Epoxidized Block and Statistical Copolymers Reinforced by Organophosphorus-Titanium-Silicon Hybrid Nanoparticles: Morphology and Thermal and Mechanical Properties.

Glycidyl methacrylate (GMA) and a mixture of alkyl methacrylates (average chain length of 13 carbons; termed C13MA; derived from vegetable oils) were copolymerized by nitroxide-mediated polymerization to form epoxidized statistical and block copolymers with similar compositions ( ∼0.8), which were further cross-linked by a bio-based diamine. Hybrid plate-like nanoparticles containing organophosphorus-titanium-silicon (PTS) with an average size of ∼130 nm and high decomposition temperature (485 °C) were synthesized via a hydrothermal reaction to serve as additives to simultaneously enhance the thermal and mechanical properties of the blend. Nanocomposites filled with PTS were prepared at different filler-loading levels (0.5, 2, 4 wt %). Transmission electron microscopy (TEM) of the cured block copolymer displayed reaction-induced macrophase-separated domains. TEM also showed an effective dispersion of PTS hybrids in the matrix without intense agglomeration. Thermogravimetric analysis at different heating rates revealed the activation energy of poly (GMA--C13MA) at maximum decomposition increased from 143.5 to 327.2 kJ mol with 4 wt % PTS. Decomposition temperature and char residue improved 12 °C and ∼7 wt %, respectively, and increased 12 °C by adding 4 wt % PTS. Targeting various PTS concentrations enabled tuning of the tensile modulus (up to 75%), tensile strength (up to 46%), and storage modulus in both glassy state (up to 59%) and rubbery plateau regions (up to 88%). Oscillatory frequency sweeps indicated that PTS makes the storage modulus frequency dependent, suggesting that the inclusion of the nanoparticles alters the relaxation of the surrounding matrix polymer.