Sustainable Vinyl Polymers via Controlled Polymerization of Terpenes

Terpene-based olefinic compounds are abundant and are promising renewable resources for polymeric materials. It has long been known that several terpenes, including β-pinene and limonene, undergo cationic polymerization or oligomerization to result in relatively low molecular weight polymers or oligomers, which are used industrially as tackifiers and additives. This chapter reviews the developments in the polymerization of terpenes and their derivatives as vinyl monomers. It specifically focuses on the design of appropriate polymerization systems depending on the terpene structure. In addition, the chapter discusses the design of characteristic polymer structures based on the specific terpene skeleton and controlled polymerization. The HCl-CEVE/TiCl3(Oi-Pr)/n-Bu4NCl initiating system has been used to synthesize various β-pinene-based block, random, graft, and end-functionalized polymers. The controlled/living radical copolymerization of β-pinene was first reported in combination with methyl acrylate (MA) using reversible addition-fragmentation chain transfer (RAFT) polymerization.