Electrochemically-Initiated RAFT Synthesis of Low Dispersity Multiblock Copolymers by Seeded Emulsion Polymerization.

We describe electrochemically initiated emulsion polymerization with reversible addition-fragmentation chain transfer (eRAFT) to form well-defined multiblock copolymers with low molar mass dispersity. We demonstrate the utility of our emulsion eRAFT process with the synthesis of low dispersity multiblock copolymers by seeded RAFT emulsion polymerization at ambient temperature (∼30 °C). Thus, a triblock, poly(butyl methacrylate)-block-polystyrene-block-poly(4-methylstyrene) [PBMA-b-PSt-b-PMS], and a tetrablock, poly(butyl methacrylate)-block-polystyrene-block-poly(styrene-stat-butyl acrylate)-block-polystyrene [PBMA-b-PSt-b-P(BA-stat-St)-b-PSt], were synthesized as free-flowing, colloidally stable latexes commencing with a surfactant-free poly(butyl methacrylate) macroRAFT agent seed latex. A straightforward sequential addition strategy with no intermediate purification steps was able to be employed due to the high monomer conversions achieved in each step. The method takes full advantage of compartmentalization phenomena and the nanoreactor concept described in previous work to achieve the predicted molar mass, low molar mass dispersity (D ∼ 1.1-1.2), incrementing particle size (Zav = 100-115 nm), and low particle size dispersity (PDI ∼ 0.02) for each generation of the multiblocks.

Selective Bond Cleavage in RAFT Agents Promoted by Low-Energy Electron Attachment.

Radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization) has been successfully applied to generate polymers of well-defined architecture. For RAFT polymerization a source of radicals is required. Recent work has demonstrated that for minimal side-reactions and high spatio-temporal control these should be formed directly from the RAFT agent or macroRAFT agent (usually carbonothiosulfanyl compounds) thermally, photochemically or by electrochemical reduction. In this work, we investigated low-energy electron attachment to a common RAFT agent (cyanomethyl benzodithioate), and, for comparison, a simple carbonothioylsulfanyl compound (dimethyl trithiocarbonate, DMTTC) in the gas phase by means of mass spectrometry as well as quantum chemical calculations. We observe for both compounds that specific cleavage of the C-S bond is induced upon low-energy electron attachment at electron energies close to zero eV. This applies even in the case of a poor homolytic leaving group (. CH3 in DMTTC). All other dissociation reactions found at higher electron energies are much less abundant. The present results show a high control of the chemical reactions induced by electron attachment.

Electrochemical Behavior of Thiocarbonylthio Chain Transfer Agents for RAFT Polymerization.

Electrochemical activation of thiocarbonylthio reversible addition-fragmentation chain transfer (RAFT) agents (S=C(Z)S-R) is explored as a potential method for initiating RAFT polymerization under mild conditions without producing initiator-derived byproducts. Herein we apply cyclic voltammetry to establish a predominant reduction mechanism, where electrochemical reduction is coupled to an irreversible first-order chemical reaction. Structure-dependent trends in cyclic voltammograms (CVs), and comparison to absorption spectra, clarify the role of R- and Z-groups in determining reduction processes. The major reduction peak moves to more cathodic potentials in the series dithiobenzoates > trithiocarbonates > heteroaromatic dithiocarbamates > xanthates ∼ N-alkyl-N-aryldithiocarbamates, due to the Z-group influence on thiocarbonyl bond reactivity. More active (electron-withdrawing, radical stabilizing) R-groups shift the reduction peak anodically, in part due to their influence on the rate of the coupled chemical reaction. Analysis of CVs across a range of scan rates revealed that kinetic control over the reduction mechanism is influenced by both the charge transfer rate and chemical reaction rate.

UV-Cross-linkable Donor-Acceptor Polymers Bearing a Photostable Conjugated Backbone for Efficient and Stable Organic Photovoltaics.

High-performance photovoltaic polymers bearing cross-linkable function together with a photorobust conjugated backbone are highly desirable for organic solar cells to achieve both high device efficiency and long-term stability. In this study, a family of such polymers is reported based on poly[(2,5-bis(2-hexyldecyloxy)phenylene)- alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[ c]-[1,2,5]thiadiazole)] (PPDT2FBT), a high-performance photovoltaic donor-acceptor polymer, with different contents of terminal vinyl-appended side chains for cross-linking. The polymers were named PPDT2FBT-V x and prepared by varying the feeding ratio ( x mol %, x = 0, 5, 10, and 15) of the vinyl-appended monomer in polymerization. It was found that the vinyl integration did not sacrifice the original high photovoltaic performance of the polymers, as evidenced by comparable average power conversion efficiencies (PCEs) (6.95, 7.02, and 7.63%) observed for optimized devices based on PPDT2FBT-V0, PPDT2FBT-V5, and PPDT2FBT-V10, respectively, in blending with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM). Unlike thermal cross-linking that greatly reduced device efficiency, UV cross-linking has proven to be an effective way to achieve both high device efficiency and thermostability for PPDT2FBT-V10 solar cells. UV-cross-linked PPDT2FBT-V10 solar cells displayed an initial average PCE of 5.28% and almost no decrease upon heat treatment at 120 °C for 40 h. Morphology studies revealed that UV-cross-linking did not only alter initial nanophase separation but also suppressed morphology evolution by aggregation in bulk heterojunction blend films. Photo-cross-linking requires material photostability. It is therefore worthwhile to note that these polymers and their blends with PC71BM were found to be extremely photostable, even upon continuous exposure to concentrated sunlight (up to 200 suns), and UV-cross-linking does not hamper this photostability. Further studies found that the devices fabricated with the UV-cross-linked PPDT2FBT-V10/PC71BM active layer can endure continuous light exposure to a solar simulator without deteriorating their performance.

Graft Copolymers with Conducting Polymer Backbones: A Versatile Route to Functional Materials.

Graft copolymers with a conducting polymer backbone are a promising class of materials for diverse applications including, but not limited to, organic electronics, stimuli-responsive surfaces, sensors, and biomedical devices. These materials take advantage of the unique electrochemical and optoelectronic properties of conducting polymers, complemented by chemical and/or physical properties of the grafted sidechains. In this Personal Account, we discuss our work in designing functional surfaces based on graft copolymers with a conducting polymer backbone, in the context of broader developments in the field. We review the synthetic approaches available for the rational design of conducting-polymer-based graft copolymers, and examine the types of functional surfaces and soluble materials that may be engineered using these techniques.