Synergetic Effect of Water-Soluble PEG-Based Macromonomers and Cellulose Nanocrystals for the Stabilization of PMMA Latexes by Surfactant-Free Emulsion Polymerization

Abstract

The combination of cellulose nanocrystals (CNCs) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) was evaluated to synthesize stable latexes by surfactant-free emulsion polymerization of methyl methacrylate (MMA). Cellulose-particle interaction was provided due to the dual role of PEGMA, acting as water-soluble comonomer with MMA under emulsion polymerization conditions and able to interact with CNCs -recovered from sulfuric acid hydrolysis (H2SO4-CNCs). After preliminary experiments designed to validate the affinity between CNCs and PEG-stabilized PMMA particles obtained by MMA/PEGMA emulsion copolymerization, the effect of the PEGMA content and molar mass, and also of the content of CNCs on the kinetics of the polymerization and the stability of the latexes were investigated. The use of PEGMA300 (Mn = 300 g mol -1 , 2 to 10 wt%) allowed the formation of a stable latex, however with a broad particle size distribution and the presence of both small (ca. 25 -50 nm) and large (ca. 425 -650 nm) particles (at 10 wt%, Dn = 278 nm and Dw/Dn = 1.34). Increasing the molar mass of PEGMA (PEGMA950 or PEGMA2080) significantly increased the fraction of small particles. This was explained by the nucleation and growth of small polymer particles adsorbed at the CNCs' surface, resulting in a particular organization where the CNCs were covered by several polymer particles. The influence of the initial amount of CNC in these systems was finally evidenced, the polymerization being faster as the content of CNCs increased, but only the latexes prepared with 2 and 5 wt% of CNCs were stable.

Functionalization of Poly(styrene-co-methyl methacrylate) Particles for Selective Removal of Bilirubin

“…As observed in the LALLS results ( Table 4 ), the particle size from the St-MMA-GMA-PEGMA reaction is clearly smaller than the others, although the stirring and the surfactant concentration were the same in all the cases. This reduction in the particle size has been previously observed when PEGMA is added for the synthesis of polymeric particles [ 49 , 50 ].…”

“…The particles containing the hydroxyl functionalization with PEGMA represented the best support for albumin immobilization, with an average value of immobilized albumin of 2.6 ± 0.69 mg BSA/g of particles. The best behavior of the particles having only hydroxyl groups functionalized can be attributed to the presence of more long-length filaments, which improves the access of large molecules such the BSA to the functional group [ 49 ]. The St-MMA-GMA and St-MMA-GMA-PEGMA particles immobilized 1.0 ± 0.27 and 1.26 ± 0.15 mg BSA/g of particles, respectively, while the value for particles without functionalization was just 0.6 mg BSA/g.…”

Polysaccharide‐Based Nanoparticles as Pickering Emulsifiers in Emulsion Formulations and Heterogenous Polymerization Systems

“…Similarly, Griveau et al. [ 157 ] modified CNCs in situ with poly(ethylene glycol) methyl ether methacrylate (PEGMA), which was copolymerized during the surfactant‐free emulsion polymerization of MMA. Rather than a CNC‐armored PMMA latex, the authors observed a novel morphology with multiple latex particles adsorbed to one nanocrystal ( Figure ).…”

Polymer Colloids: Synthesis Fundamentals to Applications

“…Articles on the synthesis using emulsion polymerization were presented from latex stabilization, hybrid nanocapsules by nanoprecipitation, and vesicle formation . RAFT microwave assisted emulsion polymerization was used to produce novel biobased terpenoid acrylates, while the self-assembly of MacroRAFT agents were studied using solvachromatic dyes .…”

“…This special issue of "Polymer Colloids: Synthesis Fundamentals to Applications" starts with comprehensive reviews for the nonexpert on the various synthetic pathways to produce and control the size, composition, and morphology of polymer colloids. 1−3 Articles on the synthesis using emulsion polymerization were presented from latex stabilization, 4 hybrid nanocapsules by nanoprecipitation, 5 and vesicle formation. 6 RAFT microwave assisted emulsion polymerization was used to produce novel biobased terpenoid acrylates, 7 while the self-assembly of MacroRAFT agents were studied using solvachromatic dyes.…”