Renewable Terpene Derivative as a Biosourced Elastomeric Building Block in the Design of Functional Acrylic Copolymers

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.