by the filler concentration, the pastes based on higher molecular weight polymers exhibit faster crosslinking (corresponding to higher catalyst turnover numbers) and their crosslinked elastomers show transient strain-induced crystallization. The latter appears in networks from terpolymers with degrees of polymerization (DP) of 240 and above (corresponding to about one half of the critical polydimethylsiloxane chain length for entanglement formation of DP = 460), within the temperature range of -80 to -30 °C, characteristic for polydimethylsiloxane melting transition. It is believed that this is the first time an observation of this chain length effect is reported for polysiloxane elastomers and that the properties reported herein can be expected to have major implications on the application potential of these polymers in both additive manufacturing and performance of their elastomers at sub-ambient temperatures.

Structure and properties of triolein-based polyurethane networks.

Polyurethane networks based on vegetable oils have very heterogeneous composition, and it is difficult to find a close correlation between their structure and properties. To establish benchmark structure-properties relationships, we have prepared model polyurethane networks based on triolein and 4,4'-diphenylmethane diisocyanate (MDI). Cross-linking in the middle of fatty acid chains leaves significant parts of the triglyceride as dangling chains. To examine their effect on properties, we have synthesized another polyurethane network using triolein without dangling chains (removed by metathesis). The structure of polyols was studied in detail since it affects the structure of polyurethane networks. The network structure was analyzed from swelling and mechanical measurements and by applying network and rubber elasticity theories. The cross-linking density in both networks was found to be close to theoretical. The triolein-based model network displayed modulus (around 6 MPa), tensile strength (8.7 MPa), and elongation at break (136%), characteristic of hard rubbers. Glass transition temperatures of the networks from triolein and its metathesis analogue were 25 and 31.5 degrees C, respectively.