Influence of Oligopeptide Length and Distribution on Polyisoprene Properties

Abstract

The tuning of binding modes of polar groups is the key step to mimicking the structure and properties of natural rubber through the molecular design of synthetic polyisoprenes. Herein, the ordering and binding distances of oligopeptides could be altered systematically by changing their lengths and distribution along the polyisoprene chain, which impose huge impacts on the mechanical properties and chain dynamics of green rubber. In detail, a series of peptide-functionalized polyisoprenes with terminal blocks (B-2A-PIP, B-3A-PIP) or random sequences (R-2A-PIP, R-3A-PIP) are fabricated by using dipeptides (2A) or tripeptides (3A) as crosslinkers to explore the mechanism of terminal interaction on mechanism properties and chain dynamics. B-4A-PIP and R-4A-PIP served as control samples. It is found that the increased oligopeptide length and the block distribution improves the mechanical properties and confine the chain movement by elevate the contents of ordered and compact microstructures, which is indicated by XRD, broadband dielectric spectroscopy (BDS) and consistent with the result of molecular dynamics simulation. New relaxation signals belonging to oligopeptide aggregates are found which showed elevated dielectric strengths upon temperatures increase. Additionally, it also reveals that the binding modes of oligopeptide do not significantly influence the entanglements of polyisoprene.