A set of poly(isobornyl methacrylate)s (PIBOMA) having molar mass in the range of 26,000–283,000 g mol−1 was prepared either via RAFT process or using free radical polymerization. These linear polymers demonstrated high glass transition temperatures (Tg up to 201 °C) and thermal stability (Tonset up to 230 °C). They were further applied as reinforcing agents in the preparation of the vulcanized rubber compositions based on poly(styrene butadiene rubber) (SBR). The influence of the PIBOMA content and molar mass on the cure characteristics, rheological and mechanical properties of rubber compounds were studied in detail. Moving die rheometry revealed that all rubber compounds filled with PIBOMA demonstrated higher torque increase values ΔS in comparison with rubber compositions without filler, independent of PIBOMA content or molar mass, thus confirming its reinforcing effect. Reinforcement via PIBOMA addition was also observed for vulcanized rubbers in the viscoelastic region and the rubbery plateau, i.e. from −20 to 180 °C, by dynamic mechanical thermal analysis. Notably, while at temperatures above ~125 °C, ultra-high-molecular-weight polyethylene (UHMWPE) rapidly loses its ability to provide reinforcement due to softening/melting, all PIBOMA resins maintained their ability to reinforce rubber matrix up to 180 °C. For rubber compositions containing 20 phr of PIBOMA, both tensile strength and elongation at break decreased with increasing PIBOMA molecular weight. In summary, PIBOMA, with its outstanding high Tg among known poly(methacrylates), may be used in the preparation of advanced high-stiffness rubber compositions, where it provides reinforcement above 120 °C and gives properties appropriate for a range of applications.

For the first time, random copolymers of styrene (St) and 1,3-butadiene (Bd) (poly(Stn-r-Bdm), styrene butadiene rubber, SBR) were prepared via solution RAFT polymerization, that was further extended to produce poly[Xn-b-(Stm-r-Bdk)] block copolymers.