Anionic Polymerizable Surfactants from Biobased ω-Hydroxy Fatty Acids

Abstract

Biobased ω-hydroxytetradecanoic acid prepared via an efficient yeast-catalyzed ω-hydroxylation reaction was converted by a onestep reaction to the polymerizable surfactants ω-acryltetradecanoic acid (MA-1) and ω-maleate tetradecanoic acid (MA-2). MA-1 is a single polarheaded surfactant, whereas MA-2 is a bolaamphiphile with carboxylic acid polar groups at both chain ends. MA-1 gave a distinct critical micelle concentration (cmc) at 253 mg/L, whereas for MA-2, the surface tension decreased monotonically and a distinct cmc was not observed even up to 1800 mg/L. Experimental determination of the reactivity ratios for MA-1 and MA-2 with styrene showed that for MA-1 copolymers that approximate random structures were formed while MA-2 tends to form copolymers with an alternating nature. Emulsion polymerizations conducted with varying amounts of MA-1 and MA-2 (1−10 wt % with respect to styrene) gave colloidally stable latexes with particle sizes ranging from 52 to 155 nm. In emulsion polymerizations using either MA-1 or MA-2 at more than 5 wt % to monomer, a linear increase in latex particle volume with conversion was observed and the particle number remained constant, establishing that the polymerizations proceeded without significant aggregation or secondary particle nucleation. Potentiometric titration and 1 H NMR were used to measure MA-1 and MA-2 conversions during polymerization as well as how the surfactants were distributed between the particle surface, aqueous phase, and particle interior. Observed differences were rationalized based on the comparative structures of MA-1 and MA-2 and their corresponding partitioning behavior.

A Zwitterionic Polymerizable Surfactant from ω-Hydroxyltetradecanoic Acid Provides Stimuli-Responsive Behavior

“…In a previous study by our team on styrene emulsion polymerizations using the anionic polymerizable surfactants ω-acryltetradecanoic acid and ω-maleate tetradecanoic acid, the quantity of polymerized surfactants on the particle surface was determined by measuring the acid numbers by potentiometric titration. 24 However, since the zwitterionic polymerizable surfactant DMTA was used herein, the fraction of DMTA that resides at latex surfaces can display anionic or cationic charged groups. Hence, potentiometric titration cannot be used herein to quantify surface bound DMTA.…”

“…The first is a single polar-headed surfactant whereas the latter is a bolaamphiphile with carboxylic acid polar groups at both chain ends. Emulsion polymerizations of styrene with these surfactants gave latexes with high monomer conversion and particle sizes ≤160 nm …”

“…Emulsion polymerizations of styrene with these surfactants gave latexes with high monomer conversion and particle sizes ≤160 nm. 24 In this paper we report studies on a bio-based zwitterionic polymerizable surfactant derived from the conversion of C14methyl ester to ω-HOC14-methyl ester, catalyzed by engineered C. tropicalis. A two-step chemical conversion of this heterobifunctional precursor gave ω-O-maleate-α-2dimethylaminoethyl tetradecanamide (DMTA), with polymerizable maleate moieties.…”

Fatty Acid Hydratases: Versatile Catalysts to Access Hydroxy Fatty Acids in Efficient Syntheses of Industrial Interest

“…Hydroxy fatty acids are of the highest interest for industrial applications, since they serve as starting materials for polymers [1] or cyclic lactones [2], which are used in fragrances and antibiotics [3], as well as in plasticizers [4], surfactants [5], lubricants [6] and detergent formulations [7]. Besides being available in nature and accessible through plant oil hydrolysis (e.g., in the case of ricinoleic acid from castor oil [8]), chemical approaches towards hydroxy-functionalized fatty acids include oxygenation, epoxidation [9][10][11] and ozonolysis [12] as key reaction steps.…”

Surface-Functionalized Polystyrene Latexes Using Itaconate-Based Surfmers

“…Typically, surfactants are physisorbed on the emulsion particles; however, when surfactants that carry a polymerizable group (often termed surfmers) are used during the emulsion polymerization, the surfmer becomes covalently attached to the polymerized latexes, thereby significantly enhancing their colloidal stability . Several ionic and nonionic surfmers carrying maleate, − styrene, − and (meth)­acrylates , have been used as surfmers to prepare stable latexes, wherein the nature of the hydrophilic segments determines the surface functionality. The subtle nuances of using surfmers for the preparation of polymeric emulsions have been nicely enunciated in a recent review by Guyot …”