Modification of nanocellulose via atom transfer radical polymerization and its reinforcing effect in waterborne UV-curable resin

Abstract

Cellulose nanocrystals (CNCs) are green reinforcing materials, and their potential has been evaluated in the preparation of waterborne UV-curable resin composites with high-performance. Herein, we present a novel and scalable approach for preparing surface-modified CNCs with acrylic-based polymers to strengthen the compatibility and interaction between CNCs and UV-curable resins. Using tert-butyl acrylate as the monomer, the nanocellulose grafted copolymer CNC-g-PtBA was successfully synthesized via atom transfer radical polymerization (ATRP) in the presence of a macromolecular initiator. Then, the CNC-g-PtBA is blended into the acrylic resin as a nanofiller to prepare the UV-curable nanocomposite. The results indicated that the contact angle of the CNCs increased from 38.7° to approximately 74.8°, and their thermal stability was significantly improved after graft modification. This contributed to the effective alleviation of the agglomeration phenomenon of nanocomposites due to the high hydrophilicity of pure CNCs. Notably, not only was the UV curing efficiency of the nanocomposites greatly increased but the mechanical properties were also further enhanced. Specifically, with the addition of 0.5 wt% CNC-g-PtBA, the curing time of the nanocomposite was shortened from >30 mins down to approximately 6 mins, and the bending strength was increased from 10 MPa for the original resin and 5 MPa for the addition of pure CNCs to 14.3 MPa, and the bending modulus was also greatly increased (up to approximately 730 MPa). Compared to pure CNCs, they are compatible with the resin, exhibiting high mechanical strength and flexibility, and have virtually no effect on the light transmission of the nanocomposites. Additionally, dielectric analysis (DEA) was used to monitor the dielectric constant and conductivity of the UV-curable nanocomposites in real time to further characterize their curing kinetics. The permittivity of these nanocomposites increased by 125 % compared to pristine resin, which shows potential for applications in high dielectric composites or for improving electrical conductivity. This work provides a feasible method for preparing UV-curable nanocomposites with high curing efficiency and permittivity, realizing a wider application of this high-performance nanocomposite.

Keywords: Atom transfer radical polymerization; Cellulose nanocrystals; Curing kinetics; Nanocomposites; UV-curable; Waterborne acrylic resin.