Tunable poly(lauryl methacrylate) surface grafting via SI-ATRP on a one-pot synthesized cellulose nanofibril macroinitiator core as a shear-thinning rheology modifier and drag reducer

Abstract

The optimally one-pot synthesized 2-bromoproponyl esterified cellulose nanofibril (Br-CNF) has been validated as a robust macroinitiator for self-surface-initiated atom transfer radical polymerization (SI-ATRP) of lauryl methacrylate (LMA) in tunable graft lengths and high conversions of up to 92.7%. SI-ATRP of LMA surface brushes on Br-CNF followed first order kinetics in lengths at up to 46 degree of polymerization (DP) based on mass balance or 31 DP by solution-state ¹H NMR in DMSO-d₆. With increasing PLMA graft lengths, Br-CNF-g-PLMA cast films exhibited increasing hydrophobicity with water contact angles from 80.9° to 110.6°. The novel Br-CNF-g-PLMA exhibited dual shear thinning behavior of the Br-CNF core as evident by n < 1 flow behavior index and drag reducing properties of PLMA grafts with increased viscosity at up to 21 071×. Br-CNF-g-PLMA with 46 DP could be fully dispersed in silicon pump oil to function as a drag reducer to enhance viscosity up to 5× at 25, 40, and 55 °C. The novel macroinitiator capability of Br-CNF in SI-ATRP of vinyl monomers and the bottlebrush-like LMA surface grafted Br-CNF as highly effective viscosity modifier and drag reducer further demonstrate the versatile functionality of Br-CNF beyond hydrophobic coatings and reactive polyols previously reported.