Effect of functional-group distribution on the structure of a polymer in non-aqueous solvent

ABSTRACT

The sizes and structures of isolated functionalised polymers in a hydrocarbon solvent are studied using atomistic molecular dynamics simulations and Monte Carlo simulations of coarse-grained chains. A specific functionalised polyethylene-polypropylene random copolymer in n-heptane is studied using atomistic simulations. The functional groups contain aromatic and polar groups, and eight of them are distributed on an polymer backbone in several different ways. It is shown that the radius of gyration and the end-to-end distance depend sensitively on the functional-group distribution. A random distribution of functional groups gives the most compact polymer structure, but other distributions give values up to larger; the largest values are when the functional groups are split evenly between both ends of the polymer. This is shown to be due to the association of the polar, and hence solvophobic, functional groups. A coarse-grained bead-spring model is then studied that includes solvophilic beads (representing unfunctionalised units) and solvophobic beads (representing functionalised units). Monte Carlo simulations are used to survey functional-group concentration and distribution. The results show that the collapse of a polymer with increasing solvophobicity depends sensitively on the distribution of different beads. Form factors are presented for both the atomistic and coarse-grained models and are analysed as if they were experimental scattering measurements. The apparent radii of gyration are in good agreement with those determined directly from the simulation.

GRAPHICAL ABSTRACT

KEYWORDS:

• Functionalised polymers
• molecular dynamics
• Monte Carlo
• coarse graining

Acknowledgements

The authors are privileged to contribute this work to the special issue of Molecular Physics in honour of Daan Frenkel's birthday.

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

This work was supported by Infineum UK Ltd through a studentship to R.F.G.A. We gratefully acknowledge the support of Nvidia Corporation through the donation of a GeForce Titan Xp GPU used in this research.