In order to move away from traditional petrochemical-based polymer materials, it is imperative that new monomer systems be sought out based on renewable resources. In this work, the synthesis of a functional terpene-containing acrylate monomer (tetrahydrogeraniol acrylate, THGA) is reported. This monomer was polymerized in toluene and bulk via free-radical polymerizations, achieving high conversion and molecular weights up to 278 kg·mol–1. The synthesized poly­(THGA) shows a relatively low T g (−46 °C), making it useful as a replacement for low T g acrylic monomers, such as the widely used n-butyl acrylate. RAFT polymerization in toluene ([M]0 = 3.6 mol·L–1) allowed for the well-controlled polymerization of THGA with degrees of polymerization (DP n ) from 25 to 500, achieving narrow molecular weight distributions (D̵ ≈ 1.2) even up to high conversions. At lower monomer concentrations ([M]0 = 1.8 mol·L–1), some evidence of intramolecular chain transfer to polymer was seen by the detection of branching (arising from propagation of midchain radicals) and terminal double bonds (arising from β-scission of midchain radicals). Poly­(THGA) was subsequently utilized for the synthesis of poly­(THGA)-b-poly­(styrene)-b-poly­(THGA) and poly­(styrene)-b-poly­(THGA)-b-poly­(styrene) triblock copolymers, demonstrating its potential as a component of thermoplastic elastomers. The phase separation and mechanical properties of the resulting triblock copolymer were studied by atomic force microscopy and rheology.

Emerging pressure-sensitive adhesives (PSAs) formulations based on triblock copolymers typically rely on solvent-borne or bulk processes and are mostly composed of petroleum-derived monomers. Herein, we aim to go beyond the status quo and synthesize hard–soft–hard and soft–hard–soft triblock copolymers using tetrahydrogeraniol acrylate (THGA) and cyclademol acrylate (CDMA) as biosourced monomers. Great care is taken on the synthesis of the monomers and polymers thereof to minimize the environmental impact of the entire process. Hence, the copolymers are obtained by reversible addition–fragmentation chain transfer (RAFT) miniemulsion polymerization as a waterborne process. The process is readily scalable, as no intermediate purification of the first block is required. Good control is achieved for the triblock copolymers with high molecular weight, with M n ≈ 105 500 g·mol–1 and Đ ≈ 1.6 for the PTHGA-b-PCDMA-b-PTHGA. The nanophase segregation of the copolymers is later evidenced by atomic force microscopy (AFM) and rheological measurements. Finally, the formulations show good adhesive performance, in comparison to triblock copolymers partially based on styrene.