5. Investigating the Structure-property Behavior of Polydimethylsiloxane Based Segmented Polyurea Copolymers with a Second Polypropylene Oxide Soft Segment Component

5.1 CHAPTER SUMMARY Polypropylene oxide (PPO) was incorporated in a controlled manner between polydimethylsiloxane (PDMS) and urea segments in segmented polyurea copolymers and their solid state structure-property behavior was investigated. The copolymers contained PDMS segments of MW 3200 or 7000 g/mol and an overall hard segment content of 10-35 wt %. PPO segments of MW 450 or 2000 g/mol were utilized. Equivalent polyurea copolymers based on only PDMS as the soft segment (SS) component were used as controls. The materials (with or without PPO) utilized in this study were able to develop a microphase morphology as determined from dynamic mechanical analysis and small angle X-ray scattering. DMA and SAXS results suggested that the ability of the PPO segments to hydrogen bond with the urea segments results in a limited inter-segmental mixing which leads to the formation of a gradient interphase, especially in the PPO-2000 co-SS containing copolymers. DMA also demonstrated that the polyureas based on only PDMS as the SS possessed remarkably broad and nearly temperature insensitive rubbery plateaus that extended up to ca. 175°C, the upper temperature limit depending upon the PDMS MW. However, the incorporation of PPO resulted in more temperature sensitive rubbery plateaus. A distinct improvement in the Young’s modulus, tensile strength, and elongation at break in PPO-2000 containing copolymers was observed due to inter-segmental hydrogen bonding and the formation of a gradient interphase. However, when PPO was incorporated as the coSS, the extent of stress relaxation and mechanical hysteresis of the copolymers increased relative to the segmented polyureas based on the utilization of the PDMS soft segment component.