Modification of cellulose model surfaces by cationic polymer latexes prepared by RAFT-mediated surfactant-free emulsion polymerization

This paper presents the successful surface modification of a model cellulose substrate by the preparation and subsequent physical adsorption of cationic polymer latexes. The first part of the work introduces novel charged polymer nanoparticles constituted of amphiphilic block copolymers based on cationic poly(N,N-dimethylaminoethyl methacrylate-co-methacrylic acid) (P(DMAEMA-co-MAA)) as the hydrophilic segment, and poly(methyl methacrylate) (PMMA) as the hydrophobic segment. First, RAFT polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA) in water was performed at pH 7, below its pK_a. The simultaneous hydrolysis of DMAEMA led to the formation of a statistical copolymer incorporating mainly protonated DMAEMA units and some deprotonated methacrylic acid units at pH 7. The following step was the RAFT-mediated surfactant-free emulsion polymerization of methyl methacrylate (MMA) using P(DMAEMA-co-MAA) as a hydrophilic macromolecular RAFT agent. During the synthesis, the formed amphiphilic block copolymers self-assembled into cationic latex nanoparticles by polymerization-induced self-assembly (PISA). The nanoparticles were found to increase in size with increasing molar mass of the hydrophobic block. The cationic latexes were subsequently adsorbed to cellulose model surfaces in a quartz crystal microbalance equipment with dissipation (QCM-D). The adsorbed amount, in mg m⁻², increased with increasing size of the nanoparticles. This approach allows for physical surface modification of cellulose, utilizing a water suspension of particles for which both the surface chemistry and the surface structure can be altered in a well-defined way.