Heterotelechelic Silicones: Facile Synthesis and Functionalization Using Silane-Based Initiators.

The synthetic utility of heterotelechelic polydimethylsiloxane (PDMS) derivatives is limited due to challenges in preparing materials with high chain-end fidelity. In this study, anionic ring-opening polymerization (AROP) of hexamethylcyclotrisiloxane (D3) monomers using a specifically designed silyl hydride (Si-H)-based initiator provides a versatile approach toward a library of heterotelechelic PDMS polymers. A novel initiator, where the Si-H terminal group is connected to a C atom (H-Si-C) and not an O atom (H-Si-O) as in traditional systems, suppresses intermolecular transfer of the Si-H group, leading to heterotelechelic PDMS derivatives with a high degree of control over chain ends. In situ termination of the D3 propagating chain end with commercially available chlorosilanes (alkyl chlorides, methacrylates, and norbornenes) yields an array of chain-end-functionalized PDMS derivatives. This diversity can be further increased by hydrosilylation with functionalized alkenes (alcohols, esters, and epoxides) to generate a library of heterotelechelic PDMS polymers. Due to the living nature of ring-opening polymerization and efficient initiation, narrow-dispersity (D < 1.2) polymers spanning a wide range of molar masses (2-11 kg mol-1) were synthesized. With facile access to α-Si-H and ω-norbornene functionalized PDMS macromonomers (H-PDMS-Nb), the synthesis of well-defined supersoft (G' = 30 kPa) PDMS bottlebrush networks, which are difficult to prepare using established strategies, was demonstrated.

Improved Elastic Recovery from ABC Triblock Terpolymers.

The promise of ABC triblock terpolymers for improving the mechanical properties of thermoplastic elastomers is demonstrated by comparison with symmetric ABA/CBC analogs having similar molecular weights and volume fraction of B and A/C domains. The ABC architecture enhances elasticity (up to 98% recovery over 10 cycles) in part through essentially full chain bridging between discrete hard domains leading to the minimization of mechanically unproductive loops. In addition, the unique phase space of ABC triblocks also enables the fraction of hard-block domains to be higher (fhard ≈ 0.4) while maintaining elasticity, which is traditionally only possible with non-linear architectures or highly asymmetric ABA triblock copolymers. These advantages of ABC triblock terpolymers provide a tunable platform to create materials with practical applications while improving our fundamental understanding of chain conformation and structure-property relationships in block copolymers.