Polymer Colloids: Current Challenges, Emerging Applications, and New Developments.

Polymer colloids are complex materials that have the potential to be used in a vast array of applications. One of the main reasons for their continued growth in commercial use is the water-based emulsion polymerization process through which they are generally synthesized. This technique is not only highly efficient from an industrial point of view but also extremely versatile and permits the large-scale production of colloidal particles with controllable properties. In this perspective, we seek to highlight the central challenges in the synthesis and use of polymer colloids, with respect to both existing and emerging applications. We first address the challenges in the current production and application of polymer colloids, with a particular focus on the transition toward sustainable feedstocks and reduced environmental impact in their primary commercial applications. Later, we highlight the features that allow novel polymer colloids to be designed and applied in emerging application areas. Finally, we present recent approaches that have used the unique colloidal nature in unconventional processing techniques.

Ionic Inter-Particle Complexation Effect on the Performance of Waterborne Coatings.

The performance of waterborne (meth)acrylic coatings is critically affected by the film formation process, in which the individual polymer particles must join to form a continuous film. Consequently, the waterborne polymers present lower performance than their solvent-borne counter-polymers. To decrease this effect, in this work, ionic complexation between oppositely charged polymer particles was introduced and its effect on the performance of waterborne polymer films was studied. The (meth)acrylic particles were charged by the addition of a small amount of ionic monomers, such as sodium styrene sulfonate and 2-(dimethylamino)ethyl methacrylate. Density functional theory calculations showed that the interaction between the selected main charges of the respective functional monomers (sulfonate-amine) is favored against the interactions with their counter ions (sulfonate-Na and amine-H). To induce ionic complexation, the oppositely charged latexes were blended, either based on the same number of charges or the same number of particles. The performance of the ionic complexed coatings was determined by means of tensile tests and water uptake measurements. The ionic complexed films were compared with reference films obtained at pH at which the cationic charges were in neutral form. The mechanical resistance was raised slightly by ionic bonding between particles, producing much more flexible films, whereas the water penetration within the polymeric films was considerably hindered. By exploring the process of polymer chains interdiffusion using Fluorescence Resonance Energy Transfer (FRET) analysis, it was found that the ionic complexation was established between the particles, which reduced significantly the interdiffusion process of polymer chains. The presented ionic complexes of sulfonate-amine functionalized particles open a promising approach for reinforcing waterborne coatings.

Effect of molecular weight on the physical properties of poly(ethylene brassylate) homopolymers.

Poly(ethylene brassylate) (PEB) is a biodegradable polyester that nowadays is of particular interest owing to its poly(ε-caprolactone)-like properties (with a Tg at -30°C and a Tm at 70°C) and the low-cost of its monomer. However, it is not simple to achieve high molar masses with conventional catalysts. In this work, high molar mass PEBs, characterized by SEC-MALS, were successfully synthesized using triphenyl bismuth (Ph3Bi) as catalyst. Then, with the aim of evaluating the impact of the molecular weight on the physical properties, several PEBs ranging from 27 to 247kgmol(-1) were prepared. It was demonstrated that above a Mw of 90Kgmol(-1), PEB behaved in a constant manner. PEBs with lower molecular weight (<46Kgmol(-1)) showed lower values of Tg (~(-35°C)) and presented a melting peak that was split into three or four different peaks while their crystallites started to melt earlier (at ~30°C). In addition, these PEBs were more sensitive to thermal degradation (two additional stages of degradation were observed) and, what is more important, were found to be prone to brittle fracture. As the Mw rose, the PEB samples became more ductile and those PEBs with a molecular weight above 90Kgmol(-1) possessed deformation at break values higher than 800%, secant modulus in the 296-324 range and ultimate tensile strength of >20MPa.

New Class of Alkoxyamines for Efficient Controlled Homopolymerization of Methacrylates.

Despite significant efforts, the design of alkoxyamines for polymerization of methacrylic monomers in a well-controlled fashion with good retention of the active chain ends remains a challenge. Herein, the facile synthesis of several alkoxyamines, which are capable of achieving this long sought-after goal, is reported. Controlled homopolymerization of methyl methacrylate is achieved as determined by a linear increase in molecular weight with conversion and first-order rate plots for various alkoxyamine concentrations. The versatility of the alkoxyamines is further exemplified by the ability to control the homopolymerization of styrene and by synthesis of a block copolymer of a second methacrylate in an efficient chain extension process.