Surface-Functionalized Polystyrene Latexes Using Itaconate-Based Surfmers

Abstract

Itaconic acid was readily transformed to a series of amphiphilic diesters via stepwise esterification of itaconic anhydride; the diesters carry one alkyl (cetyl or octyl) group and either a PEG, glyceryl, or dopamine segment. These diesters were used as surfmers for the preparation of polystyrene (PS) emulsions, with the expectation that the surface of the emulsion particles would carry PEG, glyceryl or dopamine units. NMR spectroscopic studies revealed that the surfmers were covalently incorporated into the polystyrene chains; furthermore, NMR tube polymerization experiments also confirmed that when the PEG surfmer was used, the PEG segments are indeed present on the surface of the emulsion particles. The size of the PEGlyated PS emulsions was readily varied from 35 to 140 nm by changing the mole fraction of surfmer used. In the case of the glyceryl and dopamine carrying surfmers, an octyl unit was used as the hydrophobic segment to ensure appropriate hydrophobic-hydrophilic balance; it was noticed that significantly larger mole fractions of the surfmers were required (15-20 mol %) to generate stable emulsions with particle sizes of about 150 nm. The PS emulsions carrying dopamine units on the surface were found to adhere to glass surfaces; thus suggesting that such "sticky" emulsion particles could be used to functionalize different types of surfaces. Finally, itaconate diesters bearing cetyl and perfluorooctyl segments were also prepared and shown to copolymerize with styrene to generate fluoroalkyl-enriched PS copolymers; these were used to generate hydrophobic coatings, with water contact angles of over 120°. Thus, itaconate-based surfmers are readily accessible alternatives for the preparation of emulsions with tailored size and surface functionality.

Hydrophilic Porous Poly(l‐Lactic Acid) Nanomembranes: Self‐Assembly, and Anti‐Biofouling and Anti‐Thrombosis Effects

“…The hydrophilicity of the PSANMs was characterized by WCA using an Optical Contact Angle Meter (Dataphysics, OCA40 Micro, Germany). The WCA was measured similar to previously described methods . The PSANMs suspension was drop‐cast onto a dry and clear glass substrate and dried at room temperature, after which the coated substrate was further dried in a vacuum oven at 45 °C overnight.…”

“…The WCA was measured similar to previously described methods. [47] The PSANMs suspension was drop-cast onto a dry and clear glass substrate and dried at room temperature, after which the coated substrate was further dried in a vacuum oven at 45°C overnight. 16 : G1À (OH) 16 , a sixteen-arm star-shaped poly (L-lactic acid) (SSÀ PLLAÀ OH), was synthesized by ring opening polymerization (ROP) of L-lactide, in which PAMAMÀ OH and Sn (Oct) 2 were served as initiator and catalyst, respectively.…”

Recent advances in radical polymerization of bio-based monomers in aqueous dispersed media

“…Itaconic acid was also esterified to form three asymmetrical diesters and one ester amide. 104 The itaconate-diesters carried on one side an octyl or cetyl group and on the other side a poly(ethylene glycol) (PEG350), glycerol or perfluorodecane segment. The ester amide-itaconate was formed by an octyl group on one side and by dopamine on the other side (Fig.…”

Organocatalyzed Living Radical Polymerization of Itaconates and Self‐Assemblies of Rod−Coil Block Copolymers

“…[ 5,6 ] It is synthesized via a microbial fermentation process of glucose by Aspergillus terreus or thermal isomerization of citric acid. [ 7 ] Itaconic acid is considered as a renewable substitute to petroleum‐based acrylic acid and methacrylic acid and find applications in surfactants, [ 8,9 ] elastomers, [ 10,11 ] and so forth. [ 12–18 ] Itaconic acid is one of the 12 most promising bio‐based chemicals suggested by US Department of Energy.…”