Photoinduced Upgrading of Lactic Acid-Based Solvents to Block Copolymer Surfactants

Abstract

We report a new strategy toward the development of block copolymer surfactants from chemicals of the lactic acid family. A particularly unique aspect of this work is the use of green solvents as biobased platform chemicals to generate well-defined and nanostructure-forming materials. Herein, efficient functionalization of ethyl lactate (EL) and N,N-dimethyl lactamide (DML) solvents with acrylate groups generated monomers that could be polymerized by the photoinduced copper-catalyzed living radical polymerization process to yield polymeric materials with different water solubilities. These lactic acid-derived monomers were used as a major component in well-defined diblock copolymers composed of poly­(EL acrylate) and poly­(DML acrylate) segments as hydrophobic and hydrophilic building blocks, respectively. The resulting amphiphilic copolymers could self-assemble in aqueous solution to form nanoparticles with different morphologies (e.g., large-compound micelles and vesicles). Subsequently, the formed amphiphilic polymers were employed as efficient stabilizers in the emulsion polymerization of methyl methacrylate and styrene, offering a facile method for the synthesis of well-defined and stable polymer latexes in the range of 100–200 nm, demonstrating the practical significance of these biobased polymers in nanomaterial synthesis.

Access to tough and transparent nanocomposites via Pickering emulsion polymerization using biocatalytic hybrid lignin nanoparticles as functional surfactants

“…3d and e), demonstrating a higher thermal stability than latex dispersions stabilized by conventional chemical surfactants or amphiphilic polymers. 64,65 Ultimately, the stability to electrolyte addition was also proved and no significant changes in particle size or emulsion appearance were observed by saturating the dispersion system with sodium chloride ( Fig. 3d and e).…”

Biosourced All-Acrylic ABA Block Copolymers with Lactic Acid-Based Soft Phase

“…As reported in previous publications, alkyl lactate solvents are appealing chemicals to prepare biorenewable acrylic/methacrylic polymers [23][24][25][26][27][28][29]. Here, BuLA was prepared from L-butyl lactate (BuL) by acylation with acryloyl chloride in the presence of base using a solvent with low environmental impact such as Me-THF (Figure 1).…”

“…In this regard, our group reported that poly(alkyl lactate ester) (meth)acrylates with controlled molecular weight, narrow molecular weight distribution and high end-group fidelity are also easily accessible by Cu(0) wire-mediated single-electron transfer living radical polymerization (SET-LRP) [27,28]. In a more recent effort, the different water solubility of poly(ethyl lactate acrylate)s (hydrophobic and water-insoluble) and poly(N,N-dimethyl lactamide acrylate) (hydrophilic and water-soluble) was exploited to design amphiphilic AB block copolymers from neoteric lactic acid-based solvents, i.e., ethyl lactate and N,N-dimethyl lactamide, that could self-assemble in aqueous solution to form nanoparticles with different morphologies including large-compound micelles and vesicles [29].…”

Lignin-based smart materials: a roadmap to processing and synthesis for current and future applications

“…182 Especially biomass-derived solvents such as ethyl lactate already used in the production of polymeric materials could be assessed in the future. 183 Although frequently neglected, another important consideration about these lignin nanomaterials is their biodegradability. While many of the reports focus strictly their attention on the cytotoxicity and biocompatibility studies, the biodegradability of these materials remains largely unexplored.…”