Synthesis and characterization of poly(vinylcyclohexane) derivatives

Abstract Six nearly monodisperse substituted poly(styrene) homopolymers, poly(styrene) (PS), poly(2‐methylstyrene) (P2MS), poly(3‐methylstyrene) (P3MS), poly(4‐methylstyrene) (P4MS), poly(tertiary‐butylstyrene) (PtBS), and poly(α‐methylstyrene) (FαMS) were anionically polymerized and subsequently saturated using heterogeneous hydrogenation techniques to poly(vinylcyclohexane) (PVCH), poly(2‐methylvinylcyclohexane) (P2MVCH), poly(3‐methylvinylcyclohexane) (P3MVCH), poly(4‐methylvinylcyclohexane) (P4MVCH), and poly(tertiary‐butylvinylcyclohexane) (PtBVCH), respectively. In each case, except PαMS, the materials were saturated to > 99% conversion with no chain degradation. PS hydrogenations required the addition of small amounts of tetrahydrofuran to the reaction solvent cyclohexane to enhance miscibility and eliminate large‐scale chain degradation. Density gradient and differential scanning calorimetry (DSC) measurements were used to characterize the density and glass transition temperature, T g , of the unsaturated and saturated polymers. Saturation reduces the density by 3% to 11% and changes T g substantially. The greatest variation in T g is obtained with the 3‐methyl substituted species where a 63°C increase is observed, while the highest measured T g is 186°C for P2MVCH. Small‐angle neutron scattering (SANS) experiments on binary mixtures of hydrogenous and deuterium labeled PVCH derivatives provided a determination of bulk chain statistics. The statistical segment length is relatively insensitive to vinylcyclohexane ring substitution, except with P3MVCH where a 20% greater value is obtained. ©1995 John Wiley & Sons, Inc.