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

• Published in: Biomacromolecules 2019-06, Vol.20 (6), p.2241-2251
• Main Authors: Noppalit, Sayrung, Simula, Alexandre, Ballard, Nicholas, Callies, Xavier, Asua, José M, Billon, Laurent
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Polymers
• ISSN: 1525-7797; 1526-4602
• DOI: 10.1021/acs.biomac.9b00185

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.