Polycondensation techniques are effective methods to produce a wide variety of polymers for various applications. The chain-growth condensation (CGC) process allows for controlled synthesis of block copolymers, and most interestingly, the synthesis of surface-initiated polymer brushes of polymers such as aromatic polyamides that contain many industrially relevant properties. However, the factors dictating the kinetics and termination of aromatic polyamide polymer brush growth are relatively unknown. In this investigation, the effect of different leaving groups on a variety of ester-based monomers was performed to computationally probe the chemical properties that govern the CGC polymerization. Linear and branched alkane ester leaving groups were compared to phenyl-based leaving groups with varying functionality to observe the effect on the polymerization rate and by-product formation. It was found that for the alkyl-based leaving groups, steric hindrance and pKa are the dictating factors limiting polymer growth, while for the phenyl-based leaving groups, electron withdrawing character improves the CGC kinetics by stabilizing the phenoxide leaving group. Additionally, the effect of varying the protecting group on the nucleophilicity of the attacking amine will be presented.

Computational investigation of the effects of leaving groups and protecting groups on the kinetics of chain-growth polycondensation polymerization

256th National Meeting (2018)

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